JPH049043A - Silver halide photographic sensitive material with matting agent - Google Patents

Abstract

PURPOSE:To prevent the generation of rubbing flaws on an emulsion surface side in spite of the contact friction of the emulsion surface and a backing layer by incorporating matting agents into the uppermost layer having silver halide emulsion layers and the uppermost layer on the side having a backing layer, respectively, and specifying the differences in the average grain size of the respective matting agents. CONSTITUTION:This photosensitive material has the silver halide emulsion layers on one side of a substrate and the backing layer on the other side. The matting agents are incorporated into the uppermost layer on the side having the silver halide emulsion layers and the uppermost layer on the side having the backing layer, respectively. The difference between the average grain size of the matting agent added to the uppermost layer on the side having the silver halide emulsion layers and the average grain size of the matting agent added to the backing layer side is so specified as to be kept in a 1 to 10mum range. The rubbing flawing generated by the contact of the photosensitive materials with each other is prevented in this way.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material, and more specifically, the uppermost layer on both sides contains a pine agent to prevent scratches on the emulsion surface during transportation. This invention relates to a silver halide photographic light-sensitive material.

[Background of the Invention] Generally, a protective layer is provided on the emulsion surface of a silver halide photosensitive Hamura to protect the emulsion surface from scratches, etc., and this protective layer is usually made of a hydrophilic binder such as gelatin. It is configured.

Therefore, under high temperature and high humidity conditions, the adhesiveness of the surface increases, and when photosensitive materials come into contact with each other and stick together, or when a photosensitive material comes into contact with other materials or equipment that handles photosensitive materials, the surface of the photosensitive material increases. Accidents that may cause damage may occur.

In order to prevent such accidents with photosensitive materials or when using or handling photosensitive materials, matting agents are added in order to reduce gloss and improve ease of writing.

This matting agent is usually a solid having a particle size in the range of 1 to 15 μm, such as titanium dioxide, silicon dioxide, etc. When these matting agents are added to the surface of the uppermost layer of a photosensitive material, their portions protrude from the surface, thereby preventing the contact surfaces from sticking together.

In this case, the larger the particle size of the particles of the matting agent, the greater the effect of preventing sticking, and a sufficient effect can be exerted even with a small amount of the matting agent.

Incidentally, in recent years, it has become mainstream to develop silver halide photographic light-sensitive materials using automatic processors, but in this case, stains that adhere to the backing layer side of the light-sensitive material become a problem. In order to prevent this, it has become common practice to add a matting agent to the backing layer of the photosensitive material.

However, when such photosensitive materials are packaged and transported as sheets or rolls, friction occurs between the emulsion surface of the photosensitive material and the backing layer due to vibrations, etc.
As a result, scratches and the like occur on the emulsion surface, which has become a problem.

Further, such problems are likely to occur when an inorganic matting agent such as silicon dioxide is used as a matting agent in the backing layer.

Therefore, as a result of various studies on the above-mentioned problems, the inventors of the Wood Company and others decided that by regulating the difference in the particle size of the solid particles added to both sides of the photosensitive material within a specific value range, it would be possible to improve the transportability of the photosensitive material. It was discovered that it is possible to prevent the occurrence of scratches, and this led to the present invention.

[Objective of the Invention] An object of the present invention is to provide a silver halide photographic material that does not cause scratches on the emulsion surface side even if the emulsion surface and the backing layer are brought into contact and rubbed during transportation of the material.

[Structure of the Invention] The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on one side of a support and at least a backing layer on the other side. The uppermost layer on the side having the silver halide emulsion layer and the uppermost layer on the side having the backing layer each contain a matting agent, and the average grain size of the matting agent on the silver halide emulsion layer side This was achieved using a silver halide photographic material characterized in that the difference in average particle diameter of the matting agent is in the range of 1 μm to 10 μm.

The present invention will be explained in more detail below.

The present invention is characterized in that a matting agent is added to each uppermost layer provided on both sides of a support of a photosensitive material, and the difference in particle size of the matting agent particles is limited to a range of 1 μm to 10 μm. It is something.

The material of the matting agent used in the present invention is not particularly limited, and includes, for example, inorganic compounds such as titanium dioxide, silicon oxide, barium strontium sulfate, starch (such as rice starch), and polymethyl methacrylate. Organic compounds such as water-dispersible vinyl polymers are preferably used.

The matting agent added to the uppermost layer on the side having the silver halide emulsion layer is preferably polymethyl methacrylate or silicon dioxide, and the matting agent added to the uppermost layer on the side having the backing layer is similarly Polymethyl methacrylate or silicon oxide are preferred.

The amount of these matting agents added varies depending on each layer, and the amount of the matting agent added to the top layer on the side having the silver halide emulsion layer is 0.005 g/m2 to 1 g.
/m2, more preferably 0.01g
/m2 to OJg/m2.

Further, the amount of the matting agent added to the top layer on the side having the backing layer is Q, QIQ g/m2 to 2 g/m
It is preferable that it is 2, more preferably 4 years old 041g7m
It is 2 to 1.5 g/m2.

Among the matting agents used in the present invention, the particle size of the matting agent particles added to the uppermost layer on the side having the silver halide emulsion layer is 1 μm to 10 μm, preferably 3 μm to 7 μm.
m, and the particle size of the matting agent particles added to the uppermost layer on the side having the backing layer is 1 μm to 10 μm, preferably 2 μm to 5 μm.

Also, the difference in grain size between the two grains is that the grain size of the matting agent added to the top layer on the side having the silver halide emulsion layer is larger than that of the matting agent added to the top layer on the side having the backing layer. The particle diameter is 1 to 9 μm larger, preferably 1 to 5 μm larger than the particle size of the particles.

By thus limiting the difference in particle size of the matting agent particles (4), it is possible to prevent scratches due to contact friction between the emulsion surface and the backing layer during transportation.

Here, the difference between the average grain size of the matting agent on the silver halide emulsion layer side and the average grain size of the matting agent on the backing layer side is 171 m
In the following cases, the difference is small, so some of the relatively large matting agents among the matting agents on the backing layer side are more aggressive than the matting agents on the emulsion layer side, causing scratches on the emulsion surface. As a result, the effects of the present invention cannot be obtained.

If the difference is 9μIl1 or more, the size of the matting agent on the silver halide emulsion layer side will increase, causing pinholes to appear in the silver image area after development, and the smoothness of the edges of the image area to be impaired. It is not practical.

In the present invention, at least one silver emulsion layer is provided on one side of the support, or this silver emulsion layer is further provided with at least one protective layer. be.

In the present invention, the above-mentioned matting agent is contained in the uppermost layer of this protective layer.

In addition, at least a backing layer is provided on the external force side, and in this case as well, there may be two backing layers, and this uppermost layer contains a matting agent.

Examples of the support used in the present invention include cellulose nitrate, cellulose acetate, cellulose acetate butyrate, borisdylene, polyvinyl chloride, and polyethylene terephthalate-1.
・Films made of semi-synthetic or synthetic polymers such as polycarbonate, baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/
Paper coated or laminated with a butyne copolymer (butyne copolymer) or the like is used.

Preferred resin-coated papers in the present invention include paper supports coated on both sides or with polyolefin.

In addition, the polyolefin of polyolefin coated paper is as follows:
A copolymer consisting of two or more olefins and a mixture of dried polymers such as low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polyethylene, polybentene, etc. Those having various densities and solvent viscosity indexes (melt indexes) can be used alone or in combination.

Furthermore, in the resin layer of the polyolefin resin-coated paper used in the present invention, in addition to white pigments such as titanium oxide, zinc oxide, talc, and calcium carbonate, stearamide,
Fatty acid amides such as araxinic acid amide, fatty acid metal salts such as zinc stearate, calcium stearate, magnesium stearate, calcium valmidate, ultramarine,
Pigments and dyes such as Cobalt Bio Lt, antioxidants,
It is possible to add various additives such as optical brighteners and ultraviolet absorbers in appropriate combinations.

In particular, when adding titanium oxide to the resin layer on the side where the true emulsion layer (of resin-coated paper) is coated, the amount of titanium oxide added is between 5 and 20% by weight based on the resin layer. That's good.

In addition, when ultramarine is added to the resin layer using a white pigment such as titanium oxide (71), the amount of ultramarine added is preferably in the range of 0.01 to 1.0% by weight based on the resin layer. .0
It is preferably in the range of 4 to 05% by weight.

The polyolefin resin-coated paper used in the present invention is usually produced by melt-extruding a resin composition containing a heated +8 melted titanium dioxide pigment into a film onto a running substrate through a slit die. In addition, the melt extrusion temperature is 200°C ~
Preferably, the temperature is 350°C.

Furthermore, before applying the resin composition to the paper substrate, it is preferable to subject the paper substrate to a surface activation treatment such as corona discharge treatment or flame treatment.

The thickness of the resin layer of the resin liquid M paper is not particularly limited, but it is generally advantageous to extrusion coat it to a thickness of about 5 to 50 microns.

In addition, in ordinary resin-coated paper in which both sides of the paper base are coated with resin, the resin surface containing titanium dioxide pigment has a glossy surface, a matte surface, a silky surface, etc., depending on the use. However, the surface on the photographic emulsion layer side preferably has a center line average roughness of 2 μm or less.

The opposite back surface is usually a matte surface, and if necessary, the back surface can also be subjected to activation treatment such as corona discharge treatment or flame treatment.

The paper base of the polyolefin resin-coated paper used in the present invention may be either ordinary natural valve paper or synthetic paper, but natural valve paper whose main component is wood valves such as softwood valves, hardwood valves, and mixed softwood and hardwood valves. is advantageously used.

There is no particular restriction on the thickness of the paper base, but a paper base with good surface smoothness is preferred, and its basis weight is 50g/
Preferably, it has a weight of m2 to 120 g/m'.

The paper substrate mainly composed of natural bulbs, which is advantageously used in the practice of the present invention, can contain various polymeric compounds and additives.

For example, dry paper strength enhancers include cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol, gelatin, etc., and sizing agents include fatty acid salts, rosin derivatives, dialkyl ketene dimer emulsions, petroleum resin emulsions, and styrene. - Ammonium salts of maleic anhydride copolymer alkyl esters, pigments such as clay, kaolin, calcium carbonate, barium sulfate, titanium oxide, etc. wet paper strength agents such as melamine resin, urea resin, epoxidized polyamide resin, fixing agent Examples include polyvalent metal salts such as aluminum sulfate and aluminum chloride, cationically modified polymers such as cationized starch, pH regulators such as caustic soda, soda carbonate, and hydrochloric acid, inorganic electrolytes such as salt and Glauber's salt, other dyes, optical brighteners, Latex and the like can be contained in an appropriate combination.

In the photographic material of the present invention, each photographic constituent layer may contain the following binder.

For example, hydrophilic colloids include proteins such as gelatin, colloidal albumin, and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, compounds such as agar, sodium alginate, and starch derivatives;
Examples of synthetic hydrophilic colloids include polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, and derivatives and partial hydrolysates thereof. Note that a mixture of two or more of these colloids may be used if necessary.

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

In addition to being able to replace part or all of gelatin with synthetic polymeric substances, so-called gelatin derivatives, that is, groups that react with amino, imino, hydroxy, or carboxyl groups as functional groups contained in the molecule, can be used. It is also possible to use a reagent that has been modified with a reagent having one of the above, or a product that has been replaced with a graft polymer in which molecular chains of a high-molecular substance are bonded.

The silver halide emulsion used in the photographic light-sensitive material of the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing below.

As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used.

Photographic emulsions can be subjected to spectral sensitization or superchromatic sensitization as necessary by using polymethyl sensitizing dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. .

Furthermore, various compounds can be added to the photographic emulsion used in the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material.

These compounds include 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene-3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, and many other ring compounds, hydrated silver-containing compounds, etc. A large number of compounds, such as chemical compounds, mercapto compounds, and metal salts, have been known for a long time.

Halogenated SR'': When a true emulsion is used for a color photographic light-sensitive material, a coupler may be included in the silver halide emulsion layer.

Such couplers include 4-equivalent diketomethylene yellow couplers, 2-equivalent diketomethylene yellow couplers, 4-equivalent or 2-equivalent pyrazolone magenta couplers, indashilon magenta couplers,
An α-naphthol cyan coupler, a phenol cyan coupler, or the like can be used.

The silver halide emulsion layer and other layers in the photographic light-sensitive material of the present invention contain various organic or inorganic hardeners (,!f
Cured vines (either singly or in combination).

Typical examples are mucochloric acid and polmaldehy].
, trimethylolmelamine, glyoxal, 2,3-dihydro-waxy-1,4-diogysan, 2,3-dihydro-waxy-1,4-dioxane, succinic aldehyde, glutaraldehyde and other aldehyde-based compounds, divinyl sulfone , methylene bismaleimide, 135
-Trivinylsulfonyl-hexahydro-6-triazinebis(vinylsulfonylmethyl)ether, 1.3-
Active vinyl compounds such as bis(vinylsulfonylmethyl)propanol-2-bis(α-vinylsulfonylace[·amido)ethane, 2,4-cyclo-6-hydroxy-5-triazine sodium salt, 2.4- Examples include active halogen compounds such as cyclo(6-meth)xy-8-triazine, and ethyleneimine compounds such as 2,4,6-triethyleneimino and -triazine.

A surfactant may be added to the photographic constituent layer of the present invention either alone or in combination.

Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, sensitization and other improvements in photographic properties, and antistatic properties.

These surfactants include natural surfactants such as saponin, nonionic surfactants such as algylene oxide type, brecerin type, and glycidol type, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, and phosphonium. or cationic surfactants such as sulfoniums,
Divided into anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, and Nisdel phosphates, and amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric or phosphoric acid esters of amino alcohols. .

Some of these examples of surfactant compounds used are U.S. Pat.
No. 288,226, No. 2,739.891, No. 3,0
No. 68,101, No. 3158.484, No. 3.201
．． No. 253, No. 3.210.191, No. 3,294.
No. 540, No. 3,415,649, No. 3,441.4
No. 13, No. 3,442.654, No. 3,475.17
4, No. 3,545,974, No. 3666.478, No. 3,507,660, No. 1.198,450, and Ryohei Oda et al.'s "Synthesis of Surfactants and Their Applications"
(Yokoshoten, 1964), “Surfice Active Agency” by A.W. Berry (Interscience Publications, Inc., 1958)
It is described in books such as J., P. Sislow, "Encyclopedia of Active Agents, Volume 2" (Chemical Bubbles Company, 1964).

Various other photographic additives may be used in the photographic material of the present invention, if necessary.

For example, ultraviolet absorbers, optical brighteners, antioxidants, stain inhibitors, sequestrants, thickeners, matting agents, antihalation dyes, antiirradiation dyes, and the like can be used.

In the present invention, a protective layer is provided as the outermost layer of the silver halide emulsion layer, and the protective layer contains particles having an average grain size of 1 μm as described above.
Contains the above matting agent.

In addition to the above-mentioned matting agents, various other matting agents can be used, including, but not limited to, organic and inorganic matting agents. Specific examples include the following.

For example, glass powder described in French Patent No. 1,296,995, inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc. described in British Patent No. 1,173,181. , the starch described in U.S. Patent No. 2,322,037, the starch conductor described in Belgian Patent No. 625.451 or U.S. Pat. polyvinyl alcohol as described in Swiss Patent No. 330,158, polystyrene as described in Swiss Patent No. 3,079;
, 257, and organic particles such as polycarbonate described in US Pat. No. 3,022,169.

Further, the thickness of the protective layer containing the matting agent is not particularly limited, but for example, if it is in the range of 08 to 20 μm, the desired effects of the present invention can be sufficiently obtained.

[Examples] Examples of the present invention will be described in detail below. However, it goes without saying that the present invention is not limited to these examples.

[Coating liquid for photographic emulsion layer] Silver halide composition: 90 mol% silver bromide, 9 mol% silver chloride
, consisting of 1 mol% silver iodide, with an average grain size of 0.6μ
A tetradecahedral silver halide emulsion of m was prepared and subsequently subjected to gold sensitization and ion sensitization.

The following structural formulas (I) and (I
100 mg 1 mol Ag of each compound of I) was added, and 4-hydroxy-6-methyl-
1,3,3a,7-chitrazaindene 1 g 1 mole 8 g
, a heterocyclic compound having a mercapto group, sodium tripropylnaphthalene sulfonate as a coating aid 1 g1
Polyethylene acrylate latex 80 g/mol Ag and diethylene glycol 2 og/mol 8 g as film property improvers, Styrene-maleic anhydride copolymer 5 g 1 mol Ag 1 as a thickener, Tetrakis (vinylsulfonyl methyl) as a hardening agent. ) Add 30 mg per 1 g of methane and potassium taurine, and use citric acid to make pl+=5.5
A coating solution for a photographic emulsion layer was prepared.

Sensitizing dye ■ CH2CII 200 Sensitizing dye II [Coating solution for protective layer] The matting agent listed in Table 1 was added to the gelatin binder, and 2-sulfonate bis(2) succinate was added as a coating aid.
-ethylhexyl) ester sodium salt 30 B7m
2. As a fluorine-containing surfactant, the following compound [III] was added at 20 mg/m2. A styrene-maleic anhydride copolymer (100 mg/m2) was added as a thickener, and a 1:0.25 mol reaction product of tetrakis(vinylsulfonylmethyl)methane and taurine potassium salt was added as a hardening agent per 1 g of gelatin. A coating solution for a protective layer was prepared by adjusting to pos and s with acid.

[III] C) I2-[:0OCth-(f:Fz) 6-HNI
]03S-CH-COOCH2-(CF2)s-H The photographic emulsion layer coating solution and the protective layer coating solution prepared in this way are coated with a hydrophilic colloid backing layer (the silver halide emulsion layer of the support is at least A multilayer coating was applied on the surface of a polyethylene coated paper having a thickness of 110 μm and having an undercoat layer (on the opposite side to the surface with the backing layer) and an undercoat layer on which the backing layer was not provided. The gelatin coating amount on the backing layer side was 2.5 g/m2.

The amount of coated silver was 0.9 g/m2, and the amount of gelatin coated was 2.5 g/m2 for the emulsion layer. J/m2, and the protective layer was 1.2 g/m'.

The sample thus obtained was mixed with a developer [I
V] under development conditions of 38° C. and 20 seconds. Furthermore, fixing, washing with water, and drying were carried out in the usual manner.

Developer solution [IVl pure water (ion exchange water) 800n1
111′i Potassium sulfate H
g-Tylenediamine/tetraacetic acid-di-strium salt
2g potassium hydride IO, 5g
5-Methylbenzotriazole 300mgDiethylene glycol 25g1-phenyl-4,4-dimethyl-3-pyrazolidinone 300mg1-
Phenyl-5-mercaptothi] Razol 60 mg Potassium bromide 3.5 g HydroN77 20 g Potassium carbonate 15 g Add pure water (ion-exchanged water) and heat to 10100 O+. It is shown in Table-1.

[Scratch evaluation] Evaluation of scratches is based on 8 tests * 420cm x 20cm
Prepare two sheets of the same size, stack them on top of each other with the emulsion sides squared up, place a 2 kg weight on top to fix the lower sample, then pull the lower sample horizontally, and The sample was processed using the above-mentioned developer [+v] at 38° C. for 20 seconds, and then fixed, washed with water, and dried in a conventional manner.

Observe the blackened marks caused by scratches on the sample obtained in this way, and visually evaluate it on a 5-level scale, with those with no scratches ranked 5 and those with significant scratches ranked 1. did.

Rank 3 or above means that it can withstand practical use.

As is clear from the margin table 1 below, the present invention; (Samples 1 and 1
It can be seen that the scratch resistance is superior to that of the comparative example. In addition, the particle size of the matting agent in the table is cork-nay 1.
The measurement was carried out using a Coulter Counter Model TA-II manufactured by Co., Ltd.

[Effects of the Invention] As described above, the photosensitive Hamura of the present invention has the average particle diameter of the matting agent added to the top layer on the side having the silver halide emulsion layer, and the average particle size of the matting agent added to the backing layer side. - The difference in the average particle diameter of the nodule agent is in the range of 1 μm to 10 μm, and this has the excellent effect of preventing scratches caused by contact with the photosensitive material.

L11 applicant

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on one side of the support and at least a backing layer on the other side, the uppermost layer on the side having the silver halide emulsion layer and A matting agent is contained in each of the uppermost layers on the side having the backing layer, and the difference between the average grain size of the matting agent on the side of the silver halide emulsion layer and the average grain size of the matting agent on the side of the backing layer is 1 μm or more.
A silver halide photographic material characterized by having a particle size in the range of 10 μm.