JPS5862651A - Antistaticized silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enhance antistatic property without impairing photographic characteristics, by providing a layer contg. conductive particles made of a specified metal oxide and a layer contg. at least one UV absorber. CONSTITUTION:At least one layer contg. fine conductive particles consisting mainly of a crystalline metal oxide selected from oxides of Zn, Ti, Sn, In, Si, Mo, and W, or a metal composite oxide composed of them is formed on or above a photosensitive emulsion layer. A coat layer contg. at least one UV absorber is formed to cover the conductive layer in order to control diffusion of light from the conductive layer, thus permitting this coat layer to serve also as the protective layer of the conductive layer, accordingly the conductive layer to prevent electrostatic charge without impairing photographic characteristics in a silver halide photographic material of a type for observing a light-transmitted image.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is an I-silver tetragenide photographic light-sensitive material K111 with improved electrostatic resistance.
The purpose of the present invention is to improve the band-resistance without giving any damage to the allied black light material.

Photographic light-sensitive materials generally consist of an electrically insulating support and a regenerating layer, so during the manufacturing process of the original material and during use, there is no direct contact with the surface of the material in a mold vat or during use. II or 7t is silent due to exfoliation, 1!
Electric charge is often accumulated. This accumulated electrostatic charge causes many problems, but the most serious problem is that the photosensitive emulsion layer is exposed to light due to the discharge of the accumulated electrostatic 1iL' charge before the development process, and the photographic film is exposed. This is a process that produces dot-like spots or resin-like or feather-like coarseness during development. These so-called static marks can seriously damage the quality of photographic film, and in some cases cause them to disappear altogether.

It is only when you take a closer look at this phenomenon that it becomes clear that it is K, and it is one of the most troublesome problems.

As mentioned above, such static charges are often accumulated during the manufacture and use of re-emerging photosensitive materials, or, for example, due to contact between photographic film and rollers during the manufacturing process.
11 rolls of scratched or scratched photographic film*p.

During the unwinding process, KL, such as m1, is generated between the support direction and the emulsion direction. It can also occur due to the separation of the base direction and emulsion direction when photographic film is changed in the finishing process, or due to contact between other colors in the bulk image processing machine and the loading material. do. Static marks on the photographic light-sensitive material induced by the accumulation of electrostatic charges are caused by an increase in the sensitivity of the photographic light-sensitive material and an increase in the grain speed.
* becomes. Particularly in recent years, the increased sensitivity of photographic materials and the increased use of high-speed photography, high-speed automatic processing, etc. have resulted in harsher handling of static marks. It is becoming more likely to occur.

A good way to eliminate these static electricity problems is to increase the electrical conductivity of the material so that the static charge increases by 1! before the accumulated charge is discharged. - H5. The objective is to ensure that static light tm does not appear on the photosensitive phase material as a static mark even if discharge occurs.

Conventionally, methods have been used to increase the conductivity of the surface layer of the support for photographic light-sensitive materials, including water-soluble inorganic salts, certain surfactants, and polymer layers in the hygroscopic substances of plants. Attempts have been made to use For example, the United States%11f總2.11ko, /1
No. 7, same, 27, j3j, 1IIJ, 04, 7
No. 11, rim roller λ.

No. 107, 1-cho J, j/Tao, -21, No. 3,61j,
! No. 31, same J, 7! J, 7/base number, 319JI,
94th issue etc., for example,
Wooden bone #! F No. ko, Riko, ,, a J No. 7, same 3
,4421,4A! No. 4, same J, No. 44!7,076,
1 river 3. The surfactants described in Approx., No. 421, J, No. 11, No. 7λ, rJJ, BSS, Jly No. 1, and US pin @J.

12! , 4J1, is known.

However, many of these qualities are due to the WI of the film support.
I show threat sex due to differences in class I and photographic compositions.
Foot film supports and photographic emulsions and other revival configurations 1j! Although the results are good, it lasts a long time, but if you have to use a different film support, the overall cost of the film will not be useful for preventing static electricity, and it may have negative effects on the photographic performance. . The important thing is that many of these materials have a major drawback in that their conductivity is highly dependent on humidity, and they lose their function as a conductive wax layer under low humidity.

In addition, a technique using iris tin tin as an antistatic treatment agent is described in Kokoan 31-44/Haruka No. KFii.
The technology used for ρ is the one that uses a colloid of stannic oxide in the form of an oxide, and its conductivity depends on the humidity Wk.At low humidity, the feather loses its conductive layer Qk6. Essentially the aforementioned shield II! ! Buying something is not something you can ask for.

Type blades, such as Mokukokufuken No. J, 04, , No. 700, %
g! Fall jko, -//J-ko sango and the same! j-/λ227
1. iiL-photographing It is known to use metal oxides such as ditin and indium oxide. However, the use of these crystalline metal oxide particles Q/% as an antistatic agent in silver halide emulsions has never been reported, and there is no evidence that these 4111C properties 1
The interaction between the G material and the I/U silver oxide emulsion layer was completely unpredictable and rare. By the way, US%J'F dropped J.

Halogen f, scissors, and 'copper halide' are used as conductive shavings as described in No. 131, but these conductive shaving wood--eaves Jμ'e''
As shown in No. 7, it is clearly shown that there is an interaction between the silver halide emulsion layer and the photographic properties are adversely affected.

Images obtained using the material kR may be observed by transmitted light or by pre-irradiation light. It is preferable that the reflectance of the material is as high as possible. In the former case, it is preferable that the light transmittance of the part without the husk is increased to reduce light scattering by the photographic light-sensitive material. For the purpose of reducing light scattering,
4 solder layers on photographic material T74), L? There are major limitations when it comes to preventing static electricity, but the aforementioned conductive polymers have the drawback that their conductivity is tM dependent and they lose their function as conductors at low humidity. Therefore, it was necessary to use surfactants and the like in a way that they were compatible with the binder to form microscopic micelles. Therefore, the above-mentioned US Policy No. J.

Zinc oxide described in No. 72227, etc.
For this reason, conductive tin oxide and indium oxide can be used for 4% strength paper for electrophotography or electrostatic recording, but they cannot be used for transmitted light! j) It cannot be used as is for silver halide photographic photosensitive VC of the type that detects 1 meter images.

In addition, the recent VCiIiIII high-speed shooting and high-speed processing are 1
When it comes to static generation, it is becoming difficult to provide conductivity until it is completely eliminated.

Maki of the present invention/(D purpose is antistatic photographic photosensitive razor [
iI is to provide.

The object of the present invention is to provide a photosensitive material that has excellent antistatic properties even at low temperatures.

The third purpose of this invention is to provide an effective method for preventing charging of photographic light-sensitive materials without impairing photographic properties.

The purpose of the ML reference of the present invention is to prevent the generation of static marks and to provide a subsequent photographic light-sensitive material.

The above objects of the present invention are Zn,'l'i,8n,In夛8
At least seven types of crystalline metal oxides selected from 4, Mo, and W are/and at least a layer containing 4'#L fine particles mainly composed of composite oxides thereof. In addition, it is possible to have at least 47 layers containing an ultraviolet absorber (KJj).

The crystalline metal oxide or composite oxide fine particles used in the present invention have a volume resistivity of 10'Ω-1 or less,
L value is 111 or less than 10 Ω-1.

The particle size of the crystalline metal oxide particles used in the present invention is preferably small in order to reduce light scattering t-'t' as much as possible, but it is determined by the Kitakami parameter of the refractive index of the particles and the binder. It will be done.

Therefore, depending on the particulates and binder used, the particle size will be S, CI','j: Nl / ~ 0.7
By using particles of 0.02-0.1 .mu., preferably KL9, it is possible to form a practically transparent film 1.

Regarding the method for producing conductive crystalline gold Ii4 oxide or image complex fine particles conveniently used in the present invention, Fi*mt
Showa s - Part 7 a a J No. 1j Thin IKtFaK
A method in which metal oxide fine particles are prepared by firing and then heat treated in the presence of different atoms to improve conductivity.
- A method of coexisting different types of particles in order to improve conductivity during production. 11!
There are ways to introduce t-.

An example containing an S atom is At for znO.

■n, etc., for T s Ox, Nb, 'l'a, etc.
For 8nUz, 9b, Nb, No. 1, etc. are equalized. Imenhara pre-pigmenting amount is 0.0/-JOmo1%
It is preferably in the range of 00l to 000%.

The conductive N (D"ing) used in the present invention includes O-proteins such as srs gelatin, coquit'-like alpine, and zein; Snout: Sugar derivatives such as agar, alginate sorg, starch derivatives; Synthetic hydrophilic colloids such as vinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide t
7t refers to these derivatives, 7711 moisture compounds, polyvinyl acetate, polyacrylic acid ester, vinyl polymers and their copolymers, soluble polyesters, H
I bathable nylon rosin, shellac and its I conductor, and many other types of resins are used. Also used are styrene-butadiene copolymers, polyacrylic acid, polyacrylic esters and their derivatives, polyvinyl acetate, vinyl acetate-acrylic ester copolymers, polyolefins, olefin-vinyl acetate polymers, and water emulsions. can do.

The conductive layer used in this @ Ming KR includes the conventionally known 41
1L sex south molecule t that pinter's -i! Or can be used as a whole. These compounds include, for example, "Vinylbenzyltrimethylammonium chlorite", U.S. Pat.
101, 1σ co-issue, - reference, //I.

Ko J/-S! , same concern, lko 4. Young No. 17, Norisan, /J7
, U.S. Pat. No. 1, 070. IIf No., 0L8J, IJo.

These are the cross-jam polymer latexes described in No. 747 (U8 8er Atlai Core), etc.

In order to reduce the number of conductive layers, the following points should be kept in mind: be. That is, light scattering occurs not only within the conductive field but also in the field r# where the conductive layer is in contact with other substances. When a conductive layer is placed inside a photographic light-sensitive material, as an undercoat for a light-sensitive emulsion layer, or as an intermediate layer in a multi-layered light-sensitive emulsion layer, a binder for the conductive layer and a binder for the light-sensitive emulsion layer are used. Because it has a poor refractive index, the light scattering effect at the interface between both layers is not large. On the other hand, when the conductive layer is placed on the upper part of the photosensitive emulsion 9, on the back side of the photosensitive material, that is, in the position where the photosensitive side is in contact with the external medium (usually air), the 411 layer and the medium are Light scattering stops at the interface. In order to suppress light scattering, a method of providing a covering layer in addition to the conductive layer is proposed. This wingman layer can also function as a conductive layer, so it is one of the preferable Wia+ layers of the present invention.

Use of conductive particles per square meter
B'rc, go, or~iat are good, 0, /~i
oy is preferred.

The ultraviolet absorber used in the present invention is one that cuts discharge light 6! It is used in the photosensitive materials of II-&. For example, wood nationality #'F happyi, ≦rr, 207
No. 3, 7 Rihiro, 4I Ri No. 3, I.

Specific examples of the compounds listed in 1Wj, 2nd issue, etc. are as follows.

Compound Example 1) 10) 12) 1g) 0 IIH1l 27) One or more of these ultraviolet absorbers may be used in the support, pack layer, underplow layer, or intermediate layer between the undercoat layer and the emulsion layer of the light-sensitive photographic material. It may be contained in one or more of the layer and the emulsion protective layer.

If the stone is to be contained in a support, and if it is to be contained in a cellulose derivative system such as 41IK nitrocellulose or acetylcellulose, it may be added by dissolving it in a vCFs doping agent.

When an ultraviolet absorber is provided on a support, it can be applied by incorporating it into a binder using a conventional method.

Generally, it is possible to use a binder of the same type as the binder in which the conductive metal oxide is dispersed, and the binder is: 1°. The solid support used in the present invention is 1. Any material that is generally used for photography may be used, such as cellulose derivatives such as cellulose cyanatate, cellulose acetate propionate, and cellulose nitrate; polyethylene terephthalate; polyester resins such as polyethylene naphthalate; Polystyrene, polycarbonate, polyolefin paper, etc. can be used.
One liter of surfactant is added to the photographic constituent layer K of the present invention! II or may be added in a mixture, they are used as fabric aids φ
However, it is sometimes applied for other purposes, such as emulsification and dispersion, sensitization and other photographic properties modification, and charge series adjustment.

These surfactants include natural surfactants such as saponin, sex agents, O-nonionic surfactants such as alkylene oxide type, glycidol type, and glycidol type, higher alkylaines, tertiary ammonium salts, and pyridine. Other complex s
cationic surfactants of the si, phosphonic or suhoeum group; anionic surfactants that meet the acidic groups of si, sulfonic acid, sulfonic acid, sulfuric acid, phosphoric acid ester, annoic acid chain; AminosulfoneilI! -,
There are seven types of amphoteric surfactants based on sulfur or phosphate esters of amino alcohols.

In the present invention I8, seven bulky surfactants can be used in combination, and such fluorine-based surfactants include:
The following compound examples are shocking.

For example, British Patent No. 310,316, ibid.

! ko44, 63/issue, rice 13inken'e441p, 44
No. 71, same J,, No. 119,904, Tokuko Akira! --J4
6t7, 'Unexamined Japanese Patent Application Publication No. 17JJ, zi-J-
The fluorine-based surfactant described in 23 Co., Ltd., et al.

Also, in the present publication, lubricating compositions, such as U.S. Pat.

J/No.7 1. Same No. J, j@j,? No. 70, jiIJ11
11JtJ? ! , No. 137 and Nippon Kinkai-Xu Zhao J-Ko/Jji! It is possible to include a modified silicone portion as shown in No. JO in the photographic constituent layer.

The photographic light-sensitive material of the present invention has the first US Patent No.
．． The polymer latex described in Japanese Patent Publication No. Sho-j-1111, etc., as well as silica monosulfate, barium sulfate, polyamide Methyl methacrylate at.

Other configurations of the silver halogenide photographic light-sensitive material of the present invention,
For example, silver halide grains, anti-capri agents, hydrophilic colloid binders, hardeners, color blur, spectral sensitizing dyes, anti-fading types, etc., as well as their manufacturing methods and processing methods, are limited to %. For example, Research Disclosure magazine (Re5ea, rch Disel
osere) / Volume 76, pages 1 to JO (December 1971) can be referred to.

The present invention will be made more specific by Examples and Comparative Examples below, but the present invention is not limited to the following Examples.

In the following examples, all parts 1 indicate "parts by weight."

Example [Manufacture of conductive oxide fine particles] Irrigation of stannic chloride-6j parts by weight and antimony trichloride IO
Part by weight was dissolved in 100 weight sVc of ethanol to obtain a homogeneous solution. This solution of sodium hydroxide was added dropwise until the pH of the solution reached jVc to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The resulting coprecipitate was allowed to stand for an hour to obtain a reddish-brown colloidal precipitate.

A reddish brown colloidal precipitate was separated from the centrifuged animal. Water was added to the concentrated precipitate to remove excess ions, and the precipitate was washed with water by centrifugation. This operation was repeated 13 times to remove excess ions.

IOO parts by weight of the colloidal precipitate from which excess ions had been removed were redispersed in 900 parts by weight of water and sprayed with calcined Pt1C heated at 40'' CK to obtain a fine powder 11- with a realistic average particle diameter of O1λμ.

This mixture /l/ was put into an insulating cylinder with an inner diameter of 1.4CIII, and stainless steel electrodes were placed from the top and bottom to make a 10DD4/c
Pressure is applied at a pressure of y*2 (volume specific resistance of the powder).

When anti-ts was determined, it was tΩ-1.

[Application of conductive layer]

The above conductive powder 11 parts by weight gelatin
l - parts by weight water
/ 000 evening: A dispersion having the above composition was dispersed for 1 hour using 4 Indoshaker (manufactured by Toyo Seiki Seisakusho) to prepare a coating solution.

This dispersion was coated with VC* on a cellulose triacetate support with a base coat/J of 7μ so that the dry film thickness was oaJμ.The surface resistivity of the resulting conductive layer was measured using CRH. It was !×IOΩ.

[Applying photosensitive photographic layer]

The support provided with the above-mentioned conductive layer and the support only coated with an undercoat,
anti-no-ration layer, red photosensitive layer, intermediate layer, green photosensitive layer,
A sample (Il(It)[1[]t-) was made consisting of one yellow filter layer, a back light layer, and a protective layer.

The composition of each layer is as follows (antihalation layer) Binder: Gelatin, tiv7m"Yugsaij: t
+ j-bis(vinylsulfonyl)-probanol-J/, λtiioot Binder coating aid: Sodium dodecylbenzenesulfonate W/m" Antihalation component: Black colloidal silver O, -t/m" (red Photosensitive layer) Binder: Gelatin 797m" Dura coating /, J-bis(vinylsulfonyl)-propano, '≠ Roux J /, 21/1009 Binder: Cypress cloth Auxiliary agent: Sodium nidodecylbenzenesulfonate ioq/m" Coated silver Amount: i, /l/m” Silver halide group E: A g Icomoru 2 and Ag
Brat mole coupling inhibitor = 4A-hydroxy-4-methyl-/,
j, 31.7-chitrazaindene 0.19/A g/
00 as color former: l-hydroxy-4'-(J-acetyl 7 x
2#) 7 no N-[4g-[J, 44-Gte
rt-amylphenoxy]butyl]-corner 7 toamide J If/A g/00 f sensitizing dye; anhydro-I, jI-cycloterethyl-1,II-
Di(J-J' Lufoprovir J Thiacarbocyanine hydroxide viridine invasive salt 0.3f/kg100? (middle layer) Binder: Gelatin λ, at/m"' Hardener: / * j-His(vinylsulfonyl) )-propanol-J/, 2t/10at binder fabric aid: F
Sodium tesilbenzenesulfonate 17m
” (Green photosensitive layer) Painter: Gelatin 4. t/m Hardener: /, j-bis(vinylsulfonyl)-propanol/, 29// 00 t Binder coating aid Nidodecylbenzene sulfonate/sodium acid 2 /-2 Coating scissors it, λ, f/m'' Hydroxylene chemical record set K: A 'g I 3 , j mol S ν and A g Br 26.7 mol Sound stabilizer: San-hydroxy-6-methyl-1 ,1゜3a,
7-Chitrasainden 0, 4 f/kg100? Coloring agent: /-+2. Hiroshi, 6-Dorikuro i Fueni k) -J-(
j-(4!-Cter t-amylphenoxyphacetamide)benzamide-(methoxyphenyl)Azoterpyrazolone 379/Ag10
0f Sensitizing dye: anhydro-*', ``t-diphenyl-terethyl-3,3I-di(cosulfoethylta□ Oxacarpositinhydroxide pyridinium salt 0
．． 3t/kg1009 (yellow female filter 1 layer J Binder: Gelatin-0it7 layer 2 Filter component: ★Colored colloidal silver 0.797m” acid 11
Agent: /, J-bis(vinylsulfonyl)-propanol 1. Cot // 00 f Binder surfactant =
-bis(coethylhexyl) monosulfonatosuccinate
Ester sodium salt 7kg/mjl (blue photosensitive layer J binder: gelatin yt7'm hard taminating agent: /, i-His (vinylsulfonyl J-pronoha-nor-21,2t/1009 binder auxiliary agent:
Sodium dotecylbenzenesulfonate curvature/vn2 Amount of coated silver: Co, Cot7m" Silver halide group: A g I J , 1 mol % and AgBrf 4.7 mol % tiI: Building agent: hydroxyl-6- Methyl-7,3゜Ja, 7-chitrazye/den 0.#t7 people 111001
Color former = λ'-chloro-11
rt-amylphenoxyJbutylazdo]-α-(1,
j'-dimethyl-co,4c-oneoxo-3-oxazolidinyl J-α-(4I-methoxybenziylmiacetanilide xi s t/1111001 (lower protective layer) Binder: Ceratin/, Otsu,, f/m 2 hard I
HIJ: /, J-bis(vinylsulfonyl J-
Prono Hair Nor-λ/, Cot/100t Binder application aid Nidioctyl sodium sulfosuccinate bzwg7m
” ・ Ultraviolet absorption-2 (tinuvin Ps) (4Ma1 upper layer J Via 1-: #-t = Inic acid treated gelatin (isoelectric point 7
) / f 7m” Acid 11 agent: z, 3-bis(vinylsulfonyl)-prono
” Matting agent: Copolymer of polymethyl methacrylate and polymethacrylate (copolymer: 1 [Affiliation ratio j:l, average particle size 3μ) JOag/m” Polymethylmethacrylate (average particle size JμJ 10ql)
/m'' Sample CI) is obtained by applying the above composition to a support containing a conductive layer, and Sample [I] is obtained by removing the ultraviolet ll1Ill absorption from the composition of sample CI). ,sample〔
] is a substrate coated with only an undercoat and coated with the above composition.

The samples were discharged for a period of λ in the IRH mode, and sample T was rubbed with a rubber roller and a Delrin roller in a dark room, then developed, and the degree of occurrence of static marks was compared.

The results are as shown in the table below, and no static marks were observed in sample 1.

A: Not occurring at all B: Slightly occurring C: Occurring slightly D: Occurring completely Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment filed on March 77, 1939 Commissioner of the Japan Patent Office Shima 1) Haruki Tono 1. Display of the incident 1924 patent application No. 14/100
No. 2. Name of the invention Relationship to the antistatic silver nine halide photographic sensitivity incident Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Telephone (406) 25
37 Table Date of amendment order Date of January 1920 & Subject of amendment Specification & Contents of amendment 1. We will submit an engraving of the specification (with no changes in 1!).

Claims (1)

[Claims] At least one type of gold^ oxide '*'fc selected from Zn, Ti, '8n, In, 8i', Mo, and W is /
and a mixture of these metals] is composed of 7j/Yuzu or higher metal wei compound as the main conductive material! ! 1 grain - containing layer at least i m! L/, or □/[At least one layer containing the above ultraviolet absorber is considered a t-sign) Silver halide**WS optical material.