JPS5862644A - Photographic support - Google Patents

Abstract

PURPOSE:To obtain a photographic support good in adhesion and charging characteristics, by providing 2 subbing layers consisting of hydrophobic and hydrophilic polymers on at least one side of the support. CONSTITUTION:A first subbing layer consisting essentially of polystyrene or polyester or the like hydrophobic polymer high in adhesion is formed on at least one side of a photographic transparent support. On this layer a second subbing layer is formed contg. a conductive crystalline metallic oxide selected from ZnO, TiO2, SnO2, Al2O3, In2O3, MgO, BaO, MoO3, etc., or their composite, or contg. fine particles of a small amount of different atoms, and a hydrophilic binder of gelatin, polyvinyl alcohol, or the like so as to control light diffusion efficiency not over 50% when a photographic layer is formed on this layer, thus permitting the support to be given high adhesion to the photographic layer, and good cargeability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention improves the application of liquid to a halogenated photographic layer (hereinafter referred to as a photographic layer) coated with a coating material, and at the same time improves the charging characteristics of the support. This relates to a practical support.

The properties that are admired by the 1cFi support are, on the one hand, its strong adhesion to subsequently constructed photographic layers, and on the other hand, on the other hand, the 1cFi support's strength. The support for the yoshin generally has electrical insulating properties V, which prevents contact between it and the face of the same aII''t or the other god's proboscis during the manufacturing process and use of photographic materials. It is doubtful that static electricity accumulates when exposed to peeling.What is this accumulated static electricity that causes life-threatening damage?However, the most serious electrostatic discharge is caused by the During the process of applying the emulsion for printing, the air on the support film generated between the support film and the conveyance roller etc. is discharged near the emulsion for photographic cloth head, and the air generated at that time is Dot-shaped Xti dendritic or feather-like particles are formed on the emulsion layer by
This is what happens. This is what is called a static mark.
1! L1r gets used up considerably, and in some cases it is completely lost. For example, a dusty machine, such as medical or industrial X-ray film, will easily be exposed to a 0 left, which can lead to very dangerous markings. This phenomenon becomes apparent only after the image is developed, and is one of the most complex problems. In addition, these accumulated electrostatic charges may cause secondary failures such as adhesion of particles to the surface of the 71 lumen or inability to apply uniformly.

Various methods have been tried in the past for adhering the photographic layer to the t@ side of the photographic support. The method is to apply a photographic layer directly after surface activation treatment such as n+ music treatment, discharge treatment, and outside line treatment (after applying surface oil treatment, undercoat layer tm! A method of applying a photographic layer on top of this (-Once the surface is activated, a first undercoat layer Tml is applied, and then a second undercoat layer/mk coating consisting mainly of a hydrophilic polymer is applied. There is a method of placing a photo pigeon sedge on top of this.

These methods are described in US Pat. No. 9491,
241/issue, 2.7th issue, jλθ issue.

Same No. ko, l, 6th, 7j! No. 2. It da, 7j6
No. J, 4A7! , / No. 93, British Patent No. 7
11.341 issue, $10g, 001 issue, co-author/,
It is described in No. 4C4P etc.

Among these methods, generally 1 method (80 methods is widely used).When the support is polyethylene terephthalate (hereinafter referred to as PE'l), polystyrene, etc., tk surface activation is used. Processed food, further subtracted pigeon,
Lowering I! Without the second layer, the adhesion between the support and the photographic layer was weak.

However, even with this method (2), the adhesion is not sufficient, and for example, rice 1. i! As seen in 1% Iff Edition No. 3711114, a method of mixing latex into the second undercoat layer has been attempted. Therefore, if this method is used, in the support manufacturing process, when the support shaft provided with the second undercoating layer is rolled up, the second undercoating layer on the negative side or the second undercoating layer on one side will be removed. This makes it very easy to make contact with the layer on the opposite side.
In the next photographic layer coating process, the roll that is adhered to the photographic layer becomes an inner ring for unwinding and feeding out the roll for coating the photographic layer', and in fact, there is no need for any trouble in the photographic industry.

The best way to eliminate the problems caused by static electricity described in Section 11 is to increase the electrical conductivity of materials so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged. be. Various efforts have been made in the past to provide such an electrically conductive layer to a support. For example, US Patent @J, 14 Da.

As described in Section 13-1, the method for producing a sound pattern on a deposited layer of metal oxide is difficult to obtain, and when this method is applied to the photographic industry, capital investment for vapor deposition equipment is required, and the vapor deposition process is difficult. The speed is the coating processing speed W generally used in the photographic industry.
Since it is slower than L, it must be considered as a method with less chance of decapitation.
As a method to overcome this drawback, there is a method using an electrically conductive water-dispersible polymer and a hydrophilic latex, such as that disclosed in 1971/171J. However, since this method uses hydrophilic ° latex, if this layer is used as the second undercoat layer, the same effect as when polymer latex is mixed in the second undercoat layer. Is it unnecessary to use the second undercoat layer or the second undercoat layer and the opposite side of the support? Adhesive T
There is a worry that the erecting and lowering corner rolls will not come loose.

Nine, if the conductive latex is cationic latex,
When used for the second layer of undercoat! Agricultural effects on the photographic properties of thionic substances may occur.

For example, in US Pat. It is known that metal oxides such as solid zinc oxide, stannic oxide, and indium oxide are used as conductive materials for the support. However, these metal oxide particles of Ifi+8 and the antistatic agent of the silver halide emulsion (Te1+4
95 is completely unknown, and furthermore, these 9. The interaction between the conductive material and the halogenated complex light-sensitive emulsion layer was completely unexpected. Incidentally, silver halide and halogenated steel are used as conductive materials for the ridges in the US Patent No. 3J, TI, and SG, but these 24-gold materials are used in the US Patent No. 3. As shown in Reference No. 1, ≠ J1, it has been clearly shown that there is an interaction with the halogenated string emulsion layer, which is expected to have an adverse effect on photographic properties.

Furthermore, in the case of 0wk people who use materials in the photography department to observe the 1- in the transmitted light and in the case of the 0wk who observes in the reflected light, the 1- is observed in the part where there is no image. It is preferable that the reflectance is as low as possible. On the other hand, in the former case, it is preferable to increase the light transmittance of the area where there is no image, and it is desirable to reduce the light scattering by the photosensitive material. tt - for the purpose of reducing as much as possible,
There are major limitations when introducing a conductive layer into a photographic light-sensitive material to prevent static electricity, and the above-mentioned metal oxide vapor deposition layer, which is disadvantageous in terms of the manufacturing process, and unnecessary adhesion properties are present. It was necessary to use conductive water-dispersible polymers.

Therefore, the zinc oxide, conductive tin oxide, and indium oxide described in the above-mentioned U.S. Patent No. 3,062,700, Japanese Patent Application Laid-open No. Although this meaning can be used for conductive paper for electrophotography or electrostatic recording, it cannot be used as it is for halogenated scissors photographic light-sensitive materials of the type where images are observed using transmitted light. .

A first object of the present invention is to provide a support that has improved adhesion to photographs.

The second object of the present invention is to charge Il! The sex is improved, breast,
u+m! The object of the present invention is to provide a support that can be coated uniformly with less concern about the generation of static marks on the root of the film or the adhesion of dust to the film surface.

A third object of the present invention is to provide a method for improving the charging characteristics of a support without impairing its photographic characteristics.

A fourth object of the present invention is to provide a photographic material that satisfies the above three objects and is suitable for single-frame observation using transmitted light.

These objects of the invention include ZnU, TiUl.

S'n02, ktziJa, Ins,! , Mg(J
.

BaU, at least l selected from M o U 3
The second layer of undercoating is a crystalline metal oxide or a composite oxide thereof or mold particles containing a small amount of foreign atoms dispersed in a hydrophilic binder.

The light scattering efficiency of the light-sensitive material when coated on the support coated with the first undercoat layer 1 and with the Yoshin MK provided thereon was 30.
Characteristic charging properties and photographic adhesion of less than % are achieved with improved photographic supports.

Preferred conductive particles used in the present invention are crystalline metal oxide particles, but those containing oxygen vacancies,
and metal oxides used: Those containing a small amount of heteroatomic groups that form donors are generally preferred because they have high conductivity, and the latter is particularly preferred because it provides a turnip IJ k to the silver halide emulsion. This is particularly preferable. Gold m#1. The chemical paulownia is Zn (J.

110g, 8nL) g, A tQ U
3, I n 2 U 3 .

Some of these composite oxides such as Mg(J, BaU, MoL)s are good, especially Z n U , Ti (J 2
and S n U 2 are preferable (71, examples containing different atoms include ZnU, At, In, etc., TiL) 1, Nb, 'l'a, etc., M n U 2 is 8
b, Nb.

Halogen elements, etc. are destroyed. The amount of foreign atoms added is o,
The range of oi to J0 mol duck is preferable, but 0, / to
/, Omo 1% is F! Particularly preferred.

The particle size of the amorphous gold III 4 oxide particles used in the present invention is preferably small in order to minimize the original scattering ratio, but the ratio of the refractive index of 1 particle to the binder is V, and 0M to be determined
By the way, using Isu's theory! Scattering efficiency for the wavelength source of jOnm! .

10.30.10 Table 1 shows the particle size corresponding to saliva. Although a table similar to Table 1 can be made for each wavelength, it is omitted here and Table 1 is used as a guide for light scattering for white light.

Among photographic materials, X-ray film
For photosensitive materials of the type that can be observed with the naked eye, it is preferable that the scattering efficiency of the highlight part of the image is less than j0@°, and for light-sensitive materials such as color slides, color negative films, black and white negative films, and movie films. In a type of photosensitive material that uses 1IIIi° projection, the scattering efficiency of the highlight portion is preferably less than 0.

Color prints, black and white stamps - Light #121 for paper, etc. Although it is not necessary for women to be infertile, it is obvious that there will be no inconvenience if the present invention is applied to them.

Examples of the refraction of metal oxides that serve as the base of the main conductive particles used in the present invention are shown in Table 1.

Table 2 znL) ko, f T凰Os 2.7~2.9 5nL) 1 J,'(' 11: At2L)s/-'~1.1 The binder used in the present invention will be described later. However, the refractive index is ↓1. It is in the range of 7.6 to 7.6. Therefore, judging from the values in Table 7, if conductive particles with a size of 0.2μ or less are used, most of the present invention can be put into practice, and if conductive particles with a size of 0.2μ or less are used, light scatters. It is possible to obtain a sensitive material with extremely high light transmittance and an efficiency of 10 N or less.

The conductive layer used in the present invention is made by Koz Qc, 21 Nuru, H
Table l1Oa resistivity t O even in a low humidity situation of o
It is desirable that Z Ω or less, preferably 10 9 Ω or less. For this purpose, assuming a coating thickness r of 0.1 to 111 m8 degrees, which is used as a normal second undercoat layer, the volume resistivity of the conductive particles is 10Ω-■ or less - preferably 10
It is desired that it is Ω-■ or less. The conductive fine particles of crystalline gold monooxide used in the present invention are produced by the following method.

Firstly, metal oxide fine particles are produced by calcination, and then heat treated in the presence of heterocysts to improve conductivity.Firstly, when manufacturing metal oxide fine particle tubes by calcination. A method of coexisting different types of atomic hairs to improve conductivity - Thirdly, when manufacturing 19 metal fine particles during firing, it is easy to lower the acid concentration in the atmosphere and introduce an oxygen-deficient tube. .

In the first method, the conductivity of the surface of the fine particles can be effectively improved, but since particle agitation may occur during the heat treatment, it is necessary to select condition II-.

Further, it may be better to perform the heat treatment in a reducing atmosphere.

Method #I is preferable because it seems to require the least production cost.
Mn0 by spraying stannic acid colloid (amorphous) into the firing furnace
In the method for obtaining Snug 4 particles, if hydrates of antimony chloride, antimony nitrate, antimony oxide, etc. are allowed to coexist in β-stannic acid colloid, Snug4 particles can be obtained by oxidative decomposition. L) 2, T i
(J 2 In the Shingeki vapor phase method of producing grapes, during oxidative decomposition! When a salt association of 14 types of atoms coexists, conductive Sn
L) 2, T i (J @ 2 can be obtained. Gold II% can be obtained by thermally decomposing the metal's 4-caric acid compound.
As a method for obtaining oxides, there is also a method in which 14 yuzu metals are allowed to coexist during thermal decomposition.

As an example of the third method, in the vacuum evaporation method in which gold Isk is evaporated in a strict atmosphere and gold 114ftK compound particles are present, there is a method in which #itt is slightly insufficient, or a method in which acid 'S is not sufficiently supplied. There is a method to heat the salt.

It is desirable that the IIL-conducting particles used in the present invention be as small as possible; however, in the particle production method of #1, fine particles with a size of just over 1<S will end up becoming coarse particles. Gwaru. In order to avoid this, when preparing conductive particles, it is often effective to coexist with 2 as a fine particle atomization aid that does not directly contribute to improving release properties.

Particles used for this purpose include fine metal oxide particles not made for the purpose of conducting conductivity (e.g. Z n Ll , T i U 2 , A t 2
(J @ , S iυ2゜M g (J , B
a (J, W L) 3, M o L) 3
, P z (J@, etc.), Ba8 (J4, MrSi
Ja, Ca2O3Mg8 (J4 etc.) fine particles of acid salts,
There are fine particles of carbonates such as MgC (J3) and CaCUa.

The nine particles listed here as an example have little coloring, so they can be used by being dispersed in a binder together with conductive fine particles. In addition, in order to remove most of the auxiliary particles and coarse particles, physical or chemical treatment may be applied. You can also do 11r. That is, the obtained particles t' are put into a liquid, pulverized with a ball mill, sand mill, etc., and then filtered,
An effective method is to selectively collect the conductive particles using water or centrifugal sedimentation, or to dissolve the auxiliary particles by crushing them as described above. be. It goes without saying that by repeating or combining these operating tubes, the KM fine conductive particles become even more effective.0 ParticlesIn the liquid in which the particles are dispersed, a surfactant is used as a dispersion aid, and a small amount of the present invention is used. By adding a binder wA that can be used in the process or a small amount of Lewis acid or Lewis base, fine conductive particles shaped like hinoki cypress can be obtained more effectively.

It is obvious that if chemical treatment is used in combination, a wider range of particles can be used as moving image particles.

Binders for the conductive layer used in the present invention include proteins such as gelatin, derivative gelatin, colloidal albuin, and casein; cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, diacetyl cellulose, and triacetyl cellulose; agar, sodium alginate, and starch derivatives. sugar derivatives such as; synthetic hydrophilic colloids such as polyvinyl alcohol, polyvinyl alcohol, etc.;

Lidone, polyacrylic acid copolymers, polyacrylamide or their rice paddies, partial hydrolysates, polyvinyl acetate, vinyl polymers such as acrylic esters, and 70-kyoto polymers, rosin, siezil, etc. Natural products, their derivatives, and many other synthetic resins are used.

In addition, styrene-phtadiene copolymer, polyacrylic acid, polyacrylic ester and its conductor, polyvinyl acetate, vinyl acetate-acrylic ester copolymer, 1
,.

Water emulsions of polyolefins, olefin-vinyl acetate copolymers, etc. can also be used.

Among these, gelatin is most preferred.

Alternatively, it can also be used as a colloidal binder for hydrates of saponified metals such as aluminum oxide, tin oxide, and vanadium oxide.

In the second undercoat layer used in the present invention, a conventionally known conductive polymer can be used as part or all of the binder. These compounds include,
iot, toλ issue, open-.

//I, J, No. 31, Dohiro, No J4. ≠No. 47, same u,
/J7,277, etc., quaternary salt polymers, US%
Xuan Ping San, No. 070,119, LJL8λ, IJo, 74
No. 7 (US Setum 114/λ7) cross-linked polymer latex.

In the present invention, a layer consisting of electrically conductive inorganic metal oxide particles and a hydrophilic inder is provided in the second subbing layer of a photographic support. In order to reduce light scattering by the second layer, the following points should also be considered.

That is, the y'F-scattered circles occur not only inside the second undercoat layer but also in the field (2) where the second undercoat layer is in contact with the intermediate substance. In this case, since the binder for the second undercoat layer and the binder for the photosensitive emulsion layer #1 have the same refractive index, the influence of light scattering at the interface of the inner layer is not very large.

On the other hand, when the second undercoat layer is placed on the back side of the photosensitive material, that is, at a position where the photosensitive material contacts an external medium (usually air), light scattering occurs at the interface between the second undercoat layer and the medium. In order to suppress this light scattering, there is a method of providing a conductive layer 11, a thin layer am'. This coating layer can also function as a security layer for the second undercoat layer, so it is one of the preferred embodiments of the present invention.

The thickness of the second layer of undercoat is usually about 0.0.2 to 3μ, and the particle diameter of the inorganic oxide particles is preferably about 0.01-/-, and more preferably 0.02 to 0゜jμ. If the 0 particle is too large, then the particle is subtracted l! It does not fit within the second layer, and light scattering becomes somewhat large.

Conductive particles 11 - In order to use the conductive particles more effectively and lower the resistance of the second undercoat layer, it is better to have a high volume content of conductive particles in the second undercoat layer. If the volume content of conductive particles is low, the strength of the second layer of sublayer S will be weakened.
L <UJ O~IO Yu, preferably 30~ for history
The range of the 7Q sound is one tier.

However, the above range is based on the aI of the photographic film base used.
Types, Photos 1, Composition, form, and fabrics vary by 1.

Of course.

Examples of the support used in the photographic material of the present invention include ktK polyesters such as cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, and polyethylene terephthalate film. (Terephthalic acid, inphthalic acid, phthalic acid, J, j'-":, Ko, Bu-Original.

7-su7talenedicarboxylic acid, succinic acid, sepa-7anoic acid,
Adipic acid, azelaic acid, dinoenyldicarphonic acid,
A dicarboxylic acid or its lower alkyl diester, such as hexahydroprephthalic acid, t or his-p-carphoquinolphenoquinethane, or a lower alkyl diester thereof, where t1 or more is used, where L is the phosphoric acid of pino-zeta. In combination with monocarboxylic acid #, -1311- or higher glycols such as ethylene glycol, -/, j-propanediol,
Polycarbonate films are obtained by condensation with /, l-hebutanediol, neopentyl glycol or /, cyclohexane dimetatool. To the east, IfI specifies that baryta is α-olefin polymer special polyethylene,
Polymer t* cloth or laminated paper of α-olefins with carbon S atoms λ to 101 wA, such as polypropylene and ethylene-butene copolymers, can be coated.

These supports are used depending on the purpose of use of the photosensitive material:::
,.

A transparent material or an opaque material can be selected for use. In the case of transparent materials, it is possible not only to make them colorless and transparent, but also to make them colored and transparent by adding dyes and pigments.

The monomer or copolymer component of the first undercoat layer can be selected from any monomer or copolymer that has strong adhesive strength to the support film.

This independent adhesive strength must be maintained both in the dry state of drying when processed with normal photographic processing liquids and in the moist state of ffl during processing with normal photographic processing liquids. Suitable polymers or copolymers are, for example, copolymers of styrene: butadiene and ac, carboxylated copolymers of rylonitrile, copolymers of styrene, butadiene and acrylic esters, styrene, butadiene and acrylic acid. Co-electrolytic polymer of ester and divinylbenzene, butadiene co-carmer, ester and divinylbenzene, vinyl ester, vinyl ester, acrylamide copolymer, polyester and copolyester water. Polynisal copolyesters such as dispersions, such as copolymers of sulfoterephthalic acid, terephthalic acid, isophthalic acid, ethylene glycol and neopentyl glycol (in % K; astman k3in
(commercially available as der"D k'B); edge polyester urethane (% "Deamacol" 106 &,
Copolymers containing polyurethane diacrylic esters and/or methacrylic esters (commercially available), such as itaconic acid, acrylamide or methacrylamide. Copolymers containing / or it moles; vinyl chloride copolymers, such as acrylic esters and/or methacrylic esters and itaconic acid.

Hydrophilic vinyl chloride copolymers of acrylamide or methacrylamide, as well as vinylinane chloride copolymers, such as vinylidene chloride, acrylonitrile, itaconic acid copolymers or vinylitine chloride,
You can choose from methyl acrylate and acrylic acid copolymer.

At this time, the polymer for the first undercoat layer, copolymer riI4, can be used without being limited to the above example.

One group of copolymers preferably used in the first undercoat layer is, for example, % Kaisho 1! -4,tri4IP1 rule 11-/72324
No. 1/-//7bu/No. 7, same! l-l co/JJJ issue, same 11-/λ313? No. 11-/J9JλO, an aqueous dispersion of a comonomer consisting of a diolefin conjugate, one or more vinyl oboromers, and optionally Lv and other components, as described in JP-A-Sho! Ko Otsu! Thing, No. 2-, 1 mj j / −
/ / u / J Even if it is a blend wisdom like the one described in No. 0, it will work.

Another class of cunning copolymers suitable for use in undercoat layers is vinyl chloride-IJ-Dene copolymers, such as those patented in the United States! ! There are some known photographic undercoat layers in the art, such as the one described in Kot No. 27011.

Suitable copolymers to be copolymerized with vinylidene chloride include, for example, acrylonitrile.

methacrylonitrile, acrylamide, methacryl urea i
Do, hemethylol acrylamide, cytodiconic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, itaconic acid, monoalkyl ester of itaconic acid in which the alkyl group has 1 to 1 carbon atoms, itaconic anhydride, maleic acid Acid anhydrides, acrylic acid, methacrylic acid, alkyl esters of acrylic acid or methacrylic acid whose alkyl group has carbon atoms of 1 to 1, vinyl acetate, heel chloride,
styrene.

Halokeno fn# vinyl, allyl halogenoacetate.

When carrying out the present invention, if necessary, the support surface t
It may be subjected to conventional pretreatment such as corona discharge, ultraviolet irradiation, flame treatment, and glow discharge treatment.

The coating liquid for undercoating according to the present invention is generally applied by 1.a known coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire barcoding method, a gravure coating method, or It can be coated by an extrusion coating method using a hopper as described in US Pat. No. 1,41/Kota et al. U.S. Patent Nos. 27417-1 and 27417-1, as necessary.
1019 Hiro No. 7, 2y4Iiryr"4. and J1
241 Co. No. 1 Specification, Seiki Ozaki [Coating'::・ Engineering'', page 2!3 (Published by Asakura Futen, 1997J), etc., can be used to simultaneously coat the scales of the Jericho layer and above. .

11 of the subbing liquid according to the present invention! The amount of Li is preferably 0.0/-/act, particularly 0.1 to Ju per 7 square meters of support in terms of solid volume.

The undercoating liquid thus applied is then dried in a drying process under conditions of i, 2o"c to -200°C.
The temperature and time r can be adjusted as appropriate within this range.

The first layer of undercoating according to the present invention L/%L< is undercoating L! A crosslinking agent, a surfactant, a sizing agent, a hydrophilic polymer, a matting agent, and an antistatic agent 11 may be added to the second layer as necessary.

As a crosslinking agent, for example, U.S. Patent No. 3,3 Co! .

No. 117, same J, Ko II, No. 771, Oka 3. ! dream' *
” ' ``Is he'''P % I'F 4 #
4 (Triazine compounds described in 7J-J J No. 4, etc.; U.S. %F Jg' sλP/, 4 Ko No. 3, No. 74 Da, French Patent No. 974/, J No. 3
．． ≦Dialdehyde compounds described in Riga No. 1, British Compilation, Core No. 0.171; U.S. Patent No. 3,0 Ri/, 137
No. Tokko Akira? -Evoquin compounds described in US Pat. 1 in O-san No.
1efI1. Aziridine-based compounds; ethyleneimine-based compounds described in US 1fi1% Ken No. 3, No. 37μ, etc.; Fii, i-bis(peelsulfonyl)propanol-λ, and it is light and heavy to use 0.00/~1 ott per undercoat layer coating for red polishing.

Although it is not necessary to add a swelling agent, for example, phenol, resorcinol, etc. may be added.

The amount of the additive is ~10f/1 subbing liquid.

As a matting agent, the particle size is 0. /-10μ silicon dioxide (silica), polystyrene, polymethyl methacrylate are preferred.

Antistatic agents include anionic or cationic surfactants,
Ionene-based polymers, maleic acid-based copolymers described in JP-A No. 9-Jf72, etc. can be used.

In addition, hydrophilic boromers such as natural polymers such as gelatin, gelatin cast conductors, polyvinyl alcohol, vinegar 6-vinyl-maleic anhydride combination, styrene, etc.
A synthetic polymer such as maleic anhydride copolymer may be added, and the amount added is 0.0j-7j per subbing liquid/1.
% to 0. /S/l is preferable.

In the photographic light-sensitive material of the present invention, each photographic constituent layer may also contain one of the following types of paint.

For example, hydrophilic colloids include proteins such as gelatin, colloidal albuquin, and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar casting conductors such as agar, alkyne finely divided, and starch sieve conductors; synthetic tough aqueous colloids such as Polyvinyl alcohol, polyN-hinylpyrrolidone, polyacrylic iron copolymer, polyacrylamide or sieve conductors and partial hydrolysis of these are preferred, optionally mixtures of two or more of these colloids are used. .

Among these, gelatin is most used, and gelatin specifically refers to so-called lime-treated gelatin, acid-treated gelatin, and base-treated gelatin.

Part or all of gelatin can be replaced by molecular substances, so-called gelatin haze conductors, i.e. amino groups, imino groups, hydroxy groups or carboxyl groups as functional groups contained in the molecule react with them. Treated with a reagent that has a functional group k/4Wil, some are treated with a graft polymer sweetened with the molecular chain tv1 of a polymeric substance 1! It is also useful to use it instead.

The halogenated emulsion of the photographic light-sensitive material used in the present invention usually contains a water-soluble iron salt (for example, @acid bale), a water-soluble halogen salt (for example, potassium chloride), and a highly water-soluble emulsion such as gelatin. It is made by mixing in the presence of molecular liquid. As for this silver halide, in addition to silver chloride and silver bromide, mixed halide complexes such as silver bromide, silver iodobromide, and silver iodobromide can be used. Silver particles are produced according to known and commonly used methods.Of course, it is also useful to produce them using the so-called single jet method, double jet method, controlled double jet method, etc.These photographic emulsions Fi
T,)1. James and C.h., arrived at Mees, j.
The Theory of the Photog
rapic ProcassJ Jth edition.

MacM mouth Ian company HP', Qraf mouth 1des arrival,
[chemie PhotographiqueJ
Published by Pau1Mont@1 Co., Ltd. It can be prepared using a number of commonly used methods such as the ammonia method, neutral method, and acid method. Prepared using this one)・
Chemical sensitizers (e.g. sodium thiochloride, N,N,N'-)-limethylthiourea, thiocyanate complexes of -valent gold, thio-complexes of -valent gold, chloride salts, hexamethylene lenticules, etc. Heat sensation in the presence of
kL, the sensitivity can be increased without making the particles coarser.

Photographic emulsions may be spectral sensitized or supersensitized as necessary by using single or combinations of polymethine sensitizing dyes such as cyanine, merocyanine, and calphocyanine, or by using them in combination with styryl dyes, etc. I can do it.

Further, the photographic emulsion of the photographic light-sensitive material used in the present invention can be added with various compounds in order to prevent a decrease in sensitivity and the generation of fog during the manufacturing process, storage, or processing of the light-sensitive material. Those compounds are I-hydroxy-1-methyl-/, J, Ja.

7-teto2sinden-J-methyl-benzothiazole, /-722ru! -A large number of compounds have been known for a long time, including mercaptonato dizole, many complex salt compounds, mercury-containing compounds, mercapto compounds, and metal salts. Examples of compounds that can be used for stool include T, H, Jam
es and C.E., Mees, “The Theo
ry of the Photography
The original document is listed in ProcessJ 3rd edition (1946), published by MacMj.

When a silver halide photographic emulsion is used as a color photographic light-sensitive material, a coupler may be included in the silver halide emulsion layer for 4 hours. , 2-equivalent diketomethylene thread yellow couplers, such as U.S. Pat.
77, /-17, same 3゜da01, /? (Compounds described in No. 1, J, No. 11/, /11, JP-A No. 7-2zIJJ, No. 11-44tJt); reference equivalent type or coequivalent type pyrazolone mazezota coupler and indazone The example of magenta coupler is US 4?I!iFwJ
Compounds described in Ko, 100゜7Jt, flijJ, λll, da37, 31st 7t, zto, JP-A-7-tlJJ, etc.: α-naphthol-based cyanide cup- and phenol-based cyanide Couplers such as U.S. Special Forces Co., Ltd.
1su, No. 293, J, J//, Hiroshi No. 74, J, 41
1/, No. 7 Jt, etc. are used. the#'! i crab US patent @'#cocoa, 1jt4
No., J, ljJ, 9th No., J, J7f, j?
No. J, j/7. Ko? / No. J, 770, ≠
Development inhibitor releasing couplers such as those distributed in No. 34 may also be used.

In the photographic light-sensitive material of the present invention, the halogenated milk (layer 1) and other hydrophilic colloid layers are hardened by an organic or inorganic hardening agent (either alone or in combination). Examples include mucochloric acid, formaldehyde, trimethylolmelamine, glyoxal, J.
J-dihydroxy-l.

Hiro-dioxane, -93-dihydroxy-! -Methyl-
7. Aldehyde thread compounds such as dioxane, saccunaldehyde, borutal aldehyde; divinyl sulfone, methylene bismaleimi)'', i.

3, Z-)! Acryloyl-hexahydro-S-triazine, /, J, j-)rivinylsulfonyl-hexahydro-5-triazine his(vinylsulfonylmethyl)
Ether, t,3-bis(vinylsulfonyl)propanol-λ,bis(α-vinylsulfonylacetamide)
Active compound such as ethane "'h compound #J, 4
Active halogen compounds such as L-dichloro-4-hy)axy-1-triazine sodium, λ, dichloro-s-triazine, s-triazine; Examples include triazine, an ethyleneine-based compound.

Surfactants may be added alone or in combination to the photographic structure layer of the present invention. They are used as coating aids, but are sometimes used for other purposes, such as emulsification, dispersion, and sensitization. It is also applied to improve other photographic characteristics, adjust the charge series, etc.

These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type, glycerin thread, and glycidol type, crow-grade alkylamines, and #!
Hiroclass ammonium salts, pyridine and other multiple tA rings,
Cationic surfactants such as phosphonium or sulfonyl: carboxylic acids.

Anionic surfactants containing acidic groups such as sulfonic acid, phosphoric acid, sulfuric acid esters, and phosphorus esters; amphoteric surface oil-based agents such as amino acids, aminosulfonic acids, amino alcohols, or phosphoric acid esters; . Also, fluorine-based # for the same purpose! It is also possible to use surfactants II.

Some of the examples of surfactant compounds used are U.S. Patent Nos.
Same, 2rt, issue here, same, 7Jt, issue 191,
Same J, No. 041, 10, same J.

izt, 4At Hiro issue, same J, Ko0/, JjJ issue, same J,
Ko10, /9/issue, same 3.2? ≠, z4Ao.

Same j, 4'/j, jFP issue, same 3. aai, pis issue,
Same J! $, 2. G31, same 3. Hiro 7! , No. 171,
same! , No. 1441.9744, same j, jjj.

≠No. 71, same! , 107, Otsu No. 60, British Patent No. 1, /91:, Hirojo No. t, Ryohei Oda et al. [kai@t
Synthesis of active agents and their applications (Shin Shoten, / 941) "Surf S Active Agents" by W. Perry (Interscience/ξiS), / 9 Jt), J.

P. Zosley, "Encyclopedia of Active Agents, Volume λ" (Keikalpa Pritzsch Company, /94 (1st year)).

In the present invention, when used in combination with a surfactant, it is highly effective in preventing static marks. As the fluorine-containing surfactant that can be used in combination, the following compound examples can be used.

For example, British Patent/JJO, No. JJT, ibid.

jko4! , 4Jt, U.S. Pat.
No. 17, % Kai Akihiro 9-da No. 673J, same zi-323-
There is a thread interfacial occupancy agent that is listed in the - issue and odd number.

Typical examples of compounds include, for example, N-perfluorooctylsulfonyl-N-propylglycine potassium salt, co(~-perfluorooctylsulfonyl-N-ethylamine)ethylphosphate), N-(4'
-(/<-fluorononenyloquine)Henshill]-~,
~-Dimethylammonio-7tate, N-(J-(N/
, N/, N'-trimethylammonio)furobylcoperfluorooctylsulfonamide iodide, N-(polyoxy7ethylenyl)-N-propylperfluorooctylsulfonamide (CsF17SL) 3N
(Cs Hy ) (CH2CHs L))n H),
and fluorine-containing succinic acid compounds.

Father, in the present invention, Wei:'I! 1111i'? compositions, such as U.S.%fgmJ, Oyq, IJ7, IJJ
, o, 5o.

□ No. 377, 11! IJ 纂J, j(II, No. 970,
Same No. 3゜29da, No. 537 and Japan Publication% IFF Shoj-
-/λ9! ↓Modified silicone shown in No. 0 can be included in the photographic constituent layer.

The photographic light-sensitive material of the present invention has a US pin number 3 in the photograph m*I-.
．． Reference//, No. 9//, 3. Polymer lacquer T1 described in μ//, RI No. 72, Tokuko Anhiroj -j j j j /, etc. Also, as a matting agent, warping force, strontium sulfate,
Barium fluoride, polymethyl methacrylate, etc. can be included.

By implementing the present invention, failures caused by static during the manufacturing process or during use of photographic light-sensitive materials have been improved.

Unexpected effects of the practice of the present invention include contact between the emulsion side and hack side of a photographic light-sensitive material, contact between the emulsion side and the emulsion side, and materials with which photographic light-sensitive materials generally come into contact, such as rubber. , gold members, plastic and fluorescent screens! The occurrence of tick marks due to contact with the skin has been reduced by seven times.

Next, the effects of the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

In addition, the adhesion test in Examples was carried out by the following method.

1) Adhesion test during drying On the emulsion side of the raw film and the dry film that has been processed by the present company, use a razor blade to apply St in a mesh pattern at approximately l-intervals, and apply adhesive tape (Sumitomo 3M) on top of it. Company-made scooter
Tsuchi Perma Cell Tape, )K Paste/Apply - Peel off approximately. If the peeled part is less than O~J whisper by the method, grade A, 1
- If it is less than 30, it is classified as VB class and LO-7100 QC class.

1) Wet adhesion test At each stage of incubation, fixing, and water washing, we apply an iron chain to the emulsion side of the film in a processing solution by applying a forceful s1rλ cross.
Point your finger in the direction perpendicular to the scar km.

If the emulsion layer does not peel off more than smoothly when rubbed, it is grade A.
.

Maximum peeling is in progress! ■If it is less than B@, if it is larger than this, it will be grade 0.

Example 1 Irrigation of stannic chloride-tz parts by weight of antimony trichloride i,
z＠Kobe t f＠ was dissolved in 1000 parts by weight of ethanol to obtain a uniform amount along the railway line. To this hot liquid /N sodium hydroxide aqueous solution 1f
A solution of tlIiI was added dropwise in a trench where the pH reached 3, and a co-precipitation meeting of loidal tin oxide and antimony oxide was carried out.

The resulting mixture was allowed to stand for a normal time to obtain reddish-brown colloidal wrinkles.

The reddish-brown colloidal state $1 was separated into L9 by centrifugation. −
In order to remove excess ions, water was added to the sediment and the mixture was washed by centrifugation. This operation was repeated 11-3 times to remove excess ions.

Excess ion r removed colloid status #100 parts by weight, average grain @ 0.3μ barium sulfate 10 parts by weight and water 100 parts by weight
A powdery mixture of stannic oxide and stannic oxide A with an average particle size of 0.0 μm and a bluish color was obtained by mixing 0 parts of couloid and injecting it into a firing furnace heated by voo'cyc. This mixture was placed in an insulating cylinder with an inner diameter of 7.60 mm and heated using stainless steel electrodes from above and below.

The specific resistance of the powder was measured while being pressurized at a pressure of A/(m'') and found to be //Ω-(2).

Example λ A biaxially stretched and oriented crystallized polyethylene terephthalate film was coated with an undercoating solution having the following composition.

Then, it was immersed at /r00c for 1 minute and heat treated to obtain a memorized set 1s with a film thickness of O0jμ of the first layer of Inumori undercoat.

Lower price! ! Coating liquid for first layer Example 3 8 n L obtained in Example I) 1% powder io heavy weight ice water a
Mixed WV consisting of o**m NaL) Hilk p
After dipping in H4.1 w4, the mixture was dispersed in a paint shaker for 1 hour to obtain a uniform dispersion. This dispersion f100o
It was centrifuged for r ptnt o minutes to remove coarse particles. The degree of roughness of this liquid was /4 (kiqb1f!L).

This 8 n (J 2 Kei and pHJ, 70 @ 94% of j
The gelatin solution and distilled water were mixed at a mixing ratio of ↓, and using a wire bar R.
! It was coated on a support rod with a scale. This undercoat second H7# was coated vk/reference θ° (dried for 1 minute).

3 n 02 Absence % (setting value) in the second layer ) ratio 1itij, l:L, ze5
Calculated as f (D ratio 111i/, J).

The thickness of each layer of undercoating is approximately 0.3μ.The sound of the base is 2! λ under the condition of 0C10%H
After several hours of IIF, the surface resistance value of the second undercoat layer was measured using an insulation resistance #j meter (ME-Jo type, manufactured by Yoromtan Co., Ltd.). The light scattering of this support was measured using a light scattering measuring device (manufactured by Narumi). A silver halide emulsion (AgBri, I=J,
! 7%) Pot Jf and gelatin per 11tl square meter 3.
! The work shown in 2 is sea urchin m! The adhesive force was set to 61i using cloth f*.

The results are as follows, and it can be seen that those with a volumetric stability of 8 n L) H have good charging properties and that the emulsion layer adheres to the support very strongly.

/' Example μ A large number of 1092 halogenated emulsions (i #l + sensitized negative emulsion) having the composition shown below were prepared, and 8 n (J2 powder t, the content of which was added in Example 1) was varied. Mix all of the dispersion dispersed in water and mix emulsion 1 for ao @c, iz.
jtpa, then pooc, shake for io minutes, then cool to 0°C1! The mixture was allowed to stand still for 8 minutes to prepare a silver halide emulsion containing 8 n (J2 powder).

[Silver halide emulsion composition]

[Additive composition] Polyvinylbenzene sulfonic acid IJ Rum (Co 11
; Sodium tothenebenzene sulfonate (1 tonne soap solution) per α/emulsion toy;
λce/per emulsion toy (d n L) 2 Powder/Water dispersion dispersion] Water Ju
M n in C1 (J 2 end t respectively j~, -〇■
, 10 to 200111i dispersed dispersions.

- Upper - What content is 8 n (including J2 powder wood ≠ al
A dry coating of 3.5 cm of silver halide emulsion was applied to a 100 μm polyethylene terephthalate film. -～! , Jf//m2, and dried to form 1:
i n L)! A halogenated light-sensitive material containing powder was prepared. For comparison, 8n03 powder with similar formulation but no halogenated f1! A Yoshin photosensitive material was prepared.

Next, this material was gradually created, and this material H'k
)':;(?-Mo (7 days under 10'C, 209kkLH) and wet thermostat (7 days under !O0C%to%K1-1) Fog and dust were investigated. As the liquid, υ74@wei liquid (manufactured by Eastman Kodak Company) was used, and the dust image condition was 0"C.

As a result, no increase in fog was observed depending on the presence or absence of mF), 8 nL)1 particles shown in Table 3.

Furthermore, regarding these, the concentration of Fog Plus 0.2
A comparison of the sensitivity of b n
J2 particle #Ir, when the sensitivity of the comparison plate of shi was f/00, the dry thermo test # showed a sensitivity of σl/ko, and the wet thermo test showed a sensitivity of 63. 7 (Incidentally, only those containing 8 nUz f200 and subjected to wet thermometry are shown as IOO.) As a result of the above, the use of the conductive gold m oxide used in the present invention is superior to silver halide. It was found that there was no effect on the photographic properties of the milk.

Example! Zinc oxide ioo heavy iit part At
(N0g) 3・? 10% water bath solution of H2U
5 parts by weight water
A mixture consisting of 100M parts) was irradiated with ultrasonic waves for 2 hours to obtain a uniform dispersion. This dispersion H1 (dry for 1 hour at tio"c, 1xto'Torr%too'c
in! Baked for minutes, resistivity λX10”Ω-Japanese zinc oxide II
-I got it.

The particle size was λμ. The particles were ground in an 11-ball mill to obtain particles with an average polarity inversion of 0.7μ.

Example 4 ZnO powder obtained by the process of Example j io weight ice water
/! A mixture consisting of parts by weight of O is dispersed in a paint shaker for 1 hour to form a uniform dispersion.
Obtained. This dispersion was centrifuged at 11,000 rpm for 30 minutes to remove coarse particles.

Remaining top @'2aooorpm% 1 hour mind separation a
A ZnO paste consisting of m particles was prepared.

Above Z n L) 1 part by weight of paste IO, 1 part by weight of Cenotine IO, 1 part by weight of Cenotine IO water soap, crystallized in 700 parts by weight of water, dispersed in a paint shaker for 1 hour, and 1 penny of embroidery fabric liquid for two layers of underbiki. did.

This coating solution was applied to the film of Example A in the same manner as in Example J so that the dry fish weight was 1: λ97 m, and was applied to the conductive support.

This support T! When the surface resistance was measured after being left for 2 hours under the conditions of @C1 coil h, it was JX/(7'Ω).

% 1 person Fuji Photo Film Co., Ltd. Procedural Amendment (
J month / 7, Showa J 7, Commissioner of the Patent Office Shima 1) Haruki Tono 1, Display of the incident Showa! 4th year patent application 1st/JO/
No. 2, Name of the invention Photographic support 3, Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Telephone: (406) 2537 Table Date of the amendment order Showa JJ $λ month date & Subject of amendment: Specification a. Contents of amendment: We will submit an engraving of the specification (with no changes to the content).

Claims (1)

[Claims] Photographic support: At least one side of the material is provided with a first undercoat consisting of a hydrophobic polymer as the main component □, and on the first layer of the polymer are monoacid fL@ particles, a hydrophilic binder, and a t-base undercoat. The 4I feature is the provision of a support for Yoshin.