JP3682883B2 - Photosensitive material - Google Patents

Description

  The present invention relates to a photosensitive material on which an image is formed by heat development.

  A photosensitive material on which an image is formed by heat development has not been sufficiently considered for the generation of a static mark because the sensitivity is low. However, the generation of static marks becomes a problem when the sensitivity is increased or when a photosensitive material is used for medical diagnosis.

An object of the present invention is a light-sensitive material is thermally developed is to provide a photographic material that occurrence of static marks not contaminate the heat developing apparatus is suppressed.

It has been found that a silver halide photographic material to be thermally developed has at least one conductive layer containing a metal oxide and contains a low molecular curing agent . The above problems are more strongly demanded when the heat development is performed at a temperature of 80 ° C. or higher, and the photosensitive material exhibits stronger and more powerful power. Further, the temperature for heat development is preferably 90 ° C. or higher and 160 ° C. or lower.

In addition, since the static mark is easily supplemented and easily seen when high-illuminance exposure is performed later like laser light, the photosensitive material is effective for laser light exposure.
This viewpoint is very important when used for medical diagnosis.

The conductive material used in the present invention is crystalline metal oxide particles, and those that contain oxygen defects and those that contain a small amount of hetero atoms that form donors with respect to the metal oxide used are generally referred to. In particular, the latter is particularly preferable because it has high conductivity, and the latter is particularly preferable because it does not give fog to the silver halide emulsion. Examples of metal oxides include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O _5, etc., or composite oxides of these, especially ZnO, TiO ₂ and SnO ₂ are preferred. As an example of containing a heteroatom, addition Al, or In respect ZnO, Sb for SnO _2, Nb, P, the addition of such a halogen element, also Nb for TiO _2, Ta etc. Is effective. The amount of these different atoms added is preferably in the range of 0.01 mol% to 30 mol%, but particularly preferably 0.1 mol% to 10 mol%. Furthermore, a silicon compound may be added at the time of producing fine particles in order to improve fine particle dispersibility and transparency.
The metal oxide fine particles of the present invention have conductivity, and their volume resistivity is 10 ⁷ Ω-cm or less, particularly 10 ⁵ Ω-cm or less. These oxides are described in JP-A Nos. 56-143431, 56-120519, and 58-62647.
Furthermore, as described in Japanese Examined Patent Publication No. 59-6235, a conductive material in which the above metal oxide is attached to other crystalline metal oxide particles or fibrous materials (for example, titanium oxide) may be used. .

The particle size that can be used is preferably 1 μm or less, but if it is 0.5 μm or less, the stability after dispersion is good and it is easy to use. In order to make the light scattering property as small as possible, it is very preferable to use conductive particles having a particle size of 0.3 μm or less because a transparent photosensitive material can be formed.
When the conductive material is needle-like or fibrous, the length is 30 μm or less and the diameter is preferably 1 μm or less, and particularly preferably the length is 10 μm or less and the diameter is 0.3 μm or less. Is 3 or more.
These conductive metal oxides of the present invention may be applied from a coating solution without a binder, and in that case, it is preferable to further apply a binder thereon.

The metal oxide of the present invention is more preferably applied together with a binder. The binder is not particularly limited, but binders can also be used. For example, water-soluble binders such as gelatin, dextran, polyacrylamide, starch, and polyvinyl alcohol, poly (meth) acrylic acid ester, and polyacetic acid can be used. Synthetic polymer binders such as vinyl, polyurethane, polyvinyl chloride, polyvinylidene chloride, styrene / butadiene copolymers, polystyrene, polyester, polyethylene, polyethylene oxide, polypropylene, polycarbonate, etc. may be used in organic solvents, and these The combined binder may be used in the form of an aqueous dispersion.
These metal oxides may be used in a mixture of spherical and fibrous ones. The content of the metal oxide of the present invention is 0.00051 g / m ² , more preferably 0.0009 to 0.5 g / m ² , and particularly preferably 0.0012 to 0.3 g / m ² .

In addition, a heat-resistant agent, weathering agent, inorganic particles, water-soluble resin, emulsion, etc. may be added to the layer made of the metal oxide of the present invention for matting and improving the film quality within the range not inhibiting the effect of the present invention. good.
For example, inorganic fine particles may be added to the layer made of the metal oxide of the present invention. Examples of the inorganic fine particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like. The fine particles preferably have an average particle size of 0.01 to 10 μm, more preferably 0.01 to 5 μm, and preferably 0.05 to 10 parts by weight with respect to the solid content in the coating agent, particularly preferably 0. .1-5 parts.

Various organic or inorganic curing agents may be added to the coating agent of the present invention. These curing agents may be low molecular compounds or high molecular compounds, and these may be used alone or in combination.
As the low molecular weight curing agent, for example, “The Theory of the Photographic Process” by TH James, 4th edition, pp. 77-88. Are used, and among them, those having a vinyl sulfonic acid, an aziridine group, an epoxy group, and a triazine ring are preferable, and in particular, JP-A-53-41221 and JP-A-60-225143. The low molecular weight compounds described are preferred.
The polymer curing agent is a compound having a molecular weight of 2000 or more, preferably having at least two groups opposite to the hydrophilic colloid such as gelatin in the same molecule, and the group that reacts with the hydrophilic colloid such as gelatin. Examples thereof include an aldehyde group, an epoxy group, an active halide (dichlorotriazine, chloromethylstyryl group, chloroethylsulfonyl group, etc.), an active vinyl group, an active ester group, and the like.
Examples of the polymer curing agent used in the present invention include dialdehyde starch, polyacrolein, a polymer having an aldehyde group such as an acrolein copolymer described in US Pat. No. 3,396,029, US Pat. Polymers having epoxy groups described in No. 623,838, polymers having dichlorotriazine groups described in Research Disclosure Journal 17333 (1978), etc., having active ester groups described in JP-A-56-66841 Polymer, active vinyl group described in JP 56-142524 A, US Pat. No. 4,161,407, JP 54-65033 A, Research Disclosure 16725 (1978), etc., or a precursor thereof A polymer having a group which becomes Such as described in EP 524, which long spacer by active vinyl group or to become group precursors thereof, are coupled to the polymer main chain.

  The conductive metal oxide additive layer used in the present invention is not particularly limited, and examples thereof include a protective layer, an intermediate layer, an emulsion layer, a UV layer, an antihalation layer, an undercoat layer, a back layer, and a back protective layer. it can. Among these, a protective layer, an intermediate layer, an antihalation layer, an undercoat layer, a back layer, and a back protective layer are preferable, and an undercoat layer, a back layer, an intermediate layer, and an antihalation layer are particularly preferable.

The image forming method used in the present invention is not particularly limited, but (1) a method using a combination of an electron-donating colorless dye and an electron-accepting compound, or (2) a diazonium salt compound and the diazonium salt compound. It is preferable to use a combination of a coupler which reacts with heat and develops a color. All of these methods are conventionally used for heat-sensitive recording materials, pressure-sensitive recording materials, diazo copying materials and the like, and many of them are known.
In each of the combinations (1) and (2), it is preferable that at least one of the compounds is a polymerizable compound and has a polymerizable ethylene group.
The coloring method used in the present invention is particularly preferably a method using a combination of a diazonium salt compound and a coupler that reacts with the diazonium salt compound to produce a color.
Other constitutions of the light-sensitive material of the present invention, for example, an electron-donating colorless dye, an electron-accepting compound having a polymerizable ethylene group, a diazonium salt compound, a coupler that reacts with the diazonium compound when heated, and a basic With respect to the compound, silver halide emulsion and its additives, for example, the compounds, techniques and methods described in Japanese Patent Application No. 6-9828 can be preferably used.

The method for heating the photosensitive material may be contact with a heat roller or the like, or non-contact type such as heat radiation. The method described in “Prior Art” (1991.3.22) is also preferably used.
The support for the photosensitive material may be cellulose-based or polyethylene terephthalate, but preferably polyethylene naphthalate described in JP-A-2-271349.

Laser light preferably used for optical information is preferably 633 nm or more, and more preferably an infrared laser of 700 nm or more.
The sensitizing dye preferably contains an infrared sensitizing dye and a supersensitizer. The compounds described in Japanese Patent Application No. 5-188036 are preferably used as compounds, and the compounds described in No. 5-18600 are preferably used as dyes for improving sharpness.

Example 1
[Preparation of Capsule Solution (CB-1) of Diazo Compound] “Parts” are all parts by weight.
After dissolving 2.8 parts of the following (E-1) and 0.56 parts of the following (E-2) in 19 parts of ethyl acetate, 5.9 parts of tricresyl phosphate, 2.5 (C-3) of the following Parts were added and mixed uniformly. Next, 7.6 parts of the following (C-1) was added to the mixed solution as a wall agent and mixed uniformly to obtain a liquid I.

  Next, solution I was added to 46.1 parts of an 8% by weight aqueous solution of phthalated gelatin, 17.5 parts of water, and 2 parts of 10% aqueous solution of sodium dodecylbenzenesulfonate at 40 ° C., and the homogenizer was added. Was emulsified and dispersed at 40 ° C. and 10,000 rpm for 10 minutes. After adding 20 parts of water to the obtained emulsion and homogenizing it, the mixture was allowed to undergo an encapsulation reaction at 40 ° C. for 3 hours with stirring, and then the ethyl acetate was removed (reduced pressure) and the diazo was removed from the capsule with an ion exchange resin. The compound was removed to obtain a capsule liquid (CB-1). The capsule particle size was 0.35 μm.

[Preparation of coupler emulsion (CN-1)]
11.2 parts of ethyl acetate, 3 parts of the following coupler (C-11), 3 parts of the following (C-12), 6 parts of the following (C-13), 6 parts of the following (C-14), and (C-15) 3 parts, 0.48 part of tricresyl phosphate, 0.24 part of diethyl maleate and 0.53 part of a 70% methanol solution of calcium dodecylbenzenesulfonate were dissolved to obtain a II liquid.

  Next, II solution was added to 41.7 parts of 15% by weight aqueous solution of lime-processed gelatin and 33.9 parts of water uniformly mixed at 40 ° C., and 10 minutes at 10000 rpm at 40 ° C. using a homogenizer. Emulsified and dispersed. After removing ethyl acetate from the obtained emulsion, the weight of the stripped ethyl acetate and water was supplemented by addition of water to obtain a coupler emulsion (CN-1).

Preparation of silver halide emulsion A After dissolving 10 g of polyvinyl alcohol (average molecular weight 30,000) in 1 liter of water and heating to 40 ° C., 1.35 g of sodium chloride and 50 ml of 10% phosphoric acid were added, and then 75 g 150 ml of an aqueous solution containing silver nitrate and 27 g of sodium chloride and 150 ml of an aqueous solution containing 4.0 mg of K ₂ RuCl ₆ were added by a double jet method over 3 minutes and 30 seconds, and then containing 150 ml of an aqueous solution containing 75 g of silver nitrate and 27 g of sodium chloride. 150 ml of aqueous solution was added by the double jet method over 7 minutes. Thereafter, 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, 5 g of gelatin was added, and cubic silver chloride having an average grain size of 0.05 μm and a coefficient of variation in projected diameter area of 10% was added. Particles were obtained.
This emulsion was coagulated and precipitated using a gelatin flocculant, and after desalting, 33 g of gelatin and 1.75 g of phenoxyethanol were added to adjust the pH to 5.65 and pAg 7.5.
Thereafter, the temperature was raised to 60 ° C., 3 mg of sodium thiosulfate and 1.5 mg of selenium compound I, 5.5 mg of chloroauric acid and 55 mg of potassium thiocyanate were added, and after aging for 100 minutes, the mixture was rapidly cooled to 35 ° C. for chemical sensitization. finished.

Preparation of Emulsion Coating Solution The following chemicals were added to Emulsion A per mole of silver halide to prepare an emulsion coating solution.
A. Spectral sensitizing dye [I] 138mg
B. Spectral sensitizing dye [II] 42.5mg
C. 567 g of polyvinyl alcohol
D. F-1 0.6g
E. F-2 0.6g
F. F-3 1g
G. R-1 162g
H. CN-1 (coupler emulsion) 6210 g
Li. KBr 6.8g
Nu. T-1 27g

Preparation of coating solution for surface protective layer of emulsion layer The container was heated to 40 ° C. and the following chemicals were added to prepare a coating solution.
A. Polyvinyl alcohol 100g
B. R-2 12.5g
C. T-1 1g
D. CB-1 (capsule solution) 380 g

Preparation of Back Layer Coating Solution The container was heated to 40 ° C. and the following chemicals were added to obtain a back layer coating solution.
A. Gelatin amount 100g
B. Dye [I] 2.39 g

C. 1.1 g sodium polystyrene sulfonate
D. Phosphoric acid 0.55g
E. Poly (ethyl acrylate / methacrylic acid) latex 2.9g
F. Compound [II] 46mg
G. Oil dispersion of dye [II] described in JP-A-61-285445 246 mg as dye itself

H. Oil dispersion of dye [III] described in JP-A-61-285445 46 mg as dye itself

Preparation of Back Surface Protective Layer Coating Solution The container was heated to 40 ° C. and the following chemicals were added to prepare a coating solution.

A. 100g gelatin
B. Sodium polystyrene sulfonate 0.3g
C. Polymethyl methacrylate fine particles (average particle size 3.5 μm) 4.3 g
D. 1.8 g sodium t-octylphenoxyethoxyethanesulfonate
E. Sodium polyacrylate 1.7g
G. C ₈ H ₁₇ SO ₃ K 268mg
H. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ -SO ₃ Na 45 mg
Li. NaOH 0.3
Nu. Methanol 131ml
Le. 1,2-bis (vinylsulfonylacetamido) ethane
Back layer and surface protective layer
2.2 for total gelatin
Adjust the weight so that it becomes% by weight. Compound [II] 45mg

Preparation of coating sample The back layer coating solution is coated on one side of a blue-colored polyethylene terephthalate support together with the surface protective layer coating solution of the back layer, and the gelatin coating amount of the back layer is 2.69 g / m ² . The surface protective layer was coated so that the gelatin coating amount was 1.3 g / m ² . Subsequently, the emulsion coating solution and the surface protective layer coating solution are applied to the opposite side of the support, the coating Ag amount of the emulsion coating solution is 0.1 g / m ² and the binder amount of the surface protective layer is 4.4 g. / M ² was applied in order with a wire bar to obtain a coated sample. (Comparative sample-1)

Preparation of Comparative Sample-2 Same as Comparative Sample-1, except that the back surface protective layer coating solution
C ₁₈ H ₃₇ O— (CH ₂ CH ₂ O) ₁₅ —H 3.8 g
Compound N 3.8 g

  Was added.

Preparation of Inventive Samples-3 and 4 Comparative Sample-1 was similarly prepared except that an SR layer was provided under the back layer.
SR layer (undercoat layer) coated with wire bar, compound gelatin listed in Table 1 22 mg / m ²

Test Method The coated sample thus prepared was sensitometrically measured by the following method to measure a photographic image.
The coated sample was kept at 25 ° C. and 60% temperature and humidity, allowed to stand for 7 days after coating, and exposed using a 633 nm He—Ne laser exposure unit of AC-1 manufactured by Fuji Photo Film Co., Ltd.
Moreover, even if the exposure and exposure part of the FCR-7000 manufactured by Fuji Photo Film Co., Ltd. are modified with a 780 nm semiconductor laser, and the AlGaInP 5 mW, 678 nm semiconductor laser light emitting part manufactured by NEC Corporation is used. Exposed.

(SR measurement)
The sample that has been subjected to the above treatment is cut into a width of 1 cm and a length of 5 cm, silver paint is applied in the length direction, the temperature is adjusted at 25 ° C. and a humidity of 10% RH for 2 hours, and then the conductivity in the width direction is measured. Examined.
(Evaluation of dirt)
60,000 sheets were uniformly heated at the temperature shown in Table 1 for 30 seconds per sheet, and the contamination of the heat plate, particularly precipitation, was evaluated.
○: No practical problem ×: Bad practical problem ××: Very bad

Only the sample of the present invention has low SR and achieves contamination prevention.

Example 2
Similar results were obtained when the support was replaced with polyethylene-2,6-dinaphthalate.

Claims (6)

A silver halide photographic light-sensitive material to be heat-developed, comprising at least one conductive layer containing a metal oxide and containing a low molecular curing agent . 2. The photosensitive material according to claim 1, wherein the layer containing the low molecular curing agent is a surface protective layer on the side opposite to the photosensitive layer with respect to the support. The photosensitive material according to claim 1, wherein the photosensitive material is thermally developed at a temperature of 80 ° C. or more. The photosensitive material according to claim 1, wherein the photosensitive material is for medical use. Light-sensitive material according to any one of claims 1 to 4, the metal oxide is characterized in that it is a composite oxide. Optical information is provided by a laser beam, the light-sensitive material according to any one of claims 1 to 5, the wavelength of the laser beam to provide a light information is characterized in that at 633nm or more.