JPS6083936A - Photosensitive silver halide material for photomechanical process and reducing method using it - Google Patents

Abstract

PURPOSE:To improve the suitability to reduction by making the melting time of at least one of nonphotosensitive upper layers on a silver halide emulsion layer longer than that of the emulsion layer and by incorporating acid treated gelatin into one of the upper layers. CONSTITUTION:When a photosensitive silver halide emulsion layer and nonphotosensitive upper layers are formed on a support to manufacture a photosensitive silver halide material for a photomechanical process, the melting time of least one of the upper layers is made longer than that of the emulsion layer, and acid treated gelatin is incorporated into at least one of the upper layers. The upper layers are hardened by separate hardening techniques using a polymer hardening agent, etc. By forming the nonphotosensitive upper layers provided with said characteristics, the photosensitive material can be prevented from causing reticulation, and a silver image is oxidized and dissolved with a reducer at different speeds, so the reduction latitude can be increased. Thus, the suitability to reduction is improved, and the reduction latitude can be increased while reducing the amount of silver coated per unit area.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material for plate making and a reduction processing method using the same.

Silver halide photographic material for plate making (referred to as photosensitive material for plate making)
is a photosensitive material used in photolithography processes such as converting grayscale images into halftone images and photographing line images in fields such as the printing industry.

Normally, when obtaining printing master plates using these plate-making photosensitive materials, in order to satisfy the delicate tone reproduction of images and artistic expressions that match the printing characteristics, 1. It is often the case that images are partially or completely modified by a process called processing, such as reducing the halftone dot area or enlarging or reducing the width of line drawings/JX.

For this reason, one of the extremely important performances of photosensitive materials for plate making is whether or not they have suitability for reduction processing.

K involves reducing the pressure of the photosensitive material for plate making on which a halftone image or line image has been formed through exposure and development, by bringing the metallic silver resulting from the formation of the halftone dot or line image into contact with a reduction liquid. method is used. Many things are known as reducing fluids,
For example, Mies, r T HE T I-I E OR
Y OF T HEPI-10TOGRAPHICPR
OCESSJ 731~7j Tabeji, (lri!μ year,
Macmillan) contains permanganate,
Reducing fluids have been described using reducing components such as iron salts, ceric salts, red blood salts, persulfates, dichromates, and the like.

However, since power reduction processing ultimately oxidizes and dissolves the silver image, when reducing the power of a halftone dot image, if the halftone dot area is reduced by power reduction processing, the halftone dot area will be reduced at the same time. A decrease in blackening density occurs.

Therefore, the range that can be corrected by power reduction processing is limited by the degree of decrease in black density per halftone dot that occurs when the halftone dot area is reduced. In other words, the measure of the correctable range of the halftone dot image can be expressed by how much the halftone dot area can be reduced while keeping the blackening density per halftone dot above a certain value.

In this specification, when the blackening density of the halftone dot is reduced by -F to the limit value required in the photolithography process by force reduction processing, the halftone dot area is compared to the halftone dot area before processing. We will use the term "reducing force" to indicate how much the force has decreased.

It goes without saying that the wider the force reduction period, the higher the suitability for force reduction processing.

Suitability for reducing force? As a technique for improving the force reduction, for example, a method of using a reducing force containing a mercapto compound during the force reducing process is known, which is described in JP-A-52-TRPI. The speed is different from commonly used reducing fluids, making it difficult to use. In addition, if the emulsion film is made into a soft film and the covering power is increased to increase the density, it is possible to widen the area during reduction and improve the reduction processing characteristics, but this method does not provide the necessary film strength. Among the techniques for increasing the zero force reduction width and improving the suitability for force reduction processing, the most effective method is to increase the amount of food used to form an image.

This is because the larger the amount of silver forming the silver image per unit area, the wider the range in which the image can be corrected by the reduction process. Therefore, increasing the coating amount per unit area of silver halide used in photosensitive materials for plate making will make the reduction area wider, but as is well known, silver is extremely expensive and valuable, so It is undesirable to increase the amount of Vc coated silver and gold from the viewpoint of the cost of the photosensitive material for plate making.

Therefore, one of the important challenges in the industry is to produce a photosensitive material for plate making having the necessary properties using as little silver as possible.

Percentage of requests related to applicant Motoyama's application (
In order to solve the above problem, in JP-A-5TR-Hiroko No. 03), a non-photosensitive upper layer having a melting time longer than that of the silver halide emulsion layer was provided on top of the silver halide emulsion layer. A means to provide such information has been proposed. By this means, it is possible to greatly improve the suitability for reduction processing without increasing the amount of coated silver, but there are problems such as reticulation occurring during high-temperature rapid development, and further improvement is possible during reduction processing. It is hoped that this will happen.

Therefore, the first object of the present invention is to provide a photosensitive material for plate making that has improved suitability for reduction processing, and second, the suitability for reduction processing does not deteriorate even if the amount of coated silver per unit area is reduced. The purpose of the present invention is to provide a complete photosensitive material for plate making, in which the third Vζ coating is thermal sprayed, the retigulation Q ratio is 1A, and the suitability for reduction processing is improved.

Another object of the present invention is to provide a wide range of reduction processing methods during reduction while using a plate-making sensitive material with a reduced amount of coated silver per unit area.

The object of the present invention is to provide a photosensitive material for plate making comprising at least one photosensitive silver halide emulsion layer on a support and at least one non-photosensitive upper layer on top of the emulsion layer. A photosensitive material for plate making in which at least one non-photosensitive upper layer has a melting time longer than that of the emulsion layer and the non-photosensitive upper layer contains acid-treated gelatin, and this photosensitive material for plate making is exposed and developed. This was achieved using a force reduction method that also performs force reduction processing.

It is known that acid-treated gelatin can be used in photographic light-sensitive materials to improve the physical properties of the film. It is not known to improve. Furthermore, the use of acid-treated gelatin can further improve suitability for reduction processing, but this effect cannot be predicted from the prior art.

In the present invention, at least seven of the non-photosensitive upper layers have a melting time tM greater than that of the emulsion layers located below them.
One of its characteristics is that it does so.

By providing a non-photosensitive upper layer with such characteristics, it is possible to create anisotropy in the rate at which the reducing solution dissolves the silver image, and to reduce the area of the image relative to the reduction in the density of the silver image. It becomes possible to increase the amount during reduction, that is, during reduction in force.

In the present invention, the melting time of at least one of the non-photosensitive upper layers is greater than the melting time of the emulsion layer.
This means that the non-photosensitive top layer is more strongly hardened than the emulsion layer. Here, the melting time refers to the entire period of time during which the cured film is maintained at a constant temperature and immersed in VC solution until the film begins to melt. Melting time measurements are best (but not necessarily) carried out in an O0λNNaOH solution maintained at Ku, 7s6C.

In the present invention, in order to make the melting time of at least seven layers of the non-photosensitive upper layer longer than that of the photosensitive halogenated emulsion layer, a layered curing technique is used to cure the non-photosensitive upper layer. The degree of hardening may be selectively made greater than that of the light-sensitive silver halide emulsion layer. In this case, at least one of the non-photosensitive upper layers
It is preferable to carry out selective hardening so that the melting time of the layer is longer than that of the emulsion layer by at least 0 seconds, especially at least 200 seconds, as determined by the above-mentioned measuring method.

To selectively harden the at least one non-photosensitive top layer, various methods can be used, such as those described in JP-A-5R-1/-, No. 2O3, among others using a polymeric curing agent. The method is preferred.

As this polymer curing agent, JP-A-Shoj! f-μ2032, US Patent≠, /l/, 1107, British Patent/,
, t311, those described in the Hirojyo issue are preferred, and those of the following general formula (I) are particularly preferred.

R.

+A +

In the formula, R1 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Q is either 1 ■ -C02-1-C:0-N- (wherein R1 represents the same as above) or an arylene group having 10 carbon atoms from t. L is 1 - CQ2-1-CON- (where R represents the same as above) 3 to i containing at least one bond
a divalent group having s carbon atoms, 1 or -〇-1-N-1-〇〇-1-SO-1-so
2-1-8Oa-1-8O2N-1-NCON-1R.

-NCO2 (R1 represents the same as mentioned above) A divalent group having from 1 to 1 carbon atom and containing at least one bond. i (2 represents a vinyl group or a functional group serving as its precursor, -CH:CH2
, -CH2CH2X. X represents a group that can be substituted by a nuclear group or a group that can be eliminated in the form of HXO by a base.

In the formula, X1y represents a mole percentage, and X is 0 to ta,
y takes a value from 1 to ioo.

Examples of ethylenically unsaturated monomers of the formula CI) are ethylene, propylene, l-butene, isobutyne, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N , N, N-) dimethyl-N-vinylbenzylammonium chloride, N
, N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, V-vinylpyridine, 2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, / - vinyl-2-methylimidazole, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, acrylic acetate), ethylenically unsaturated monocarboxylic or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itacon acids, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, n-hexyl acrylate, hydroxyl Ethyl acrylate, cyanoethyl acrylate, N, N-diethylamine ethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N, N -) diethyl-N-methacryloyloxyethylammonium p-toluenesulfonate, N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-) toluenesulfonate
-, dimethyl itaconate, maleic acid monobenzyl ester), amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylamide, N.

N-dimethylacrylamide, N-methylolacrylamide, N-(N,N-dimethylaminopropyl)acrylamide, N,N,N-trimethyl-N-(N-acryloylpropyl)ammonium p-toluenesulfonate, 2-acrylamide- 2-Methylpronog sodium sulfonate, acryloylmorpholine, methacrylamide, N+N-dimethyl-N'-acryloylpropanediamine probionate betaine, N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine).

In addition, when the polymer of the present invention is used as a crosslinked latex, in addition to the above-mentioned ethylenically unsaturated monomers, at least two copolymerizable ethylenically unsaturated groups are used as A.
Monomers having more than 100% monomer (for example, divinylbenzene, methylene bisacrylamide, ethylene glycol diacrylate, trimethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, etc.) are used.

Examples of R1 in formula (I) include methyl, ethyl, butyl, and n-hexyl groups.

Q includes the following groups.

I4a -CO2-1-CONI(-1-4:0N-1L includes the following groups.

-CH2CO2CH2- -CI-12C02CH2CI 2- - CH2CH2C02CH2CH2--'r Cl-
12+ 5 CO2CH2C: H2-+CH2÷+n
C02CH2CH2- -CH2N HCOCH2- 1-CH2N HCOCH2CH2- +CH2+s N HCOCH2C[-12-+ CH
2+ s N HCOCH2CH2--(CH2→-1
o N HCOCH2C)] 2-- CH20CH2
- -C112' Cll 20 CH2CH2CH2--
COCH2CH2- -CI(2COCl-12CI-12--S OCI-
12CH2- -CH2SOCH2CH2- 8U 2 CH2CH2- -802CI-] 2 CH2S 02 CH2CI-
12-(J 1-J -S Oa CH2CH2CH2- -S Oa CH2C02C) 12 CI-12--S
Oa CH2CH2C02CH2CH2--8O2N
HC)12CO2CH2CH2--802NHCH2C
I-12C02CI-12CH2--N I-I CO
N II CI-f 2 CH2--CH2N HCO
N i-1(zuH2CH2--NHC02CH2(,:
'H2--(,: I-12N I-I C02CH2CH2 R2 in formula (I) includes the following groups.

-CH=CH2, -CH2CH2CX -CH2(1-
12Br.

-CH2C)120H1-CH,2CI4202CCH
3, -CHzCHz02CCFa, -CH2CII2U
2CCHQ! 2. Next, specific examples of compounds that can be used in the present invention will be shown, but the compounds are not limited thereto.

P-/ +CHz, CH+1 C0NHC(CHa)zcHzsOaNaP-2+CH
2CH-)-.

CoNHC(CHa) 2cH2sOaNaP-3-(
-CH2CH+C0NHC(CHa)zcHzsOaNaP 4' +
cH2cH+KonatsuC0NHC(CHa) 2cH2sOaNa+ CH2
CH+ y x/y23//C00CH2CH20CO
CH2SO2CH=CH2+CH2CH+y x/V=
3/' C0NHCHi2NHcOcH2CH2SO2CH::
CH2+cCH2CH+y x/'i=3/' C0NHCH2CH2CH2NHCOCH2CH2SO
2CH:Cl42+C 802CH2CH2SO2CI-i:CH2P-4+C
H2CH+Work1 CONHC(CHa)2CH2SO3NaP-♂ +C
)42C)l+ 工OOM P-7+CH2CH+ 工OOM +CH2CH+y xl y23// C00CH2CH20COCH2SO2CL12CI-
12α+C) i2CH÷yX/y-3/l C0NHCOC142CH2SO2CH2CH2α+C
H2CI4+y x/y':/'/'C(,)NH
CH□COCH2CH25O2CH2CH2α-4C)
i2CH→-X/y=10//CUN'l-1cI(2
For curing of the NHCOCH2CH2So2CH:CH2 non-photosensitive upper layer, the above-mentioned polymer curing agent may be used alone, but it may also be used in combination with a diffusible low-molecular curing agent. In this case, the low-molecular hardening agent also diffuses into the emulsion layer and hardens the emulsion layer, but the non-photosensitive upper layer is hardened by both the low-molecular hardening agent and the diffusion-resistant polymer hardening agent. Selective curing is achieved. These diffusible low-molecular-weight curing agents include various organic or inorganic curing agents (alone or in combination); typical examples include TEHA, mucochloric acid,
Formaldehyde, trimethylolmelamine, glyoxal, 2,3-dihydroxy-1, Hiro-dioxane,
λ, 3-dihydroxy-methyl-1, ≠-dioxane, aldehyde compounds such as succinic aldehyde, glutaraldehyde; divinyl sulfone, methylene bismaleimide, 3. r-) lyacryloyl-hexahydro-8-) riazine, / , J , ! -trivinylsulfonyl-hexahydro-s-)'J azine,
Bis(vinylsulfonylmethyl)ether+, 7 3
y--xl Ladder -TI-FlI+-→-n+1 -
→'ry Active vinyl compounds such as noruco, his(α-vinylsulfonylacetamido)ethane, l,2-bis(vinylsulfonyl)ethane, l,l'-bis(vinylsulfonyl)methane, 4A-dichloro Examples of gelatin hardening agents well known in the art include active halogen compounds such as -6-hydroxy-s-h liazine; ethyleneimine compounds such as 6-triethyleneimino-S-triazine; be able to. Particularly preferred is the combination with an active vinyl-based low-molecular curing agent described in % Guzhao, t7-/≠/12λ.

As for the method of adding the polymer curing agent, the curing agent dissolved in water or an organic solvent is directly added to the layer whose hardening properties are to be controlled. When using a diffusible hardening agent together, use 1! of a polymer hardening agent! It may be added to the non-photosensitive upper layer with J≦, or it may be added to another non-photosensitive upper layer and diffused into the entire layer. The diffusion-resistant polymer curing agent is added in accordance with the reaction group of the polymer curing agent.

In the present invention, acid-treated gelatin is contained in the non-photosensitive upper layer whose melting time is significantly longer than that of the emulsion layer as described above, the other non-photosensitive upper layer, or both layers. This prevents the occurrence of reticulation and further improves the performance during force reduction.

The acid-treated gelatin used in the present invention is gelatin made from pig skin, cow bones, etc., and treated with hydrochloric acid, etc. in the collagen production process, and treated with lime, etc., which is usually used in the photographic industry. This is different from alkaline-processed gelatin, which is accompanied by The manufacturing method of these gelatins,
Details of properties can be found in Arthur Veis.
is), The Macromolecular Chemistry of Gelatin
Chemistry of Gelatin), (Academic Press),
The biggest difference is that the isoelectric point of acid-treated gelatin is pal,
0 to pH 7,j, whereas alkali-treated gelatin has a pH of pHμ,j to pHj, 3.

Jelly strength (P) of acid-treated gelatin used in the present invention
A G G I method, Bloom type jelly strength meter)
As for 200f or more, especially -'t4Ao~300? It is preferable that

Along with acid-treated gelatin, other hydrophilic colloids such as dialkali-treated gelatin, modified gelatin, polyvinyl alcohol, polystyrene sulfonic acid, etc. can be used in combination with acid-treated gelatin, if necessary, but preferably, tro weight percent or more of the bangu consists of acid-treated gelatin. At least one non-photosensitive top layer is used.

There is no particular limit to the coating thickness of the non-photosensitive upper layer containing acid-treated gelatin, but it is preferably 0.0000. /~jμ, especially 0.
It is set to 6-2μ. The amount of acid-treated gelatin applied is θ, /-4A? /m2, particularly preferably in the range of 0.1 to 127 m2.

The non-photosensitive upper layer of the photosensitive material for plate making of the present invention may contain a polymer latex for the purpose of improving dimensional stability or preventing the occurrence of reticulation. Polymeric latexes suitable for use include, for example, U.S. Pat.
77λ, No. 04, same j, j, 2j, 2g No. 6, direction 3
．． G//, Ri No. 3, 3//, No. 27λ, J,
3+2! , tλ0 issue, 'Research Disclosure (
Research Pisclosure) Magazine A
It is a hydrate of a vinyl polymer such as acrylic ester, methacrylic ester, styrene, etc., as described in /511z/rijjt/ (/ri♂July 0). Particularly preferred are alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, homopolymers of alkyl methacrylates, or homopolymers of these alkyl acrylates, alkyl methacrylates and other vinyl polymers, e.g. , acrylic acid, copolymers with N-methylol acrylamide and the like.

The preferred range of average particle size of polymer latex is 0.0
06~/It especially o, oλ~o, lμ. Further, among the above-mentioned polymer latexes, latexes having a high glass transition point (T2) are preferable in order to further improve adhesive resistance. Particularly preferred are those having a Tf of room temperature or higher. for example,
Hydrates of homovinyl polymers such as methyl methacrylate, ethyl methacrylate, and styrene, or these vinyl polymers and other vinyl polymers, such as acrylic acid, N-
Copolymerization with methylol acrylamide and the like is particularly preferred. The addition rate of polymer latex is as follows: 1) R~200%, especially io~
100 inches is preferable.

The polymer latex may be added to the non-photosensitive top layer with a melting time greater than that of the emulsion layer, but if more than one non-photosensitive top layer is provided, the melting time may be greater than that of the emulsion layer. It may be added to non-photosensitive top layers other than the non-photosensitive top layer. For example, it is also preferable to provide a λ-th non-photosensitive upper layer made of acid-treated gelatin between the emulsion layer and a thin gelatin layer containing a polymer hardener, and add the polymer latex therein.

In addition, the non-photosensitive upper layer of the present invention may contain surfactants, antistatic agents, matting agents, lubricants, colloidal silica, gelatin plasticizers, and the like.

As the matting agent, particles of polymethyl methacrylate or silicon dioxide having a diameter of about 1 to 10 μm, particularly about 1 to 10 μm, are preferable.

The dry thickness of the non-photosensitive upper layer of the present invention is the entire thickness. .

3~! μ, especially O0! It is preferable to apply the coating to a thickness of ~3μ.

The photosensitive material for plate making in the present invention is, as mentioned above, a photosensitive material used in printing halftone images or line drawings by photolithography in the printing industry, and its type, Although the performance is not particularly limited, the most common photosensitive material is a high-contrast photosensitive material such as so-called lithium film.

The silver halide used in the photosensitive silver halide emulsion layer of the photosensitive material for plate making of the present invention is not limited, and silver chlorobromide, silver chloride,
Silver chloroiodobromide, silver iodobromide, silver bromide, etc. can be used, but in particular, silver chloride can be used in an amount of at least 1 to 10 molar (preferably 7 molar).
More than molti) Contains silver iodide θ~! Silver chlorobromide or silver chloroiodobromide containing molar ratio is preferred. There are no particular restrictions on the morphology, crystal habit, size distribution, etc. of silver halide grains.
Preferably, the thickness is 7μ or less.

Silver halide emulsions include gold oxides such as chlorauric acid salts and gold trichloride, salts of noble metals such as rhodium and iridium, sulfur compounds that react with silver salts to form tin sulfate, stannous salts, Sensitivity can be increased by using reducing substances such as amines without making the particles coarser.

Further, salts of noble metals such as rhodium and iridium, and iron compounds such as red blood salts may be present during physical ripening of silver halide grains or during nucleation.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, supersensitizing dye combinations and supersensitizing substances are available from Research Disclosure (rLe
searcll Disclosure )/7A
It is described in Section 5 of Volume 23 (■) of Vol.

Hiro-hydroxy-t is used as an antifoggant in photographic emulsions.
-methyl-/, 3.3B,, 7-thitraazaindene,
3-Methylbenzothiazole, /-phenyl-j-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercaptated fractions, etc., as well as JP-A-Sho≠Tarza1
0λ Hiro, same jθ-t301. same! 0-/? As 1A2, those well known in the art, such as those described in US Pat.

A surfactant can be added to the photosensitive silver halide emulsion layer of the present invention for purposes such as a coating aid and improvement of photographic properties.

As surfactants, natural surfactants such as saponin,
Nonionic surfactants such as alkylene oxide and glycidol, carboxylic acids, sulfonic acids (e.g. surfactants described in US Pat. No. 3.PII, B), phosphoric acid, acidic groups such as sulfuric ester groups, and phosphoric ester groups. Amphoteric surfactants such as anionic surfactants containing amino acids, amino sulfones, and sulfuric acid or phosphoric acid esters of amino alcohols are preferably used.

The polyalkylene oxide U product used in the present invention is an alkylene oxide having a carbon number of norhiro, such as ethylene oxide, propylene-/, low oxide, butylene-/,
a polyalkylene oxide consisting of at least 10 units, such as 2-oxide, preferably ethylene oxide, and water, an aliphatic alcohol, an aromatic alcohol, a fatty acid, 41
It includes condensation products with compounds having at least one active hydrogen atom such as organic amines and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides.

The photosensitive silver halide emulsion layer includes US Patent 3゜4A//
, Ri No. 11, same, 3.4+, //, Ri No. 12, same! ,/
412. JTT issue, same! , jJ, j, 21ft
, No. 43. ! 4A'/, No. 610, Special Public Sho≠j-33
Polymer latexes made of homo- or copolymers of alkyl acrylates, alkyl meta-azilylates, acrylic acids, cricidyl acrylates, etc. described in No. It can be included for any purpose.

When a polymer hardener is used in the non-photosensitive upper layer, reticulation becomes more likely to occur as the amount of polymer latex added to the emulsion layer is increased, but acid-treated gelatin is used in the non-photosensitive upper layer. This type of reticulation is thereby effectively prevented.

As the hydrophilic colloid binder used in the photosensitive silver halide emulsion layer of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein:
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. Gelatin includes lime-processed gelatin, acid-processed gelatin and Bull.

Soc, Sci, Photo, Japan,
Enzyme-treated gelatin as described in A/A, p. 30 (19t6) may be used, and hydrolyzed gelatin or enzymatically decomposed products of gelatin may also be used.

The weight ratio of silver halide to hydrophilic colloid binder in the photosensitive silver halide emulsion layer of the present invention is preferably 1/2 or less of hydrophilic colloid binder to silver halide.

In the present invention, one photosensitive silver halide emulsion layer means
The structure is not limited to two layers or more.

For example, when the photosensitive silver halide emulsion layer consists of two layers, the total amount of "silver halide/hydrophilic colloid binder" in the two layers is 2 or less, and the upper photosensitive emulsion layer is larger than the lower layer. It is more preferable that the emulsion layer contains more hydrophilic colloid binder than the emulsion layer.

The coating amount of silver halide is i, o~60, θ1, especially i, 3~t per 1 square meter in terms of silver amount.

Preferably, θ2.

The effects of the present invention are particularly noticeable when the amount of coated silver is small.

For curing the photosensitive silver halide emulsion layer, it is preferable to use the above-mentioned low-molecular hardening agent, but in some cases, the above-mentioned high-molecular hardening agent or a combination of a high-molecular hardening agent and a low-molecular hardening agent may be used. You can also do it.

As the support for the photosensitive material for plate making of the present invention, polyester films such as polyethylene terephthalate film and cellulose ester films such as cellulose triacetate film are preferably used.

In the present invention, exposure for obtaining an image may be carried out using a conventional method.

There are no particular limitations on the method of developing the photosensitive material for plate making of the present invention, and any method generally used for processing photosensitive materials for plate making can be used.

The processing temperature is usually selected between /J"C and zooc, but temperatures lower than /J"C may be higher than 500C.

The developer solution can contain known developer chemicals.

As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-
phenyl-3-pyrazolidone), amine phenols (
For example, N-methyl-p-aminephenol), l-phenyl-3-pyrazolines, ascorbic acid, and US Pat.

OA7. Described in Za No. 72 (DI, 2, 3. II-TE)
Bicyclic compounds in which a hydroxyphosphorus ring and an intrene ring are condensed can be used alone or in combination. The developing solution generally contains other known preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like.

Particularly preferably used in the present invention is a so-called squirrel developer, which basically consists of ortho- or hapara-dihydroxybenzene, an alkaline agent, a small amount of free sulfite, a sulfite ion buffer, etc. . The ortho- or para-dihydroxybenzene used as the developing agent can be appropriately selected from those well known in the field of photography. Specific examples include hydroquinone, chlorophenohydroquinone, bromohydroquinone, isoprobylnohydroquinone, toluhydroquinone, methylhydroquinone,
Co, 3-dichlorohydroquinone, Co.

Examples include j-dimethylhydroquinone.

Among these, hydroquinone is particularly practical.

These developing crude drugs may be used alone or in combination. The amount of the developing agent to be added is approximately 100f/-100f per developing solution. The sulfite ion buffer is used in an amount effective to keep the sulfite concentration in the developer almost constant, and includes aldehyde bisulfite alkaline adducts such as formalin sodium bisulfite adduct, acetone sulfite water, hydrogen adduct, etc. Examples thereof include ketone-bisulfite alkali adducts such as, carbonyl bisulfite-amino condensation products such as sodium-bis(2-hydroxyethyl)amine methanesulfonate, and the like. The amount of sulfite ion buffer used is the developer solution ltk) t3~/JOf
It is.

The free sulfite ion concentration can be controlled by adding an alkali sulfite salt such as IJium sulfite to the developer used in the present invention. The amount of sulfite added is determined by the developer/
Normally a hit! It is generally 1 or less, particularly preferably 31 or less, but it may of course be more than 1.

In many cases, it is preferred to include an alkali halide (particularly a bromide such as sodium bromide or potassium bromide) as a development regulator. The alkaline halide agent is 90.0/-10f per liter of developer! , preferably 0. /～! ?
It is preferable to add.

Total pH in the developer is 2 or higher (especially pH 2.7 to li, s)
An alkaline agent is added to make it.

Sodium carbonate or potassium carbonate is used as an alkaline agent in ordinary liquids, and there are various amounts of the added amount.

As the fixer, one having a commonly used composition can be used.

As a fixing agent, in addition to thiosulfate and thiocyanate,
Organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied.

The developing method may be carried out manually or by using an automatic developing machine. When processing with an automatic developing machine, the transportation method (e.g. roller transportation, belt transportation)
There are no particular restrictions, and any conveyor-type automatic developing machine used in the industry may be used. In addition, regarding the composition of the processing solution and the developing method, see U.S. Pat. lλko, ort issue,
Same 3, /4L, sri, same 3. lit, /73 issue,
3, 22μ, 3!6, 3, 173, 9/II
You can refer to the descriptions such as numbers.

Regarding the silver halide emulsion layer, other layers, support, processing method, etc. of the photosensitive material for plate making of the present invention, please refer to Rissanichi.
You can refer to the description in Disclosure Magazine, Volume 74, pages λ-ko to λ (11/7/, February).

There are no particular limitations on the reducing fluid used in the present invention, and for example, those described in "The Theory of the Photographic Process" by Mies mentioned above can be effectively used.

That is, reducing force components such as permanganates, persulfates, ferric salts, cupric salts, ceric salts, red blood salts, dichromates, etc. are used alone or in combination, and if necessary, ) A reducing liquid containing inorganic acids such as sulfuric acid, alcohols, or reducing components such as red blood salt, ferric ethylenediaminetetraacetic acid salt, thiosulfate, rhodan salt, thiourea or its rust conductor, etc. A reducing solution containing a silver halide solvent and, if necessary, an inorganic acid such as dioxysulfuric acid is used.

The reducing liquid used in the present invention may further contain a compound having a mercapto group as described in JP-A No. 62-Af Koli, if necessary.

There are no particular restrictions on the composition of the power-reducing liquid used in the power-reducing treatment of the present invention and the treatment conditions (temperature, time, etc.), and those skilled in the art can appropriately determine them.

Regarding the force reducing liquid and the force reducing method, the descriptions in the following patents can be referred to.

Unexamined Japanese Patent Publication No. 3/-/≠0733, same J Co. 6g Hiroki, same 1
3-/Hori oi, same j≠-115P236, same jl-/
/ri237, j3-2.211j, jj-224A
4A1 16-/7/23, 4Lμμ, 31-Z 1311g The present invention will be described in more detail with reference to Examples below, but the technical scope of the present invention is limited to the following Examples. The number of ships is not limited, and various embodiments are possible.

Example 1 A silver halide emulsion consisting of to mol percent of kX conversion fm, / Y, j mol, e-cent of silver bromide, and 0.05 mol percent of silver iodide was gold sensitized and sulfur sensitized by a conventional method. I felt and prepared it. The gelatin contained in this emulsion was lime-treated gelatin and had a concentration of 30 percent based on silver halide.

3-carboxymethyl-j-(,2-(3-
Ethylthiazolinylidene) ethylidene] rhodanine (spectral sensitizing dye), Hiro-Hydroxy-l.

! , 3a,7-chitraza-renden (stabilizer), polyoxyethylene nonylphenyl ether containing 50 ethylene oxide groups, polymer latex (L-/ ) as a hardening agent, 2-ethylene-bis(hinylsulfonylacetamide) was added per 1 square meter;
ojr was added to prepare a coating solution for a photosensitive silver halide emulsion layer.

On the other hand, polymer latex (L, 2) is added to the gelatin aqueous solution.
And average particle size 0.3! After adding po and oty of micron polymethyl methacrylate (matting agent) per 7 square meters, a polymer curing agent (P-2) was added to prepare a non-photosensitive upper layer coating solution. A sample was prepared by coating both coating solutions in multiple layers on a polyethylene terephthalate film base.

The amount of silver applied was 1 square meter! l13. j2, the amount of gelatin applied in the non-photosensitive upper layer is per square meter/
, Off.

(L-1) H H20H Next, a halftone image was formed on the sample using the first method.

Commercially available gray contact screen for negatives (lSO line/
(inch) is brought into close contact with the sample, and there is no difference in level between the two. White tungsten light was exposed for 70 seconds through a stepped wedge. This sample was processed at 3rC for 20 minutes using the following developer.
Develop quickly at high temperature for seconds, fix with water and wash using the usual method.
Dry.

Developer solution Sodium carbonate iii Potassium bromide 3f Hydroquinone 23f l-phenyl-3-pyrazolidone o, ay Sodium sulfite 671 Potassium hydroxide //S' Add 1 liter of water and add the resulting halftone strips to the reducing solution shown below. After soaking, it was washed with water.

Reducing liquid Ceric sulfate 23f Concentrated sulfuric acid 30? Add 1 liter of water and measure the changes in the dot area and the density per dot of the dot strips thus obtained using a microdecintomer.
Measured using a tar.

The halftone dots of the halftone dot area jO percent of the halftone dot strips are reduced to 2. Table 1 shows the halftone dot area at dusk, the required reduction time, and the reduction period.

In addition, the above-mentioned development treatments and 4-- were carried out, and after treatment with a hypo heavy solution fixer, the samples were washed with water, and the degree of reticulation generated after each sample was observed and evaluated using a microscope.

The degree of occurrence of reticulation is as follows: A, B.

It is shown in three stages C.

A: No reticulation is observed when observed under a microscope with 100 times magnification.

B: Slight reticulation is observed when observed under a microscope at 100 times magnification.

C: Significant reticulation is observed when observed under a microscope with 100 times magnification.

Table 1 shows the degree of occurrence of reticulation.

Furthermore, for the obtained samples f/) to (17),
An adhesion test was conducted using the adhesion test method described in the i-tot'y issue, Examples-/. The results were evaluated on a scale of ≠ and shown in Table 1 (in the order of D<C<B<A). Edition!~j and A10~/3, it has excellent adhesion resistance, and the occurrence of reticulation is well prevented during high-temperature rapid processing, and surprisingly, it is even stronger during deceleration. It shows an excellent effect.

In addition, in the sample plate in which no polymer hardener was used in the non-photosensitive upper layer, the reticulation was not bad even if lime-treated gelatin was used in this layer, but when the polymer hardener was used in the non-photosensitive upper layer, the reticulation was not bad. When used, the more polymer radicals are added to the emulsion layer for the purpose of dimensional stability, the more the reticule becomes
(sample A2~j1b10~
13).

It is clearly understood from Table 1 that the use of acid-treated gelatin in the C1 non-photosensitive upper layer is an extremely effective solution to such defects.

Claims (3)

[Claims] (1) A silver halide photographic light-sensitive material for plate making, comprising at least seven photosensitive silver halide emulsion layers on a support and at least one non-photosensitive upper layer on top of the emulsion layers; at least one of the non-photosensitive top layers has a melting time greater than the emulsion layer, and this or at least seven of the other non-photosensitive top layers contain acid-treated gelatin. A silver halide photographic material for plate making. (2) A silver halide photographic light-sensitive material for plate making according to claim 1, characterized in that the non-photosensitive upper layer having a longer melting time than the emulsion layer is hardened with a commercially available molecular curing agent. . (3) A silver halide photosensitive material for plate making, comprising at least one photosensitive silver halide emulsion layer on a support and at least one non-photosensitive upper layer on top of the emulsion layer. at least one of the non-photosensitive top layers has a melting time greater than the emulsion layer, and the non-photosensitive top layer or at least one of the other non-photosensitive top layers contains acid-treated gelatin. A method for reducing power of a silver halide photographic light-sensitive material for plate making, which comprises subjecting a silver halide photographic light-sensitive material for plate-making to light-reducing processing to a silver image obtained by exposing and developing the silver halide photographic light-sensitive material for plate making.