JP2002182352A - Titanium oxide-containing ultraviolet ray shielding filter material and color diffusion transfer photographic film unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a titanium oxide-containing UV shielding filter material having improved dispersibility and age stability and a color diffusion transfer film unit parted by peeling and having improved stain, light resistance and physical properties of the films. SOLUTION: The UV shielding filter material contains fine particulate titanium oxide having 1-45 nm average primary particle diameter or average primary minor axis size and 20-70% rutile crystallinity and a polyhydric alcohol. The color diffusion transfer photographic film unit has an image receiving element having a neutralizing layer, an image receiving layer and a peeling layer in this order on the base, a photosensitive element having at least one silver halide emulsion layer combined with at least one dye image forming compound on the base having a light shielding layer and an alkaline processing composition spread between the image receiving element and the photosensitive element. The alkaline processing composition is spread between the image receiving element and the photosensitive element after exposure and then the elements are peeled from each other to obtain an image. In the film unit, a UV shielding layer formed by applying the UV shielding filter material is included in the image receiving element.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color diffusion transfer photographic film unit, and more particularly to a peel-apart type photographic film unit for separating a photosensitive element and an image receiving element after processing.
The present invention relates to a photosensitive material which is excellent in light fastness, has small peeling time dependency of image density change, has little haze and stain on an image due to a processing solution remaining on an image receiving element at the time of peeling, and has good surface gloss. Further, the present invention relates to an ultraviolet ray shielding filter agent containing titanium oxide, which does not change with time and has low chemical activity (toxicity), which can be used for producing the above-mentioned photographic film unit.

[0002]

2. Description of the Related Art An ultraviolet shielding filter agent using an organic ultraviolet absorber is widely known. The ultraviolet absorbers used for these are organic substances and have high p
There are many problems such as coloring with H, decomposition by reaction with light or other chemicals, low water solubility, and the production method and usage method have been limited depending on the purpose of use. Furthermore, they were not always satisfactory in terms of chemical safety and the like. Therefore, there is a demand for a highly safe ultraviolet shielding filter agent which does not undergo absorption change over time. Color diffusion transfer using an azo dye image-forming substance that forms an azo dye having a diffusivity different from that of the image-forming substance itself after the image-receiving element and the photosensitive element are integrated, developing and developing an alkaline thickening liquid between them Photography is well known in the art. In this photographic method, a peel-apart method in which the thickening liquid is developed between the elements, and after development and transfer, the two are peeled off from each other to separate an image is also well known. Dye-donating substances described in U.S. Pat. No. 3,928,312 are known as dye-releasing compounds used in this transfer system.

In order to fix the released anionic dyes, US Pat. No. 3,958,9 is applied to an image receiving layer in an image receiving element.
It is known to use a quaternary ammonium salt polymer as a mordant as described in JP-A Nos. 95 and 3,898,088. Further, in order to improve the light fastness of the immobilized dye, US Pat.
5,124, 4,282,305, 4,27
No. 3,853, a polymer having a tertiary imidazole ring on the side chain is known.
No. 18, tertiary imidazole copolymers described in JP-A-8-62803 and copolymers having a quaternary ammonium base and a tertiary imidazole group described in JP-A-60-60643 are known. Further, Japanese Patent Laid-Open No. 10-1
No. 42765 describes an example of a peel-apart photographic film unit using a mordant containing an imidazole group. In addition, it is known to use a polymer having a pyridine ring in a side chain as a mordant. Such a polymer mordant has been developed for the purpose of increasing the holding power of the transferred anionic dye and increasing the stability of the dye to light. In the system, only the quaternary ammonium salt polymer and the polymer having a pyridine ring have been put to practical use. Japanese Unexamined Patent Application Publication No. 10-142
No. 765, etc., the haze and stain etc. could be considerably improved, but the physical properties of the film after and after peeling were still insufficient, and further improvements in these respects have been desired.

[0004] On the other hand, the improvement of photobleaching stability using fine particles of titanium oxide is disclosed in Japanese Patent Application Laid-Open No. 6-118591, but the titanium oxide used in the examples has a sphere-equivalent particle diameter of 50 nm. As described above, it was found from the subsequent research that in this region, there was a problem that transparency was insufficient and image density was lowered. In addition to this optical effect,
In the case of a peel-apart type instant photograph, the titanium oxide-containing layer serves as a diffusion path for the dye forming the image,
It was found that titanium oxide physically delays the diffusion of the dye, lowering the image density, and in this case also correlates with the particle size, with the density drop increasing in the region above about 50 nm. The above-mentioned Japanese Patent Application Laid-Open No. 6-118591 does not disclose any method for producing fine titanium oxide which does not affect the photographic density. Furthermore, dispersion of titanium oxide in a hydrophobic binder system,
Although it is described that use is preferred, in the case of instant color photography, the dye forming the image is water-soluble, and the dye is not diffused at all with the hydrophobic binder described in JP-A-6-118591, resulting in a photograph. There is no disclosure that suggests instant color photography.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a titanium oxide-containing ultraviolet shielding filter agent having improved dispersibility and stability over time.
Another object of the present invention is to provide a peel-apart type color diffusion transfer film unit having improved stain, light fastness and film physical properties.

[0006]

As a result of a study by the present inventors, it has been found that the use of titanium oxide having a primary particle size of 45 nm or less greatly improves the in-screen stain, light resistance, film physical properties, and the like. It has been desired to improve the stability of the dispersion and the photographic quality. Therefore, the present inventors have further studied and completed the present invention. An object of the present invention is to provide the following (1) to
Achieved by (5). (1) Average primary particle diameter or average primary short axis particle diameter is 1
An ultraviolet shielding filter agent comprising: a fine particle titanium oxide having a rutile crystallinity of 20 to 70% and a polyhydric alcohol. (2) An image-receiving element comprising a layer having a neutralizing function, an image-receiving layer and a release layer, and at least one dye image-forming compound on a support having a light-shielding layer. A photosensitive element having one silver halide emulsion layer, and an alkaline processing composition developed between the image receiving element and the photosensitive element, and after exposure, the alkaline processing composition is mixed between these elements. After the developing process, in the color diffusion transfer photographic film unit that peels off the image receiving element and the photosensitive element to obtain an image, in the image receiving element, the average primary particle diameter or the average primary short axis particle diameter is 1 to 45 nm, And rutile crystallinity of 20 to 70%
1. A color diffusion transfer photographic film unit comprising an ultraviolet shielding layer formed by applying an ultraviolet shielding filter agent containing fine particle titanium oxide and polyhydric alcohol. (3) The color diffusion transfer photographic film unit according to item (2), wherein the fine particle titanium oxide is a spindle type. (4) The color diffusion transfer photographic film unit according to the above (2) or (3), wherein the polyhydric alcohol is glycerin. (5) The ultraviolet ray shielding layer in the image receiving element is located on the image receiving layer and / or above the image receiving layer as viewed from the support of the image receiving element. 4) The color diffusion transfer photographic film unit according to the above item.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail. First, the ultraviolet shielding filter agent of the present invention will be described in detail. The ultraviolet shielding filter agent of the present invention is a dispersion in which the above-mentioned fine particle titanium oxide is dispersed in a medium (preferably water) containing a polyhydric alcohol. The rutile crystallinity that greatly affects the effects of the present invention will be described. For the calculation of the rutile crystallinity, the titanium oxide and silicon (specifically, silicon oxide or the like) to be measured are mixed at a weight ratio of 1: 5. Then, the ratio between the peak area of the rutile (1,1,0) plane and the peak area of silica is determined by X-ray diffraction. MT600B as standard sample
(Fine particle titanium oxide manufactured by Teica Co., Ltd., average primary particle diameter 50 nm, surface-free treatment) is measured, and this is taken as rutile crystallinity 100%, and the ratio to each measurement sample is calculated. In the present invention, this value is defined as rutile crystallinity. If the rutile crystallinity is large, the crystal is formed firmly and has excellent chemical resistance and weather resistance, but the refractive index is high and optical transparency may be disadvantageous. Conversely, if the rutile crystallinity is low, the chemical resistance and weather resistance are reduced, but the refractive index is lowered. Therefore, undesired refraction, interference, total reflection, etc. at the interface with the medium (air, water, etc.) Is less likely to occur, and as a result, the transparency of the film may be advantageous. In the present invention, the range of the rutile crystallinity is 20 to 70%,
A preferred range is 30-60%, and a more preferred range is 35%.
~ 55%. In the present invention, if this value is too large, the film may look rainbow depending on the observation angle, and if it is too low, at the time of intense light irradiation, cracks in the film due to the influence of active oxygen, and the coexisting organic Coloring occurs due to oxidation of the compound. The control of rutile crystallinity can be controlled by the firing temperature, drying temperature and time after surface treatment, and the temperature, concentration and time of post-treatment (leaching) with acid and alkali in the manufacturing process of fine particle titanium oxide described later. It is possible. Also related to this, it can be controlled also by the particle size. Various production methods can be used for the titanium oxide that can be used in the present invention, such as a neutralization hydrolysis of a titanium salt, a neutralization method of sodium titanate, a hydrolysis method of a titanium alkoxide, and a gas phase decomposition method of a titanium alkoxide. It can be manufactured by To specifically explain the neutralization hydrolysis method of titanium salt, after hydrolyzing titanium tetrachloride, baking, pulverizing and sizing,
It can be manufactured from the process of surface treatment, washing, drying and finishing grinding. In the sodium titanate neutralization method, after hydrolysis, alkali and acid leaching treatments are performed, and the process proceeds to a surface treatment step without passing through a firing process. This manufacturing process that does not go through calcination is defined as a wet process. The raw material titanium oxide that can be used in the present invention can be used by a firing method or a wet method, but a columnar or spindle-shaped titanium oxide is generally prepared by a wet method. The difference in particle size and aspect ratio depends on the purity of raw material titanium tetrachloride, hydrolysis rate, firing temperature, drying temperature, post-treatment (leaching) conditions with acid and alkali.
(Concentration, time, temperature) and surface treatment agent (type and amount) can be controlled. Further, the wet method has a feature of being easily dispersible. On the other hand, in the firing method, the crystal system and the amount of the surface treatment agent can be adjusted by the firing temperature and time. It has excellent weather resistance.

The average primary particle diameter or the average primary short axis particle diameter of titanium oxide is 1 to 45 nm, preferably 3 to 4 nm.
0 nm, more preferably 5 to 30 nm. Here, the “average primary particle diameter” is the average value of the sphere equivalent diameter when the primary particle shape is spherical or almost spherical, and the “average primary short-axis particle diameter” is that the primary particle shape is cylindrical. Also, it is the average value of the minor axis particle diameter in the case of a spindle shape. In the case of spindle-shaped or cylindrical (preferably spindle-shaped) particles,
The major axis diameter is preferably 3 to 200 nm, more preferably 5 to 200 nm.
To 150 nm, more preferably 10 to 100 nm. Further, the ratio of the long axis diameter to the short axis diameter (hereinafter referred to as the aspect ratio) is preferably 2 to 10, more preferably 2.5 to 10.
8, more preferably 3 to 6. As the fine particle titanium oxide of the present invention, those which have been surface-treated with aluminum oxide and / or silicon oxide can be used. The preferred use amount of aluminum oxide is 1 to 30% by mass based on titanium oxide,
More preferably, it is 2 to 20% by mass. Silicon oxide is also 1
-30% by mass, preferably 2-20% by mass. If the amount of the surface treatment agent is too small, poor dispersion or sedimentation of the dispersion over time occurs, and if it is too large, the amount of titanium oxide is substantially reduced, and the undesired result is that the intended ultraviolet absorbing ability is reduced. Become. In addition, regardless of inorganic or organic substances, those treated with a surface treating agent can also be preferably used. As the inorganic surface treating agent, zirconium oxide, zinc oxide and the like are preferable. Examples of the organic substance include siloxane, stearic acid, and trimethylolpropane. The use amount of the treating agent is preferably 3 to 45% (mass) with respect to titanium oxide,
More preferably, the content is 5 to 35% by mass. The larger the amount of the treatment agent used, the better the dispersibility and the like, but the amount of titanium oxide is relatively reduced, so the absorption of ultraviolet light is reduced,
Since the intended purpose, light stability, is impaired, it is preferable to select appropriately so that the above two performances are compatible. Such a surface treatment of titanium oxide can be performed, for example, as follows. The synthesized titanium oxide is dispersed in a phosphate such as sodium hexametaphosphate or the like, and the pH is adjusted according to the solubility of the surface treatment agent. A suspension of aluminum oxide and / or silicon dioxide is mixed therein, and the pH is adjusted to a value at which the solubility of the surface treating agent decreases after mixing. This results in the surface treating agent depositing and adhering to the surface of the titanium oxide. If necessary, the adhesion amount and form can be changed by adjusting the concentrations of the surface treatment agent and titanium oxide, or by performing a reaction temperature and a high temperature treatment after the reaction. The coating amount of the ultraviolet shielding filter agent of the present invention can be selected according to the purpose, but it is preferable to use the titanium oxide so that the titanium oxide is 0.01 to 20 g / m ² . If the amount used is large, the absorption of ultraviolet rays increases, but there is a disadvantage that the transparency is reduced. Further, when used in a color diffusion transfer photographic film unit, the content is preferably 0.01 to 2
A usage of 0 g / m ² is preferred. If the amount used is large, the amount of ultraviolet absorption increases, but there is a disadvantage that the photographic density is slightly lowered. Therefore, it is preferable to select an appropriate amount. A more preferred amount is 0.02 to 10 g / m ² , and still more preferably 0.05 to ² g / m ² .

As the titanium oxide described above, commercially available products can be used. For example, TTO-55, 51, S,
Any of the M and D series (trade name, manufactured by Ishihara Sangyo Co., Ltd.) can be used.

[0010] Titanium oxide can be made into a dispersion by solid dispersion. Water is preferably used in an amount of 0.67 to 32 times, more preferably 1 to 19 times, the mass of titanium oxide. As the dispersant, a polyanion compound and / or
Alternatively, a condensed phosphate is used. Specific examples of the polyanion compound that can be used in the present invention include polyacrylates (such as sodium polyacrylate), polymethacrylates (such as sodium polymethacrylate), polymaleates (such as sodium polymaleate), and acrylates. (Sodium acrylate) and methyl acrylate; maleic acid and methyl vinyl ether; carboxymethyl cellulose, carboxyethyl cellulose, and carboxyl-modified polyvinyl alcohol. Preferably, it is a polyacrylate or polymethacrylate. Examples of the condensed phosphate include sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate. In addition, commonly used surfactants (such as sodium dodecylbenzenesulfonate, polyoxyethylene nonyl phenyl ether), and water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, hydroxymethyl cellulose, polysaccharides), etc., are used in combination. can do. The amount of the polyanion compound and / or the condensed phosphate is preferably 0.5 to 50 relative to titanium oxide.
It can be used in the range of mass%. If the amount used is large, the amount of titanium oxide is substantially reduced, so that the amount of blocking ultraviolet rays is reduced. If the amount is too small, the dispersion stability cannot be secured. The amount used varies depending on the desired degree of dispersion and dispersion state, but is preferably 1 to 30% by mass, and more preferably 3 to 25% by mass.

Further, in the present invention, glycols, which are dihydric alcohols, are used to prevent aggregation of titanium oxide after dispersion.
Polyhydric alcohols such as glycerin which is a trihydric alcohol, pentite which is a pentahydric alcohol, and hexit which is a hexahydric alcohol are used. Among the polyhydric alcohols, those having a relatively small molecular weight and those having high hydrophilicity are preferable, and glycerin and ethylene glycol can be preferably used. The polyhydric alcohol may be added at the time of dispersion, or may be added after the dispersion is completed. The amount of the polyhydric alcohol to be used is preferably from 1 to 100% by mass, more preferably from 5 to 50% by mass, and still more preferably from 10 to 30% by mass, based on titanium oxide. As the solid disperser, any one that can be generally used can be used, but dissolvers, ball mills, paint shakers, sand grinders, horizontal media dispersers (commercially available under the names of Dyno mill, Eiger mill, etc.), kneaders, ultrasonic dispersers and A dispersing machine such as a roll mill can also be used. The ultraviolet shielding layer in the present invention can be applied by a known method. As the binder, a water-soluble polymer such as gelatin, polyvinyl alcohol, and carboxymethyl cellulose is desirable. The amount of the binder can be arbitrarily selected depending on the required target, but is desirably 0.1 to 10 times the mass ratio of titanium oxide. More preferably, it is 0.2 to 6 times. Well-known surfactants can be selected as coating aids, but alkylphenoxyethoxysulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkylsulfate, alkylsulfosuccinate, sodium oleylmethyltauride, naphthalenesulfone Anionic dispersants such as formaldehyde degenerate of acid, polyacrylic acid, polymethacrylic acid, maleic acrylic acid copolymer, carboxymethylcellulose, cellulose sulfate; polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Nonionic dispersants such as esters; cationic dispersants, betaine dispersants, etc .; and non-fluorinated nonions, cationic and anionic surfactants, and the like can be used. The ultraviolet shielding layer may be applied independently, or may be applied by simultaneous multilayer coating with the mordant layer. The mordant layer may contain fine particle titanium oxide.

Next, the color diffusion transfer photographic film unit of the present invention will be described. The color diffusion transfer photographic film unit of the present invention has, in an image receiving element, an ultraviolet shielding layer formed from a coating solution containing the above-mentioned ultraviolet shielding filter agent of the present invention. The ultraviolet shielding layer may be a single layer or two or more layers, and is preferably provided on the image receiving layer and / or above the image receiving layer (a layer further away from the support). In the photographic film unit of the present invention, the ultraviolet ray shielding layer and / or the image receiving layer contain fine particles of titanium oxide and, if necessary, a hydroxyarylbenzotriazole compound,
Organic ultraviolet absorbers such as benzoxazole compounds, hydroxyaryltriazine compounds, benzophenone compounds, cinnamate compounds, and butadiene compounds may be used in combination. Hydroxyaryl benzotriazole compounds and hydroxyaryl triazine compounds are particularly preferred because yellow coloring at the time of image completion due to high pH is small.

Next, the mordant used in the photographic film unit of the present invention will be described in detail. The mordant used in the photographic film unit of the present invention can be added alone or together with a hydrophilic binder such as gelatin or polyvinyl alcohol to the image receiving layer of the image receiving element, and immobilizes the image-forming diffusible dye. Is a polymer for As the mordant, at least one kind of a repeating unit represented by the following general formula (I) and a repeating unit selected from the general formulas (II), (III), (IV) and (V) Is preferred.

Formula (I)

[0015]

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(Wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L is 1 to 20)
Represents a divalent linking group having carbon atoms. m is 0 or 1. )

General formula (II)

[0018]

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(In the formula, R ₁ has the same meaning as in formula (I). R ₄ represents an alkyl group, an aryl group, an aryl group or an aralkyl group. N is 0 or 1.)

Formula (III)

[0021]

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(Wherein R ₁ has the same meaning as in 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. P,
q is 0 or 1, respectively. )

Formula (IV)

[0024]

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(Wherein R ₁ has the same meaning as in formula (I). D together with a nitrogen atom and a carbonyl group is 5 to 5)
Represents a divalent linking group necessary for forming a 7-membered ring. )

General formula (V)

[0027]

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(Wherein R ₁ , L and m have the same meanings as in formula (I). E is a divalent linking group necessary for forming a 5- to 7-membered ring, and M is hydrogen or an alkali. Represents a metal element.) The polymer mordant used in the present invention includes two or more types of compounds represented by different general formulas among general formulas (II), (III), (IV) and (V). It may contain a repeating unit or two or more kinds of repeating units contained in the same general formula. In the general formula (I), R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an n
-Butyl group, n-amyl group, n-hexyl group and the like,
A hydrogen atom, a methyl group and an ethyl group are particularly preferred.

L is a divalent linking group having 1 to 20 carbon atoms, for example, an alkylene group (for example, methylene group, ethylene group, trimethylene group, hexamethylene group, etc.), a phenylene group, (for example, o-, p- or m- phenylene group, etc.), arylenealkylene _{groups, -CO 2 -, - CO 2} -
R ₂₃ - (where R ₂₃ represents an alkylene group, a phenylene group, an arylenealkylene _{group.), - CONH-R 23} -
(However, R ₂₃ represents the same as above), -CON (-R
₂₁ ) -R ₂₃ (where R ₂₁ represents the same as R ₁ ;
₂₃ represents the same as above. ) And the like, and the following groups and the like are particularly preferable.

[0030]

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Preferred specific examples of the repeating unit represented by the above general formula (I) are shown below.

[0032]

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In the general formulas (II) and (III), R ₄ ,
R ₅ and R ₆ each represent an alkyl group (preferably having 1 to 6 carbon atoms;
For example, unsubstituted alkyl groups (methyl, ethyl, n-propyl, n-butyl, iso-butyl, n-amyl, hexyl, n-nonyl, n-decyl, n-
Dodecyl group), substituted alkyl group (methoxyethyl group,
3-cyanopropyl group, ethoxycarbonylethyl group,
Acetoxyethyl group, hydroxyethyl group, 2-butenyl group, etc.)), aryl group (preferably having 6 to 30 carbon atoms,
For example, a phenyl group, a tolyl group, a naphthyl group and the like, or an aralkyl group (preferably having 7 to 30 carbon atoms, for example, an unsubstituted aralkyl group (a benzyl group, a phenethyl group, a diphenylmethyl group, a naphthylmethyl group and the like), a substituted aralkyl group ( 4-methylbenzyl group, 4-isopropylbenzyl group, 4-methoxybenzyl group, 4- (4-methoxyphenyl) benzyl group, 3-chlorobenzyl group, etc.), a methyl group, an ethyl group, an n-butyl group , An iso-butyl group, a phenyl group, a benzyl group and the like are particularly preferred. R ₅ and R ₆ each represent a hydrogen atom in addition to the above, and a hydrogen atom may be particularly preferable in some cases.

Preferred specific examples of the repeating unit represented by the general formula (II) are shown below.

[0035]

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As the repeating unit represented by the general formula (III), N-vinyl compounds described in "Synthetic Polymer III" by Murahashi, Imoto, and Tani, pages 1 to 51 of Asakura Shoten (Showa 46) are polymerized. And the like. Preferred specific examples of the repeating unit represented by the general formula (III) are shown below.

[0037]

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In the general formula (IV), a nitrogen atom and a carbonyl
D together with the group is a divalent linkage required to form a 5- to 7-membered ring.
Represents a linking group and is a repeating unit represented by the general formula (IV)
The N-vinyl compound described in the above “Synthetic polymer III”
An example is a material having a structure obtained by polymerizing a product. Communicating
The linking group D is, for example, a divalent linkage composed of carbon atoms.
Linking group (for example, -CH_TwoCH_TwoCH_Two-, -CH_TwoCH_TwoCH_Two
CH_Two-, -CH_TwoCH _TwoCH_TwoCH_TwoCH_Two-, -C (=
O) -CH_TwoCH_Two-, -C (= O) -CH_TwoCH_TwoCH_Two
-Etc.), divalent composed of carbon and nitrogen atoms
(E.g., -NHCH_TwoCH_Two-, -C (= O)-
NH-C (CH_Three)_Two-, -C (= O) -NHCH_TwoCH_Two
-Etc.), divalent composed of carbon atoms and oxygen atoms
(For example, -OCH_TwoCH_Two-, -C (= O) -O
CH_TwoCH_Two-, -C (= O) -OC (CH_Three)_Two−
Etc.), divalent composed of carbon and sulfur atoms
Linking groups (for example, -SCH_TwoCH_Two-, -C (= O) -S-
CH_TwoCH_Two-Etc.), and the carbon atom and the nitrogen atom
A divalent linking group composed of General formula (I
Preferred specific examples of the repeating unit represented by V) are shown below.
Show.

[0039]

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In the formula (V), the divalent linking group E required to form a 5- to 7-membered ring is preferably a group which forms a benzene ring. M is preferably hydrogen, potassium or sodium.

In the polymer mordant which can be used in the photographic film unit of the present invention, the repeating unit represented by the general formula (I) is preferably from 10 to 98 mol%, more preferably from 40 to 90 mol% of all repeating units. And the repeating unit represented by the general formula (II), (III), (IV) or (V) is 2 to 60 mol% of all repeating units.
And more preferably 3 to 50 mol%.
It is also preferable to include other repeating units,
In that case, the ratio is preferably 40 mol% or less of all the repeating units. Among the repeating units represented by formulas (II), (III) and (IV), a repeating unit selected from formula (IV) is particularly preferred. The terminal of these polymers is not particularly limited, and may be any of a hydrogen atom, an alkyl group, and the like.

The molecular weight of the polymer mordant used in the photographic film unit of the present invention is preferably from 5 × 10 ³ to 1 × 10 ⁷ . If the molecular weight is too small, the polymer tends to move, and if the molecular weight is too large, it may hinder the coating on the image receiving material. More preferably, 1 × 10 ⁴ to 2
× 10 ⁶ . Preferred specific examples of the polymer mordant used in the photographic film unit of the present invention are shown below.
The terminal of these compounds is not particularly limited, and may be any of a hydrogen atom, an alkyl group and the like.

[0043]

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[0044]

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The above-mentioned polymer mordant is, for example,
No. 17418, and other compounds can be synthesized by the methods described therein. In the present invention,
As coating aids, alkylphenoxyethoxysulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkylsulfate, alkylsulfosuccinate, sodium oleylmethyltauride, formaldehyde degenerate of naphthalenesulfonic acid,
Anionic dispersants such as polyacrylic acid, polymethacrylic acid, maleic acrylic acid copolymer, carboxymethylcellulose and cellulose sulfate; nonionic dispersants such as polyoxyethylene alkyl ether, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester A cation-based dispersant, a betaine-based dispersant, and the like, and a fluorine-containing nonion, a cationic and anionic surfactant, and the like can be used.

In the photographic film unit of the present invention,
The amount of the coating aid to be used with respect to the polymer mordant is preferably 0.01 to 0.5, more preferably 0.1 to 0.3 by mass ratio.

The method for dispersing the polymer mordant in the present invention is not particularly limited, and can be prepared by a known method. For example, gelatin (including its derivative) is used alone in the mordant layer of the image receiving material, or gelatin and another binder are used in combination. As the binder, a hydrophilic binder can be used. As a hydrophilic binder other than gelatin, a transparent or translucent hydrophilic colloid is representative.For example, cellulose derivatives, starch, natural substances such as polysaccharides such as arabic gum, polyvinylpyrrolidone, acrylamide polymer, polyvinyl alcohol And synthetic polymer substances such as water-soluble polyvinyl compounds.

The mixing ratio of the polymer mordant and the binder and the amount of the polymer mordant applied in the present invention can be easily determined by those skilled in the art according to the amount of the dye to be mordant, the type and composition of the polymer mordant. / Binder ratio 20/80 to 90/10 (mass ratio) is preferred,
The coating amount of the mordant is preferably 0.2 g to 15 g / m ² ,
More preferably, it is used at 0.5 to 8 g / m ² .

The layer containing the polymer mordant can be applied by a usual coating method, and drying is also carried out by a commonly used means (a gelatin film is solidified at a low temperature, and then dried).
(A method of gradually removing water at 〜50 ° C.), but in order to increase the effect of the present invention, 80 to 12
Drying at a high temperature of 0 ° C. is preferred. For the layer containing the polymer mordant, a usual hardener (aldehyde, vinyl sulfone, epoxy, active halogen compound, etc.) can be used. In the present invention, the amount of such a hardening agent used is 0.01 to 15 with respect to the gelatin in the mordant layer.
% By mass is preferable, and 0.1 to 5% by mass is more preferable.

Next, a hardener containing an epoxy group, a vinyl sulfone group and an aldehyde group which can be used in the photographic film unit of the present invention will be described. The compound is intended to cross-link the polymer mordants described above, the polymer mordant and a binder such as gelatin, and / or a binder such as gelatin, and to satisfy the water resistance and film physical properties of the layer containing the polymer mordant. .

Preferred specific examples of epoxy hardeners that can be used in the photographic film unit of the present invention are shown below.

[0052]

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Specific examples of the vinyl sulfone hardener include the following.

[0054]

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The amount of the hardener used in the photographic film unit of the present invention (when used in combination) is preferably 0.01 to 30% by mass based on the gelatin in the mordant layer.
0.1-15 mass% is more preferable.

In the present invention, by using hydrophobic particles in the image receiving element, the adhesiveness of the photographic material surface can be improved.
preferable. Particularly useful are matting agents capable of roughening the surface, such as polymethyl methacrylate, methyl methacrylate / methacrylic acid copolymer, silica, barium strontium sulfate, and silver halide non-photosensitive fine particles. In terms of changing the surface properties, fluorine surfactants, silicone compounds, liquid paraffin, etc. can also be chemically modified, but in the present invention, a matting agent which is a physical modifier is preferable. Give the result. The larger the particle size of the matting agent is, the more preferable it is, particularly, larger than the thickness of the image receiving layer to be added. The preferred amount of addition varies depending on the material and particle size of the matting agent to be used. If the amount is too large, the above-mentioned adhesiveness is improved, but haze and feel are deteriorated and undesired results such as a rough feeling are brought. Therefore, the preferable range is 0.003 to 0.10 g / m ² . In the invention, the hydrophobic particles can be added to the ultraviolet shielding layer and the release layer of the invention in addition to the image receiving layer. In the photographic film unit of the present invention, the thickness of the image receiving layer is preferably from 2 to 15 μm, more preferably from 4 to 8 μm. The ultraviolet shielding filter agent of the present invention is not limited to photographic ones, but can be used as a filter agent by mixing it with plastic.

Hereinafter, each component included in the photographic film unit of the present invention will be sequentially described. I. Photosensitive Element A) Support The support for the photosensitive element used in the present invention may be any smooth support commonly used in photographic light-sensitive materials, such as paper, cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferable to provide an undercoat layer. Preferably, the support usually contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping. Support thickness is 50
To 350 μm, preferably 60 to 210 μm, and more preferably 70 to 150 μm. On the back side of the support, a curl balance layer or a layer described in JP-A-56-
An oxygen barrier layer described in JP 78833 can be provided.

B) Light-Shielding Layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the support and the photosensitive layer. As the light-shielding agent, any material having a light-shielding function is used, and carbon black is preferably used. U.S. Pat. No. 4,615,96
Degradable dyes described in No. 6, etc. may be used. As the binder for coating the light-blocking agent, any binder capable of dispersing carbon black may be used, and gelatin is preferred. As a carbon black raw material, for example, Donne
l Voet "Carbon Black" Marce
l Dekker, Inc. Any production method such as a channel method, a thermal method and a furnace method described in (1976) can be used. The particle size of the carbon black is not particularly limited, but is preferably 30 to 180 μm. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the photosensitive material to be shielded from light, but is preferably about 5 to 10 in optical density.

C) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image-forming substance is provided above the light-shielding layer. Hereinafter, the components will be described. (1) Dye image-forming substance The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in connection with silver development, or has a diffusivity of itself. Is changed, and the “photography process theory” (The The
Theoryof the Photographi
c Process, Macmillan) 4th edition. All of these compounds can be represented by the following general formula (X). Formula (X) (DYE-Y) _n -Z ｛DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents an image A difference in diffusivity of the compound represented by (DYE-Y) _n -Z corresponding to or inversely corresponding to a photosensitive silver salt having a latent image, or release DYE and release DYE And (DYE-Y) _n -Z represent a group having a property that causes a difference in diffusivity, and n represents 1 or 2, and when n is 2, two DYE-Ys are the same. But they may be different.機能 Due to the function of Z, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion. Specific examples of the negative type Z include those which are oxidized and cleaved to release a diffusible dye as a result of development.

A specific example of Z is disclosed in US Pat. No. 3,928,312.
Nos. 3,993,638 and 4,076,529
Nos. 4,152,153 and 4,055,428
Nos. 4,053,312, 4,198,235
Nos. 4,179,291 and 4,149,892
No. 3,844,785, No. 3,443,943
Nos. 3,751,406 and 3,443,939
Nos. 3,443,940 and 3,628,952
Nos. 3,980,479 and 4,183,753
No. 4,142,891, No. 4,278,750
Nos. 4,139,379 and 4,218,368
No. 3,421,964, 4,199,355
No. 4,199,354, 4,135,929
No. 4,336,322, 4,139,389
No. JP-A-53-50736 and JP-A-51-104343.
No. 54-130122, No. 53-110827
Nos. 56-12642, 56-16131, 57-4043, 57-650, and 57-207
No. 35, No. 53-69033, No. 54-130927
Nos. 56-164342 and 57-119345. Among the Z of the negative dye-releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). Representative groups of Z are exemplified below, but are not limited thereto.

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For positive-type compounds, see Angev. Chem. Inst. Ed. Eng.
l. ), 22, 191 (1982).
Specific examples include compounds (dye developing agents) which are initially diffusible under alkaline conditions but are oxidized by development to become non-diffusible. As the effective Z for this type of compound, those described in U.S. Pat. No. 2,983,606 are representative. Another type is a type in which a diffusible dye is released by, for example, self-cyclization under alkaline conditions, but the dye is substantially not released when oxidized during development. Specific examples of Z having such a function are described in US Pat. No. 3,980,479,
Nos. 3-69033, 54-130927, U.S. Pat. Nos. 3,421,964 and 4,199,355. Another type does not release the dye itself, but releases the dye when reduced. Compounds of this type can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, see, for example, U.S. Pat. Nos. 4,183,753 and 4,142,89.
No. 1, 4,278,750, 4,139,379
No. 4,218,368, JP-A-53-11082.
7, U.S. Pat. Nos. 4,278,750 and 4,356,
Nos. 249 and 4,358,525, JP-A-53-11
0827, 54-130927, 56-164
No. 342, published technical report 87-6199, European Patent Publication 2
20,746A2. Specific examples will be described below, but the present invention is not limited thereto.

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When a compound of this type is used, it is preferably used in combination with a diffusion-resistant electron-donating compound (known as an ED compound) or its precursor (precursor). Examples of ED compounds include, for example, US Pat.
Nos. 263,393 and 4,278,750;
No. 6-138736. Specific examples of other types of dye image-forming substances include the following.

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The details are described in US Pat. Nos. 3,719,489 and 4,098,783. On the other hand, specific examples of the dye represented by DYE in the above general formula are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. JP-A-51-114930, 383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322.
No. 56-71072: Research Discl
No. 17630 (1978), 16475
(1977). Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, and 3,954 No. 4,476, No. 4,233,237, No. 4,255,509, No. 4,250,246, No. 4,142,891, No. 4,207,104, No. 4,287,292 No .: JP-A-52-106727,
Nos. 53-23628, 55-36804, 56
No. -73057, No. 56-71060, No. 55-13
What is described in No. 4.

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 3,929,760, No. 4,013,63
No. 5, 4,268,625, 4,171,220
Nos. 4,242,435 and 4,142,891
Nos. 4,195,994 and 4,147,544
No. 4,148,642; British Patent 1,551,1
No. 38; JP-A-54-99431, JP-A-52-8827.
No. 53-47823, No. 53-143323,
Nos. 54-99431 and 56-71061; European Patents (EP) 53,037 and 53,040;
Research Disclosure 17630
(1978) and No. 16475 (1977). These compounds are disclosed in JP-A-62-2.
No. 15272, pages 144 to 146. These dispersions are described in JP-A-62-2.
Compounds described in No. 15272, pp. 137-144 may be included.

(2) Silver halide emulsion The silver halide emulsion used in the present invention may be a negative emulsion which mainly forms a latent image on the surface of silver halide grains,
An internal latent image type direct positive emulsion which forms a latent image inside silver halide grains may be used. The internal latent image type direct positive emulsion includes, for example, a so-called "conversion type" emulsion which is prepared by utilizing the difference in solubility of silver halide, and a metal ion-doped or chemically sensitized or both. There is a "core / shell type" emulsion in which at least the light-sensitive sites of the applied silver halide inner core (core) grains are coated with an outer shell (shell) of silver halide. 592,250, 3,206,313
No. 1,027,146, U.S. Pat.
Nos. 1,276, 3,935,014, 3,44
7,927, 2,297,875, 2,56
3,785, 3,551,662, 4,39
No. 5,478, West German Patent 2,728,108, U.S. Pat. No. 4,431,730 and the like.

When an internal latent image type direct positive emulsion is used, it is necessary to give a surface fog nucleus using light or a nucleating agent after image exposure. As a nucleating agent for that,
U.S. Pat. Nos. 2,563,785 and 2,588,982
Hydrazines described in US Pat. No. 3,227,5
No. 52, hydrazines and hydrazones described in British Patent No. 1,283,835, JP-A-52-69613.
No. 3,615,615 and 3,719,4
Nos. 94, 3,734, 738 and 4,094,68
Heterocycle 4 described in No. 3, No. 4, 115, 122, etc.
Grade salt compounds, sensitizing dyes having a substituent having a nucleating effect described in US Pat. No. 3,718,470 in dye molecules, US Pat. Nos. 4,030,925 and 4,031,1
No. 27, No. 4, 245, 037, No. 4, 255, 51
No. 1, 4,266,013, 4,276,364
Thiourea-bonded acylhydrazine compounds described in U.S. Patent Nos. 2,012,443 and U.S. Patent Nos. 4,080,270 and 4,278,748; An acylhydrazine-based compound in which a heterocyclic group such as a thioamide ring or a triazole or tetrazole described in (1) is bonded as an adsorbing group is used.

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

(3) Composition of the photosensitive layer In order to reproduce a natural color by the subtractive color method, the dye which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the spectral sensitizing dye is used. A photosensitive layer comprising at least two of the combination with an image forming substance is used. The emulsion and the dye image-forming substance may be coated as separate layers,
Alternatively, they may be mixed and applied as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming substance layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, JP-B-60-1
It is also possible to increase the color image density by providing a partition layer described in No. 5267, or to increase the sensitivity of a photosensitive element by providing a reflective layer. The reflective layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The coating amount of titanium oxide is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.2 g / m ^2.
a ^{g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354. In a preferred multilayer structure, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion, and a combination unit of a red-sensitive emulsion are sequentially arranged from the exposure side. Arbitrary layers can be provided between the emulsion layer units as needed. In particular, it is preferable to provide an intermediate layer in order to prevent an unfavorable effect of the development effect of one emulsion layer on other emulsion layer units.

When a developer is used in combination with a non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent to prevent diffusion of the oxidized developer. Specific examples thereof include non-diffusible hydroquinone, sulfonamidophenol, and sulfonamidonaphthol, and more specifically, JP-A-50-21249, and JP-A-50-21249.
No. 0-23813, JP-A-49-106329, and JP-A-49-106329.
No. 9-129535, U.S. Pat. No. 2,336,327,
2,360,290, 2,403,721, 2,544,640, 2,732,300, 2,782,659, 2,937,086, and 3 637,393, 3,700,453, British Patent 557,750, JP-A-57-24949, and 58-21249. The dispersing methods are described in JP-A-60-238831 and JP-B-60-18978. Japanese Patent Publication 55-7
In the case of using a compound capable of releasing a diffusible dye by silver ions as described in JP-A-576-576, it is preferable to include a compound that captures silver ions in the intermediate layer. In the present invention, if necessary, an anti-irradiation layer, UV
An absorbent layer, a protective layer and the like are provided.

II. Image receiving element A) Support In the present invention, a support capable of withstanding the processing temperature is used as the support of the image receiving element. In general,
Paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarbonate,
Synthesis of polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetyl cellulose) or those containing pigments such as titanium oxide in their films, and film-processed synthetic paper made of polypropylene, etc., and synthesis of polyethylene, etc. Mixed paper made from resin pulp and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used. These can be used alone or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, a material obtained by kneading carbon black into polyethylene inside the paper may be contained in a form sandwiched between the papers to provide a light-shielding property. In addition, JP-A-62-253159 (29)-
The support described on page (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

B) Release Layer In the present invention, a release layer is provided in order to peel off the image receiving element in the unit at an arbitrary place after the treatment. Therefore, this release layer must be easily peelable after the treatment. Materials for this purpose include, for example, JP-A-47-8237 and JP-A-5-8237.
Nos. 9-220727, 59-229555 and 49
-4653, U.S. Pat. Nos. 3,220,835 and 4,359,518, and JP-A-49-4334, 5
Nos. 6-65133, 45-24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746 and 4,366,227. Can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. Other examples include various natural polymers, such as alginic acid, pectin, gum arabic, and the like. Various modified gelatins such as acetylated gelatin and phthalated gelatin can also be used. Still another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, polybutyl methacrylate, or a copolymer thereof, or the like.
The release layer may be a single layer or, for example, disclosed in JP-A-59-2
As described in No. 20727, No. 60-60642, etc., it may be composed of a plurality of layers.

The color diffusion transfer photosensitive material of the present invention preferably has a neutralizing function between the support and the photosensitive layer, between the support and the image receiving layer, or on the image receiving element.

C) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali introduced from the treatment composition. Accordingly, a multilayer structure including layers such as a neutralization rate control layer (timing layer) and an adhesion strengthening layer may be used. Preferred acidic substances are those containing an acidic group having a pKa of 9 or less (or a precursor group that provides such an acidic group by hydrolysis), and more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in US Pat. Ester copolymers; U.S. Pat. No. 4,139,383 and Research Disclosure
e) No. 16102 (1977). In addition, U.S. Pat. No. 4,088,493,
Nos. 2-153739, 53-1023 and 53-4
No. 540, No. 53-4541, No. 53-4542 and the like. Specific examples of the acidic polymer include a copolymer of ethylene, vinyl acetate, a vinyl monomer such as vinyl methyl ether and maleic anhydride and its n-butyl ester, a copolymer of butyl acrylate and acrylic acid, cellulose, and acetate. -Hydrogen phthalate and the like. The polymer acid may be used as a mixture with a hydrophilic polymer. Examples of such a polymer include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred. Further, a polymer other than the hydrophilic polymer, such as cellulose acetate, may be mixed with the polymer acid.

The amount of the polymer acid applied is controlled by the amount of alkali developed between the photosensitive element and the image receiving element. The equivalent ratio of polymer acid to alkali per unit area is 0.9 to
2.0 is preferred. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stain is generated on a white background portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.
0 to 1.3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The mass ratio of the hydrophilic polymer to the polymer acid is from 0.1 to 10, preferably from 0.3 to 3.0. In the layer having a neutralizing function of the present invention, additives can be incorporated for various purposes. For example, hardeners well known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film.
In addition, if necessary, an antioxidant, a fluorescent whitening agent, a development inhibitor and a precursor thereof may be added. Timing layers used in combination with the neutralizing layer include polymers that reduce alkali permeability such as, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like; Useful are latex polymers made by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer to increase the activation energy of alkali permeation; and polymers having a lactone ring.

Among them, JP-A-54-136328,
U.S. Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849 and the like, a timing layer using cellulose acetate;
No. 335, No. 56-69629, No. 57-6843
No. 4,056,394 and 4,061,4
Nos. 96, 4,199,362, 4,250,24
No. 3, 4,256, 827, 4,268,604
A latex polymer prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid; a polymer having a lactone ring disclosed in U.S. Pat. No. 4,229,516; -25735
Nos. 56-97346 and 57-6842, European Patent (EP) 31,957A1, 37,72
The polymers disclosed in Nos. 4A1, 48,412 A1, and the like are particularly useful. In addition, those described in the following documents can also be used. U.S. Pat. Nos. 3,421,893, 3,455,686, 3,575,701, 3,778,265, 3,785,815, 3,847,615 and 3,847,615 4,088,493, 4,123,275, 4,148,653, 4,201,587, 4,288,523, 4,297,431, West German Patent Application (OLS) 1,6
No. 22,936, No. 2,162,277, Research
rch Disclosure 15162, No. Fifteen
1 (1976).

The timing layer using these materials can be used as a single layer or as a combination of two or more layers. In addition, for example, US Pat. No. 4,009,029 and West German Patent Application (OLS) 2,9
13,164, 3,014,672, JP-A-54
Development inhibitors and / or precursors thereof disclosed in JP-A-155837 and JP-A-55-138745, hydroquinone precursors disclosed in U.S. Pat. No. 4,201,578, and other useful photographic additives Alternatively, it is also possible to incorporate the precursor or the like. Further, as a layer having a neutralizing function, provision of an auxiliary neutralizing layer as described in JP-A-63-168648 and JP-A-63-168649 reduces the change in transfer density with time after processing. effective.

D) Image-Receiving Layer The layer having the above-mentioned polymer mordant is effectively used. E) Others In addition to the layer having the neutralizing function, a layer having an auxiliary function may have a back layer, an intermediate layer, and the like. The back layer is provided for adjusting curl, providing slipperiness, and providing a light-shielding function.

III. Alkaline Processing Composition The processing composition used in the present invention is developed uniformly between the photosensitive element and the image receiving element after exposure of the photosensitive element, and develops the photosensitive layer. For this purpose, the composition contains an alkali, a thickener, a developing agent, and further, for adjusting the development,
It contains a development accelerator, a development inhibitor, an antioxidant for preventing the deterioration of the developer, and the like. Alkali adjusts the pH of the solution to 12 ~
14, alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal phosphates (eg, potassium phosphate), guanidines, and quaternary amines. Hydroxides (for example, tetramethylammonium hydroxide, etc.) are exemplified, and potassium hydroxide and sodium hydroxide are particularly preferred. The thickener is required to spread the processing solution uniformly and to maintain the close contact between the photosensitive layer and the cover sheet.
For example, alkali metal salts of polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used. Preferred developing agents can be used as long as they cross-oxidize the dye image-forming substance and do not substantially cause stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor form. These developing agents may be contained in an appropriate layer of the photosensitive element, or may be contained in an alkaline processing solution. Specific examples of the compound include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferable because they generate less stain. For example, 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-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-
4-hydroxymethyl-3-pyrazolidinone, and the like. In addition, these alkaline liquid compositions have a developed thickness (the amount of the processing liquid per 1 m ² after the transfer of the processing liquid) of 20 μm to
It is desirable that the image is transferred onto a photosensitive material at 200 μm.
The processing temperature when processing the light-sensitive material of the present invention is 0 to 50.
C is preferable, and 0 to 40 C is more preferable.

Any of the light-sensitive element, the image-receiving element and the alkali processing composition described in JP-A-62-215272.
Development accelerator described on page 91, hardener described on pages 146 to 155, surfactant described on pages 201 to 210, 210 to 22
Fluorine-containing compounds described on page 2, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, 230-2
Polymer latex described on page 39, matting agent described on page 240 and the like can be included.

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The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
“Parts” and “%” mean parts by mass and% by mass, respectively, unless otherwise specified. Example 1 Fine particle titanium oxide TI-A (spherical shape, average primary particle size 12
nm, rutile crystallinity 44%, aluminum oxide 10%
(Surface treatment with titanium oxide) 35 parts, 5.2 parts of dispersant sodium polyacrylate (Poise-530 (trade name, manufactured by Kao Corporation)), 10.5 parts of glycerin, an anticoagulant, and 49 parts of water. And 3 parts were mixed and dispersed by a dissolver (Tokusai Kika Kogyo Co., Ltd.) at 3000 rpm for 30 minutes. Thereafter, the mixture was passed through a horizontal sand grinder five times at 2500 rpm to obtain a dispersion A. Dispersion A and gelatin are mixed such that the titanium oxide / gelatin ratio is 2/1,
Further, on a polyethylene terephthalate support, 350
The sample was coated so that the optical density in nm became 1 (sample A). Further, Sample B was prepared in which the above fine particle titanium oxide TI-A was changed to an average primary particle diameter of 55 nm and aluminum oxide of 10%). In addition, 2 g of each of the following compounds A and B was added to 4 g of tricresyl phosphate, 5 ml of ethyl acetate,
The mixture was mixed with 2 g of gelatin and emulsified and dispersed at 5,000 rpm for 5 minutes using a dissolver (Tokusai Kika Kogyo Co., Ltd.). Similarly to Sample A, a polyethylene terephthalate support was coated so that the optical density at 350 nm was 1 (Sample C). Sample D was prepared by removing glycerin from Sample A.

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Table 1 shows the optical density of each sample at 400 nm, the density change rate (durability) when exposed to 100,000 lux of xenon light for 3 weeks, and the results of visual state change.

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[Table 1]

From Table 1, it can be seen that the sample using the filter agent using the fine particle titanium oxide of the present invention is superior in all of the ultraviolet blocking, the visible light transparency and the durability as compared with the sample of the comparative example. I understand. Furthermore, it was also found that the increase in haze observed in Sample C and the occurrence of the fine cracks observed in Sample D were not observed in Sample A, indicating that it was an excellent ultraviolet shielding filter agent. Example 2 A photosensitive element (101) was prepared by coating a 90 μm-thick transparent polyethylene terephthalate film support with the following layer structure. Back layer side: (a) the light-shielding layer containing carbon black 6.0 g / m ² and gelatin 2.0 g / m ^2. (B) A protective layer containing 0.5 g / m ² of gelatin. Emulsion layer side: (1) Titanium dioxide 3.7 g / m ² and gelatin 0.
Layer containing 5 g / m ² . (2) The following cyan dye releasing redox compound 0.46
g / m ² , 0.07 g of tricyclohexyl phosphate
/ M ^2, dispersion aids following (A) 0.05g / m ^2, dispersion aids below (B) 0.06g / m ^2, and gelatin 0.
Color material layer containing 5 g / m ² .

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(3) Gelatin 0.5 g / m^TwoContains
layer. (4) Red-sensitive internal latent type direct positive silver bromide emulsion (average grain size
0.65 μm, 0.11 g / m^Two), Gelatin
0.3g / m^TwoThe following nucleating agent 0.003 g / m ^TwoAnd
And 2-sulfo-5-n-pentadecylhydroquinone.
Sodium salt 0.02 g / m^TwoRed-sensitive emulsion containing
layer.

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(5) Red-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.98 μm, silver amount: 0.23 g /
m ² ), gelatin 0.4 g / m ² , 2-sulfo-5-n-
Pentadecyl hydroquinone sodium salt 0.04g
/ M ² and the same nucleating agent as layer (4) 0.005 mg /
a red-sensitive emulsion layer containing m ² . (6) 2,5-di-t-pentadecylhydroquinone 0.61 g / m ² , the following polymer dispersant 0.33 g /
an anti-color mixing layer containing m ² and gelatin 0.3 g / m ² .

[0092]

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(7) An intermediate layer containing 0.2 g / m ² of gelatin. (8) The following magenta dye-releasing redox compound is used in 0.1.
46 g / m ² , the same dispersing aid (A) as layer (2) 0.04
g / m ^2, a dispersion aid (B) 0.07g / m ^2, and the color material layer containing gelatin 0.7 g / m ^2.

[0094]

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(9) Green-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 μm, silver amount: 0.11 g /
m ² ), gelatin 0.2 g / m ² , the same nucleating agent as in layer (4) 0.005 mg / m ² and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.02 g / m 2
A green-sensitive emulsion layer containing ² . (10) Green-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.26 g / m ² ), gelatin 0.6 g / m ² , same nucleation as layer (4) Agent 0.004
A green-sensitive emulsion layer containing mg / m ² and 0.04 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt. (11) 2,5-di-t-pentadecylhydroquinone 0.91 g / m ² , the following polymer dispersant 0.29 g /
an anti-color mixing layer containing m ² and 0.4 g / m ² of gelatin.

[0096]

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(12) Same layer as in (7). (13) 0.53 g / m ² of a yellow dye-releasing redox compound having the following structure, 0.16 g / m ^{2 of} tricyclohexyl phosphate, and the same dispersing aid (A) as in the layer (2).
05 g / m ² , dispersing aid (B) 0.03 g / m ² , the following dye release accelerator (Q) 0.035 g / m ² , (R) 0.0
A coloring material layer containing 18 g / m ² and gelatin 0.5 g / m ² .

[0098]

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[0099]

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(14) Blue-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 μm, silver amount: 0.15 g /
m ² ), gelatin 0.2 g / m ² , the same nucleating agent as in layer (4) 0.006 mg / m ² , the following compound (S) 0.0014
g / m ² and 2-sulfo -5-n-pentadecylhydroquinone sodium salt blue-sensitive emulsion layer containing 0.01 g / m ^2. Compound (S)

[0101]

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(15) Blue-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.23 g /
m ² ), gelatin 0.3 g / m ² , the same nucleating agent as layer (4) 0.005 mg / m ² and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.01 g / m 2
Blue-sensitive emulsion layer containing ² . (16) The following UV absorbers (A) and (B)
Ultraviolet absorbing layer containing 2 g / m ² and gelatin 0.5 g / m ^2.

[0103]

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(17) Matting agent (PMMA) 0.2 g /
m ^2, a hardener described below (A) 0.11g / m ^2, the following hardener (B) 0.03g / m ² and gelatin 0.4 g / m ²
A protective layer containing.

[0105]

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Next, an image receiving element (101) was prepared by applying the following layer composition on a paper support having a thickness of 150 μm and a polyethylene having a thickness of 20 μm laminated on both sides.

[0107] Back layer side: (a) the light-shielding layer containing carbon black 2.8 g / m ² and gelatin 4.8 g / m ^2. (B) 4.1 g / m ^{2 of} titanium dioxide and gelatin 1.
White layer containing 0 g / m ² .

(C) A protective layer containing 0.5 g / m ² of gelatin. Image receiving layer side: (1) diacetyl cellulose (54.5% acetylation degree)
9 g / m ² , methyl vinyl ether / maleic anhydride copolymer (molar ratio 1: 1, average molecular weight 20,000) 5.9
g / m ² , 0.09 g / m ^{2 of} the following compound (B), and 0.0 g / m ² of (C).
17 g / m ² , (D) 0.12 g / m ² , (E) 0.08 g /
Neutralizing layer containing m ² and (F) 0.40 g / m ² .

[0109]

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(In the formula, Bu represents a butyl group.)

(2) Diacetyl cellulose (degree of acetylation: 5
1.3%) 5.3 g / m ² , styrene / maleic anhydride copolymer (molar ratio 1: 1, average molecular weight 10,000)
A timing layer containing 16 g / m ² and the following compound (G) 0.35 g / m ² .

[0112]

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(3) Polymer latex (styrene / butyl acrylate / N-methylol acrylamide emulsion-polymerized at a mass ratio of 49.7 / 42.3 / 8)
0.05 g / m ² and polymer latex (emulsion polymerization of methyl methacrylate / acrylic acid / N-methylolacrylamide at a mass ratio of 93/3/4) 0.0
Timing layer containing 5 g / m ² .

(4) The following mordant (H): 3.0 g / m ² ,
(I) 0.6 g / m ² , the following anti-fading agent (J) 0.05 g / m ²
m ² , 0.2 g / m ^{2 of} the following hardener (K), 0.10 g of (L)
/ M ² , and a mordant layer containing 2.8 g / m ² of gelatin.

[0115]

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[0116]

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[0117] (5) was formed from the coating liquid containing titanium oxide dispersion A of the present invention example was prepared in Example 1, titanium oxide 0.6 g / m ^2, gelatin 0.5 g / m ^2, the following surfactants A titanium oxide layer containing 0.01 g / m ² of the agent (M).

[0118]

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(6) Acrylic acid / butyl methacrylate copolymer (molar ratio: 85:15, average molecular weight: 100,00
0) Release layer containing 0.04 g / m ² . Further, an alkali treatment composition was prepared in which 1 g of a treatment solution having the following composition was filled in an aluminum foil pod laminated with vinyl chloride under a nitrogen atmosphere.

Hydroxyethyl cellulose 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 sulfite 1.0 g 1-phenyl -4-hydroxy-4-hydroxymethyl-3-pyrazolidone 13.0 g potassium hydroxide 63 g water 854 ml

Image receiving elements (102) to (106) are exactly the same as image receiving element 101, except that fine particle titanium oxide TI-A is changed to TI-B to TI-F as shown in Table 2. ) Was prepared. Further, TI-A
Receiving element (1) in which glycerin was changed to a dispersion in which glycerin was not added.
07) was prepared. At the same time, for the purpose of measuring the spectral absorption of the titanium oxide layer, a sample was prepared in which the same amount as the amount applied to the image receiving element was applied to the transparent base.

Next, after imagewise exposure is given to the photosensitive element (101), the image receiving elements (101) to (107) are superposed, and an alkali treatment composition is developed between the two elements so as to have a thickness of 51 μm. did. The processing is performed at 25 ° C., and the photosensitive element and the image receiving element are peeled off 90 seconds after the processing, and the temperature is reduced to 30 ° C.-40%
85,000 lux xenon light under RH atmosphere
The amount of decrease in magenta concentration after irradiation on the day (concentration before irradiation 1.0) was measured. The minimum density was measured using a Fuji automatic recording densitometer (Fuji Photo Film Co., Ltd.). For the spectral absorption, the ratio between the absorbance at 350 nm and the absorbance at 400 nm was calculated and used as an index of the increase in visible light absorption that occurs as a result of blocking ultraviolet rays and its adverse effect. The larger the ratio, the smaller the haze and the greater the blocking of ultraviolet light, which is preferable. Table 2 shows the results of the above minimum density, light fading performance (light fastness), and absorbance ratio.

[0123]

[Table 2]

From the results shown in Table 2, the image receiving elements 101 to 105
In the case of using (Example of the present invention), it can be seen that the absorbance ratio is high, the minimum concentration is low, and the xenon light resistance is high. The TI-F having too low a rutile crystallinity had a high reactivity, and the film was modified and the weather resistance was low. Haze also occurred on the surface. In addition, it can be seen that in the (107) sample to which glycerin was not added, fine cracks were generated at the time of xenon fading, resulting in deterioration of the fading property. Even when the treatment was carried out for 5 minutes and 10 minutes instead of the 90-second peeling, improvement of the light fading was confirmed in the examples of the present invention. This shows that the stain has also been improved.

Embodiment 3 The above-mentioned image receiving element 104 is provided with fine particle titanium oxide TI-
The image receiving elements (109) to (109) are exactly the same as the image receiving element 104 except that D is changed to TI-GI to I as shown in Table 3.
(112) was produced. In the same manner as in Example 2, a sample was prepared in which the same amount as that applied to the image receiving element was applied to the transparent base.

Next, the same expansion processing as in the second embodiment is performed.
The highest concentration was measured along with the lowest concentration. Table 3 shows the results of the minimum density, the maximum density, the light fading performance (light fastness), and the absorbance ratio.

[0127]

[Table 3]

As can be seen from Table 3, it is understood that the sample of the present invention can maintain high photographic performance and also improve the light-fading property. Example 4 An image receiving element (111) was prepared in the same manner as in the image receiving element 101 except that the titanium oxide dispersion A was added to the mordant layer in the same amount, and the titanium oxide was removed from the titanium oxide layer. When evaluated by the same method as in Example 2, it was 85%.
From this, it was found that even if titanium oxide was contained in the image receiving layer, it was effective.

Comparative Example 1 An image receiving element prepared by removing glycerin from a titanium oxide dispersion was prepared for the image receiving element 101 and tested. As a result, improvement in light-fading was confirmed. It caused an increase in viscosity, which was not sufficient from the viewpoint of long-term production stability.

Example 5 A photosensitive element (502) was formed on a 90 μm-thick opaque polyethylene terephthalate film support in the following layer configuration. 1. Undercoat layer Cellulose sulfate sodium salt (Coating amount: 19 mg / m
² ) 2. Cyan dye developer layer The following cyan dye developer (960mg / m ^2), gelatin (540mg / m ^2), a cellulose sulfate sodium salt (12mg / m ²⁾ and phenyl norbornenyl hydroquinone (245mg / m ²⁾ Including. Cyan dye developer

[0131]

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3. Red-sensitive silver iodobromide emulsion layer Silver iodobromide emulsion grains having a grain diameter of 0.6 μm and a silver iodide content of 1% (780 mg / m ² ), a grain diameter of 1.5 μm,
Silver iodobromide emulsion grains having a silver iodide content of 3% (420 mg / m 2
² ) and polyvinyl hydrogen phthalate (18m
g / m ² ). 4. Intermediate layer 1 A copolymer of butyl acrylate / diacetone acrylamide / methacrylic acid / styrene / acrylic acid (2325)
mg / m ² ), polyacrylamide (97 mg / m ² ),
Contains hydantoin hardener (124 mg / m ² ) and succindialdehyde (3 mg / m ² ). 5. Magenta dye developer layer The following magenta 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. Contains sodium salt (12 mg / m ² ).

[0133]

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6. Mid layer 2 Carboxylated styrene butadiene latex (Dow
620 latex: 250 mg / m ² ), gelatin (83 mg / m ² ) and polyvinyl hydrogen phthalate (2 mg / m ² ). 7. Green-sensitive silver iodobromide emulsion layer: silver iodobromide emulsion grains (540 mg / m ² ) having a grain size of 0.6 μm and a silver iodide molar ratio of 1%, and a grain size of 1.3 μm and a silver iodobromide molar ratio of 3%. Silver iodobromide emulsion grains (360 mg / m ² ),
Contains gelatin (418 mg / m ² ) and polyvinyl hydrogen phthalate (23 mg / m ² ). 8. Intermediate layer 3 Phenylnorbornenyl hydroquinone (263 mg / m
² ), gelatin (131 mg / m ² ) and cellulose sulfate sodium salt (4 mg / m ² ). 9. Intermediate layer 4 Copolymer of butyl acrylate / diacetone acrylamide / methacrylic acid / styrene / acrylic acid (1448
mg / m ² ), polyacrylamide (76 mg / m ² ) and succindialdehyde (4 mg / m ² ). 10. Scavenger layer 1- octadecyl-4,4-dimethyl-2- {2-hydroxy -5-N- (7- Kapurorakutamido) sulfonamide} thiazolidine (1000mg / m ^2), gelatin (405mg / m ^2), cellulose sulfate Sodium salt (12 mg / m ² ) and quinacridone red zeta (7
mg / m ² ). 11. Yellow filter layer benzidine yellow (241mg / m ^2), containing gelatin (68mg / m ²⁾ and cellulose sodium sulphate (3mg / m ^2). 12. Yellow dye releasing layer The following yellow dye releasing compound (1257 mg /
m ² ), gelatin (503 mg / m ² ) and cellulose sulfate sodium salt (20 mg / m ² ).

[0135]

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13. Intermediate layer 5 Phenyl-, t-butylhydroquinone (450 mg / m
² ), 5-t-butyl-2,3-bis {(1-phenyl-1H-tetrazol-5-yl) thio} -1,4-benzenediolbis {(2-methanesulfonylethyl)
Carbamate (100 mg / m ² ), gelatin (25
0 mg / m ² ) and polyvinyl hydrogen phthalate (33 mg / m ² ). 14． Blue-sensitive silver iodobromide emulsion layer Silver iodobromide emulsion grains having a grain size of 1.3 μm and a silver iodide molar ratio of 1% (37 mg / m ² ), iodide having a grain size of 1.6 μm and a silver iodide molar ratio of 3% silver bromide emulsion grains (208mg / m), containing gelatin (78mg / m ^2), and polyvinyl hydrogen phthalate (7mg / m ^2). 15. UV filter layer Tinuvin (Tinvin manufactured by Ciba-Geigy;
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 Contains gelatin (300 mg / m ² ) and polyvinyl hydrogen phthalate (9 mg / m ² ).

Next, an image receiving element (501) having the following layer constitution was formed on an opaque polyethylene clad paper support having a thickness of 160 μm. 1. Neutralizing layer Contains a mixture of polymer A and polymer B at a weight ratio of 9:11 (22219 mg / m ² ). Polymer A: copolymer of methyl vinyl ether and maleic anhydride (GAF Corp .: GANTREZ S
-97, trade name) Polymer B; vinyl acetate ethylene latex (Air
Products Co. Made: AIRFLEX 46
5. Product name) Timing layer Hycar 26349 (BF Goodrich)
Co. (Trade name) and Polymer C in a ratio of 1: 3 by mass (2691 mg / m ² ). 2. Polymer C: copolymer of acrylamide and a copolymer obtained by graft copolymerizing diacetone alcohol with polyvinyl alcohol (the mass ratio of the three is 1: 8.2: 1.1) Image receiving layer Polymer D having the following structural formula and superhydrophilized polyvinyl alcohol (manufactured by AirProducts Co .: A)
A mixture of IRVOL 165 (trade name) and butanediol at a mass ratio of 2: 1: 1 (3983 mg /
m ² ). Polymer D;

[0138]

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4. Release layer Contains polyacrylic acid (162 mg / m ² ). Next, Table 2
(1) was prepared.

[0140]

[Table 4]

Further, an image receiving element (502) was prepared in which the same fine particle titanium oxide TI-A 600 mg / m ² as used in Example 1 was added to the image receiving layer.
Next, after imagewise exposure is given to the photosensitive element (502), the image receiving elements (501, 502) are superimposed, and the alkaline processing composition (501) is developed between both elements so as to have a thickness of 60 μm. Then, the same evaluation as in Example 2 was performed. In the image receiving element 502 of the present invention, it was found that the light fading performance was improved.

[0142]

The ultraviolet shielding filter agent of the present invention is excellent in dispersibility and stability over time, and is suitable for photographic use. The color diffusion transfer photographic film unit of the present invention using the ultraviolet shielding filter agent exhibiting the above effects has improved light fastness and physical properties of the film, improved stain, excellent photographic image quality, and stable production. Excellent in nature.

Claims (5)

[Claims] An average primary particle diameter or an average primary short axis particle diameter of 1 to 45 nm and a rutile crystallinity of 20 to 70.
% UV-filtering agent, which contains a fine particle of titanium oxide and a polyhydric alcohol. 2. a layer having a neutralizing function on a support,
An image receiving element having an image receiving layer and a release layer, a photosensitive element having at least one silver halide emulsion layer combined with at least one dye image forming compound on a support having a light-shielding layer, and Having an alkaline processing composition developed between the image receiving element and the photosensitive element, and after developing the alkaline processing composition between these elements after exposure, peeling off the image receiving element and the photosensitive element. In a color diffusion transfer photographic film unit that obtains an image by
In the image receiving element, the average primary particle diameter or the average primary short axis particle diameter is 1 to 45 nm, and the rutile crystallinity is 20 to
A color diffusion transfer photographic film unit comprising an ultraviolet shielding layer formed by applying an ultraviolet shielding filter agent containing 70% of fine particle titanium oxide and a polyhydric alcohol. 3. The color diffusion transfer photographic film unit according to claim 2, wherein said fine particle titanium oxide is a spindle type. 4. The color diffusion transfer photographic film unit according to claim 2, wherein the polyhydric alcohol is glycerin. 5. The image receiving element according to claim 2, wherein the ultraviolet ray shielding layer in the image receiving element is located on the image receiving layer and / or above the image receiving layer as viewed from the support of the image receiving element. Color diffusion transfer photo film unit.