JPS61230136A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain superior antitackiness and good antistaticness by using a specified matting agent for roughening the surface of a photosensitive material. CONSTITUTION:The matting agent to be used for roughening one surface of the photosensitive material is as follows: A) particles, such as PMMA particles coated with an F-contg. compd., such as CF3COOH, on the surfaces; B) F-contg. polymer particles capable of being dissolved off in the development processing stage, such as particles of a copolymer of an F-contg. monomer and a monomer having a vinyl group and a carboxylic group; or C) an F-contg. polymer particles represented by the formula shown on the right in which A is a monomer having at least 2 ethylenically unsatd. double bonds; B is a monomer having an alpha,beta-ethylenically unsatd. double bond; C is an F-contg. monomer having an alpha,beta-ethylenically unsatd. double bond; x is 0.5-50mol%; y is 0-49.5mol%; and z is 50-99.5%. One of these particles A, B, C are dispersed into gelatin or the like, and applied to the front or reverse surface of a support to form a roughend surface, thus permitting the photosensitive material to have good antitackiness at the time of producing it, and good electrostatic characteristics under low humidity, to be prevented from issue of the matting agent, and impairment of image quality, especially when the particles B are used, and widely used for various kinds of photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photographic material, and more particularly to a photographic material having excellent adhesion resistance and antistatic properties.

[Conventional technology]

In general, silver halide photographic light-sensitive materials (c) are hereinafter simply referred to as light-sensitive materials. ) The outermost layer (top layer or back layer) uses a hydrophilic colloid typified by gelatin as a binder. Therefore, when the surface of a photosensitive material is in a high-temperature, high-humidity atmosphere, its adhesion or tackiness increases, and when it comes into contact with another object, it easily adheres to it. This adhesive development occurs between the photosensitive materials or between the photosensitive materials and other objects that come into contact with them during the production, storage, and photographing of the photosensitive materials, often resulting in serious malfunctions. Particularly in color photosensitive materials, adhesiveness has been a major problem since the photographic layer contains many additives such as color couplers.

, silicon dioxide, magnesium oxide, titanium dioxide,
A method has been proposed in which fine particles of an inorganic substance such as calcium carbonate or an organic substance such as polymethyl methacrylate or cellulose acetate propionate are contained to cross-section the surface of a photosensitive material to make it so-called matte and reduce adhesiveness. In color photosensitive materials, it is necessary to use a large amount of matting agent for the reasons mentioned above.

Such matting agents also have the effect of slightly improving the electrostatic properties of photosensitive materials, as described in US Pat. No. 2,322,037.

Generally, photographic materials consist of an insulating photographic constituent layer on an insulating plastic film support.

For example, it is constructed by coating a photosensitive layer or the like.

Therefore, when handling photographic materials, 1) they are easily charged due to friction or peeling, and dust is attracted.

To give an example of a lie that is known to cause various phenomena such as electric shock and ignition, which may impair commercial value, silver halide photographic light-sensitive materials are manufactured using insulating plastic film supports such as those mentioned above. A photosensitive layer with high sensitivity is coated on top, and the manufacturing process,
In other words, the surface of the coating layer of the photosensitive material is subjected to friction or peeling from other substances during the transportation process during winding and rewinding of the photosensitive material, or coating and drying of various constituent layers including the photosensitive layer. When charged and discharged, the photosensitive material is exposed to light, and after development, uneven exposure due to irregular static electricity called so-called static marks may occur.

Furthermore, photographic materials are not only affected at the time of their manufacture.

Static electricity is also generated during processing to obtain images, and the above-mentioned matting agents can cause static electricity, adhesion of dust, and static marks as described above, which can cause malfunctions. Regarding the antistatic effect, the surface that comes into contact with other surfaces of adjacent photosensitive materials or the surface of the conveyor roll during the manufacturing process should be made as small as possible to prevent static electricity caused by contact separation between the surface tiles. It is thought that the purpose is to reduce the occurrence.

However, most of the conventionally known matting agents are
Although it tends to reduce static electricity by itself, considering the amount of static electricity generated.

It cannot be said that it is very effective, and furthermore, given the recent trends in the thinning of photographic materials, the dramatic increase in coating speed during manufacturing, and the increase in opportunities for harsh mechanical handling due to high-speed automatic processing, etc. However, the contribution of these matting agents to antistatic properties was very small, which was problematic.

[Purpose of the invention]

An object of the present invention is to provide a photosensitive material having a matting agent suitable for improving adhesion resistance and antistatic properties.

As a result of various studies regarding matting agents, including materials, structures, etc., we have arrived at the present invention. That is, the photographic light-sensitive material of the present invention is characterized in that at least one surface of the photographic light-sensitive material is roughened with a matting agent, and the matting agent is selected from the following groups A to C.

A Particle B whose surface is coated with a fluorine-containing compound Contains 7? Elementary polymer particles C Fluoropolymer particles represented by the following general formula % Formula % () [In the formula, mono Y-1B having at least two ethylenically unsaturated double bonds is α, Monomer having β-ethylenically unsaturated double bond, C is α.

It represents a fluorine-containing monomer having a β-ethylenically unsaturated double bond, where X is 0.5% by mole and y is 0 to 49.
5 mole%, 2 represents 50 to 99.5 moA/%. ] Hereinafter, the present invention will be explained in more detail.

In the particles of Group A, the core substances whose surfaces are coated with fluorine-containing compounds include 1, for example, inorganic compounds such as silica, titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, calcium carbonate, glass spheres, and talc; Particles known as matting agents, such as organic compounds such as methyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl alcohol, cellulose acetate propionate', ethyl heptamine, starch, R-nzoguanamine-form, and aldehyde condensates. can be mentioned.

Particles other than those mentioned above can also be used for self-examination as long as they do not adversely affect photographic properties.

Examples of the fluorine-containing compound in the particles of Group A include low-molecular compounds and high-molecular compounds. Typical specific examples of the low molecular weight compounds are shown below.

(Exemplary Compounds) (1) CF, C,00H (2) CaF+. C00H (0) C,F,, C184S i (OCHI)1 The compounds according to the present invention as exemplified above can be obtained as commercial products as shown below.

For example, trifluoroacetic acid as exemplified compound (1) and hexa7/I/oloisopropanol as exemplified compound (5) and exemplified compound (6) are available from Asahi Glass Co., Ltd.
Ortho-trifluoromethylbenzyl alcohol of Exemplified Compound (9), Exemplified Compound 4? Ortho-trifluoremethylbenzaldehyde of F (10), Exemplary Compound (1)
), ortho-trifluoromethylbenzoyl chloride, and ortho-trifluoromethylbenzoic acid, exemplified compound (3), are manufactured by Central Glass Co., Ltd.

Exemplary compound (13) is available from Shin-Etsu Silicone Co., Ltd. as a commercial product.

Among the above-mentioned fluorine-containing low-molecular-weight compounds, compounds having a carboxyl group, hydroxyl group, aldehyde group, carbonyl chloride group, or epoxy group at the terminal have particularly excellent ability to cover the nuclear surface, and are preferably used in the present invention. can. The 7y element-containing low molecular weight compounds of the present invention are not limited to the above-mentioned exemplified compounds.

As a method for coating the above-mentioned low-molecular-weight compound, for example, the nuclear material is immersed in a solution of a fluorine-containing low-molecular-weight compound that does not dissolve the above-mentioned nuclear material, and dried, so that a fluorine-containing low-molecular compound is coated on the surface of the nuclear material. can be made to exist.

Further, as the polymer compound constituting the surface of the particles of group A, a polymer having one fluorine-containing monomer unit having an α,β-ethylenically unsaturated double bond is preferable.

Examples of such monomers are shown below.

(Exemplary monomer) (1) CH,=CHF (2) CB, = CF.

(3) CHF=CF.

(4)　CF, =CF.

(5) CF, = CFCI! (6) C) I, =”C(CF,,)F(7) C
F, =C(CF, )FCB, =C(CH,)-CO
OCR, CF, (18)
(1]) C)i, =C(OH,) -COOCH,C,F.

CDI=C-CB.

CHt=CCHs, 1. ) c° 0° acclimatization) 1.0 (CF, )・F (n=2
~8) CB, = C) 1 C00CH, CHI (CF,) F (n =
2-8) C is also =CH CH, = C-C) 1°C00CHCFI'lCF.

C,H.

CHs C00C-CF, CF'HCF.

Examples of monomer units copolymerizable with the fluorine-containing monomer include monomers having, for example, at least one ethylenically unsaturated double bond.

Specifically, olefins such as ethylene, propyrene, l-butene, isobutyne, 2-methylbenzene, 2-methylbutene, 1,1,4,4-tetramethylbutadiene, styrene, α-methylstyrene, etc. Styrenes such as, olefin alcohol esters such as vinyl acetate and allyl acetate, esters of olefin carboxylic acids such as methyl methacrylate and ethyl acrylate, carboxylic acids having a vinyl group such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid; Its anhydride, divinylbenzene, allyl acrylate, allyl methacrylate, 1,3-butylene diacrylate, 1,3-butylene dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, vinyl acrylate, vinyl methacrylate, triethylene glycol diacrylate, Ethylene glyfur dimethacrylate, ethylene diacrylate, ethylene dimethacrylate), 1,6-hexane diacrylate, 1
．． Examples include those having two or more ethylenically unsaturated double bonds such as 6-hexane dimethacrylate.

Specific examples of the polymer compound include those shown below and those shown as specific examples of Group B and Group 0, which will be described later.

polymer compound COOCHgC00CH*H 1-(smell) C.B.

C00CR, (CF,)4B 1-(4) C)11÷CI(,
-〇+ C00C)ICFHCF.

C,H.

(CH, -CHsuC00C)I, CH, (CF, ), Fl -(6) -(-CF, -CF, + +CH, -CH, +CF, -CF, The molecular weight of these polymer compounds is 5 ,000 to 1,000,000 are preferable, and 10,000 to 20,000 are more preferable.

The above-mentioned exemplary polymers or copolymers can be easily produced by conventionally known polymerization methods such as solution polymerization, bulk polymerization, or suspension polymerization.

The method for synthesizing the fluorine-containing resin used in the present invention will be described below.

Synthesis Example 1 (Production method of exemplified polymer compound 1-(1)) CH
,=CH ■ C00CH, (CF, ), HZoo II.

α,α′-Azobisisobutyronitrile (AIBN)2
．． 0 Ii and 500 cc of methyl ethyl ketone
The mixture was placed in a double flask and refluxed for 10 hours.

Thereafter, the reaction solution was poured into a large amount of water with vigorous stirring to precipitate the reaction product. The precipitate was then filtered, washed with water, and dried in air at ω°C to obtain a polymer according to the present invention. The yield was 92.3 g (theoretical yield of 92.3
%)Met. NMR1 elemental analysis etc. confirmed that this substance had a polymer □ composition of the above monomers.

The intrinsic viscosity in acetone at 6°C is 0.15 j! j/,
It was 9.

Synthesis Example 2 (Production method of Exemplary Polymer Compound 1-(2) C) I
,=C−CB.

coocn, (crt)4n 1001
*AlBN2.0.9 was subjected to reaction treatment in the same manner as in Synthesis Example 1 to obtain a polymer. The yield was 931i (yield 93%), and it was confirmed by NMR, elemental analysis, etc. that this substance had a polymer composition of the above monomer. The intrinsic viscosity in acetone at 5°C was 0.12 ILt/li.

Synthesis Example 3 (Production method of exemplified polymer compound 1-(3)) AI
2.0 g of BN was reacted and treated in the same manner as in Synthesis Example 1 to obtain a polymer. The yield was 911 (91% yield), and NMR
, elemental analysis etc. confirmed that this substance had a polymer composition of the above monomers. The intrinsic viscosity in acetone at 5 °C was 0.121114/g.

Synthesis Example 4 (Production method of exemplified polymer compound 1-(4)) CH
,==C-CH.

C00CHCF, HCF.

C, H5100II.

AlBN2. ON was reacted and treated in the same manner as in Synthesis Example 1 to obtain a polymer. The yield was 92I (92% yield), NM
R, elemental analysis, etc. confirmed that this material had a polymer composition of the above monomers. The intrinsic viscosity in acetone at 5°C was 0.13 Ki/9.

Synthesis Example 5 (Production method of exemplified polymer compound 1-(5)) CB
! = OH 000C8,CH,(CP″t)*F Zoo
j'.

AlBN2. OII was reacted and treated in the same manner as in Synthesis Example 1 to obtain a polymer. The yield was 93.5 N (yield 93.5%
), and it was confirmed by NMR1 elemental analysis etc. that this substance had a polymer composition of the above monomers.

Intrinsic viscosity in acetone at 5°C is 0.13117/J
It was iJ.

The matting agent according to the present invention is prepared by, for example, immersion treatment in a solution of a fluorine-containing resin that does not dissolve the above-mentioned core substance.

The resin containing element 79 can be made to exist on the surface of the nuclear material by drying or by grafting a fluorine-containing monomer onto the surface of the nuclear material by plasma polymerization.

Compounds represented by the following general formula are preferred as the pufferfish graft-containing monomer used in the polymer constituting the particles of group B described above.

General formula [1] R C) I, =C 0ORf In the formula, R represents a methyl group which may be substituted with a hydrogen atom or a fluorine atom, and Rf is a linear, branched or cyclic alkyl substituted with a fluorine atom. This alkyl group preferably has 1 to 0 carbon atoms, and may be substituted with a group or atom other than a fluorine atom, such as 1, for example, a human tetraxy group, Examples include halogen atoms (for example, Cl, Br, etc.). Further, this alkyl group may have a linking group such as an oxo group or a thio group interposed between the carbon chains.

Among the fluorine-containing monomers represented by general formula (I), typical examples of those preferably used in the present invention include:
Examples of the fluorine-containing monomers (10 to (20)) shown for the particles of Group A mentioned above may be mentioned.

Here, "able to be dissolved and removed during the development process" means that it is not necessary that all of the matting agent particles used be dissolved and removed during the processing process.
A portion of it may remain as long as it does not significantly deteriorate the performance of the photographic image obtained by the development process.

The polymer constituting the particles of group B preferably has one unit of a fluorine-containing monomer (a) and one unit of a carboxylic acid monomer having a vinyl group (b).

Carboxylic acid having a vinyl group or its anhydride
Examples include acrylic acid, methacrylic acid, itaconic acid, maleic anhydride.

Among them, acrylic acid and methacrylic acid are preferred.

Among the polymers having one monomer unit (a) and (b), 10 to 3 mol% of the fluorine-containing monomer (a) and 2o
It is preferable that it is a copolymer consisting of monomers of carboxylic acid or its anhydride having 8 hemo%, more preferably 20 to 700 to 70 mol%, and further 0 to 70 mol% of the above (a) and the above ( A monomer (c) having a vinyl group that can be copolymerized with 0) may be included as a copolymerization component.

(c) is a compound having a vinyl group that can be copolymerized with monomer (a) and monomer (1), such as acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, Ethyl methacrylate, cyclohexyl methacrylate.

Methacrylic acid esters such as sulfoprupyl methacrylate, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl ketones such as methyl vinyl ketone and methyl vinyl ketone, styrene, methyl styrene, Examples include styrenes such as chloromethylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride, butadiene, and isoprene.

Two or more types of each of the above (a), (b) and (c) can be used.

Specific examples of copolymers used as group B matting agents will be given below.

COOCH, CF, C00HCH8 CH.

Ko CH8 C.B.

C.B.

C00CH,CF, CoonCHl C00CH,CF, COOCH3C0OHC
B.

CH.

■ CH.

■ C00CH,CF, C00CH,C0OH
CH.

coocn, c et al. C00CH,Coo)ICH
.

” C00CR, CF', C00CHs
C00I(COOCH, CF, C
00HCOOCH, CF', COOH0
000B, CF, C00HCOOCH, C)
IC) I, (OFl), F' The above copolymer can be easily synthesized by conventionally known methods such as solution polymerization, bulk polymerization, and suspension polymerization. For example, in solution polymerization, a mixture of 2811 type monomers or three types of monomers at an appropriate concentration in an appropriate solvent (e.g. ethanol, methanol, etc.) (usually less than 1% by weight based on the solvent, preferably 10
28II or a mixture of three monomers at a concentration of 1% by weight) in the presence of a polymerization initiator (e.g. benzoyl peroxide, azobisisobutyronitrile, etc.) at a suitable temperature (
The copolymerization reaction is carried out by heating 4ON to 120°C, preferably 100°C. Thereafter, the unreacted mixture is separated off by pouring the reaction mixture into a medium such as water, allowing the product to settle, and then drying.

Preferably, it is 0.08 to 0.2511j/I.

Next, a synthesis example of a copolymer of group B will be shown.

Synthesis Example 6 (Exemplary Compound 2- to) CH.

0H,=C C00CR,CF, 81.01 (0.50 mol), nimu43.0 N (0.50 mol), α, αI
-Put 2.01 of azobisisoptiloe)lyl (AIBN) and 3 of 500IR1 of ethanol into a flask,
This mixture was refluxed for 10 hours. Thereafter, the reaction solution was poured into a large amount of water while stirring vigorously to precipitate the reaction product. The precipitate was then filtered, washed with water, and dried in air at 60'C to obtain copolymer exemplified compound 2-1O according to the present invention. The yield was 116.6.9 (9 of the theoretical yield)
4-). NMR1 elemental analysis and the like confirmed that this substance had the composition of Compound Example 2-1O. 5
The intrinsic viscosity in °C ethanol is 0.11514/II
Met.

Synthesis Example 7 (Exemplary Compound 2-6) C.B.

CB! =C-COOCB(CF,), 94.4 I
I (0.40 mol), acrylic acid C (hereinafter abbreviated as Mumu) 4
3.2 # (0,60 mol) Mu! nN2.0Il was reacted and treated in the same manner as in Synthesis Example 6 to obtain Copolymer Exemplary Compound 2-6 according to the present invention. The numerical value was 129.3jl (yield 94%), and it was confirmed by NMR, elemental analysis, etc. that this substance had the composition of Compound Example 2-6. 2
Intrinsic viscosity in 5℃ ethanol is 0.151Lt/l
Met.

Synthesis Example 8 (Exemplary Compound 2-18) Hs CI(,=C-C00CH,CI', 76.89 (0
, 40 mol), MMM2O309 (0.20 mol), A
Mu, 28.81 (0.4 Ov-ru), AIBV2.0
11 was reacted and treated in the same manner as in Synthesis Example 6 to obtain Copolymer Exemplary Compound 2-18 according to the present invention. Yield is 115.6
．． 9 (yield 92%), and NMR1 elemental analysis etc. confirmed that this substance had the composition of Compound Example 2-18.The intrinsic viscosity in ethanol at 5°C was 0.123.
It was 11t/II.

Synthesis Example 9 (Exemplary Compound 2-22-23) 30.019 (0.30 mol), MA person 34
．． 41 (0.40 mol), AlBN2.01 in Synthesis Example 6
The reaction and treatment were carried out in the same manner as above to obtain copolymer exemplified compound 2-23 according to the present invention. The yield is 115.9,? (Yield: 95%), and NMR1 elemental analysis etc. confirmed that this substance had the composition of Compound Example 2-23.

Intrinsic viscosity in 6℃ ethanol is 0.17114/II
Met.

Synthesis Example 0 (Exemplary Compound 2-2-2 6) Mu50.71 (0.60 mol), MuBN2. O
Ii was reacted and treated in the same manner as in Synthesis Example 6 to obtain Copolymer Exemplary Compound 2-26 according to the present invention. Yield is 122.4
g (yield 96-), and NMR1 elemental analysis etc. confirmed that this substance had the composition of Compound Example 2-26. The intrinsic viscosity in ethanol at 6°C was 0.1311114/I.

Next, we will show examples of the production of typical matting agents of Group B.Production Example 1 80g of copolymer 2-10 obtained in Synthesis Example 6 was added to a mixed solvent of ethyl acetate 190I and n-butanol 6oIi.
Dissolved at 0'C. Also, 4o! 1.01 l of sodium r-decylbenzenesulfonate was dissolved in water of i.

Add 409 gelatin to a 500ml beaker and add 33ml of water.
After adding 201 and swelling for a while, it was dissolved at ω°C. Next, the dissolved gelatin solution and the aqueous sodium dodecylbenzenesulfonate solution were placed in a three-bottle flask with an internal volume of 11, and the mixture was heated to 35"C. , enter, 1 per minute
The mixture was stirred at a speed of 0.000 rpm for an additional period. As a result of observing the obtained emulsion 1 with an optical microscope, it was found that 2 to 511 ta
Polymer oil droplets were observed. This emulsion adventure 1
The solvent was removed by vacuum drying at 00 nmHg and 45°C. Then, by centrifugation, particles size 2-5
pm matting agent (average particle size 3.5 xi) was obtained.

Production Example 2 Copolymer 2-6 obtained in Synthesis Example 7 was treated in the same manner as in Production Example 1 to give S, - particle size of 2 to 4 μm (average particle size of 3 μm).
A matting agent was obtained.

Production Example 3 Copolymer 2-18 obtained in Synthesis Example 8 was treated in the same manner as in Production Example 1 to obtain particles with a particle size of 2 to 44EII (average particle size of 3
A matting agent of μ) was obtained.

Production Example 4 Copolymer 2-23 obtained in Synthesis Example 9 was treated in the same manner as in Production Example 1, and the '4-particle size was 2 to 4 pm (average particle size 3 μm).
) was obtained.

Production Example 5 Copolymer 2-26 obtained in Synthesis Example 0 was treated in the same manner as in Production Example 1 to obtain a particle size of 2 to 5 μm (average particle size of 3 μm).
A matting agent was obtained.

Next, particles of group C will be explained.

Specific examples of monomers constituting 7g of component A represented by the general formula +A-)-+B+-E-c+ include monomers having two or more ethylenically unsaturated double bonds as described for the particles of group A above. The ones listed above are listed.

Examples of the monomer represented by monomer unit B include ethylene, tetrapyrene, 1-butene, isobutyne, 2-
Olefins such as methylbutene and 1,1,4.4-tetramethylbutadiene, styrenes such as styrene and α-methylstyrene, olefin alcohol esters such as vinyl acetate and allyl acetate, olefin carboxyls such as methyl methacrylate and ethyl acrylate. Examples include fermented esters. Among these monomers represented by B, methyl methacrylate and styrene are preferred from the viewpoint of hardness.As for the monomer represented by C, examples of the fluorine-containing monomers mentioned above for the particles of group A are given. can be mentioned.

Furthermore, regarding the molar ratio represented by "e)'t" in the above general formula, in order for the mating agent itself to be insoluble in the solvent, X must be 0.5 or more, and the electrostatic properties In order to improve this, it is necessary to increase 2 to (equity) or higher.

Typical specific examples of the fluorine-containing copolymer represented by the general formula are described below.

No. 3-(2) ”“′”′=′.“9°60
) (x: y: z=lo: LO:80) The present invention is directed to the 7? The present invention is not limited only to element-containing copolymers. 7 above? The element-containing copolymer particles can be produced as follows.

Production Example 6 Add 12 g of calcium carbonate to a 2% gelatin aqueous solution of 200 IILt and disperse for m minutes using a homogenizer.

Next, 1.3 g of divinylbenzene and 70 g of hexa
Add 13.3 Ii of leuisoprobyl acrylate, 3.0 N of methyl methacrylate, and 0.5 II of benzoyl peroxide, and heat at a speed of 1000 revolutions/min for 45 minutes at ~δ°C in a nitrogen stream. Polymerization was carried out with stirring. As a result of observing the obtained emulgene with an optical microscope, polymer oil droplets of 2 to 5 microns were observed.

This emulgene is centrifuged and the particle size is 2 to 5.
A matting agent of μ was obtained. The yield was 96%, and elemental analysis confirmed that it was the desired exemplary copolymer compound 3-(1).

The photographic light-sensitive material referred to in the present invention refers to a support used for the photographic light-sensitive material, as well as a support (including one that has been subjected to a lower layer treatment or a backing layer coated as necessary), Photos with one or more layers! A photographic light-sensitive material as an intermediate product coated with a four-sakaki layer, and a silver halide emulsion layer, a subbing layer, an intermediate layer, a filter layer, a helage layer, a protective layer, and a backing layer on the support. It includes all photographic materials as finished products coated with photographic constituent layers such as layers, etc. The photographic materials of the present invention are preferably silver halide photographic materials, and general black and white photographic materials. , special black and white photosensitive materials, color photosensitive materials, printing photosensitive materials, XG photosensitive materials, and various other intermediate and finished products.At least one surface of the above photographic photosensitive material is roughened with a matting agent. For example, a wood-philic colloid such as gelatin, which is a binder for the photographic constituent layer (preferably the outermost layer), and a matting agent may be mixed, applied by a conventional coating method, and dried. Alternatively, the matting agent of the present invention may be used alone or mixed with a binder such as gelatin, and this may be sprayed or supercoated and then dried.

It is not essential that the particles of Group B and Group 0 be made into particles in advance.
Particles are formed by dispersing a solution of ethyl acid (less than 50 lfi% butanol) and butanol-containing methanol (less than % butanol by weight) in a hydrophilic colloid liquid, such as an aqueous gelatin solution, under rapid stirring. The surface can be roughened by applying and drying this dispersion.

Examples of the outermost layer include a surface protective layer, a back layer, and a non-photosensitive intermediate layer of an intermediate product in a multilayer photosensitive material coated in multiple layers. In the present invention, the surface protective layer is particularly preferred.

The thickness of the outermost layer is preferably 0.1 to 5 μm, particularly preferably 05 to 3 μm, when gelatin is used as the binder. When a polymer compound such as cellulose diacetate is used as a binder, 0. O1-3μ is preferable, and 0.03-lp is particularly preferable.

In the present invention, at least one surface of the photographic material is
"Roughened by a matting agent" means that the surface of the outermost layer is roughened due to the presence of a matting agent.In other words, the protrusions on the surface of the outermost layer are made of the matting agent material. Of course, when the matting agent material is exposed on the surface of the protrusion, the surface of the protrusion is composed of the outermost layer material due to the particulate matter surrounding the matting agent surface being protruded to the outermost layer surface. This also includes cases where there are.

In the present invention, the average particle size of the matting agent is preferably 0.
1 to 0μ, more preferably α5 to 8μ, but when mixed with the outermost layer binder, it is preferably larger than the dry film thickness, and from the viewpoint of antistatic effect,
It is particularly preferable that the particle size of the matting agent of the present invention is at least twice as large, and particularly preferably at least 2.5 times larger than the dry film thickness.

In addition, for the purpose of improving the matting effect, the coating amount of the matting agent is more effective, and it is preferably to "IP/d or more, more preferably 201?/lo" or more, especially 501HI
/i or more is preferable.

Further, in consideration of the influence on transparency and image sharpness, it is preferably 50011v/lf or less.

In particular, it is preferable that the particle diameter is 20097d or less, but the above-mentioned group 8 particles have a good dissolution and removal property in the development process, so it is particularly preferable that the particle diameter is 400η/rr? It is preferable that it is below.

The matting agent according to the present invention can be used in combination with other matting agents, but from the viewpoint of effectiveness, it is preferable to use a smaller amount than the matting agent according to the present invention.

The matting agent of the present invention can impart good adhesion resistance to photographic materials, and can also impart good static electricity properties even in a low humidity atmosphere where static electricity is a particular problem.

Furthermore, the matting agent of the present invention can be obtained by applying a coating solution containing a matting agent,
There is also no disadvantage that a large amount of matting agent dissolves, especially during the coating process during the production of dry photosensitive materials.

Therefore, when gelatin is used as a coating liquid binder, it is not essential to deionize or deash the gelatin.

Furthermore, since the above-mentioned matting agents of Group 8 have good solubility in the developer, they rarely deteriorate the transparency of the formed image or impair the image quality.

The photographic material of the present invention is preferably a silver halide photographic material, which is an intermediate product of various materials such as a general black-and-white photographic material, a special black-and-white photographic material, a color photographic material, a printing photographic material, an XLL photographic material, etc. and finished products.

When the photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material, the silver halide emulsion used includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, etc. Any of those used in conventional silver halide emulsions can be used.

The silver halide grains used in the silver halide emulsion may be those obtained by either the acid method (%), the neutral method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling pn and pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, the halogen composition of the particles may be changed using the Funberg method.

During the grain formation and/or growth process, silver halide grains are produced by cadmium salts, zinc salts, lead salts, aluminum salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts. Metal ions can be added using at least one selected from salts (including complex salts) to contain metal elements such as C and C inside the particles and/or on the particle surfaces, and in an appropriate reducing atmosphere. By placing
Reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, use a research disk jar (Re5earch Disc).
It can be carried out based on the method described in Section 2 of No. 17643 (hereinafter abbreviated as RD).

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inner part and the surface layer of the grain.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (110) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. ) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions may be used in sensitized colors in the photographic industry, but two or more types may be used in combination. 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.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing capri during photographic processing or maintaining stable photographic performance, one photograph may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating the silver halide emulsion. Compounds known in the art as anti-capri agents or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose conductors, and synthetic hydrophilic polymeric substances such as single or copolymers may also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention are coated with a hardening agent that crosslinks binder (t or protective coating) molecules and increases film strength. It can be hardened by using seeds or 211XJ. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an 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.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred tilting agents are the compounds described in RD 17643, section 1, A.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

In the emulsion layer of a color photographic light-sensitive material, a dye is formed by a coupling reaction with an oxidized product of an aromatic primary amine developer (e.g., p-phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. A dye-forming coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer.
Depending on the purpose, a silver halide color photographic light-sensitive material may be produced using a method different from the above combination.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are tetraequivalent, which requires reduction of four molecules of silver ions in order to form one molecule of dye, only two molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. The dye-forming coupler has a color correction effect, and when coupled with an oxidized form of a developing agent, it becomes a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, and a hardening agent. Compounds that release photographically useful fragments are included, such as capri agents, anticapri agents, chemical sensitizers, spectral sensitizers, and desensitizers.

Colorless couplers that do not form dyes (also referred to as competitive couplers) can also be used in combination with dye-forming couplers, although the capling reaction is carried out with the oxidized product of the aromatic primary amine developer.

As the yellow dye-forming coupler, known azila-7toanilide couplers can be preferably used.

Among these, compounds of the benzoylacetanilide and bivaloylua heptatoeride series are preferred.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

As cyan dye-forming couplers, phenol or 7-tole couplers are generally used.

Of the dye-forming couplers, colored couplers, image stabilizers, color capri-preventing agents, ultraviolet absorbers, fluorescent whitening agents, etc. that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds can be used using the solid dispersion method or latex dispersion. Various methods can be used, such as a method, an oil-in-water emulsion dispersion method, and the like, and can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied.
Usually, it is dissolved in a high boiling point organic solvent with a boiling point of about 150° C. or more in combination with a low boiling point and/or water-soluble organic solvent as necessary, and a hydrophilic binder such as a gelatin aqueous solution is mixed with a surfactant using a stirrer. homogenizer, colloid mill,
It may be emulsified and dispersed using a dispersion method such as a flow jet mixer or an ultrasonic device, and then added to the target wood-philic colloid mill. A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include phenol derivatives that do not react with the oxidized form of the developing agent, 7-tar acid alkyl esters, phosphorus esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. with a boiling point of 150°C or higher. Organic solvents are used.

In conjunction with high boiling solvents, low boiling or water-soluble organic solvents can be used. Organic solvents with low boiling points that are virtually insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitromethane, benzene, etc., and water-soluble organic solvents include ,
Examples include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol, etc. When dye-forming couplers, colored couplers, image stabilizers, color capping inhibitors, ultraviolet absorbers, fluorescent whitening agents, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be dissolved in hydrophilic colloids as an alkaline aqueous solution. It can also be introduced into

When a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using mechanical or ultrasonic waves, anionic surfactants, nonionic surfactants are used as dispersion aids. , cationic surfactants and amphoteric surfactants can be used to transfer oxidized forms of developing agents or electrons between emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of photosensitive materials. A color anti-capri agent can be used to prevent color turbidity, deterioration of sharpness, and conspicuous graininess due to migration of the agent.

The color anti-capri agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other wood-philic colloid layers of the light-sensitive material. The compound that can be preferably used as a development accelerator is 10176
The compound is a compound described in Section XXI B to D of No. 43, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds that can be preferably used as fluorescent brighteners are described in item 7 of HD No. 17643. For photosensitive materials, auxiliary layers such as a filter layer, an anti-yelage layer, an anti-irradiation layer, etc. can be provided. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

A lubricant can be added to the photosensitive material to reduce sliding friction.

A surfactant can be used in the photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material.

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Ethylene/butene copolymer> etc.: Flexible reflective support such as laminated paper, synthetic paper, cellulose acetate, nitric acid 1! Includes films made of semi-synthetic or synthetic polymers such as cellulose, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports made of these films with reflective layers, glass, metals, ceramics, etc. It will be done.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface. It may be applied through one or more subbing layers to improve anti-halizing properties, frictional properties and/or other properties.

A thickener may be used to improve coating speed when coating the photosensitive material. In addition, for example, for substances such as hardeners, which have quick reactivity and may cause gelation before coating if added to the coating solution in advance, it is preferable to mix them using a static mixer or the like immediately before coating. As a coating method, extrusion coating and curtain footing, which allow two or more layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Any known method can be used for developing 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. If an image is to be produced by the reversal method, a black-and-white negative development process is first performed, and then a color development process is performed by applying white exposure or processing with a bath containing a capri agent. [Also, silver dye bleaching may be used, in which a dye is contained in the photosensitive material, a black and white development process is performed after exposure to form a silver image, and the dye is bleached using this as a bleaching catalyst. ] As for Kuroichi development processing,
A developing process, a fixing process, and a washing process are performed. When a stopping process is performed after the development process or a stabilizing process is performed after the fixing process, the washing process may be omitted. Alternatively, a developing agent or its precursor may be incorporated into the sensitive material, and the developing process may be performed using only an alkaline solution. A development process using a lithium developer as a developer may also be performed.

Color development processing includes a color development processing process, a bleaching processing process,
A fixing process, a water washing process and, if necessary, a stabilizing process are performed, but instead of the process using a bleach solution and the process using a fixer, a 1-bath bleach-fix solution is used to perform the bleach-fix process. Alternatively, a monobath processing process using a one-bath development, bleaching and fixing solution that allows color development, bleaching and fixing to be carried out in one process can also be carried out.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator two process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator two process may be performed in which the monobath process is performed using an activator solution. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as a final step, including either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Processes: Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary information Color development process - Stop process - Bleach process Constant fixation process/Activator process - Bleach-fix process/Activator process - Bleach process Constant fixation process/Monobath process Process 'fiA Maro is usually The temperature is selected to be in the range of 10°C to 10°C, but the temperature may be higher than 66°C. Preferably δ℃
Processed at ~45°C.

The black-and-white developer used in black-and-white development processing is the so-called black-and-white first developer used in the processing of color photographic light-sensitive materials, or the one used in the processing of black-and-white photographic light-sensitive materials, and is generally used in black-and-white development. Various additives added to the liquid can be included.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, surface overdevelopment inhibitors consisting of iodides and mercapto compounds. etc. can be mentioned.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic and inorganic acids;
For example, a salt bridge acid, a sulfate, a p-)luenesulfonate, a sulfite, a chelate, a benzenesulfonate, etc. can be used.

These compounds are generally used in color developer II! preferably a concentration of about 0.1 to 3 ON, more preferably a color developer of 11! It is used at a concentration of about 1 to 15 I.

Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-amino-2
-oxy-toluene, 2-ami2-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups may be substituted or unsubstituted. Among these, particularly useful compound examples include N-N-dimethy/S'-p-phenylenediamine hydrochloride and N-methyl-p-7enylenediamine hydrochloride.

N,N-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β- and diethylaminoaniline, 4
-amino-3-methyl-N,N-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-9-)luenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above-mentioned color developing agent may be incorporated into the color photographic material.

In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, aqueous potassium, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. In addition, various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, preservatives such as hydrolyzylamine or sulfite, etc. May contain.

Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The p)I of the color developing solution used in the present invention is usually 7 or more, preferably about 9-13.

In addition, the color developing solution used in the present invention may optionally contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroacetone, aromatic secondary alcohol, hydroxamic acid, hentosemata, etc. is hexose, pyrogallol-1,
S-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1'-diphosphonic acid, aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, etc. Polyhydroxy compounds such as aminophosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, polyphosphoric acids such as trimellilic acid or hexametaphosphoric acid, etc. Can be mentioned.

As described above, the bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleaching agent, a metal complex salt of an organic acid is used. For example, an organic acid such as polycarboxylic acid, aminocarboxylic acid, oxalic acid, or citric acid, coordinated with a metal ion such as iron, chloride, or steel. used.

Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids.

Specific examples thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ethylenecyano-N-(β-oxyethyl#)-N.

N', N'-) diacetic acid, tetrapyrene diamine tetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glyfur ether cyano Examples include tetra vinegar, ethylene diamine tetra acetic acid, and phenylene diamine tetra acetic acid.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaches are used at 5 to 4501/l, more preferably 20 to 250.9/l. .

The bleaching solution may contain, in addition to the above-mentioned bleaching agent, sulfite as a preservative if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron(1) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. In addition to ammonium bromide, the halides include hydrochloric acid,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

The bleaching solution used in the present invention includes JP-A-46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770.910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleaching solution used is above 2.0, but it is generally used between 4.0 and 9.5, preferably between 4.5 and 8.0.
and most preferably 5.0 to 7.0.

A fixer having a commonly used composition can be used. As the fixing agent, compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, etc., which are used in ordinary fixing processing, are used.
Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, and thioethers. These fixatives are 51
/1 or more, and is used in an amount that can be dissolved, but generally 70 to 250 N/l! Use with. Note that a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

In addition, the bleaching solution and/or the fixing solution include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, 7
Various pH buffering agents such as sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more.

Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as amino l dicarbonate, stabilizers such as nitro alcohol and nitrates, hardening agents such as water-soluble aluminum salts, The pH of the fixer, which can contain appropriate organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc., is used at a pH of 3.0 or higher, but generally the pH is 4.
．． 5 to 0, preferably 5 to 9.5, and most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the organic metal complex salts described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent, and if necessary, contains subsulfite as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (1) #salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, Bleach-fix solutions with a composition containing a large amount of halides, and even ethylenediaminetetravinegar iron (
1) A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide may also be used. As the halide,
In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the above-mentioned fixing process.

The pH of the bleach-fix solution is used at 40 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.5.
The present invention will be described in more detail with reference to Examples below.
The present invention is not limited thereby.

Example 1 Silica matting agent with average particles r & 3μ (matting agent-1) 1
011 as a fluorine-containing low molecular compound (feeding compound-13) 3
A matting agent obtained by immersing in 00 g of liquid, dispersing an additional amount using an ultrasonic dispersion machine, and then spraying the resulting dispersion into hot air at 100 to 120°C with a spray gun and drying. is referred to as matting agent-2.

Next, a silver iodobromide gelatin high-sensitivity After gold-sulfur sensitization, 4-hydroxy-6-
Methyl-1,3#3a,7-tetrazaindene compound,
Glyoxal was added as a hardening agent and saponin was added as a coating aid, and the mixture was coated and dried to a dry film thickness of 7μ on a 175μ thick polyethylene terephthalate film support that had been subbed treated, and then a protective layer having the following composition was prepared. Sample 1 was obtained by applying and drying the film to a dry film thickness of approximately 0.5 μm.

(Protective film composition) (1/m") Gelatin 0.5 II Sodium ethylhexyl sulfosuccinate 0.01 g Glioyazar 0.01 Ii The above matting agent-1 at a ratio of 50 Q/m" The sample obtained by adding the above-mentioned protective film composition so that The obtained sample is designated as sample-3.

Next, for each sample, 4
The humidity was controlled for a period of time, and the amount of frictional charge using neoprene rubber was measured and a static mark generation test was conducted, and the results shown in Table 1 below were obtained.

The above charge amount is the amount of frictional charge between the neoprene rubber and the sample, and was measured at 6℃, 20% RI (atmosphere), and the static mark indicates the amount of friction charge between the neoprene rubber and the sample.
After adjusting the humidity of the sample in a concave atmosphere for 4 hours, the sample was rubbed with an open rubber rod and developed.The degree of blackening was observed and judged according to the following grade.

Grade 1: No occurrence, 12: Slight occurrence, 13: Occurrence, 14: Slightly frequent occurrence, I5: Occurrence all over the surface As shown in Table 1 above, a matting agent was applied to the protective layer. Sample-1 to which no silica matting agent was added and sample-2 to which silica matting agent was added were both highly positively charged and had strong static marks.

On the other hand, a sample to which matting agent-2 according to the present invention was added
In No. 3, the amount of charge was small, and there were almost no static marks.

In addition, the samples of the present invention showed no decrease in sensitivity or occurrence of fog.

Example 2 Titanium oxide matting agent (matting agent-3) I with an average particle size of 5μ
ON is a 10% by weight acetone solution of polymer compound 1-(1) 5001! li! After being immersed in the liquid and dispersed for a while using an ultrasonic dispersion machine, the resulting dispersion was sifted in a suspended state with a spray gun and sprayed into hot air at 0°C to 90"C. A titanium oxide matting agent whose surface was coated was obtained.This matting agent was designated as matting agent-4.

Next, a protective layer having the following composition was coated on the protective layer of Sample 1 of Example 1 so that the dry film thickness was about 1.0 μm and dried to obtain Sample-4.

(Protective film composition) (11/m") Gelatin 1.0g Sodium di-2-ethylhexyl sulfosuccinate 0.0111 Glyoxal 0.0111 The above protective film composition so that the ratio of the above matting agent - 3t30119/m" The sample obtained by adding the above-mentioned matting agent-4 to the above-mentioned protective film composition at a ratio of 3 Drtv/m'' is designated as sample-6.

Next, each sample was subjected to humidity conditioning under the same conditions as in Example 1, and the amount of frictional charge was measured and a static mark generation test was conducted, with the results shown in Table 2 below.

Table 2 As shown in the above table, both Sample-4 to which no matting agent was added to the protective layer and Sample-5 to which silica matting agent was added were positively charged to a large extent and had no static marks. The occurrence of is also strong.

On the other hand, a sample to which matting agent-4 according to the present invention was added,
In case of -6, the amount of charge was small and there was almost no static marring.

In addition, the samples of the present invention showed no decrease in sensitivity or occurrence of fog.

Example 3 Matting agent-5 obtained in Production Example 6 was added in place of the matting agent of Sample 6 of Example 2 at a ratio of 50/ze,
The obtained sample was designated as Sample-7.

On the other hand, for comparison, a sample obtained by adding PMMA (matting agent-6) having an average particle size of 3 .mu.m to the above-mentioned protective layer composition at a rate of 50 .mu.m/cm was designated as sample 8.

Next, each sample was subjected to humidity conditioning under the same conditions as in Example 1, and triboelectrostatic foot measurement and static mark generation tests were performed, with the results shown in Table 3 below.

Table 3: As shown in the table above, a comparative matting agent-6 was added to the protective layer.
Sample 8, which contained A, was positively charged to a large extent and had strong static marks. However, in sample 7 to which the matting agent-5 according to the present invention was added, the amount of charge was small, and the occurrence of static i-k was hardly observed.

Example 4 The following composition solution was applied to the surface of the cellulose triacetate film support at a ratio of about 2011/i by roll coating method, (a) it was dried at ℃ for 3 minutes, and the surface of the support was constantly coated. After subbing according to the method, the same high-sensitivity X-ray emulsion and protective layer as Sample-1 prepared in Example 1 were applied in order.
It was dried to obtain Sample-9.

(Composition liquid) Cellulose diacetate 20I methanol
700 d acetone
30011Ll On the other hand, a sample prepared in the same manner as Sample-9 was designated as Sample-10, in which 11 g/W11 of the matting agent-5 according to the present invention was added to the above-mentioned composition liquid.

Each sample obtained above was treated in the same manner as in Example 1,
The results obtained are shown in Table 14 below.

@Table 4 As shown above, sample-10 in which the matting agent of the present invention was added to the surface coating layer of the support had a small amount of charge,
Kakustatic! -Almost no occurrence of oxidation was observed.

Although a matting agent such as polymethyl methacrylate and polystyrene was added to Comparative Sample-9, it swelled and dissolved in the liquid and was not usable.

Practical row 5 1 mole of silver halide! 7300.9 gelatin't-
In addition, as a yellow cobra, α-viveroyl α-(1-benzyl-2,4-dioxyimidacylin-3-yl)-2-chloro-5[r-('l, 4-
A color blue-sensitive silver iodobromide (7 mol silver iodide) emulsion containing 2.5×10 □1 mol of tcrt-aminophenoxy)butylamide dolacetanilide was prepared. Along with this emulsion, matting agent-7 I 3 9 1511 obtained in production row 1, matting agent-12 with a particle size of 2 to 4 μm having a composition of MMA/MAA = 6/4 for comparison, and comparison for the protective layer were used together with this emulsion. BMA/
MAA=60/407) composition (molar ratio) with a particle size of 2 to 4 μm, a matting agent, a coating aid (sodium di-2-ethylhexyl sulfosuccinate), a hardening agent (gelatin III 0.02 II) Samples 11 to 17 were obtained by preparing an emulsion layer and a capture layer on a cellulose triacetate film support having a subbing layer using a slide hopper.

Each matting agent did not dissolve during application.

Sample 18 without a matting agent was also prepared. The amount of blood is matting agent 10100II/ba, gelatin 0.51/r
r? Met.

The antistatic property of each sample was examined using the following method.

After conditioning the unexposed sample at 5°C and 25°RH for 2 hours,
After rubbing the emulsion side of the sample with a neoprene rubber roller in a dark room under the same air-conditioning conditions, the sample was developed with the following processing solution.
Bleaching, fixing, water washing and stabilization Processing process Temperature Processing time (1) Developing solution 38°C 3 minutes 15 seconds Q) Bleaching ・
・・・・38℃ 4 minutes (9) seconds (3) constant
Arrival: 38°C, 4 minutes msec) Wash with water: 38°C, 3 minutes 15 seconds G) Stabilization...
...38°C 1 minute 5 seconds The compositions of the developing solution, bleaching solution, fixing bath and stabilizing bath are as follows.

Developer (p)I = 10.05) Add water and 1! shall be.

White bath (pH=5.70) Add water to make 11.

Fixing bath (, 9H”’6.50) Add water to make 1j.

Stable bath (p) I zero 7.30) The antistatic test results of these samples are shown in Table 5.

In the table, the evaluation of the degree of static mark occurrence is A: No static marks observed at all B: Some static marks observed C:
9. The results are divided into four stages.

As is clear from Table 5, the samples antistatically treated using the compound of the present invention have an excellent antistatic effect with almost no static marks observed.

Example 6 Samples 11 to 18 in Example 5 were cut into two pieces each with a size of 5 cWL square, and heated in an atmosphere of 23'C, 80S R, H, so as not to touch each other.
After being stored for several days, the two protective layers of the same sample were brought into contact with each other, a load of 800 g was applied, and the samples were heated at 40°C for 13Q [
The sample was stored in an atmosphere of R, H. After that, the sample was peeled off and the area of the bonded part was measured to measure the adhesiveness. The evaluation criteria are as follows.

Rank Area of adhesive part λ 0~2o- B　　　　　　21～4ochi 0　　　　　41～60chi D 61 S or above The above results are shown in Table 6.

From the results shown in Table 6, it can be seen that the adhesion resistance of the matting agent of the present invention is superior to that of the conventional matting agent.

Further, similar evaluations were performed on Samples 3, 6, 7, and 10, and good results were obtained in all of them.

Example 7 The sharpness of Samples 11 to 16 and Sample 19 below was examined by the following method.

After the unexposed sample was exposed to normal wedge light using a tungsten lamp, the development process according to Example 5 was performed, and M TF (
Modulation Transfer Function
ion) was measured. Spatial frequency is 10 lines/m
The MTF values at a value of m and 30 lines/mm were compared. Sample 19 has M with MMA/MAA=6/4 of sample 16.
A stone made with the same amount of MA homopolymer.

The results are shown in Table 7.

As is clear from Table 7, even when the matting agent of the present invention is used, the sharpness does not deteriorate.

Example 8 A matting agent produced using Exemplified Compound 2-10 and having a particle size shown in Table 8 was added to the protective layer of Sample 1 of Example 1 in the amount shown in Table 8, and the protective layer was further added. Samples 20 to 25 were prepared by changing the film thickness as shown in Table 8.

Next, each sample was subjected to humidity conditioning under the same conditions as in Example 1, and the amount of frictional charge was measured and a static mark generation test was conducted, and the results shown in Table 8 below were obtained.

Table 8 As shown in the above table, the outermost layer matting agent is 509/m'
From the above, it can be seen that as the ratio of the average particle size of the matting agent to the thickness of the outermost layer increases, the charging characteristics are further improved.

(Effects of the Invention) By using such particles as a matting agent for photographic light-sensitive materials, not only the adhesion resistance but also the antistatic property can be improved.

Applicant: Konishiroku Photo Industry Co., Ltd. □98n

Claims (1)

Claims: A photographic light-sensitive material in which at least one surface is roughened with a matting agent, wherein the matting agent is selected from the following groups A to C. A Particles whose surfaces are coated with a fluorine-containing compound B Fluorine-containing polymer particles that can be dissolved and removed during the development process Fluorine-containing polymer particles represented by the following general formula -(A)_x-(B)_y-( C)_z- [wherein A is a monomer having at least two ethylenically unsaturated double bonds, B is a monomer having α,β-ethylenically unsaturated double bonds, and c is α,β-ethylene represents a fluorine-containing monomer having a sexually unsaturated double bond, x is 0
．． 5 to 50 mol%, y is 0 to 49.5 mol%, z is 50
It represents ~99.5 mol%. ]