JPS5862646A - Antistaticized silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To prevent triboelectrification by forming a layer contg. conductive particles disolving during photographic developing process. CONSTITUTION:Conductive particles having 0.5-5.0mum average particle diameter and made of a metallic oxide dissolving substantially during a photographic developing process is dispersed into a binder and coated. For these particles, zinc oxide is particularly suitable, and they are doped with aluminum or indium to make them as conductive as <=10<7>ohm.cm. The conductive layer 3 formed by coating is arranged between a subbing layer 4 and a photosensitive silver halide emulsion layer 2 on a photographic material support 1, or as a backing 5. Even if there is haze of color in the conductive layer 3, superior transparency is obtained by dissolution of them during a processing stage.

Description

[Detailed description of the invention] This invention #4 is a silver halide copy with improved antistatic property.
The present invention relates to GZ materials (hereinafter referred to as "photographic light-sensitive materials"), and particularly to 4^ photosensitive materials with improved antistatic properties without adversely affecting photographic properties.

Photographic light-sensitive materials are generally made of a support having piezoelectric insulating properties.
During the busting process and during use of photographic materials, static electricity is often accumulated due to contact friction or peeling between the surfaces of four or different materials. .

However, the electrostatic shock caused by the electrostatic shock caused by many disturbances.

The most serious problem wFi#L The static charge accumulated before processing is discharged, the photosensitive photographic emulsion layer is exposed, and the photographic film IR
When dust images are processed, dot-like spots or Fi dendritic or feather-like lines 1&1 are produced. This is what is called a static mark, and it seriously impairs the commercial value of the photographic film, or in some cases completely destroys it. For example, if it appears on medical or industrial X-ray film, it will be easily recognized that it will lead to extremely dangerous judgments.
PK is very 1r! , is one of the most important turtles.

In addition, these accumulated electrostatic charges may cause dust to adhere to the surface of the Fi film, or the soap may not be applied evenly.
.

It can also cause the next failure of imvs.

Such electrostatic charges are often accumulated during the production and use of photographic light-sensitive materials, as described above.
Alternatively, it may occur due to improper winding of photographic film or separation of the support surface and emulsion surface during the unwinding process. In the case of finished products, the separation of the base side and emulsion side when changing the photographic film T11 also results in ll1X.
- Occurs due to contact separation between the ray film and the mechanical part or fluorescent intensifying screen in an automatic imager.

It can also occur due to contact with other obsessive materials. 1P2)
Static marks in photographic light-sensitive materials, which are induced by the accumulation of electrostatic charges caused by electrostatic charges, have recently decreased to 0%, which has become more noticeable as the sensitivity of photographic light-sensitive materials increases and the processing speed increases. High-sensitivity materials, high-speed imaging,
Four-layer static marks are more likely to occur as a result of the increased number of opportunities for high-speed automated processing and harsh handling.

The best way to eliminate these static-induced hair debris is to increase the electrical conductivity of the material so that the static charge can be quickly dissipated before the accumulated charge is discharged.

Therefore, conventional methods have been considered to improve the conductivity of the support of photographic light-sensitive materials and the surface layer of each woven fabric, using various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. Attempts have been made to use it.

For example, U.S. Pat.

97 pieces! 3rd issue, J, Otko, 71! No. 3.2
No. 62, 107, 4 J, j/II, Co No. 91.

Same J, t/j, jJ1,! , 7jJ, 7/4 issue,! ,
Polymers such as those listed in 9JI, No. 999, etc., 8 pages, for example, t H1 wood special ntip, 2*vl**4j1, 3,4A col., Hiro! No. J, No. 17゜074, J,! 31, 4.2j issue, same j, 11th, 97th issue, same J, 4! Z, JI No. 7, etc., and surfactants such as U.S. Percent No. 3. ! A colloidal silica group described in No. 4λ1 is known.

However, many of these materials exhibit percent isomerism due to the allgjs of the film support and the propagation of photographic compositions, and may have poor results for certain film supports, photographic emulsions, and other four-dimensional components. However, photographic components made with 11 different film supports are not only completely useless in preventing static electricity, but may also have some effect on photographic properties. Another major drawback is that the conductivity of many of these materials is dependent on humidity, and they lose their function as conductive layers under low humidity.

My father, Special Publication No. Sho Jj-4476, describes a technology for using tin oxide as an antistatic treatment agent, but the technology used is based on the use of amorphous tin oxide colloids. It is a material whose conductivity is humidity-dependent and loses its function as a conductive layer under low humidity, and is essentially the same as the various substances described above.

On the other hand, U.S. Pat. As a conductive material for a conductive support, the conductivity is largely dependent on humidity, and crystalline gold S densities such as zinc oxide, stannic oxide, and indium oxide can be used. I'm being asked.

However, the use of these conductive wing materials in silver halide photographic materials is completely unknown.

Moreover, it can be obtained using light-sensitive photographic materials.

In some cases, the transmitted light may be detected or printed on the photographic paper, and in this case, the area without the image must have sufficient light sensitivity. However, the cable material that can be used for conductive materials for electrostatic recording may not always be used for silver halide photographic materials. It is to provide a photographic material that has been stopped.

The first object of the present invention is to provide a photographic material which has excellent antistatic properties at low humidity.

A third object of the present invention is to provide an effective method for preventing charging of a photographic light-sensitive material without impairing its inherent properties.

An object of the present invention is to provide a photographic material suitable for DI observation under transmitted light.

The object of the present invention is to use a treatment technique that allows dust to settle down and wash with water.
l)! It has been found that this can be achieved by providing a conductive layer of conductive fine particles dispersed in a binder between the back layer of the VGFT-type halogenated steel photographic material or the halogenated steel photographic emulsion layer and the support. Ta.

The conductive layer used in the present invention is treated in order to be dissolved in the processing step.
A: Even if there is haze or coloring in the conductive layer, his film disappears and becomes a highly transparent film after processing, lll111! A film suitable for observation. Furthermore, since the conductive layer of the present invention is provided between the back layer or photographic emulsion layer and the support, even if L is applied to the conductive particles before processing.
There is some haze and coloration, and this photograph does not have any negative effects.

As the conductive particles for forming the conductive layer of the present invention 9, it is possible to use a material that dissolves in the photographic processing process, has no humidity dependence of conductivity, and has low resistance without adverse effects on photographic properties. In particular, conductive zinc oxide is preferred, and conductive zinc oxide is generally a type of atom other than zinc oxide.

For example, it can be obtained by doping aluminum or indium. The volume resistivity of the conductive particles of the present invention is io'Ω-(
(to) The following is 1, preferably 106Ω-■ or less.

In the present invention, even if there is haze before photographing,
9 particle size does not necessarily have to be small enough because there is no problem! μ or less is 1 <preferably 3μ or less is 1,
Special request! ! -≠7463, particles of 0.2μ or less were processed, but in the case of the present invention, there is no problem even with larger particles.

In order to provide the conductive layer of the present invention, it is sufficient to disperse the conductive particles in a binder which is dissolvable in a treatment bath and apply the dispersion.

Examples of binders include gelatin, modified gelatin, polyvinyl alcohol, vinyl alcohol copolymer,
Carboxymethylcellulose, polyacrylic acid, acrylic acid copolymer, polyvinylpyrrolidone, vinylpyrrolidone copolymer, hydroxyethyl acrylate copolymer,
Water-bathable polymers such as acetylcellulose, acetylbutylcellulose, acetylpropylcellulose, phthaloxyacetylcellulose, etc., styrene, α-methyxstyrene, hydroxystyrene, vinyl acetate, alkyl (alkyl group with carbon number 1 to 1) Homopolymers such as acrylate, alkyl (alkyl group with carbon number l to μ) methacrylate, vinyl chloride, vinylidene chloride, and copolymer containing these heptamers, copolymer polyester containing maleic anhydride, soluble nylon, #1
I can name one such as 1 Note Polynisder.

A specific example of a photosensitive silver halide photographic material containing a conductive layer of the present invention is shown in cross-sectional views in FIGS. 1g7 to 1.

1IQ and FIG. 2 show the case where a conductive layer is provided between the support 12 and the photographic emulsion layer.
It can also be applied separately to the undercoat layer 4', or 1 in Figure 1.
It can also be used as both a conductive layer and an undercoat layer.

Figure 1 shows the case where the conductive layer is provided on the opposite side of the photographic emulsion layer, and Figure 97 shows the case where the conductive layer and Vs are used as the back layer 4k [! This is a method of applying an undercoat layer when the conductive layer 7 is provided on a pack. This is a method of providing a layer JP'4 having functions such as matte properties, slip properties, and scratch resistance on the conductive layer shown in Figure Fi.

It goes without saying that Figures 1 to 1 show typical examples and are not limited thereto.

A crosslinking agent that reacts with the binder, a dispersant, a surfactant, a matting agent, etc. may be added to the conductive layer of the present invention.Dispersants include, for example, sodium metaphosphate.

Phosphates such as sodium pyrophosphate can be harsh.

To provide the layer of the present invention, a dispersion of conductive particles dispersed in a binder may be coated, and the solvent for the dispersion may be water or a conventional organic drilling solution. Examples of organic heating agents include alcohols such as methanol, ethanol, and propatool; esters with methyl acetate and ethyl acetate; and complex salts such as methylene dichloride, ethylene dichloride, chloride, and chlorocene. Hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, among them methyl cellosolve, ethyl cellosolve, dioxane, methyl selon lupus acetate, benzene phenol.

These stimulants, such as resorcinol and cresol, can be used alone or in combination.

Application methods for preparing these dispersions include air knife coating, gravure coating, roller beat coating,
Barcodes, extrusion coating methods, etc. can be used.

Supports used in the present invention include cellulose triacetate, cellulose acetate butyrate,
Polycarbonate, polystyrene, poly, ethylene naphthalate, polyethylene naphthalate, polyolefin: laminates, etc. can be used.

The structures of the light-sensitive non-logenated complex emulsion layer and other layers of the photographic light-sensitive material of the present invention are not particularly characterized, and any known materials can be used.

For example, gelatin! Aqueous colloid, No. 10 Genka Roku, sensitizer, antifoggant, hardener, surfactant, polymer border, Chikara 2-Kab 2-1 anti-fading agent, ultraviolet absorber, strong light brightening Regarding agents, matting agents, slip agents, spectral sensitizing dyes, etc., please refer to Research Disclosure Magazine No. 17.
It can be made into an 11th review of volume A, pages 9 to 9 (J month, 971).

In the present invention, any known method can be used for photographically processing the photographic material. Any known treatment liquid can be used. Processing temperature is 1tQc)
However, it is also possible to use a low temperature t or a temperature exceeding 0Cp depending on the purpose. Any of the two photo-processing methods can be applied, consisting of on-site processing.

The developer # used in black and white photographic processing can include known developing agents. As developing agents, dihydroxybenzene (e.g. hydroquinone), 3-
Pyrazolidones (e.g. l-phenyl-3-; pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), l-phenyl-3-pyrazolines, buscorbin I
P, and U.S. Pat. No. 047,172, 7. Ko, 3. Compound compound compounds in which a Hiroshi-tetrahydroquinoline field and an intrene ring are condensed can be used either individually or in combination. In general, other well-known preservatives are added to the lump solution.

Contains alkaline agents, pH@Lin agents, antifoggants, etc.
In addition, if necessary #i decomposers, color toning agents, dust accelerators,
It may also contain surfactants, antifoaming agents, water softeners, hardeners, viscosity imparting agents, etc.

As the fixer, one having a commonly used composition can be used.

As the fixing agent, thiocyanate salts, thiocyanate salts, and organic sulfur compounds known to have similar effects as fixing agents can be used.

Even if the fixing solution contains a water-bathable aluminum salt as a hardening agent, a conventional method can be applied when the hair is formed in a low color.

Negative-positive method (for example, “Journal of th
e9ociety of Motion Pictu
re and'l'evision Engine
eers 6/vol. (1951), pp. 447-70).

A negative image 11' is created by dusting with the staining liquid contained in black and white imager 4, and then subjected to at least the same fogging process of 11m of uniform light or light, followed by color development 3J1.
The power to gain strength and self-improvement in doing things 2〒Reversal method,
The color ST-containing Yoshin emulsion is used by Koko I11iJ4 to produce a silver image, and the color SS white method, which uses the color ST as an autocatalyst, is used.

Color development #1, generally consisting of an alkaline bath solution containing a color developing agent. Herbal medicines include well-known "primary aromatic amine illumination agents, such as Phoenix diamine field (
For example, Hiro-amino-N, N-diethylaniline, 3-methyl-amino-N, N-diethylaniline, μm amino-he-ethyl-he-β-hydroxyethylaniline, 3-methyl-+ -amino- N-ethyl-~-β-hydroxyethylaniline, 3-methyl-Hiro-ami/-N
-ethyl-N-β-methanesulfamide ethylaniline, ≠-7mi/-J-, I'thiru~-ethyl-N-β-
methoxyethylaniline, etc.) 1-can be used.

This tLl] L, F, A, Mison @
Photographic Processing C
hemistry (1'ocal Press, 1
ttt year) here 6~. 2.29 negative, US patent co, /9
! ,0/! No., same, ztλ, No. 34, JP-A No. 1-
611tJJ issue, etc.
゛The photographic emulsion layer after color development is usually treated with J-film white. - The self-processing can be done simultaneously with the fixing process or separately.
Compounds of polyvalent metals such as cobalt (it), chromium (Vj), and copper (II), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, weight t
lA acid salt - organic anchor ring of iron (臘) or cobalt (臘),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, ditolyltriacetic acid, J-diteminocopropanoltetraacetic acid, etc., or complex salts of 1W and acids such as citric acid, tartaric acid, and malic acid; persulfuric acid and 1 permanganese. Acid salts; nitrosophenol, etc. can be used.Among these, potassium ferricyanide, ethylenediamine, and sodium ethylenediamine are used.
1i1 iron(mountain) ammonium is particularly useful. Ethylenediaminetetraacetic acid iron (&l1) fd salt is useful both in a stand-alone solution and in a -bath solution fixer.

The Hw of the present invention will be explained in more detail below by listing actual examples, but the present invention is not limited to these examples.

Example l Zinc oxide ioo parts by weight At(N
us) s・9H2 (J's lQ4 water) aqueous bath liquid
! I water
100 # sword) mixture l
A homogeneous dispersion was obtained by irradiating with Guan Zhao sonic waves for 1-10 minutes.

This dispersion y (after drying with LiO'C for 1 hour lx/0
It was fired for 3 minutes at 'Torr, t 00 'C to obtain conductive zinc oxide having a volume of 1 and a resistivity of λX10 Ω-(2).

The particle size was microμ. Grind the grains in a T-ball mill,
Particles r having an average particle size of 0.7μ were obtained.

Take the above conductive zinc oxide Jltl, add 0.3 ft of metaphosphoric acid to 0 oct of steamed water and add #1 [K added,
Paint shaker (Toyo n Tsukuda Seisakusho 1ll)/Time dispersion.

Add gelatin to this dispersion, add JO
OC1t1M Einto Shaker! Dispersed for minutes. Add a gelatin hardening agent to this Tani powder (CH2=CH
-8(J2-CHs-CL)NH-)1 CH211-
In addition, it was used as an m-replacement fluid.

/ 00 fi, thick polyethylene terephthalate film & C91 vinylidene/ethyl acrylate/a”
Acrylic acid (Ij:/0:j) copolymer latex was coated with a conductive zinc oxide dispersion on a support of 11/J.
A sample was prepared by drying at J"c for io minutes. This sample was designated as (mu).

As a comparative sample, gelatin was applied to vinylitine chloride copolymer latex undercoat, and hardening agent (C
I(2=C)1-8L), -CH,-CONl-1-)
, C) Apply the liquid ktm @tari JOu with i, added,
Dry scissors for 10 minutes with tJz"c to make #A, family and this 2 (B
).

The surface resistivity of Arai (A) and (k3) is 1r'iz'C! It was measured under the conditions of %hHm and z'cto 僑H1l (J conditions. The Onokuni Enaichi sample (H) had a ton of 1014 or more.

The haze of Samples A and B was measured after processing. Both A) and (B) were 7s, and the difference between them was an incredible force.

Example λ Conductive zinc oxide of Example 1! ! Part by weight Nitrocellulose lI Methyl ethyl ketone
J20'i 1g portion A mixed solution having the above composition was dispersed in a paint shaker for 30 minutes.

Acetone (60v methanol bogt) was added to the above dispersion and stirred to obtain a coating liquid.

This l1I7tb-liquid 11-/, was applied to a 27μ thick three-vinegar plate cellulose lambda paste at a ratio of Oct/m'', /2
．． Dry at 0''C for 70 minutes.

Furthermore, the following bath solution was applied on top of this layer at a ratio of /Oac/m.

Heptalulose diacetate 7 parts by weight acetone /DO#methanol
40s behenic acid amide,
0.0/# The surface of the support opposite to this layer was coated with gelatin, and a halogenated image emulsion for micro was coated to prepare a photosensitive material for micro. The surface resistivity of the conductive zinc oxide kllll-covered surface of the film is Fi! "C, J x 101 under the condition of 10 14H
0Ω, showing excellent antistatic properties.

Further, the haze of this film was 1%, which was good.

wm Example 3 A support consisting of an irop polyethylene terephthalate film 1 was coated with a gelatin undercoat after corona discharge treatment. On one side of this, the gelatin dispersion of zinc oxide used in Example 1 was applied to the dry gland thickness of lμ.

A halogenated button emulsion for medical X-rays was coated on both sides of this support to prepare a photosensitive material for X-rays (K Group A
) As a comparative sample, a sample (13)k was prepared in which a gelatin undercoat layer was coated directly with a halogenated emulsion layer.

The milked surface of the film was rubbed with white rubber in a dark room under the following conditions and treated with fjL*.

Sample A had no static marks, but sample BK
Seven marks were generated for each of the t and t statistics. In addition, □ Haze from Langwei's office was to become a foreigner sooner or later.

[Brief explanation of drawings]

FIGS. 1-J are cross-sectional views of one typical photographic material according to the present invention. In each figure, l indicates support 1. ．． 2 is a photosensitive silver halide emulsion layer, J is a conductive layer, and Yume is lower l-! is the pack layer, tFi
7 is a conductive layer, l is an undercoat layer for the back conductive layer, and - is a pack overcoat layer. Patent applicant: Fuji Photo Film Co., Ltd.
No change in content) Figure 1 Figure 2 ＼ Figure 3 Figure 4 Procedural amendment (Blade side Showa J 7 J Jl / 6 Fl Commissioner of the Patent Office Shima 1) Spring #4 Tono 1, Indication of the case Showa j 1 Patent Application No. 1, No. 1, 2, Title of the Invention: Antistatic Halogenated tS^ Photosensitive Material 3, Person Making the Amendment Relationship with the Case Patent Applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Amendment Order date of book
1935/1939 Date & Subject of amendment Autumn specification We will submit the amended specification and an engraving of the drawings (no changes to the content).

Claims (1)

[Claims] A silver halide photographic light-sensitive material having an average grain size of 1zo, z~2.0 μm'' cID and at least I layer containing a metal oxide that is substantially dissolved in a photographic development process. ,.