JPH0252332A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a lith type photosensitive material which has extremely high contrast, surface mat property, a less tendency for generating a pinhole and high sensitivity by incorporating a specified compd. having a polyalkylene oxide chain in the subject material. CONSTITUTION:The photosensitive material contains the compd. which has the polyalkylene oxide chain and is shown by formula I and the compd. shown by formula II. In formulas I and II, R1 is alkyl group, R2 is alkylene group, R is hydrogen or halogen atom or alkyl group which may be substd., A is an aromatic ring which may be substd., unit numbers (k), (l), (m) and (n) are each mean total numbers of bonding units and has the following interrelationship, namely 50>=k>=30, 5>=l>=0, 20>=m>=2 and 50>=n>=5. Thus, the obtd. lith type photosensitive material has the high contrast, the surface mat property, the less tendency for generating the pinhole and the high sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material for printing, and specifically relates to improvement of its contrast properties and halftone dot performance.

[Background of the invention]

Silver halide photographic materials for printing (hereinafter referred to as Liss-sensitive materials) have already been developed that provide ultra-high contrast and excellent halftone dot performance when combined with a Liss phenomenon liquid that does not contain preservatives such as sodium sulfite. During this period, the large-scale introduction of automatic processors brought about even greater demand for this system in the printing field.

However, the poor storage stability of the Lith developer seriously impairs the commercial viability of this system, and a Lith developing liquid with storage stability and a Lith photosensitive material that can be compatible with this are required, and in line with this demand, numerous technological efforts have been made. The fruits of these efforts are beginning to emerge.

For example, when using a stable developing solution containing a preservative, a surfactant consisting of polyalkylene oxide (Japanese Patent Laid-Open No. 58-19094
No. 9 etc.) were developed.

When making a plate using a partially lithographic material, the printing plate and the original film carrying the original image must be brought into close contact evenly over the entire surface using a vacuum printer, etc. to ensure good print quality. . It is also preferable to prevent the lithographic materials from sticking to each other.

For this purpose, various matting agents such as silica particles and fine polymeric particles are used to create a fine matte surface that does not affect the image quality on the surface of the lithium-sensitive material, and the original film and printing plate are made using sealed air bubbles. It is an essential requirement to eliminate vertical separation.

However, polyalkylene oxides of the type disclosed above produce a large number of pinholes (non-blackened spots) at the edges of the blackened image of the lithographic material, which seriously impairs the quality of the printed image.

The pinholes can be avoided due to the drying conditions, and although the pinholes can be eliminated, the maximum development density decreases, and the matting agent is buried, causing the surface to lose its mantle properties.

As a countermeasure against pinholes, a different type of polyalkylene oxide was developed (for example, JP-A-626250), and although the problem of pinholes could be avoided, the high contrast quality, which is the lifeblood of squirrel photosensitive materials, was lost. .

As mentioned above, at present, the fields of high contrast, surface captivity, and no pinholes are technically closed.

[Purpose of the invention]

An object of the present invention is to provide a high-sensitivity lithographic material that has ultra-high contrast, has a matte surface, and does not generate pinholes.

[Structure of the invention]

The object of the present invention is to provide a photographic light-sensitive material having a light-sensitive silver halide emulsion layer, and a compound represented by the following general formula [I] having a polyalkylene oxide chain and a compound represented by the general formula [■].
] This is achieved by a silver halide photographic photosensitive material containing a compound represented by the following.

General formula [■] In the formula, R1 is an alkyl group having 2 to 4 carbon atoms, R2 is an alkylene group having 2 to 4 carbon atoms, and R is a hydrogen atom, a halogen atom, or a substituent having 6 to 20 carbon atoms. The optional alkyl group A represents an aromatic ring which may have a substituent. In the number of units, ff, m, and n represent the average total number of bonding units, and are constrained to 50≧≧30.5≧a≧20.202, m≧2, and 50≧n≧5.

In the above general formula [■], the alkyl group having 2 to 4 carbon atoms represented by R1 is, for example, CH.

and R3, and examples of the alkylene group having 2 to 4 carbon atoms represented by R2 include CH2CH2-1CH2CH, C12CHzCH2,
H2CH2CH2CH2, CH2CH-CH3CH2C
It is H8.

The usage ratio of the compound represented by the general formula [I] and the compound represented by the general formula (I[) is [I]:(1=20:
80 to 80: 20, more preferably -30: 7
0-20:30.

Next, typical examples of the compound represented by the general formula [I] used in the present invention will be shown. However, these are representative examples and are not limited to these.

Exemplary compound I-1, HO(CH2CH20)n+(CH2COH)
m(CH2CH20)n2H1-2,HO(CH2CH
20) n, (CI(2CHO)m, (CHzCH20)
(2(CH2COH)m2(CH2CH20)n2H1
-3,HO(CHzCH20)n+(CH2COH)m
+(CH2COH)Q(C12CHO)m2(CH2C
H20) n2HCH2CH2CH 4 , HO(CH2CH20) n l (CH2CHO
)ml (CH2CHO)12(CHzcHo)mz
(cl(2c)I 20)n 2H1-11, HO(
CH2CH20)n l (CHzcHo)ml (
CH2CH20)+2(C)12cHo)m2(C
HzCHxO)n 2HCH20C2H5CH3CH2
0C2T.

Q=1. m-(+n++m2)=16. n=(n+
+nz)-405, HO(CH2CH20)n, (
CH2CHO)m, (CH2CH2CHO)12(
CH2C)10)m2 (CH2Cl20)n2[
(CH20C2H5CH3CH20C2H5ff=3.
m-(m++m2)=5. n-(n++n2)-1
56, HO(CH2C1(20)n, (C)12C
HO) m(CI(2CH20)n2H1-12, HO(
CH2Cl20)n, (CH2CHO)m,
(CH2CH20)12(CH3COO)m2 (CH
2Cl 20)n2H7,110(CH2CH20)n
, (CH3COO)m , (CH□CHOM(C
H2CtlO)m 2(CH2CH20)n 2H1-
14,l(0(CH2C1(20)nl(CH3COO
)m(CI(2CH20)n2H8, HO(CH2CH
20) n + (CH2CHO)ml (CH2C8
2C1(20M(CH2CHO)m2(CH2CH
20)n 2H1-15, HO(CH2CH20)Ql
(CH20HO)m(CH2CH20)n, I9, HO
(CH2CH20)n, (CH2O)10)m(CH2
CH20) n21 (CH20C3H7(+50) Q=0. m=8. n=(n++n2)-201-1
0, [(0(CH2CH2O)nl(C)120HO)
m(CH2CH20)n2H16,HO(CI(2CH
20)n, (C12CHO)m, (CH2CROM(
CH3COO)m2(CH2CH20)n2H1-17
, HO(CI(2CH20)n , (CI(zcHo
)m + (CH2CH2CH, CH20)(2(CH
2CHO)m 2 (CH2Cl 20)n 2H1-
18-HO(CH2CH20) n l (CH2CHO
)m(CH2CFI20)n x HCH20C4Hs
(SeC) Q-0, m=7. n=(n++nz)=201-19
, HO(CH2CH20)n , (CH2CHO
)m , (CH2CH20)I2(CH2CHO)m
2(CH2CH20)n 2H These compounds can be easily synthesized according to the method described in JP-A-56-30124.

Next, the amount of the compound represented by the general formula (I) (hereinafter referred to as compound [I]) used in the present invention, the added layer, etc. will be described.

The additive-containing layer may be any of the constituent layers of the light-sensitive material, but preferably a silver halide emulsion layer and/or a layer adjacent to the silver halide emulsion layer.

In order to incorporate these compounds [I] into the light-sensitive material,
It is preferable to dissolve the compound [I] in water, a water-miscible organic solvent, or a mixture thereof, and add the solution to the coating solution for forming the silver halide emulsion layer and/or its adjacent layer. , especially in a silver halide emulsion layer.

The amount of compound [I] added is lo per mole of silver halide.
omg-59 is preferred, particularly 100g-29. Further, the time to add compound [I] can be selected at any time during the process of producing a light-sensitive material, but for example, when adding it to the silver halide emulsion layer, it is added after the second ripening. It is preferable to do so.

Note that compound [I] is also effective when added to the Lith developer; in this case, the amount of compound [I] is 50 mg to 112 per 112 of the developer.
109 may be added.

Next, specific examples of the compound represented by the general formula (II) used in the present invention will be given.
The compound (ii) is not limited to this.

[Exemplary compounds]

(2) In the photosensitive material of the present invention, the polyalkylene oxide compound represented by the general formula CI [) may be added to any layer constituting the hydrophilic colloid layer. The amount added varies depending on the layer to which it is added, but generally it is necessary to add it to a layer close to the surface of the photosensitive material. When added to a silver halide emulsion layer, the amount added is usually preferably in the range of 6 mg to 6 g per mole of silver contained in the emulsion layer.

The matting agent used in the present invention for the purpose of improving adhesion, preventing sticking, distinguishing front and back sides, adding ease, and gloss is preferably silica particles, and furthermore, it has a large matting and anti-sticking effect, and has little devitrification. The particle size is from 1 to IOμ
It is preferable to have a particle size in the range of m, and particularly preferable to have a particle size of about 2 μm. Although silica particles may be added to any layer constituting the hydrophilic colloid layer, it is most preferably added to the protective layer. Silica particles can be added to the hydrophilic colloid layer by adding them directly to the coating solution for forming the hydrophilic colloid layer, or by adding water, an organic solvent, a gelatin solution, a viscosity modifier solution, a surfactant solution, or a combination thereof. It may be added to the coating solution by dispersing it in a solution. The amount added is 5 odor after application.
It is preferable to set it to ~1000 mg/m2, and it is especially preferable to set it to around 80 mg/m2.

Incidentally, the above-mentioned silica particles are easily available as commercial products. Furthermore, polymer particles such as PMMA having a particle size of 10 μm or less can also be used.

The hydrophilic colloid layer in the lithium-sensitive material of the present invention is formed by coating a support with a coating solution containing a hydrophilic colloid such as a silver halide emulsion or a protective layer solution and drying it. Coating may be performed between each layer or separately using various known coating methods, and drying may be performed using known methods. However, in order to achieve the purpose of the present invention, lapse rate drying is performed at a wet bulb temperature of 23°. It is preferable to use air at a temperature of 10°C to 20°C, particularly preferably 10 to 20°C.

The hydrophilic colloid layer coated on the support undergoes a so-called constant rate drying process in which drying progresses at a nearly constant rate in the early stage, but in the final stage the drying rate decreases as the water content decreases. It proceeds through a lapse rate drying process. The lapse rate drying is particularly important in view of the performance and physical properties of the tight squirrel sensitive material when the water content per gram of gelatin in the hydrophilic colloid layer is 5 g or less, particularly 3 g or less. It is also closely related to the occurrence of pinholes. In the squirrel-sensitive material of the present invention, by performing lapse rate drying at a relatively low wet bulb temperature as described above, it is possible to obtain a material that has a high degree of matte, has a surface that is difficult to cause sticking, and has a surface that is less likely to generate pinholes. be able to.

For the silver halide emulsion according to the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, silver chlorobromoiodide, etc. can be used, but chloride is preferably used. 50 mol% silver
In particular, silver chlorobromoiodide containing 60 mol % or more, silver bromide 40 mol % or less, and silver iodide 5 mol % or less is particularly preferred.

The emulsion grain size is expressed by taking the diameter of a circle with the same area as the projected area of the grain, and is preferably 2 μm or less, particularly 0°7 to 0.1 μm.
μm is preferred.

Regarding the silver halide emulsion according to the present invention, conventional techniques can be used.

That is, as the emulsion preparation method, any of the acid method, neutral method and ammonia method can be selected.

In addition, the silver halide grains can be formed by a forward mixing method in which either a halide solution or a silver salt solution is added to the other, a back mixing method, a simultaneous mixing method in which the two solutions are simultaneously added, and further control. A sophisticated chondral tuple jet method may be used.Alternatively, a conversion method may be applied after grain growth to change the halogen composition.

Further, in the process of particle formation, the interior and/or surface of the particles may be doped by adding Cd salt, Zn salt, Fe salt, Pb salt, TI2 salt, Ir salt or complex salt, Rh salt or complex salt.

The crystallographic shape of the emulsion grains may have any possible crystal phase of silver halide and its mixed crystal, and the crystal phase can be specified over a considerable range by a crystal phase control agent. Furthermore, it may form twin crystals and may have a unique crystal habit. Alternatively, it may have an etched image on the crystal plane using a silver halide solvent.

The internal structure of the emulsion grains may also provide a uniform composition distribution or a core/shell structure with shell layers having different compositions;
Furthermore, photosensitive nuclei may be generated inside and/or on the surface of the particles.

The grain size distribution of emulsion grains may be either polydisperse or monodisperse. Furthermore, two or more types prepared separately may be mixed to form a mixture of several types of monodisperse or polydisperse particles, or a mixture of monodisperse particles and polydisperse particles.

In the silver halide emulsion prepared as described above, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or the unnecessary soluble salts may be left in the emulsion. When removing the salts, use Research Disclosure (
Research Disclosure) 17643
It can be carried out based on the method described in No.

The silver halide emulsion according to the present invention can be chemically sensitized by a conventional method. That is, sulfur sensitization method, selenium sensitization method,
A reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion according to the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry, such as cyanine dyes and merocyanine dyes. The sensitizing dyes may be used alone or in combination of two or more.

The sensitizing dye can be added during and/or after the process of forming and/or growing silver halide grains, and during and/or after chemical ripening. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Further, in the present invention, various additives conventionally used for photography can be applied. That is, halogenation is applied during chemical ripening, at the end of chemical ripening, and/or after chemical ripening for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of photosensitive materials, or to maintain stable photographic performance. Compounds known as antifoggants or stabilizers can be added before coating the silver emulsion. for example,
Any known antifogging agent or stabilizer can be used, including azaicidenes, specifically 4-hydroxy-6methyl-1.3.3a, 7-titrazaindene, thiazoles, triazoles, and tetrazoles.

The development accelerator is not particularly limited, but compounds such as those described in JP-A No. 49-24427, quaternary ammonium salts, and the like can be used.

Further, photographic emulsion layers and other hydrophilic colloid layers can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. The hardening agent can be added in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

For example, aldehyde compounds, ketone compounds, halogen-substituted acids such as mucochloric acid, halotriazine compounds,
Epoxy compounds, ethyleneimine compounds, hynylsulfone compounds, acryloyl compounds, etc. can be used.

Furthermore, an antistatic agent for the purpose of preventing static electricity can be added.

The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used in the antistatic layer on the side where the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used as a protective colloid layer.1゜Other emulsion layers and/or other hydrophilic colloid layers may be used to improve slipperiness, prevent adhesion, improve photographic properties (development acceleration, hardening, sensitization, etc.) and coatability. Various surfactants can be used for the purpose of improvement, emulsification, dispersion, etc. Examples include saponin, lauryl or oleyl monoether of polyethylene glycol, and the like.

The lithographic material of the present invention can be provided with auxiliary layers such as a filter layer, an anti-irradiation layer, and/or an anti-irradiation layer. These layers and/or the emulsion layers may contain dyes that are leached or decolorized from the light-sensitive material during the development process. When the hydrophilic colloid layer contains a dye, it may be mordanted with a mordant such as a cationic polymer.

It is advantageous to use gelatin as the binder (or protective colloid) for the silver halide emulsion, etc. according to the present invention, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, etc. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as cellulose derivatives, monopolymers or copolymers can also be used.

To these hydrophilic colloid layers, a plasticizer can be added for the purpose of increasing flexibility and a thickener for controlling coating properties.

Furthermore, the emulsion layer and other hydrophilic colloid layers according to the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, Special Publication No. 45-5,331, No. 46-22,50
No. 6, JP-A-49-74,538, JP-A No. 55-25.0
No. 77, U.S. Patent No. 2852386, U.S. Patent No. 3,062,6
No. 74, No. 3,411,911, No. 3,411,91
No. 2, No. 3,142,568, No. 3,325,286
3,547,650, etc. (e.g., methyl acrylate, ethyl acrylate, butyl acrylate, ISO butyl acrylate, t-butyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, etc.) ),
Methacrylic acid esters (e.g. methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, etc.), acrylamides (e.g. acrylamide, N-butylacrylamide, etc.), methacrylamides (e.g. methacrylamide, N-butylacrylamide, etc.) ), vinyl esters (e.g. vinyl acetate, vinyl butyrate, etc.), vinyl halides (e.g. vinyl chloride, etc.), vinylidene halides (e.g. vinylidene chloride, etc.), vinyl ethers (e.g. vinyl methyl ether, etc.), styrene. (e.g. styrene, α-methylstyrene, p-hydroxystyrene, etc.), and other homo or copolymers of ethylene, propylene, butylene, butadiene, triprene, acrylonitrile, methacrylamide, acrylic acid, methacrylic acid, itaconic acid, etc. It's latex.

The surface of the support other than the emulsion laminated surface of the lithographic material of the present invention contains 1
It consists of at least one hydrophobic colloid layer or a hydrophilic colloid layer, and optionally contains latex, dye, mordant, hardener, surfactant, pH adjuster, antioxidant, brightener,
It may contain an antistatic agent, a thickener, a matting agent, an auxiliary agent for keeping the developer composition constant, a silver halide agent, and the like.

The support used in the lithographic material of the present invention includes σ-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of aluminum, flexible supports made of these films with reflective layers, glass, metals, ceramics, etc. Considering weight reduction and dimensional stability, preferably 100μm or more, more preferably 175μm
Polymer films with a thickness of ±25 μm are preferred.

Any known processing method can be used to develop the photosensitive material of the present invention. This development process may be either a process for forming a silver image (black and white development process) or a process for forming a color image, depending on the purpose.
Preferably, processing is carried out at 20° C. to 40° C. and 20″ to 180″ using a Lith developer using a single developing agent of hydroquinone.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

Example 1 Silver chlorobromide containing 24 mol% of silver bromide was gold-sensitized and sulfur-sensitized, and then silver chloride was sensitized with 10 mol% of silver halide.
Divided into pieces. The average grain radius of the silver halide grains used was 0.26 μm.

These emulsions were loaded with the compound according to the present invention as shown in Table 1.
:I:], 1:■) in different ratios, and optically sensitized using carboxymethyl-5-((3-ethyl-2benzoxazolidine)-ethylidene 3-phenyl-2-thiohydantoin). and 4-hydroxy-1,3,3
The mixture was stabilized with a, 7-chitrazaindene, and general photographic additives such as a hardening agent, a spreading agent, and polymaratex were added to prepare a coating solution.

On the other hand, a protective layer solution was prepared as follows.

Gelatin 6gAlkyl succinate sulfonate 150mgNacQ
160mg formalin
60mg silica with average particle size 3μm 1.2
g water
100 mff of the above emulsion coating solution and protective layer solution were coated in multiple layers on a subbed polyethylene terephthalate film base by a conventional method and dried. Further, a colloid layer containing a dye was coated as an antihalation layer on the side opposite to the emulsion layer.

Samples of photosensitive materials (Nos. 1 to 10) were prepared as described above.

These samples were subjected to camera exposure (exposure for 12 seconds at f-16 with an iodine light source on a reflective original for line drawing).

This sample was processed using the following developer ■ using a Konica G025 automatic processor (
A line image was obtained by developing the image at 31'O, 60'' using a 31'O, 60'' printer (manufactured by Konica Corporation).

The line images thus obtained were observed under a 100x magnifying glass and evaluated on a five-point scale for sharpness and pinholes. The results are also listed in Table 1. A value of 1 is a stage where practicality has been lost, a value of 3 is a stage where there is a problem with practicality, and a value of 5 is a stage where the practicality is extremely good.

Developer ■ Formalin sodium bisulfite adduct 50g hydroquinone 25g sodium sulfite
3g Sodium ethylenediaminetetraacetate 2g Potassium carbonate 40g Potassium bromide 3g 5-Ditroindazole 3mg Diethylene glycol
Adjust the pH to 1N with 40g water and adjust the pH to 10 with caustic soda.
．． Adjusted to 2.

As is clear from Table 1, in the system in which compounds [I] and (n) of the present invention are used in combination, there is almost no loss in contrast, and the wormhole-like pinholes can be significantly improved.

Example 2 A 0.25 μm cubic monodisperse silver chlorobromoiodide emulsion was gold-sensitized and sulfur-sensitized, and then divided into 10 pieces each containing 1 mole of silver halide.

As shown in Table 2, the compounds according to the present invention were added to these emulsions [
(2)] and (It) were added in different proportions, and each additive was added in the same manner as in Example-1 to prepare a coating liquid.

The same protective layer liquid as in Example 1 was used.

The above emulsion coating solution and protective layer solution were coated and dried in a conventional manner on a subbed polyethylene terephthalate film base to prepare a sample of a light-sensitive material (Noil-20).

These samples were exposed to light in the same manner as in Example 1 and developed at 31'C160'' using a Konica G025 automatic processor (manufactured by Konica Corporation) using developer ■.The results were then evaluated in the same manner as in Example 1. It is also listed in Table 2.

-Developer ■ Formalin sodium bisulfite adduct Hydroquinone Sodium sulfite Ethylene diamine Tetraacetic acid Sodium carbonate Potassium bromide Borate 5-nitroindazole deethylene glycol 2g 2g 2g 2g mg 8g As is clear from Table 2, the compound [I] of the present invention ] and [■] are used in combination, there is almost no loss in contrast, and it is possible to significantly improve the appearance of pinholes.

Claims (1)

[Scope of Claims] A photographic light-sensitive material having a light-sensitive silver halide emulsion layer, which has a polyalkylene oxide chain and has the following general formula [
A silver halide photographic material comprising a compound represented by formula [I] and a compound represented by general formula [II]. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is an alkyl group, R_2 is an alkylene group,
R represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, and A represents an optionally substituted aromatic ring. The number of units k, l, m, and n represent the average total number of bonding units, and 50≧
k≧30, 5≧l≧0, 20≧m≧2 and 50≧n≧5
is restricted to. ]