JPH07295146A - Photosensitive material - Google Patents

Abstract

PURPOSE:To restrain occurrence of static marks without staining a heat development device by forming at least one electrically conductive layer containing a metal oxide in a heat developable silver halide photosensitive material. CONSTITUTION:To heat-developable photosensitive material has at least one electrically conductive layer containing metal oxide, and preferable heat development temperature is 90-160 deg.C and conductive material to be used is crystalline metal oxide grains, and it is preferred to use a metal oxide having oxygen defect and, especially, that containing a small amount of different kind of atom forming a donor to the metal oxide to be used, because they are high in conductivity. The metal oxide is embodied by ZnO, TiO2, SnO2, Al2O3, In2O3, SiO2, MgO, BaO, MoO3, V2O3, and the like, and a composite oxide of them, preferably, ZnO, TiO2, and SnO2. It is preferred to apply this metal oxide together with a binder.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a light-sensitive material on which an image is formed by heat development.

[0002]

2. Description of the Related Art Since a light-sensitive material on which an image is formed by heat development has a low sensitivity, a sufficient consideration has not been given to the generation of static marks. However, the generation of static marks poses a problem when sensitized or when a photosensitive material is used for medical diagnosis.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a light-sensitive material in which the development of static marks is suppressed in the light-sensitive material to be heat-developed without contaminating the heat-developing device.

[0004]

Means for Solving the Problems In a silver halide photographic light-sensitive material to be thermally developed, the above-mentioned object is achieved by a light-sensitive material characterized by having at least one conductive layer containing a metal oxide. Found. The above-mentioned problems are strongly demanded when heat-developed at a temperature of 80 ° C. or higher, and the light-sensitive material exerts a stronger effect. Further, the temperature of heat development is preferably 90 ° C. or higher and 160 ° C. or lower.

In addition, since the static mark is easily assisted when exposed to a high illuminance like a laser beam and is easily seen, the photosensitive material is more effective for laser beam exposure. This viewpoint is also very important when used for medical diagnosis.

The conductive material used in the present invention is crystalline.
Metal oxide particles containing oxygen defects and used
The number of foreign atoms forming a donor is small for the metal oxide
Generally, those containing a large amount have high conductivity, so they are particularly preferable.
The latter, in particular, should not fog silver halide emulsions.
Therefore, it is particularly preferable. Examples of metal oxides are ZnO and T
iO₂, SnO₂, Al₂O₃, In₂O₃, Si
O₂, MgO, BaO, MoO₃, V₂O_FiveEtc.
Is preferably a complex oxide of these, particularly ZnO and TiO. ₂Over
And SnO₂Is preferred. Examples containing heteroatoms include
For example, addition of Al, In, etc. to ZnO, SnO₂To
On the other hand, addition of Sb, Nb, P, halogen elements, etc.
TiO₂It is effective to add Nb, Ta, etc.
It The amount of these different atoms added is 0.01 mol% to 30 mol.
The range of l% is preferable, but 0.1 mol% to 10 mol%
It is especially preferable if it exists. In addition, fine particle dispersibility and transparency
For the sake of goodness, even if a silicon compound is added at the time of making fine particles,
Good. The metal oxide fine particles of the present invention have conductivity.
And its volume resistivity is 10⁷Ω-cm or less, especially 10^FiveΩ
-Cm or less. Regarding these oxides, JP-A-56
-143431, 56-120519, 58-
No. 62647 and the like. Furthermore, Japanese Patent Publication Sho 5
Other crystalline metal oxides as described in 9-6235.
Particles or fibrous substances (such as titanium oxide) can be added to the above gold.
A conductive material having a metal oxide attached may be used.

The usable particle size is preferably 1 μm or less, but when it is 0.5 μm or less, stability after dispersion is good and it is easy to use. In addition, in order to minimize the light scattering property,
It is very preferable to use conductive particles 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 preferably 30 μm or less and the diameter is 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 coated from a coating liquid without a binder, and in that case, it is preferable to further coat a binder thereon.

It is further preferred that the metal oxide of the present invention is coated with a binder. The binder is not particularly limited, but the binder and the like used in the magnetic layer described above can also be used. For example, a water-soluble binder such as gelatin, dextran, polyacrylamide, starch, or polyvinyl alcohol, or a poly ( (Meth) acrylic acid ester, polyvinyl acetate, polyurethane, polyvinyl chloride, polyvinylidene chloride, styrene / butadiene copolymer, polystyrene, polyester, polyethylene, polyethylene oxide,
Synthetic polymer binders such as polypropylene and polycarbonate may be used in an organic solvent, and these polymer binders may be used in the form of an aqueous dispersion. Further, these metal oxides may be used as a mixture of spherical and fibrous ones. The content of the metal oxide of the present invention is
0.00051 g / m ² and more preferably 0.000
9-0.5 g / m ² , particularly preferably 0.0012-0.
It is 3 g / m ² .

In addition, heat-resistant agents, weather-resistant agents, inorganic particles, water-soluble resins, emulsions, etc. are added to the layer made of the metal oxide of the present invention in order not to impair the effects of the present invention for matting and improving the film quality. You may. For example, inorganic fine particles may be added to the layer made of the metal oxide of the present invention. Examples of inorganic fine particles to be added, silica, colloidal silica,
Alumina, alumina sol, kaolin, talc, mica,
Calcium carbonate etc. can be mentioned. The fine particles preferably have an average particle diameter of 0.01 to 10 μm, more preferably 0.01 to 5 μm, and preferably 0.05 to 10 parts by weight relative to the solid content in the coating agent, and particularly preferably 0. .1
~ 5 parts. Further, various organic or inorganic curing agents may be added to the coating composition of the present invention. These curing agents may be low molecular weight compounds or high molecular weight compounds, and these may be used alone or in combination.

As the low-molecular curing agent, for example, tea
"The Theory of the Photographic Process" by TH James
ory of the Photographic Process) ”, 4th edition, pp. 77-88, low molecular weight curing agents are used, among which those having vinyl sulfonic acid, aziridine group, epoxy group, triazine ring are preferable, The low molecular weight compounds described in JP-A-53-41221 and JP-A-60-225143 are preferable. The polymeric curing agent preferably has at least two groups in the same molecule that oppose to hydrophilic colloids such as gelatin, and has a molecular weight of 2
Examples of the group that is a compound of 000 or more and that reacts with a hydrophilic colloid such as gelatin include, for example, aldehyde groups, epoxy groups, active halides (dichlorotriazine, chloromethylstyryl groups, chloroethylsulfonyl groups, etc.), active vinyl groups, Examples thereof include active ester groups. Examples of the polymer curing agent used in the present invention include dialdehyde starch, polyacrolein, and US Pat. No. 3,396,02.
Aldehyde group-containing polymers such as acrolein copolymers described in No. 9, epoxy group-containing polymers described in US Pat. No. 3,623,838, and dichlorotriazine described in Research Disclosure Magazine 17333 (1978). Group-containing polymer, JP-A-56
-66841, a polymer having an active ester group, JP-A-56-142524, US Pat. No. 4,161,407, JP-A-54-65033, Research Disclosure 16725 (1978).
Polymers having an active vinyl group described in, for example, or a group which is a precursor thereof are preferable.
It is preferable that the active vinyl group or a group which is a precursor thereof is bound to the polymer main chain by a long spacer as described in No. 142425.

The addition layer of the conductive metal oxide 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. Can be mentioned. Of these, preferred are a protective layer, an intermediate layer, an antihalation layer, an undercoat layer, a back layer, and a back protective layer,
Particularly preferred are an undercoat layer, a back layer, an intermediate layer and an antihalation layer.

The image forming method used in the present invention includes:
Although not particularly limited, (1) a method using a combination of an electron-donating colorless dye and an electron-accepting compound, or (2) a diazonium salt compound and a coupler that develops a color when reacted with the diazonium salt compound Is preferably used in combination. All of these methods have been conventionally used for heat-sensitive recording materials, pressure-sensitive recording materials, diazo copying materials and the like, and there are many known methods. In addition, (1),
In each combination of (2), at least one of the compounds is preferably a polymerizable compound and has a polymerizable ethylene group. As the color forming method used in the present invention, a method of using a combination of a diazonium salt compound and a coupler which reacts with the diazonium salt compound to produce a color when heated is particularly preferable. 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 and a coupler which reacts with the diazonium compound to produce a color, and a basic Regarding the compound, the silver halide emulsion and its additive, for example, the compound, technique and method described in Japanese Patent Application No. 6-9828 can be preferably used.

As a method for heating the light-sensitive material, contact with a heat roller or the like or non-contact type such as heat radiation may be used. The method described in "Public Technology" (1991.3.22) is also preferably used. The support of the light-sensitive material may be cellulose-based or polyethylene terephthalate, but polyethylene naphthalate described in JP-A-2-271349 is preferable.

The laser light preferably used for optical information is 6
It is preferably 33 nm or more, more preferably 700 nm or more infrared laser. The sensitizing dye preferably contains an infrared sensitizing dye and a supersensitizer. Compounds preferably used are those described in Japanese Patent Application No. 5-188036, and dyes for improving sharpness are the same as those of Japanese Patent Application No. 5-18636.
The compounds described in No. 00 are preferably used.

[0015]

【Example】

Example 1 [Preparation of diazo compound capsule liquid (CB-1)]
All "parts" indicate parts by weight. After dissolving 2.8 parts of the following (E-1) and 0.56 part of the following (E-2) in 19 parts of ethyl acetate, 5.9 parts of tricresyl phosphate and 2.5 of the following (C-3) were dissolved. Parts were added and mixed uniformly. Then, 7.6 parts of the following (C-1) as a wall agent was added to this mixed solution and uniformly mixed to obtain a solution I.

Next, solution I was added while uniformly mixing 46.1 parts of an 8 wt% aqueous solution of phthalated gelatin, 17.5 parts of water, and 2 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate at 40 ° C. Then, using a homogenizer, 40 ° C, 1
The emulsion was dispersed at 0000 rpm for 10 minutes. 20 parts of water was added to the obtained emulsion to homogenize it, and then 40 while stirring.
After performing the encapsulation reaction at 3 ° C. for 3 hours, desolvation of ethyl acetate (reduced pressure) and removal of the diazo compound outside the capsule with an ion exchange resin were performed to obtain a capsule liquid (CB-1). The particle size of the capsule was 0.35 μm.

[0017]

[Chemical 1]

[Preparation of coupler emulsion (CN-1)] 3 parts of the following coupler (C-11) in 11.2 parts of ethyl acetate,
(C-12) 3 parts below, (C-13) 6 parts below, (C-14) 6 parts below, (C-15) 3 parts below, tricresyl phosphate 0.48 parts, diethyl maleate 0 ．
24 parts, 70 of calcium dodecylbenzene sulfonate
0.53 parts of a methanol solution of 3% was dissolved to obtain a liquid II.

Next, solution II was added to 41.7 parts of a 15% by weight aqueous solution of lime-processed gelatin and 33.9 parts of water were uniformly mixed at 40 ° C., and the mixture was mixed with a homogenizer at 40 ° C. for 1 hour.
The emulsion was dispersed at 0000 rpm for 10 minutes. After removing the ethyl acetate from the obtained emulsion, the weight of the volatilized ethyl acetate and water was supplemented with water to obtain a coupler emulsion (CN-
1) was obtained.

[0020]

[Chemical 2]

Preparation of Silver Halide Emulsion A Polyvinyl alcohol (average molecular weight 3
10) Dissolve 10 g and add 1.35 g of sodium chloride and 50 ml of 10% phosphoric acid to a container heated to 40 ° C.
150 ml of an aqueous solution containing 5 g of silver nitrate and sodium chloride 2
Aqueous solution containing 7 g and 4.0 mg of K ₂ RuCl ₆ 15
0 ml was added by the double jet method over 3 minutes and 30 seconds, and then 150 ml of an aqueous solution containing 75 g of silver nitrate and 150 ml of an aqueous solution containing 27 g of sodium chloride were added by the double jet method over 7 minutes. Thereafter, 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and 5 g of gelatin was added to give an average particle size of 0.05 μm.
Cubic silver chloride particles having a coefficient of variation of m and a projected diameter area of 10% were obtained. This emulsion was coagulated and precipitated using a gelatin coagulant, desalted, and then added with 33 g of gelatin and 1.75 g of phenoxyethanol to adjust pH to 5.65 and pAg to 7.5. Then, the temperature was raised to 60 ° C., 3 mg of sodium thiosulfate, 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, it was rapidly cooled to 35 ° C. for chemical sensitization. finished.

[0022]

[Chemical 3]

Preparation of Emulsion Coating Solution The following chemicals were added to Emulsion A per mol of silver halide to prepare an emulsion coating solution. I. Spectral sensitizing dye [I] 138 mg b. Spectral sensitizing dye [II] 42.5 mg c. Polyvinyl alcohol 567 g d. F-1 0.6 g e. F-2 0.6 g f. F-3 1 g. R-1 162 g h. CN-1 (coupler emulsion) 6210 g Re. KBr 6.8 g Nu. T-1 27g

[0024]

[Chemical 4]

[0025]

[Chemical 5]

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. I. Polyvinyl alcohol 100 g b. R-2 12.5 g c. T-1 1 g d. CB-1 (capsule liquid) 380g

[0027]

[Chemical 6]

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

[0029]

[Chemical 7]

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

[0031]

[Chemical 8]

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

[0033]

[Chemical 9]

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

B. Gelatin 100 g b. Sodium polystyrene sulfonate 0.3 g c. Polymethylmethacrylate fine particles (average particle size 3.5 μm) 4.3 g d. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g e. Sodium polyacrylate 1.7 g g. C ₈ H ₁₇ SO ₃ K 268 mg Chi. 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. NaOH 0.3 nu. 131 ml of methanol 1,2-Bis (vinylsulfonylacetamido) ethane Adjustment to be 2.2% by weight based on the total gelatin amount in the back layer and the surface protective layer. Compound [II] 45 mg

[0036]

[Chemical 10]

Preparation of Coating Sample The above coating solution for the back layer was coated with the coating solution for the surface protective layer of the back layer on one side of a polyethylene terephthalate support colored in blue, and the gelatin coating amount of the back layer was 2.6.
9 g / m ^2, a gelatin coating amount of the surface protective layer of the back layer was coated to a 1.3 g / m ^2. Following this, the emulsion coating liquid and the surface protective layer coating liquid described above were provided on the opposite side of the support, and the coating Ag amount of the emulsion coating liquid was 0.1 g / m ² and the binder amount of the surface protective layer was 4.4 g. It was coated sequentially with a wire bar such that the / m ^2, was coated samples. (Comparative sample-1)

[0038] Comparative Sample C ₁₈ similarly to produce comparative sample -1 where the surface protective layer coating solution of the back of _{-2 H 37 O- (CH 2 CH} 2 O) 15 -H 3.8g Compound N 3. 8 g

[0039]

[Chemical 11]

Was added. Production of Inventive Samples-3 and 4 Comparative Sample-1 was similarly provided with an SR layer below the back layer of the back. SR layer (undercoat layer) coated with a wire bar, compound shown in Table 1 Gelatin 22 mg / m ²

Test Method The coated sample thus prepared was subjected to sensitometry by the following method to measure a photographic image. Apply sample at 25 ℃, 6
The coated film was kept at 0% temperature and humidity 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. Also, the exposure of the FCR-7000 manufactured by Fuji Photo Film Co., Ltd. with a 780 nm semiconductor laser and the exposure unit were modified to produce A manufactured by NEC Corporation.
Exposure was also performed using a 1GaInP 5 mW, 678 nm semiconductor laser light emitting unit.

(SR measurement) The sample which has been subjected to the above-mentioned treatment has a width of 1
cm, 5 cm in length, apply silver paint in the length direction, and adjust the humidity for 2 hours at a temperature of 25 ° C. and a humidity of 10% RH.
The conductivity in the width direction was examined. (Evaluation of stains) 60,000 sheets were uniformly heated at a temperature shown in Table 1 for 30 seconds per sheet to evaluate stains on the heat plate, particularly deposition. ○: No problem in practical use ×: Bad There is a problem in practical use × ×: Very bad

[0043]

[Table 1]

Only the samples according to the invention achieve the above objectives. Example 2 Similar results were obtained even when the support was replaced with polyethylene-2,6-dinaphthalate.

Claims (4)

[Claims] 1. A light-sensitive material comprising a silver halide photographic light-sensitive material to be heat-developed, which has at least one conductive layer containing a metal oxide. 2. The photosensitive material according to claim 1, which is heat-developed at a temperature of 80 ° C. or higher. 3. The photosensitive material according to claim 1, wherein the optical information is given by laser light. 4. The medical device according to claim 1, wherein the medical device is for medical use.
3 to 3 of the photosensitive material.