JPS6148853A - Photosensitive material for silver salt diffusion transfer process - Google Patents

Abstract

PURPOSE:To prevent a photosensitive layer from damage due to sticking of the coating surface of the photosensitive sheet and trouble of white spots due to involution of foams at the time of development by incorporating a matting agent contg. a specified amt. of particles specified in size to the uppermost layer of the photosensitive material. CONSTITUTION:The matting agent to be added contains particles having >=10mum diameter in an amt. of 7-30 volume % of the total particles of the matting agent. The inorg. matting agent is embodied by oxides, alkaline earth metal salts, silver halide grains not forming an image, glass, etc., and oxides, especially, silica are preferable. The org. matting agent is embodied by starch, cellulose ester, cellulose ether, synthetic resins, etc. Their particle diameters are, preferably, 1-25mum, especially, 2-20mum. They are coated, preferably, 50-500mg/m<2>, especially, 200-400mg/m<2>. A preferable thickness of the protective layer contg. the matting agent is about 1/10-1/2 of the average particle size of the matting agent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of Application of the Invention) The present invention relates to an instant photographic light-sensitive material (particularly a peelable instant 4-photosensitive material) using a color diffusion transfer method.

(Prior art) A strong alkaline high viscosity processing solution containing crude drugs is spread between a sensitive material 7-sheet consisting of at least a silver halide emulsion layer and a slag-receiving sheet with a mordant Jψ. Peel it off from the photosensitive sheet to obtain a transferred image. In so-called peelable color instant photographic materials, the surface of the photosensitive sheet increases its adhesion or tackiness under active conditions, especially in an atmosphere of crystal temperature and humidity, and when it comes into contact with other objects, it adheres to each other. .

This phenomenon of adhesion occurs between photosensitive sheets or between the R1 & original sheet and other objects that come into contact with it during the manufacturing, processing, and storage of photographic materials, and often causes various inconveniences. Please don't invite me.

In peelable color instant photographic materials, the above-mentioned adhesion can be prevented by containing a fairly large amount of fine particle powder (hereinafter referred to as a "matting agent") in the uppermost layer. However, the viscosity processing liquid is applied between the photosensitive sheet and the photosensitive sheet at a very high speed (30-, / / ocm/
sec), air is drawn in and the area is not visualized, or the forming material is not transferred to the image, causing white spots (hereinafter referred to as "white spot failure") to appear purple on the transferred image. There was a problem with letting it happen.

(Objective of the Invention) Therefore, an object of the present invention is to prevent the J:i't Mk of the photograph 1 due to adhesion of the coated surface of the adhesive sheet, and also to prevent the white spot failure caused by the entrainment of bubbles during the spreading process. To provide a photographic material for a color diffusion transfer method, which prevents transfer color slag of excellent image quality and provides a photosensitive material.

(Tth Means for Solving the Conventional Technical Problems) The present inventor has discovered that the object of the above invention is to provide at least one photosensitive silver halide emulsion layer on a support and a fine grain powder (
Matting agent) In the photographic Ifi source material containing Jψr, does the matting agent contain particles with a diameter of 1a IQμm or more in the 7th to 30th ratio (by volume) of the total matting agent particles? It has been found that this can be effectively achieved using a photographic material for the color diffusion transfer method having the following characteristics.

(Effect of the invention) Is there a matting agent with the above average particle size in the top layer? By containing the above-mentioned bones, both the adhesion failure that occurs between 'fc photosensitive sheets and other objects that come into contact with them and the white spot failure that occurs during the unfolding process, which are conventional problems, are reduced. (Detailed Description of Means) As the matting agent added to the uppermost layer of the photosensitive material of the present invention, conventionally known matting agents can be used.

Matting agents are well known in the photographic art and can be defined as discrete solid particles of inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (e.g. silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth gold unsalts (e.g. sulfates and carbonates, specifically barium sulfate, (calcium carbonate, magnesium sulfate, etc.) silver halide grains that do not form (C silver chloride, beautified silver, etc., in which a small amount of iodine atoms may be added as an I/rogen component), glass, etc. Among the inorganic matting agents, oxides, particularly silicon dioxide, are preferred.

Further, examples of organic matting agents include starch, cellulose ester, eg cellulose acetate propionate, etc.
One example of cellulose ether is evaporated ethylcellulose @), synthetic resin, etc. Examples of synthetic resins include dispersions of water-insoluble or poorly soluble synthetic polymers, such as alkyl acrylates, alkyl methacrylates, alkoxyalkyl acrylates, alkoxyalkyl methacrylates,
glycidyl acrylate, glycidyl methacrylate,
Acrylamide, methacrylamide, vinyl ester (
For example, fa [vinyl], acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid or methacrylic acid.

α, β-unsaturated olodicarboxylic acid, hydroxyalkyl (
It is possible to create a full-circle polymer containing a combination of meth)acrylate, sulfoalkyl(meth)acrylate, and styrene sulfone as a single needle component.

Among organic matting agents, polymethyl methacrylate is preferred.

The particle size of the matting agent can be measured using an optical GI microscope, a scanning electron microscope, or a Coulter counter. Is the volume ratio of particles 1? Calculated assuming a spherical shape.

The size (diameter) range of matting agent particles is 1 μm to 25 μm
The thickness is preferably 2 to 20 μm, and more preferably 2 to 20 μm.

Appropriately, the area of the coated area of the matt agent is approximately 200 m2 to 300 m2, preferably 200 m2 to 97 m2.

The top layer to which the matting agent is added is usually one that is coated as a protective layer for the I-silver halide emulsion layer.

The thickness of the protective layer containing the matting agent is preferably about Q to about i72 of the average particle size (average diameter) of the matting agent.

The capping agent may be multi-layered, in which case the cloak agent is contained in the outermost layer, and, for example, when a two-layered structure is used, oil droplets are dispersed in at least one of these layers. is preferable.

The appropriate size of the oil droplets is approximately 0.0/μ to 20μ, and O
, OSμ~10μ is preferable.

As a substance that forms these oil droplets, a high-boiling point M-like compound that is usually used for dispersing photographic couplers is useful, and as the high-boiling point organic compound, one having a boiling point of iro'c or higher at normal pressure is preferable. For example, -1, 3'', 0.
: Described in No. 27.

Phthalic acid alkyl esters (dibutyl phthalate, octyl phthalate, etc.), phosphoric acid esters (amphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl citrate) tributyl acid), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide 1° fatty acid ester M (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. 1, trimesic acid) Examples include tributyl).

The retention layer contains 1, for example, a slip agent and an ultraviolet absorber.

Organic fluoro compounds, stain inhibitors (for example, hydroquinone derivatives, etc.), phenomenon inhibitors, and phenomenon inhibitor-releasing compounds may be added.

Furthermore, additives such as ultraviolet edge absorbers, stain inhibitors, development inhibitor-releasing compounds, etc. are preferably contained in the oil droplets.

Examples of ultraviolet absorbers include benzo)IJ azole compounds substituted with aryl groups (e.g., U.S. Patent No. 3,
J33.72μ issue and %-Kaisho! Do-no///1llf
), 4L-thiazolidone compounds (e.g., U.S. Pat.
Benzophenone compounds Cψ11, such as those described in JP-A-4-Core 14c), cinnamic acid ester compounds (for example, US Patent J, 10j, l'0!);
No. 3,107.37j), butadiene compounds (such as those described in U.S. Pat.

Alternatively, benzoxidole compounds (such as those described in US Pat. No. J, 100, S, K) can be used. Additionally, U.S. Patent J, 4L9'.

No. 762, and those described in JP-A No. 5≠-'A11.3j can also be used. UV-absorbing couplers (e.g. α-naphthol-based cyan dye-forming couplers) or UV-absorbing polymers? May be used.

More specifically, the pen/benzotriazole compound 1 is represented by the following general formula [Equation], and the specific example of this compound 51J is the one described in the above-mentioned Japanese Patent Application Laid-Open No. 2003-120002. /41g issue.

General formula [■] The application needle for the ultraviolet absorber is A2.
Approximately o, ooi for aqueous organic colloid (binder)
By the way, ~ko (overlapping ratio)' is preferable6.

The binder cloth button 1 is approximately 0.7 to J f/7.
m2 is preferred.

Examples of the slipping agent include cylindrical alkyl sodium sulfate, higher fatty acid higher alcohol ester, carbowax, AM alkyl phosphate, and silicone compounds. In particular, U.S. Pat. /2
No. 1,01,0, same No.? , rso, tao, JP-A-1978/1988/1A/1, 23, etc. are particularly effective when used alone or in combination of one or more.

It is appropriate that the slippery agent be coated in a range of about jm9 to λθθ■/m2.

Organic fluoro compounds include chain or cyclic compounds containing at least three fluorine atoms and at least three carbon atoms, and cationic, nonionic, and anionic betaine compounds can also be preferably used.

Typical organic fluoro compounds used in the present invention include 1, for example, U.S. Pat.
tt&, '171r issue, 483* 7j Hiroshi, 92μ issue,
Same No. 3,773. /λA No. 3, RSO, TUO, British Patent No. 1,330゜3JT & JP-A No. 1-10
6≠It is described in No. 1 Specification Co., etc.

Regarding representative 11 of these organic fluoro compounds,
Tokuko Shoj7-ta OjE Gomei, “Preface No. 1 Jim (~
It is described in the 17th book.

Particularly preferred organic fluorocompounds are anionic M-organic fluorine-containing surfactants.

The amount of organic fluoro compound added depends on the protective coating applied.
o, i ~ soomc), preferably u/
S, -20 o my.

As hydroquinone derivatives, for example, Japanese Patent Application No. 5R-2
It was described on pages J to J of the specification of SIXAO issue (Showa Jr./Reg., 2tI-D2S±Photographic Film ■ Application). A mixture of hydroquinone derivatives with a freezing point of too"c or less can be used.

As the hydrophilic colloid (binder) used in the uppermost layer of the photographic material of the present invention, those normally used in photographic layers can be used.

That is, as a hydrophilic organic colloid, is gelatin? Advantageously, other hydrophilic colloids can be used.

For example, gelatin derivatives, gelatin and base, 1'? Craft polymers with one molecule, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly- N-Vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimida/--ruh, various synthetic hydrophilic diamolecular substances such as single or copolymers of polyvinylpyrazole.
cx can be used.

Examples of gelatin derivatives include gelatin, acid halides, acid anhydrides, incyanates, bromoacetic acid, alkanesultones, vinylsulfonamide 9ij, maleimide compounds, polyalkylene oxides, epoxy compounds, etc. The compound obtained by reacting the compound r is used. The specific example is U.S. Patent No. 2, 1, 14.
No. 1,921, 3°/j, 2,5J μj, same! ,/
A, J'4 et al., J, 3/2,163, British patent fl, l, U-11/-, 033.112, 003,7g Hiroshi, Kosho 412-2.6g≠
It is written in S number etc.

The gelatin graft polymer may be a single (homo) or 1C polymer of vinyl yarn such as gelatin, acrylic Uλ, methacrylic acid, their esters, dT derivatives such as amides, acrylonitrile, styrene, etc. Is it copolymer grafted? Can be used. Particularly preferred are graft polymers of gelatin and polymers having a certain degree of mutual solubility, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate. These items 11 are disclosed in US Pat. No. 7Aj, No. 41/, Ibid. ,♂
J/, 7J7 issue, same, 2, ? r1. , ril
There is a description in l, issue, etc.

In addition to lime-processed gelatin, acid-processed gelatin and r[3u11. Sac, Set.

Phot, Japan J A/Otsu, 30 pages (z9.
Enzyme-treated gelatin as described in Ill. may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The silver halide photographic emulsion that can be used in the photosensitive material of the present invention may be a so-called negative emulsion or may be subjected to reversal processing. A direct positive emulsion that is not required may also be used.

The silver halide emulsions described above are used in combination with dye-providing compounds. As the dye-donating compound, a conventionally well-known diffuse dye-releasing redox compound IU) It
R compound), coupler N) DR coupler), or dye fJ4. You can use imaging agents, etc.

This dye-donating compound then undergoes negative working (
Negative working can also be positive working (in positive working).
g) may also be used.

In the practical form of the light-sensitive material of the present invention, a receiving layer (1ii dyed layer) and a silver halide hole 1111 layer are laminated on the same support, and the processing layer is the milk j-tl1 layer. It is also possible to use a sheet of paper which is placed on top of the silver halide emulsion layer and spread between the nine cover sheets, but in terms of fully exhibiting the effects of the present invention, the silver halide emulsion layer and the receptor layer (mordant layer) can be used. ) and are respectively coated on separate supports, and treatment e is a 4'fl\ composition developed between the two layers, in particular '! i'! It is preferable that the

That is, a light-sensitive element having on a support at least...a silver halide photographic emulsion layer and a dye-providing compound associated therewith; a receiving element (8) having at least a dye-providing layer on another support; Alkaline treatment developed between elements
Furthermore, the light-sensitive element and the receiving element are such that the original image has a surface coated with a silver halide emulsion layer and a surface coated with a receiving layer. However, after exposure, the surface elements are superimposed on these surfaces during processing, and after formation of the transfer envelope, the sensitive elements are separated from the elements and the transferred color image is formed. is configured so that it can be viewed from the image-receiving layer side, and a matting agent with a diameter of 101 mm is provided on the top layer of the above-mentioned photosensitive jfS element.
N or more particles are contained in a ratio of 7 to 30% (volume) of the purple matting agent particles.

Example 1 The following layers [11 to αl were coated in order on a black support]
c Preparation of light-sensitive photosensitive sheet.

0) Lower ruby cyan DI (R compound (o, 34m・mo
l/m ), tricyclohexyl phosphate (o, 0
9f/m21. J, j-di(t-pair p-decyl)hydroquinone (o, oi?7m212-containing layer).

t-C4) 19 (2) Red-sensitive internal m-type direct positive bromide emulsion [Silver 17
X#”'CO,! S'/m, Zera f 7 (0,
7Iff/m I.

The following nucleating agent (z7μm/m ) and sodium pentadecylhydroquinone sulfonate (0,0A?/ml'
layer contained in.

(3) λ,! -di(tert-bentatecyl)hydroquinone (o, 7i?, 1 m2), copolymer of vinylpyrrolidone and vinyl acetate (molarization 7:1) (θ.

21A? /ml and gelatin IO,'t? /m2
1? The layer that speaks.

(4) Layer with gelatin 7 (0,317m2)';zk.

(5) The following magenta DRR compound (0.4L:99/
ml, tricyclohexyl phosphate (0,,!
r97m), co,j-di(tert-tadecyl)hydroquinone (0,0)27m) and gelatin (o,
527m)? Containing layer.

H (6) Green-sensitive inner tube type direct positive silver bromide emulsion (silver t
Yode0.34197m Thatch, gelatin (0,4417
m), the same nucleating agent as layer (2) (/, 2.yμy/m
2) A layer having 1: sodium pentadecylhydroquinone sulfonate (0,0 μ?/m2).

(71x, j-di(tert-tatecyl)hydroquinone (0,7/'17m21, copolymer of vinylpyrrolidone and vinyl acetate C molar ratio 7:3) (0,J.

'AY/m) and Sera5-(o,≠r/m21
  Containing layer.

(8) Layer containing gelatin (0,2397 m2) f.

(9) The following Ie O-D RR compound (0,1AI?/
m2), tricyclohexyl phosphate (0°OJ
9/ml,λ,! -diI tert-pentadecyl)hydroquinone (θ, 00≠?/m2) and gelatin (0, a J ? 7m 21k sul l'
t.

C(Q43)3 aω Evening-sensitivity internal m-open type direct positive silver bromide emulsion (0.11497 m2 for silver conditions) 1. Gelatin (0, 1 layer m2
) 1 layer Same nucleating agent as (2) (29m9/rn 21 Sodium pentadecylhydroquinone sulfonate (
0,0,evening? /m ) y; z-containing layer.

aυ Gelatin (/, 097m21% As a matting agent, average particle size j, 4μ (diameter 10μm or more)
j q6) of polymethyl methacrylate (0,17
7m) f-containing layer.

Processed maki o, ryy with the following composition (filled in a rupturable container).

The following layers (12) - (16
] r A receiving edge sheet was prepared which was coated sequentially.

10:20 (weight ratio) copolymer of acrylic acid and butyl acrylate (λ2?/ml l and l.

Hirobis(2,3-evogycyproboxy)-butane to
, ≠μS'/rtz 21ge-containing layer.

(13) Acetylcellulose (hydrolyzed to 1009% acetylcellulose, yielding ≠2 acetyl groups) (3,177m) and styrene A
lt? 60 of water maleic acid to IAO (weight i;, i″ ratio)
Copolymer (molecular information approximately 50,000) (0,29/m 1 and j-(β-cyanoethylthio l-/-phenyltetrazole (0,//J?/m) layer).

α4) Copolymer latex of vinylidene hawkide, methyl acrylate, and acrylic acid at a ratio of 16 to 2 to 3 (military ratio) (
a, r? /m ] and polymethyl methacrylate latex (particle size 7-3 microns) (o, or?/m
lk gold-containing layer.

(15) The following mordant (13.017 m2) and gelatin (
3.0? /m) No mordant.

H2 (Ilil phthalated gelatin (197ml) containing M 1, the amount of matting agent for 1 Uυ)
0,149/yn, 0. A? /In sample 116-2.3% and average particle size 3.7
Particles with a diameter of 10 μm or more in μm - A matting agent containing 10% fz? , 0°/7/+tt, 0. +21 layer m
, θ, 3f/m.

Samples A4'-7 were created with the area changed to 0.1477 m2.

Sample no FL/~7 and one black base of Shio 11? ,
Cut each piece into a size of cmXjcmf)3. foC,
Section 10 +1. I-[17) After storing in the atmosphere for 3 hours, constantly align the front side of the sample with the back side of the black base,
/ 2 pieces of garlic load, IA O' C, I O% R
, H, , and then the sample was rubbed to determine the area of the bonded part. The adhesion was measured.

In addition, evaluation! ,! The standard was based on the method shown below.

In addition, the above-mentioned acceptance sheet and D
(See, during which time the rupturable container contains the processing'gJ?
The number of white spot failures is determined by placing it in the treatment liquid using a pressing member and spreading it to a thickness of Oμm. evaluated.

The development speed at this time is A OCm / 36
It was done in c. From the obtained adhesion results and the white spot failure results in Table 2, particles with a diameter of 10 μm or more τ10cl
, Contains a matting agent? It is clear that by using it, adhesion can be prevented with a small amount of cloth, and white spot failures are also greatly reduced.

Claims (1)

[Claims] In a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and a layer containing a fine grain powder (matting agent) on the uppermost layer, the matting agent has a diameter of 10 μm.
A photographic light-sensitive material for color diffusion transfer method, characterized in that it contains 7 to 30% (by volume) of the total matting agent particles as described above.