JP3005834B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having improved abrasion blackening pressure.

[0002]

BACKGROUND OF THE INVENTION Photomasks for producing electronic components, such as printed boards and lead frames, print fine patterns. Therefore, when a defect such as blackening due to pressure occurs on the photomask, it can be considerably corrected. Therefore, there has been a strong demand for improvement. The abrasion blackening pressure refers to linear blackening having a width of about several μm, which occurs when the films are rubbed when the films are transported or when they are taken out of a packaging bag. As a conventional method for improving this, for example, as disclosed in JP-A-2-54244, a large amount of an anionic surfactant is used for the protective layer to increase the surface slipperiness, and to increase the amount of binder in the protective film. And so on. However, this method has a disadvantage that dimensional stability, which is an important factor of a photomask for a printed board, is deteriorated. Also, a method of adding a compound having a mercapto group has been proposed as in JP-A-2-54246. According to this method, there is a problem that the sensitivity is lowered and the development level is sometimes lowered during running.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having significantly reduced abrasion blackening pressure without affecting dimensional stability and photographic performance.

[0004]

The object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support, on the same side as the photosensitive silver halide emulsion layer. the polymer latex containing 600 mg / m ² or more and an average particle diameter of the matting agent 0.1~0.9μm to 10mg /
This is achieved by a silver halide photographic light-sensitive material characterized by containing m ² or more.

Hereinafter, the present invention will be described specifically.

The latex polymer used in the present invention is:
Those containing (meth) acrylic acid-based polymer units are preferred. As the (meth) acrylic acid-based polymer, for example,
(Meth) acrylic acid copolymer, (meth) acrylic acid ester homopolymer, (meth) acrylic acid ester copolymer and the like can be mentioned. Specifically, a homopolymer of an alkyl acrylate, one obtained by polymerizing an alkyl acrylate and an alkyl methacrylate with each other, a homopolymer of an alkyl methacrylate, an alkyl acrylate, an alkyl methacrylate, an acrylate, a methacrylate and another ethylenically unsaturated polymerizable compound. Water-insoluble addition polymers such as those obtained by polymerizing one or more of those having —CH ＝ C <, preferably one or more of those having CH ₂ C < it can.

Specific examples of the (meth) acrylic acid-based polymer include, for example, a copolymer of acrylate and vinylidene chloride, a copolymer of methacrylate and vinylidene chloride, a copolymer of acrylate and vinyl ester, and a copolymer of methacrylate and vinyl ester. Examples include a copolymer of at least one compound selected from copolymers and at least one compound selected from acrylic acid, methacrylic acid, and itaconic acid, and these copolymers are preferable.

Specific examples of acrylates and methacrylates include, for example, ethyl acrylate, n-butyl acrylate, n-octyl acrylate, n-dodecyl acrylate, ethyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate And the like. Specific examples of the vinyl ester include, for example, vinyl butyrate, vinyl propionate, vinyl acetate, vinyl laurate and the like. The molecular weight of the copolymer is preferably about 500 to 500,000 for practical use. Specific examples of such a homopolymer or copolymer are shown below as L-1 to L-1.
-13, but is not limited to these homopolymers or copolymers.

[0009]

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[0010]

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[0011]

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In the above L-1 to L-13, x,
y and z represent mol% of each monomer component, and M represents an average molecular weight (herein, the average molecular weight indicates a number average molecular weight).

In general, the (meth) acrylic acid-based polymer includes at least 65%, preferably 75 to 95% by weight of an alkyl acrylate or alkyl methacrylate (for example,
It is desirable to use a polymer having ethyl acrylate, methyl acrylate, butyl acrylate, ethyl acrylate, octyl methacrylate, or the like. The polymers most useful in the practice of the present invention are those having an average molecular weight of about 500 to about 500,000 as described above and a particle size in the dispersion of generally 1 μm or less.

The above (meth) acrylic acid-based polymer is insoluble in water, but can be easily dispersed in water, and the (meth) acrylic acid-based polymer can be easily dispersed in water by a suitable silver halide peptizer such as gelatin. It can be used alone or in a mixture with other photographic binders.

The amount of the latex polymer contained in the silver halide photographic light-sensitive material of the present invention is expressed in units of m ^{2 in} terms of solid content.
It is preferable to add 800 mg to 10 g per 1 g, particularly preferably 1 g to 5 g.

The matting agent used in the present invention is a powder of an organic or inorganic compound. Specific examples of the organic compound include a water-dispersible vinyl polymer such as polymethyl methacrylate, cellulose acetate propionate, and starch. Particularly, a spherical matting agent of a water-dispersible vinyl polymer such as methyl methacrylate, glycidyl acrylate, a homopolymer of acrylate such as glycidyl methacrylate, or a copolymer of these acrylates with other vinyl monomers. Is preferably a spherical matting agent of ethylene tetrafluoride resin. As the inorganic compound, silver halide, barium strontium sulfate, calcium carbonate, silicon dioxide, magnesium oxide, boron nitride, hollow silica (manufactured by Nippon Philite), titanium oxide and the like are preferably used. Addition amount is 1
^{0mg / m 2 ~1000mg / m 2} , preferably from ^{20mg / m 2 ~500mg / m 2} ,
More preferably from ^{30mg / m 2 ~300mg / m 2} . The average particle size is
It is 0.1 to 0.9 μm, preferably 0.3 to 0.9 μm. 0.
If it is larger than 9 μm, there is a possibility that defects due to pinholes may occur. The layer to be added is most preferably an emulsion protective layer. The particle size can be measured by an electron micrograph or a Coulter counter, and the value is a Coulter volume average correction value.

The silver halide emulsion used in the light-sensitive material of the present invention may be obtained by any of an acidic method, a neutral method and an ammonia method, and preferably has a particle size of 0.2 μm or more and 0.5 μm or less.

In the silver halide grains used in the emulsion of the present invention, a water-soluble rhodium salt and a water-soluble iridium salt are added in the course of forming the grains, and they are contained inside the grains and / or on the grain surfaces. The addition amount is preferably from 10 ^-6 to 10 ^-9 mol per mol of silver halide.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. May be particles formed mainly on the surface, or particles formed mainly inside the particle.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having {100} planes as crystal surfaces. or,
U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-26589
No., Japanese Patent Publication No. 55-42737, etc.
Photographic Science (J.Photgr.Sc
i). 21 . 39 (1973), etc., particles having shapes such as octahedral, tetrahedral, and dodecahedral can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

Any emulsion having any grain size distribution may be used, an emulsion having a wide grain size distribution (referred to as a polydisperse emulsion), or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion). ) May be used alone or as a mixture of several types. Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

In the present invention, a monodispersed emulsion is preferred.
The monodispersed silver halide grains in the monodispersed emulsion are those in which the weight of silver halide contained within a grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. Certain are preferred, particularly preferably 70% or more, more preferably 80% or more.

Here, the average particle diameter r is the particle diameter ri at which the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle diameter ri becomes maximum.
Is defined.

(The three significant figures and the least significant figure are rounded off.) The particle size referred to here is the diameter in the case of spherical silver halide grains, or the diameter in the case of grains other than spherical.
This is the diameter when the projected image is converted into a circular image having a peripheral area.

The particle size can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter or the area at the time of projection on the print. (The number of particles to be measured is 1000 or more indiscriminately.) Particularly preferred highly monodispersed emulsions of the present invention have a monodispersity defined by the formula: particle size standard deviation / average particle size × 100 = monodispersity. It is 20 or less, more preferably 15 or less.

Here, the average particle diameter and the standard deviation of the particle diameter are determined from ri defined above. Monodispersed emulsion is disclosed in
Nos. 8521, 58-49938, 60-122935 and the like.

The photosensitive silver halide emulsion can be used as it is without a chemical sensitization, that is, a so-called unprimed emulsion, but is usually chemically sensitized. For chemical sensitization, the above-mentioned Glafkides or the book by Zelikman et al., Or H. Frieser, edited by De Grundlagen del.
Die Grundlagen der Photographischen
Prozesse mit Silberhalogeniden; Akademicche Verlag
sgesellschaft; 1968).

That is, sulfur sensitization using a compound containing sulfur capable of reacting with silver ions or active gelatin, reduction sensitization using a reducing substance, gold or other noble metal compounds can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat.
944, 2,410,689, 2,278,947, 2,728,668
No. 3,656,955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds and the like can be used, and specific examples thereof are described in U.S. Patent Nos. 2,487,850 and 2,41.
9,974, 2,518,698, 2,983,609, 2,983,610
No. 2,694,637. For noble metal sensitization, in addition to gold complex salts, platinum, iridium, complex salts of metals of the group VII of the periodic table such as palladium can be used, and specific examples thereof are U.S. Patent Nos. 2,399,083, 2,448,060, and British Patent 618,061. No. etc.

The conditions such as pH, pAg and temperature at the time of chemical sensitization are not particularly limited, but the pH value is 4 to 9, especially 5 to 8
The pAg value is preferably maintained at 5 to 11, particularly preferably 7 to 9. The temperature is 40-90 ° C, especially 45-75
C is preferred.

In the photographic emulsion used in the present invention, in addition to the above-described sulfur sensitization and gold / sulfur sensitization, a reduction sensitization method using a reducing substance: a noble metal sensitization method using a noble metal compound and the like can also be used in combination. .

As the photosensitive emulsion, the above-mentioned emulsions may be used alone, or two or more kinds of emulsions may be mixed.

In the practice of the present invention, for example, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,
Including 3,3a, 7-tetrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole,
Various stabilizers can also be used. If necessary, a silver halide solvent such as thioether or a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or the emulsion may be kept contained. When removing the salts,
It can be performed based on the method described in Research Disclosure No. 17643.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a reduction in sensitivity and generation of fog during the production process, storage or processing of the silver halide photographic material. That is, azoles such as benzothiazolium salts,
Nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazole (particularly 1- Phenyl-5-mercaptotetrazole), mercaptopyridines, the above heterocycle having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds,
Known as stabilizers such as thioketo compounds such as oxazolinethione, azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), benzenethiosulfonic acids and benzenesulfinic acid. Many compounds can be added. An example of a compound that can be used is K. Mees, The Theory.
The Theory o
f the Photographic Process, 3rd ed., 1966). For more specific examples and other uses thereof, see, for example, U.S. Pat.
No.954,474, No.3,982,947, No.4,021,248 or Special Publication No.5
The description of 2-28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention may contain, in a photographic constituting layer, US Pat. Nos. 3,411,911 and 3,411,912.
And the alkyl acrylate latex described in JP-B-45-5331.

The silver halide photographic light-sensitive material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.No. 2,960,404, Japanese Patent Publication No. 43-4939, West German Application Publication No. 1,904,604, JP-A-48-63715, Belgian Patent 762,833, U.S. Patent 3,767,410, Belgian Patent
Nos. 588 and 143, for example, styrene-sodium maleate copolymer, dextran sulfate and the like, as hardening agents, aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based As isocyanates, sulfonic esters, carbodiimides, mucochloric acids, various hardeners such as acyloyl, ultraviolet absorbers, for example, US Pat.
No. 921, British Patent No. 1,309,349, compounds described in each specification, particularly 2- (2'-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5 ′
-Di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3'-tert-butyl-5'-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5 ´-ji
-Tert-butylphenyl) -5-chlorobenzotriazole and the like. Further, coating aids, emulsifiers, improvers of permeability to processing solutions, etc., defoamers or surfactants used for controlling various physical properties of photosensitive materials are disclosed in British Patent Nos. 548,532 and 1,216,389. issue,
U.S. Patents 2,026,202, 3,514,293, JP-B-44-26580
Nos. 43-17922, 43-17926, 43-3166, 48-
20785, French patent 202,588, Belgian patent 773,459
No., anionic, cationic, nonionic or amphoteric compounds described in JP-A-48-101118 can be used, and among these, anionic surfactants having a sulfone group in particular, For example, succinate sulfonates, alkylbenzene sulfonates, and the like are preferable.
As antistatic agents, JP-B-46-24159, JP-A-48-8
No. 9979, U.S. Pat.Nos. 2,882,157 and 2,972,535,
No. 48-20785, No. 48-43130, No. 48-90391, No. 46-2
No. 4159, No. 46-39312, No. 48-43809, JP-A-47-33627
There are compounds described in each gazette. In the production method of the present invention, the pH of the coating solution is preferably in the range of 5.3 to 7.5. In the case of multi-layer coating, the pH of the coating solution obtained by mixing the coating solutions of the respective layers at the ratio of the coating amount is 5.3 to 7.5.
Is preferably within the range. If the pH is lower than 5.3, the hardening proceeds slowly, which is not preferable. If the pH is higher than 7.5, the photographic performance is not adversely affected.

In the light-sensitive material of the present invention, the constituent layers may contain a slipping agent, for example, higher aliphatic higher alcohol esters described in US Pat. Nos. 2,588,756 and 3,121,060;
Casein described in 295,979, higher aliphatic calcium salts described in British Patent 1,263,722, British Patent 1,313,384,
It may contain the silicon compounds described in U.S. Pat. Nos. 3,042,522 and 3,489,567. Liquid paraffin dispersions and the like can also be used for this purpose.

In the light-sensitive material of the present invention, various additives can be further used depending on the purpose. These additives are more particularly described in Research Disclosure No. 176.
Volume Item17643 (December 1978) and Volume 187 Item18716 (1
(November 979), and the relevant locations are summarized in the table below.

Additives RD17643 RD18716 1. Chemical sensitizer page 23, page 648 right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer / supersensitizer 23 to 24 page 648 right column to 649 Right column of page 4. Brightener page 24 5. Antifoggant and stabilizer page 24-25 page 649 right column 6. Light absorber, filter page 25-26 649 right column to 650 left column Dye and ultraviolet absorber 7 Anti-stain agent, page 25, right column, page 650, left to right column 8. Dye image stabilizer, page 25 9. Hardening agent, page 26, page 651, left column 10. Binder, page 26 Same as above 11. Plasticizer / lubricant, page 27, 650 right Column 12.Coating aids / surfactants page 26-27 Same as above 13.Static inhibitor page 27 Same as above
Various methods can be used without any particular limitation. The processing temperature is
Usually, the temperature is selected between 18 ° C and 50 ° C, but the temperature may be lower than 18 ° C or higher than 50 ° C.

The developing agents used in the black-and-white developer used in the present invention are preferably dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenol, and the like, because good performance is easily obtained. (For example, N-methyl-p-aminophenol) and the like can be used alone or in combination.

In the photographic processing of the silver halide photographic light-sensitive material of the present invention, it can be processed with a developing solution containing imidazoles as a silver halide solvent. Processing can also be performed with a developer containing a silver halide solvent and an additive such as indazole or triazole. The developer generally contains various other preservatives, an alkali agent, a pH buffer, an antifoggant, etc., and further, if necessary, a dissolution aid, a color tone agent,
It may contain a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like.

A so-called "lith type" developing process can be performed. As a special type of development processing, a method may be used in which a developing agent is contained in a light-sensitive material, for example, an emulsion layer, and the light-sensitive material is processed with an alkaline aqueous solution to perform development. Hydrophobic developing agents are researched. It can be contained in the emulsion layer by the method described in Disclosure No. 169 et al. Such a development process may be combined with a silver salt stabilization process using a thiocyanate.

As the fixing solution, those having a commonly used composition can be used. The fixer may contain a water-soluble aluminum salt as a hardener.

Exposure to the photographic emulsion used in the present invention varies depending on the state of chemical sensitization, purpose of use, and the like. Tungsten, fluorescent lamp, arc lamp, mercury lamp, xenon sunlight, xenon flash, cathode ray tube flying spot, laser Various types of light sources such as light, electron beams, X-rays, and fluorescent screens for X-ray photography can be used as appropriate.

In addition to the usual exposure time of 1/1000 to 100 seconds, a short exposure time of 1/10 ^-4 to 1/10 ^-9 seconds can be applied to xenon flash, a cathode ray tube, and laser light.

[0048]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of Coating Solution for Emulsion Layer) Solution A water 9.7 l Sodium chloride 20 g gelatin 105 g Solution B water 3.8 l sodium chloride 409 g gelatin 94 g potassium bromide 360 g 0.01% aqueous solution of potassium hexachloroiridate 28 ml hexa 14 ml of 0.001% aqueous solution of potassium bromorhodate salt solution 3.8 liters of water 1,700 g of silver nitrate The above solution A and solution C were simultaneously functionalized while maintaining pH 3.5 and pAg 8.0 in the above solution A kept at 38 ° C. , And the mixture was further stirred for 10 minutes. Then, the pH was adjusted to 5.8 with an aqueous sodium carbonate solution, and 1.7 liters of a 20% aqueous magnesium sulfate solution and 5% of polynaphthalenesulfonic acid were added.
2.55 l of an aqueous solution is added, the emulsion is flocculated at 30 ° C., decanted and washed with water to remove excess salts of the aqueous solution. Next, 3.7 l of water is added thereto to disperse the mixture, and 0.9 l of a 20% aqueous magnesium sulfate solution is again added to remove excess salts of the aqueous solution. Then add 3.7 l of water and 141 g of gelatin and disperse at 55 ° C. for 30 minutes. As a result, cubic grains having a silver bromide content of 30 mol% and a silver chloride content of 70 mol%, an average of 0.23 μm, and a monodispersity of 9 are obtained. Further, 12 ml of an aqueous solution of 1% citric acid and 60 ml of an aqueous solution of 5% potassium bromide were added to adjust the pH to 5.5 and pAg7, and then 85 ml of an aqueous solution of 0.1% sodium thiosulfate was added. The highest sensitivity was set.

Thereafter, 10 g of the compound (a) was added.

(Preparation of emulsion layer) Silver halide emulsion 0.353
The following additives are added per mole.

Sensitizing dye A 50 mg Sensitizing dye B 30 mg Compound (b) 30 mg Compound (c) 40 mg Potassium bromide 100 mg Citric acid 50 mg Styrene-maleic acid polymer 4% solution 20 cc Compound (d) 0.3 g Polymer latex Add water to make up to 600cc.

(Preparation of emulsion protective layer) Gelatin 60 g Matting agent shown in Table 1 Bis (2-ethylhexyl) sulfosuccinate 0.9 g Water was added to make 600 cc.

(Backing layer) Gelatin 70 g Compound (e) 3.2 g Compound (f) 0.6 g Compound (g) 0.6 g Saponin 4 g manufactured by Merck Ltd. Matting agent 2 shown in Table 1 Citric acid 0.5 g Styrene-maleic acid polymer 4 % Solution 45cc Add water to 1400cc.

[0055]

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[0056]

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(Preparation of Backing Protective Layer) Gelatin 60 g Bis (2-ethylhexyl) sulfone succinate 0.7 g NaCl 5 g Water was added to make 1200 cc.

A polyethylene terephthalate support coated on both sides with a solvent containing vinylidene chloride was coated with a backing layer having a gelatin of 2.3 g / m ² and a backing protective layer having a gelatin of 1.0 g / m ^2. Glioxal was added at 10 mg per 1 g of gelatin, and was applied simultaneously.

The backing-coated support was coated with 3.5 g of silver /
m ^2, so that the emulsion protective layer 0.8 g / m ^2, also gelatin 1g per triazine 16mg as a hardening agent was simultaneously coated added to a formalin 10 mg.

Using these samples, the abrasion blackening pressure was evaluated by the following method.

(Evaluation of abrasion blackening pressure) The coated sample was cut into a size of 508 x 610 mm, the EC surface and the BC surface were brought into contact, and mechanical vibration was continuously applied for 48 hours.

(Evaluation of Sensitivity) The coated sample was exposed to a wedge with a illuminance sensitometer through a 488 nm interference filter for ^10-6 seconds, and developed using Konica Squirrel Developer CDL-271 and Konica Fixer CFL-811. The treatment was performed under the conditions of 32 ° C. and 60 ″.
Shown in

(Evaluation of dimensional stability) The coated sample was 10 × 61
It was cut to a size of 0 mm, humidified under 55% for 3 hours, and then subjected to pattern exposure with a metal halide lamp. The same treatment as in the sensitivity evaluation was performed, and then the device was left under an atmosphere of 55% for 3 days. Table 1 shows the results of evaluating the change over time at a distance of 600 mm in the longitudinal direction of the pattern image.

The level of abrasion blackening pressure generated at this time was evaluated.

Table 1 shows the results.

[0066]

[Table 1]

From the results shown in Table 1, it can be seen that the sample of the present invention has less abrasion blackening pressure without adversely affecting dimensional stability and photographic performance.

[0068]

According to the present invention, it is possible to provide a silver halide photographic material having significantly less abrasion blackening pressure without affecting dimensional stability and photographic performance.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 1/04 501 G03C 1/32 G03C 1/95

Claims (1)

(57) [Claims] In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support, 600 mg / m 2 of a polymer latex is provided on the same side as the photosensitive silver halide emulsion layer. ^A silver halide photographic light-sensitive material containing at least ² mg of a matting agent having an average particle size of 0.1 to 0.9 μm and at least 10 mg / m ² .