JPS588497B2 - Sya Shinki Kyouzairiyo - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic recording material comprising a support having a transparent and electrically conductive metal oxide semiconductor layer on a polymeric material, and which exhibits remarkable antistatic property even under low humidity. The present invention relates to photographic recording materials having effects.

Almost all polymer supports have a surface resistivity of 10 13 Ω or more at room temperature and humidity.

However, with supports having a surface resistivity of 10Ω to 13Ω or more at room temperature and humidity, various problems occur during the manufacturing and processing steps, or when used as photographic films or clothing.

For example, in the past, accumulated static charges caused by contact friction, discomfort due to static electricity, adhesion of dust, ignition of flammable substances due to spark discharge, static marks (in photographic film, when the accumulated charges are discharged, the film surface becomes photosensitive). When developed, dot-like or dendritic streaks appear.

This is called a static mark.

) and various other troubles were unavoidable. As a method for preventing static electricity on polymeric substances that cause these various adverse effects,
For example, conventionally (1) a kneading type in which an antistatic agent is mixed into a polymeric substance in advance; U.S. Patent No. 2,57
No. 9,375, US Pat. Those using organic substances such as allyl sulfonate, or alternatively, U.S. Patent No. 2,758,98
Magnesium oxide as seen in U.S. Pat.
, 887,632 No. 2,9 4 0,9 4 1,
3,06 2,700, which uses metal compounds such as zinc oxide and titanium oxide) (2) Coating type, in which an antistatic agent is applied onto a polymeric material ( If necessary, for example, U.S. Pat.
9 8 4 using an alkyl sulfonate, U.S. Pat. No. 2,8 7 6,1 2 7 using a quaternary ammonium salt, U.S. Pat. No. 2,9 5 5,9
Those using organic substances such as those using polyhydric alcohol No. 60, or those using metal oxides such as titanium oxide and tin oxide as seen in Japanese Patent Publication No. 35-6616 and Japanese Patent Publication No. 40-24890. There are two methods.

However, each of these methods has some drawbacks.

For example, in the kneading type method, there is no or little effect unless the amount of antistatic agent mixed is large, and in the coating type method, it is essential to use an organic solvent that dissolves or swells the support. After that, there are problems in that drying at high temperatures impairs the flatness of the support and causes pollution in the treatment of waste solvents and exhaust gases.

In addition, when using an organic antistatic agent such as an alkyl sulfonate or a quaternary ammonium salt, the surface resistivity is highly dependent on humidity, and when the humidity is low, the adsorbed water increases due to drying. is released, the surface resistivity becomes extremely high, and the antistatic function is lost.
There was a drawback.

Products using metal oxides use organic solvents during coating or kneading, so they always pose the above-mentioned pollution problem due to waste solvents.

In addition, since all of these have metal oxide particles dispersed to form a layer, unless the amount of coating or kneading is increased, the conductivity will be poor and the antistatic effect will deteriorate.

Moreover, since the particles are dispersed, there are problems such as poor transparency.

As described above, both those using the coating method and those using the kneading method have various drawbacks.

By the way, as a method that does not have these drawbacks, although the field is different, there has recently been a method for forming a thin, uniform continuous layer of metals or metal oxides without using a solvent.
There are so-called vacuum deposition methods in which metal oxides are deposited on a support under vacuum.

As an antistatic method using a deposited layer formed by a vacuum deposition method, for example, there is a method in which a metal is deposited to prevent charging of an electron beam recording material.

(If necessary, British Patent No. 1,3 4 0.4 0 3
(See U.S. Patent No. 3,3336,596, etc.)
However, since this method relates to an electron beam recording material, it only satisfies the condition that the electron beam simply needs to pass through the metal vapor deposited layer provided.

In other words, in this method, there is no problem even if light rays with significantly lower energy than electron beams, particularly visible light, which is important in the field of photographic light-sensitive materials, do not pass through.

That is, it may be opaque when forming a latent image.

However, general photographic recording materials, especially negative film, motion picture film, and X-ray film, in which transparency is essential,
In Y-films, aviation films, etc., the vapor-deposited layer having an antistatic effect must remain transparent to be of practical use.

By the way, very recently, attempts have been made to use such a vapor deposition method as a method for preventing static electricity in photographic recording materials.

That is, a method has been developed in which a layer of a mixture of metal and inorganic oxide is formed as an intermediate layer between a polymer support layer and a photographic emulsion layer.

There, 80 to 30% by weight of a metal such as chromium, silver, nickel, or copper alone or a mixture of two or more thereof and a mixture of 20 to 70% by weight of an oxide such as silicon, magnesium, tantalum, titanium, silicon, etc. An intermediate layer consisting of was provided as an antistatic layer.

From the description in the claims, it is said that chromium is particularly excellent among these metals.

In this method, as described above, the disadvantages such as the large change in antistatic ability due to humidity when organic particles are used and the opacity or non-uniformity when inorganic particles are used are improved.

However, as is well known, chromium is an extremely harmful compound that must be handled with care.

Also, chromium, copper, silver, nickel, etc. are compounds that are easily attacked by acids, alkalis, etc.

Silver is extremely expensive and is not suitable for regular use as an industrial product.

This method also had various limitations due to the materials used.

Moreover, from the viewpoint of vapor deposition operations, since this method uses a mixture as the intermediate layer as described above, even if the mixture is vapor-deposited by a flash method or an electron beam method (L.
Maissel and R. Glang：”Ha
ndbook of Thin Film
Technology"Chapter r/.MaGl
aw Hi 11, New York +197
Compared to the deposition of a single substance, the deposition conditions for a mixture (see 0) are very complicated, and it is extremely difficult to uniformly and continuously deposit a mixture onto a wide and long polymer support.

As described above, the techniques disclosed in the prior art also have various problems.

We have attempted to form a transparent conductive layer on a polymer support by vapor depositing simple substances such as titanium, zirconium, etc. and performing subsequent treatments, and have arrived at the present invention, which has various advantages.

By the way, the present invention was developed to solve the problems of these prior art techniques.

The present invention provides photographic recording materials, particularly those with significantly improved antistatic properties.

First, metals with no or extremely low toxicity are used.

Secondly, metals that are stable against acids or alkalis are used.

The third method uses a simple substance.

Fourthly, a material that can easily provide a uniform composition is used.

Fifth, it uses very cheap and effective metals.

Sixthly, a metal oxide semiconductor (obtained by performing oxidation treatment after vapor deposition of a metal) is used.

Seventhly, elements of the lVa group and the Va group in the periodic table are used.

Eighth, it supports a polymer support with a surface resistivity of 10 11 Ω or less.

The constituent elements of the present invention will be explained in detail below.

First, as the polymer support used in the present invention, ordinary thermoplastic and thermosetting polymer substances are effective.

As mentioned above, polymer supports generally have a surface resistance of 1013Ω or more, but the method of the present invention can easily reduce the surface resistivity to 1011Ω or less, so there are no restrictions on the material of the polymeric substance. Alternatively, it may contain pigments, brighteners, antistatic plasticizers, etc.

Examples of the polymeric substance include those known as oligomers and initial condensates in addition to so-called polymeric substances in the field of ordinary polymer chemistry.

That is, synthetic resins such as addition polymers, opening polymers, and polycondensates involving so-called unsaturated bonds, synthetic polymer substances known as synthetic fibers and synthetic rubbers, natural rubber, cellulose,
Examples include natural polymeric substances such as gelatin, protein, paper, and wood, or derivatives thereof.

For example, synthetic polymer substances include olefins, allyl compounds, halogenated olefins, styrenes, heterocyclic vinyls, acetylenes, arenes, butadienes, N-vinyl compounds, vinyl esters, and vinyl ethers. , vinyl ketones, acrylic acids, acrylonitriles, acrylamides, methacrylic acids, oxiranes, and lactams.

Alternatively, polyimine, polyester, polyether, polycarbonate, polysulfide, polysulfone,
Polysulfonamide, polypeptide, polyamide, polyimide, polyurethane, polyurea, polyanhydride, alkyd resin, unsaturated polyester, epoxy resin, ketone resin, phenol resin, urea resin, melamine resin, furan resin, xylene resin, toluene resin There are various types such as thermoplastic resins, thermoplastic resins, and hardened resins such as aniline resin, diallyl phthalate resin, and silicone resin.

For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer Coalescence, vinyl styrene chloride copolymer, imbutylene chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl styrene chloride-maleic anhydride terpolymer, vinyl styrene chloride-acrylonitrile copolymer, chloride Vinyl-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl-malein chloride acid ester copolymer,
Vinyl chloride methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polynylic chloride, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, vinylidene chloride-methacrylic acid ester copolymer,
Halogen-containing synthetic resins such as vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-acrylic ester copolymer, chloroethyl vinyl ether-acrylic ester copolymer, polyvinylidene fluoride, polytetrafluoroethylene, polychloroprene, polyethylene,
α-olefin copolymers such as polypropylene, polybutene, poly-3-methylphthene, poly-1,2-bucdiene, ethylene-propylene copolymers, ethylene-vinyl ether copolymers, ethylene-propylene-1.
4-hexadiene copolymer, fluorinated polyethylene, ethylene-vinyl acetate copolymer, copolybdenum-1-propylene copolymer, butadiene-acrylonitrile copolymer, and blends of these copolymers with halogen-containing resins, acrylic Acid methyl ester-acrylonitrile copolymer, acrylic acid ethyl ester-styrene copolymer, methacrylic acid methyl ester-acrylonitrile copolymer, methacrylic acid methyl ester-styrene copolymer, butyl methacrylate ester-styrene copolymer, poly Methyl acrylate, poly-alpha-chloromethyl acrylate, polyacrylic acid methoxyethyl ester, polyacrylic acid glycidyl ester, polyacrylic acid butyl ester, acrylic acid monobutyl acrylate copolymer, acrylic ester-butadiene-styrene copolymer , methacrylic acid ester-butadiene-styrene copolymer, weight ratio 67/23/7/3 methyl methacrylate/ethyl acrylate/2-hydroxyethyl acrylate/methacrylic acid copolymer, weight ratio 72/17/ 7/3 methyl methacrylate/ethyl acrylate/2-hydroxyethyl acrylate/methacrylic acid copolymer, weight ratio 70
/20/7/3 methyl methacrylate/ethyl acrylate/2-hydroxyethyl acrylate/methacrylic acid copolymer, weight ratio 70/20/7/3 methyl methacrylate/butyl acrylate/2-hydroxyethyl Acrylic resins such as acrylate/methacrylic acid copolymers, polystyrene, polyα-methylstyrene, styrene-dimethyl fumarate copolymers, styrene-maleic anhydride copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers, etc. polymer, poly-
2,6-dimethylphenylene oxide, styrene-acrylonitrile copolymer, polyvinyl carbazole, poly p-xylylene, polyacetal, polyvinyl alcohol, polyvinyl formal, polyvinyl macetal, polyvinyl butyral, polyvinyl phthalate, cellulose, methyl cellulose, ethyl cellulose, Butylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose tetrahydrophthalate, cellulose acetate, cellulose butyrate, carboxymethylcellulose, cellulose butyrate, nitrocellulose, cellulose phthalate, pulp, nylon 6, nylon 66, nylon 12, methoxymethyl-6 - Nylon, nylon 6,10, polycapramide, poly N-butyl-nylon-6 polyethylene sebacate, polybutylene glutarate, polyhexamethylene adipate, polybutylene isophthalate, polyethylene terephthalate, polyethylene adipate terephthalate, polyethylene-2,6 - Naphthalate, pridiethylene glycol terephthalate, polyethylene oxybenzoate, bisphenol A-isophthalate, polyacrylonitrile, polyimides such as those described in U.S. Pat. Hexamethylene-m
-benzenedisulfonamide, poly4,4'-oxydiphenyl urea-2,4-tolylene urea, methylene bis-
4-phenylene urea, quanamine-melamine-formalin resin, polytetramethylenehexamethylene carbonate, polyethylenemethylenebis-4-phenylene carbonate, bisphenol A-polycarbonate, polyethylene tetrasulfide, polyethylene oxide, polytetrahydrofuran, polybischlor Methyloxetane, polyoxymethylene, butyl rubber, neophrene rubber, polyisoprene, copolyfluorylene-isoprene, styrene-butadiene rubber, silicone rubber, polyhexamethylene urea, polydimethylsiloxane, polymethylphenylsiloxane, gelatin, phthalated gelatin, maleated Acylated gelatin such as gelatin, grafted gelatin in which α, β monounsaturated acids such as acrylic acid, methacrylic acid, or amides thereof are grafted onto gelatin;
Starch, starches such as hydroxyethyl starch and hydroxypropyl starch, silica, polyglycerol monoacrylate, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, coumaron-indene resin, casein, agarose, sodium alginate,
Examples include dextran, gum arabic, albumin, polysaccharide, polyacrylamide, polytrimethylvinylbenzylammonium chloride, and polydiallyldimethylammonium chloride.

Although these resins may be used alone depending on their purpose, bundles, graft polymers, copolymers, block copolymers, etc. of these resins, or mixtures or laminates thereof may also be used.

These polymeric substances usually contain various additives.

These compounds vary depending on the field, but generally include antioxidants, stabilizers, plasticizers, fillers, dyes, pigments,
There are antistatic agents, etc.

Examples of antioxidants include 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis-6-t
-butyl-4-methylphenol, zinc dibutyldithiocarbamate, triphenyl phosphite, benzyl α-cyanoβ-phenylcinnamate, benzotriazinylphenol, etc. Plasticizers include dibutyl phthalate, dioctyl phthalate, dioctyl Examples include adipate, butylbenzyl phthalate, epoxidized soybean oil, tricresyl phosphate, trioctyl phosphate, diethylene glycol diadipate, tributylacetyl citrate, and the like.

Examples of dyes and pigments include phthalocyanine, phthalocyanine blue, dimesidinoanthraquinone, titanium oxide, glass beads, zinc white, zirconium oxide, and quinacridoshiphonamide.

As a stabilizer, tris-styrenated phenol,
Examples include phenyl-β-naphthylamine and bishydroxyphenylcyclohexane.

The types of these additives, the optimum combination with the polymeric substance, the amount added, etc. are already well known in the field of plastics, and it is convenient to take the prior art into account.

(For example, see Plastic Processing Technology Handbook, Nikkan Kogyo Shimbun, Tokyo, 1969, Inorganic and Organic Industrial Materials Handbook, Toyo Keizai Inc., Tokyo, 1960, etc.) Below are points of use in the field of recording materials. A detailed description will now be given of articles having a polymeric support and a hydrophilic layer, particularly a photographic emulsion layer, coated thereon.

That is, as the polymer support used in the present invention,
Cellulose acetate is particularly suitable for photography because of its transparency, flexibility, and other mechanical properties.
Cellulose derivatives such as cellulose acetate propionate, polystyrene, styrene-butadiene copolymers,
Styrenic polymers such as polyα-methylstyrene; polyesters such as polyethylene terephthalate, polyhexamethylene terephthalate, and polyethylene naphthalate;
Polyolefins such as polyethylene and polypropylene,
Polycarbonate, paper, etc.

Further, the support may be transparent, or may contain a dye as in the case of X-ray film, a material with a white dye such as titanium dioxide added, a laminate film made by laminating plastic on paper, or a laminate film made by laminating plastic on paper, or A surface-treated plastic film as disclosed in the above publication may also be used.

There is no limit to the film thickness of these, about 10 to 500
It can be changed widely depending on the purpose with about μ,
The shape is not necessarily limited to just a membrane.

Next, the constituent materials of the vapor deposited layer used in the present invention include titanium (Ti), zirconium (Zr), vanadium (V), niobium (Nb), etc., and one or more of them may be used.

Particularly, among these, titanium compounds are the most convenient in terms of their chemical resistance, specific gravity, price, ease of handling, and the like.

Further, on this metal oxide semiconductor layer, a black and white or color photographic emulsion layer or a non-silver salt organic sensitive layer containing silver halide or silver development nuclei is coated via a layer made of metal fluoride. be done.

In order to provide the above-mentioned metal oxide semiconductor layer on the support, the above-mentioned metals may be used alone or in combination under high vacuum (for example, 1
0' Torr to 10' Torr) by indirect resistance heating or electron beam heating, and the vapor is condensed on the surface of the support to form a deposited film of the metal or metal oxide on the surface of the support. ,
Next, this film is obtained by forced oxidation.

In addition, as a forced oxidation treatment method, under reduced pressure (for example, vacuum degree 1
0 Torr to 10” Torr) or under reduced pressure with oxygen substitution (e.g., vacuum degree 10 Torr).
There are various methods of oxidation, such as glow discharge at ~10-3 Torr), anodization under electrodeless discharge and atmospheric pressure, and oxidation with organic oxidants.

As these forced oxidation treatment methods, any conventionally known oxidation method can be applied and can be carried out using a known apparatus.

For example, regarding glow discharge, U.S. Patent No. 3.057
, 792, U.S. Patent No. 3,46 for electrodeless discharge.
It is described in No. 2, 3, No. 35, etc.

It has been found that oxidation can increase the cohesive force of the deposited layer, strengthen the film strength, and improve the transparency of the deposited film.

Furthermore, regarding the surface resistivity of the film, there is a tendency that the film without forced oxidation treatment is rather lower.

Also, the transparency of the deposited film varies depending on the thickness of the deposited film,
The effect of forced oxidation treatment is remarkable. In this example, 100 μm polyethylene terephthalate was used as the support, and a film thickness of 65 Å was used as the support.
When using a vapor-deposited titanium film of O. D
．． (Optical Density)
is 0.08, but this can be lowered to 0.05 by glow oxidation, and transparency can be significantly improved.

The surface resistivity at this time was 105Ω before the oxidation treatment and 106Ω after the oxidation treatment, which is slightly higher after the oxidation, but these values are sufficiently satisfactory in terms of antistatic effect.

As the forced oxidation treatment method, glow discharge, electrodeless discharge, etc. are preferable from the viewpoint of oxidation efficiency and process simplicity.

Further, the oxidation treatment time required to lower the optical density of the deposited film by the same amount (ie, to make it transparent) varies greatly depending on the degree of vacuum.

In oxidation treatment using electroded glow discharge, the degree of vacuum is I×IO
It is most effective to shorten the processing time if it is performed within the range of "Torr to 6×10" Torr.

On the other hand, in electrodeless discharge, the degree of vacuum varies from ITorr to 5Torr.
Within this range, the oxidation treatment time is short and there is a significant effect.

As an apparatus for producing the vapor deposition support of the present invention, a conventionally known indirect resistance heating type or electron beam heating type vacuum evaporation apparatus can be used.

(Examples include Tsukasa Sawaki; Vacuum Deposition, (Nikkan Kogyo Tokyo 196)
2. Seiji Miyake: Basic technology of thin films (Asakura Shoten Tokyo, 19
69), L. Mai sse land R.
Glang: Hand book of Thi
oFilm Technology-nology (MacGla
(W-Hill Publishing) NewYork, 1970, etc. The deposition temperature may be determined by taking into consideration the type of metal to be deposited and the fact that the boiling point of the metal varies depending on the degree of vacuum.

For example, when the degree of vacuum is I x IO' mmHg, the vapor pressure of titanium, zirconium, and vanadium is 1570°C, respectively.
Since the temperatures are 2000° C. and 1630° C., vapor deposition can be carried out conveniently by setting the vapor deposition temperature to a temperature below the vapor pressure.

Furthermore, when vapor deposition is performed on a polymeric support having poor heat resistance such as polyethylene or polystyrene, this operation may be performed while cooling the support.

Generally, at temperatures above the boiling point, the higher the deposition temperature, the faster the deposition rate, but these conditions may be selected as appropriate depending on the manufacturing conditions.

Transparency must be taken into account from the viewpoint of preventing static electricity in photographic light-sensitive materials, and the thickness of the vapor-deposited film is 2.
A range of about 0 Å to 300 Å, particularly 30 Å to 150 Å is preferable.

This is because a metal oxide semiconductor layer formed with a film thickness of 30 Å or less during vapor deposition is transparent but has a high surface resistivity.
(1011 Ω or more) Furthermore, the surface resistivity formed when the film thickness during vapor deposition is 150 Å or more is sufficiently small (103 Ω or more).
Ω or less), the optical density increases and the transparency becomes extremely poor.

Furthermore, in order to obtain a deposited film of this thickness, the time required to expose the support to the metal vapor atmosphere is generally only a few seconds, so the support is not damaged at all by heat or the like. Moreover, a sufficient antistatic effect is provided.

The degree of vacuum during vapor deposition is approximately 2 x 10"Tor, depending on the purpose.
The range from r to I x 10-6 Torr is preferred.

This is because vapor deposition can be performed most efficiently in terms of the length of the mean free path and the time required to reach the vacuum within this range.

As mentioned above, the metal used for vapor deposition is titanium (Ti).
), zirconium (Zr), vanadium (V), or niobium (Nb), all of which can achieve the effects of the present invention, but especially transparency, surface resistivity, film strength, and
Titanium and zirconium are preferred in consideration of adhesive strength with the support.

It was also found that the vapor deposited film according to the present invention had almost no humidity dependence of surface resistivity.

In addition, as a method for producing metal oxides, a forced oxidation treatment is performed after the metal is vapor-deposited onto a polymer support.As mentioned above, electroded glow discharge and electrodeless discharge in an oxygen atmosphere are effective as forced oxidation treatment methods. Effectively, the degree of vacuum is in the range of about 1 x 10-2 Torr to 6 x 10-2 Torr for electroded glow discharge, and in the range of about 1 Torr to 5 Torr for electrodeless discharge.

That is, the evaporation and forced oxidation treatments are carried out in a vacuum tank divided into two chambers, one chamber for evaporation (10' to 10-6 Torr) and the other chamber for forced oxidation (I x IO'' to 6 x 1).
If the pressure is set to 0-2 Torr or 1 to 5 Torr, a desired photographic recording support can be obtained continuously and quickly.

By the way, semiconductors generally have electrical resistances at room temperature of a conductor (~10-6Ω#77L) and an insulator (~1012Ω7).
cm to ~1022Ω #77L) 102 to 1
I'm talking about something with a value of about 010Ω7cm.

(For example, C-Kitte 1sIntrod
uction to Solid State Phy
sies, Chapter 1 3. John
Wiley & Sons. NewYork
．． 1956) In the case of a bulk substance, it is possible to determine whether it is metallic or semiconductor based on the temperature coefficient of electrical resistance.

That is, in metals, as the temperature rises, free electrons are scattered by phonons, so the resistance increases and the temperature coefficient is positive.

On the other hand, in semiconductors, as the temperature rises, bound electrons or ions are thermally given activation energy to become free, so the resistance decreases.

That is, the temperature coefficient of resistance is negative. However, in thin films, it is known that the temperature coefficient of electrical resistance of metals differs depending on the film thickness.

In general, the temperature coefficient of very thin films is negative, and for thick films it is positive, as in the case of bulk.

It is known that the temperature coefficient of electrical resistance in a titanium thin film depends on the film thickness, and becomes positive for films thicker than about 500 Å, and negative for thin films.

(For example, F. Hubers Microelec
tronics and reliability
4 283 (1965)) Similar phenomena have been studied in particular detail with respect to chromium, gold, tankle, etc.

Therefore, it is not appropriate to judge whether the obtained thin film is a semiconductor or a metal based on the sign of the temperature coefficient of electrical resistance.

On the other hand, metal oxides become conductive when their stoichiometric composition approaches. For example, it is known that titanium becomes an n-type semiconductor due to deviation from the stoichiometric composition ratio.

(For example, M.D. Earle. Phys. Re
v, 6 156 (1942)) Now, from the stoichiometric composition ratio of the titanium oxide thin film obtained by vapor depositing titanium and subsequently performing glow oxidation treatment, which one is E?
SCA (Electron Spectroseo
py for Chemical Analysis
), x of TiOx is 1.4
It is unlikely to be less than that.

Furthermore, we have discovered that the transparency of the deposited film can be further improved by providing an antireflection film on the deposited film.

A material having a refractive index of about 1.2 to 1.4 is effective.

i.e. metal fluorides such as magnesium fluoride (MgF2)
Lithium fluoride (LiF), calcium fluoride (CaF2)
By depositing cryolite (NaAAFa) or thiolite (Na5AA3F1,) on the deposited and oxidized film, the optical density can be adjusted to 0.02 to 0.
．． It has been found that 0.03 can be reduced and transparency can be improved.

Further, if desired, zinc sulfide, silicon monoxide, etc. may also be used during vapor deposition.

Among these metal fluorides, fluorides such as Na, Ad, Li, K, etc., such as cryolite, are most suitable from the viewpoint of influence on photographic emulsions and stability.

Also, among these, in that it does not have any negative effect on photographic performance (sensitivity, capri, contrast, etc.),
Cryolite is excellent.

In this case, the thickness of the anti-reflection film is 200 Å to 2
500 Å is preferably in the range of 1000 Å to 1300 Å.

In addition, in order to increase the adhesion between the deposited film and the polymer support, the support itself may be subjected to surface treatments such as glow, electrodeless discharge, electron beam irradiation, flame, corona discharge, chemicals, or so-called undercoating as a pretreatment. In the present invention, the transparent conductive layer consists of the vapor-deposited and anti-reflection film.

Now, when carrying out the present invention, the above-mentioned pretreatment vapor deposition, strong oxidation, anti-reflection film deposition, etc. may be performed individually and sequentially, or forced oxidation may be performed last. If glow discharge is used as the forced oxidation treatment method, the treatment operation can be performed continuously in one vacuum tank.

In such cases, the processing speed can be significantly faster and more efficient.

Further, when the support having the vapor-deposited film of the present invention is used for photography, the vapor-deposited layer may be provided on one side or, if necessary, on both sides of the film-like support.

On the treated support, various layers such as a back layer made of a conventional gelatin-silver halide photographic emulsion, a hydrophilic resin binder used for antihalation, anticurl, etc. purposes can be formed.

It goes without saying that it is also possible to previously provide a bank layer on the back surface of the polymer support, form the vapor deposited film on the back layer, and then provide a photographic layer on the back surface.

Whichever method is used, the support provided with the vapor-deposited film of the present invention will not be adversely affected by static electricity during the manufacturing process for providing the photographic layer or during use.

Moreover, the obtained photographic material has the advantage that no static marks occur even under any low humidity conditions.

Furthermore, as mentioned above, the metal oxide semiconductor layer of the support obtained in the present invention has a stoichiometric composition, so it is not opaque like a metal layer and has a resistance like an inorganic oxide. is not large.

Since this layer is formed by vapor deposition, an extremely thin and continuous layer (sometimes in the form of islands) is obtained, so the inherent color, transparency, and surface shape of the support are almost completely impaired. Conductivity is imparted without any problem.

Moreover, although the thin film forming method has been described in detail with respect to the case of vapor deposition, it goes without saying that methods such as sputtering method and ion plating method can also be applied as necessary.

The method of the present invention will be explained in detail below with reference to Examples.

Example 1 Film thickness was measured by the crystal oscillator method on a 0.1 mm thick film support made of polyethylene terephthalate (surface resistivity 1016 Ω or more) at a vapor deposition temperature of 1750°C and a vacuum level of 2 x 10-5 Torr. Titanium was deposited to a thickness of 50 Å using a measuring device.

This was forcibly oxidized by glow discharge (discharge output 500 W for 10 seconds) in an oxygen atmosphere at a vacuum level of 5 x 10 -2 Torr to form a titanium oxide thin film with a strong surface.

The optical density of the oxidized titanium thin film at this time is 0.02
, the surface resistivity of the thin film is I×IO9Ω, and 23
Even when the relative humidity was varied from 63% to 10% in °C, it remained the same.

This shows that it has sufficient antistatic function even under low humidity.

Furthermore, cryolite (Na3AA!F6) is applied on the titanium oxide thin film.
was deposited to a film thickness of 1100 Å under conditions of a deposition temperature of 1450°C and a vacuum of 4 x 10' Torr. As a result, the sum of the optical densities of the two layers of titanium oxide thin film and cryolite thin film was 0.01. This made it possible to further improve transparency.

Example 2 Thickness 0.18 made of polyethylene terephthalate
Titanium was evaporated onto a film support of 80 Å in thickness using a film thickness measuring device using a crystal oscillator method under conditions of a evaporation temperature of 1750° C. and a degree of vacuum of 2×10 5 Torr.

This is an electrodeless discharge (
A strong titanium oxide thin film was formed by forced oxidation using a high frequency discharge output of 600 WI O seconds).

The optical density of the titanium oxide thin film at this time was 0.07, and as in Example 1, the surface resistivity was 6 relative humidity.
2×1 remains the same even when changed from 3% to 10%.
04Ω, and the antistatic effect was sufficient even under low humidity.

Furthermore, magnesium fluoride (MgF2) is applied on the titanium oxide thin film.
at 1650°C, vacuum level 2 x 10-5 Torr, film thickness 1
As a result of vapor deposition to a thickness of 200 Å, the sum of the optical densities of the two layers of the titanium oxide thin film and the magnesium fluoride thin film was 0.
．． 05, and the transparency could be improved.

Also, in this case, when cryolite was deposited instead of magnesium fluoride in the same manner as in Example 1, the sum of the optical densities of the two layers of titanium oxide thin film and cryolite thin film could be set to 0.05. This has improved transparency.

It has also been found that the antistatic function is not impaired even in a support in which cryolite is deposited on a titanium oxide film.

Example 3 On a film support made of cellulose triacetate with a thickness of 0.1 mm (surface resistivity of 1016 Ω or more), the cellulose triacetate support was cooled to 10°C, vapor deposition temperature was 1700°C, and the degree of vacuum was Titanium was deposited under conditions of 8×10” Torr to a film thickness of 65 Å using a film thickness measuring device using a crystal oscillator method.

This was forcibly oxidized by glow discharge (discharge power 500 W for 10 seconds) in an oxygen atmosphere at a vacuum level of I×10' Torr to form a strong titanium oxide thin film.

The optical density of the titanium oxide thin film at this time was 0.05, and the surface resistivity was 63% relative humidity as in Example 1.
It remains 1×106Ω even if it is changed by 10% from
Therefore, the antistatic effect was sufficient even under low humidity.

Furthermore, cryolite was placed on the titanium oxide thin film at 1450℃ and vacuum degree 2×.
1 As a result of vapor deposition to a film thickness of 1200 Å under conditions of 0-5 Torr, the sum of the optical densities of the two layers of titanium oxide thin film and cryolite thin film was 0.04, which improved transparency. The antistatic effect was sufficient.

Example 4 Regarding the supports in Examples 1 and 3, a hydrophilic layer (high-sensitivity indirect X-ray emulsion containing 9% gelatin and 9% silver iodobromide or a high-sensitivity indirect X-ray emulsion containing 7% gelatin and 7% silver iodobromide) was applied to the vapor deposition surface. A high-sensitivity negative photographic emulsion) was coated, developed by a conventional method, and photographic performance was examined.

As a result, it was found that the deposited film of the present invention did not have any adverse effects on sensitivity, fog, gradation, etc.

On the other hand, the above emulsion was coated on the opposite side to the vapor-deposited side, and the antistatic performance was examined.

Table 1 shows the surface resistivity and static mark occurrence rate when the supports in Examples 1 and 3 and a polyester film support without a titanium oxide thin film were used as a comparative example.

The static mark generation test method is to place an unexposed film on a rubber plate with the back side (titanium oxide film side, polyester side in the comparative example) facing downward, press it with a rubber roller from above, and then peel it off to form a static mark. It depends on how it is produced.

As can be seen from the results in Table 1, in the comparative example, the surface resistivity was as high as 1016 Ω or more, and scratch marks were also significantly generated.

On the other hand, the films of Examples 1 and 3 have extremely low surface resistivities and almost no dependence of surface resistivity on humidity.

Furthermore, no scratch marks were generated, and a satisfactory antistatic effect was obtained.

The adhesion between the titanium oxide thin film and the support was excellent in the developer, fixer, and water washing.

That is, the adhesion was so strong that even if the titanium oxide film was rubbed in the liquid, it would not peel off.

Also, good adhesion was observed during the drying process after each treatment.

As described above, it can be seen that the support according to the present invention is also excellent as a photographic support.

Claims (1)

[Claims] 1 In a photographic recording material having at least one photographic emulsion layer on a support, the support has titanium (Ti), zirconium (Zr), vanadium (V) on a polymeric substance.
Alternatively, a photographic recording material comprising a layer in which niobium (Nb) is vapor-deposited and then subjected to forced oxidation treatment, and a transparent conductive layer formed by providing a layer made of a metal fluoride on the layer.