JPH08129247A - Supporting body for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain high dimensional stability and good adhesion property with a photosensitive layer by laminating polyester resin layers on both faces of a film essentially comprising syndiotactic polystyrene. CONSTITUTION: This supporting body consists of a film essentially comprising syndiotactic polystyrene and polyester resin layers laminated on both faces of the film. In this case, the polyester resin layer is a polyethylene terephthalate resin layer, polyethylene naphthalate resin layer, or modified polyester resin layer. The modified polyester resin layer consists of coupling of at least one compd. selected from among terephthalic acid, naphthalene dicarboxylic acid and 5-sodium sulfoisophthalic acid, and at least one compd. selected from between ethylene glycol and polyethylene glycol. By this method, strong adhesiveness with photosensitive layers can be maintained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a support for silver halide photographic light-sensitive materials, and more particularly to a support for silver halide photographic light-sensitive materials having excellent dimensional stability.

[0002]

2. Description of the Related Art Various photographic supports are generally used for silver halide photographic light-sensitive materials, depending on the purpose.

For example, a photographic support for a roll-shaped color photographic film includes cellulose triacetate (hereinafter referred to as TA).
A film (abbreviated as C) is used. When a silver halide photographic light-sensitive material (hereinafter sometimes abbreviated as photographic film) is wound in a roll, it tends to be curled with time. A TAC film is generally used as a photographic support for a roll photographic film such as a color photographic film because the TAC film has a property of eliminating the curl when it is immersed in water such as a developing process. .

On the other hand, the photographic film for printing is required to have a high degree of dimensional stability against changes in humidity. Therefore, as a photographic support for the photographic film, polyethylene terephthalate (hereinafter referred to as "polyethylene terephthalate" having a relatively large coefficient of elasticity and a relatively large elastic modulus) is used. A film (abbreviated as PET) is used.

In medical photographic film, a doctor sandwiches the photographic film in a Schaukasten at the time of diagnosis, so that the photographic film is required to have rigidity, and a thick PET film is used as a photographic support.

Among these photographic films, the photographic film for printing is strictly required to have no dimensional change with respect to changes in external conditions (for example, temperature, humidity, water, etc.), and various contrivances have been made in its design. . Further, due to recent technological advances, more severe dimensional stability is required.

Under such circumstances, a photographic film for printing, in which a PET film is used as a photographic support, may not meet the demands of the market, and a material having a smaller dimensional change is required. It has become.

For example, in JP-A 1-180537, a PET film having low water absorption and hygroscopicity is further formed, and a vinylidene chloride polymer layer is extremely thin on both sides of the PET film in order to reduce water absorption and hygroscopicity. A method has been proposed in which coating is performed to enhance waterproofing and moistureproof effects and further improve dimensional stability.

Further, Japanese Patent Laid-Open No. 3-113843 proposes a photographic film comprising a stretched styrene polymer (hereinafter sometimes abbreviated as SPS) film having a syndiotactic structure and a photosensitive layer. It is described in this specification that the SPS film is lightweight, mechanically strong, has a small coefficient of humidity expansion, and is a photographic support superior to PET.

[0010]

When a photographic support prepared by coating the above-mentioned photographic film with a thin film of vinylidene chloride polymer described in JP-A 1-180537 on a PET film is used, waterproof and moisture-proof effects are obtained. However, (1) the vinylidene chloride polymer gradually undergoes dechlorination during long-term storage of the photographic film, resulting in discoloration of the photographic image.

(2) When collecting the PET photographic support,
It is difficult to remove the vinylidene chloride polymer from the PET film, and the PET is contaminated, and the quality of the recovered product deteriorates.

(3) When this PET film cannot be recovered as it is and is incinerated as it is, harmful substances such as chlorine gas are generated, which causes environmental problems.

Due to the above-mentioned problems, such a photographic support is difficult to use.

On the other hand, the SPS film of JP-A-3-31848 has a small humidity expansion coefficient, and the photographic film using the SPS film has excellent dimensional stability, but the photosensitive layer or the back layer strongly adheres to the support. It has the drawback of being difficult to do. The SPS film requires a high degree of crystallization in order to enhance the dimensional stability, which makes it difficult to select an appropriate undercoat layer. Moreover, in order to firmly adhere the undercoat layer, a good solvent for polystyrene may be used in some cases, and in such a case, the flatness of the film is impaired.

The object of the present invention is to eliminate the above drawbacks,
Moreover, the object is to provide a photographic support for a silver halide photographic light-sensitive material which is highly excellent in dimensional stability and has adhesiveness for a light-sensitive layer and the like.

[0016]

Means for Solving the Problems The present inventor has conducted various studies on the undercoating method of the film containing syndiotactic polystyrene as a main component, but the photographic performance is deteriorated,
A good product could not be obtained because the transparency was deteriorated or the flatness was deteriorated. The present inventor has diligently studied to use a film containing syndiotactic polystyrene as a main component, which maintains the dimensional stability and satisfies the above-mentioned performance, as a photographic support, and as a result, obtains a photographic support as follows. I was able to do it.

That is, (1) A support for a silver halide photographic light-sensitive material, which has a structure in which a polyester resin layer is laminated on both surfaces of a film containing syndiotactic polystyrene as a main component.

(2) The support for a silver halide photographic light-sensitive material according to (1), wherein the polyester resin layer is a polyethylene terephthalate resin layer.

(3) The support for a silver halide photographic light-sensitive material according to (1), wherein the polyester resin layer is a polyethylene naphthalate resin layer.

(4) The support for a silver halide photographic light-sensitive material according to (1), wherein the polyester resin layer is a modified polyester resin layer.

(5) The modified polyester resin layer is formed by condensation of at least one selected from terephthalic acid, naphthalene dicarboxylic acid and 5-sodium sulfoisophthalic acid and at least one selected from ethylene glycol and polyethylene glycol. (4) The support for a silver halide photographic light-sensitive material as described in (4) above.

The characteristic feature of the photographic support of the present invention is that it has a structure capable of maintaining a strong adhesiveness to a photosensitive layer and the like, while hardly compromising the physical properties of a film containing syndiotactic polystyrene as a main component. It is that.

The present invention will be specifically described below.

In the present invention, the film containing syndiotactic polystyrene as a main component is a styrene polymer whose main chain is a racemo chain or a composition containing the same, and a styrene homopolymer. If so, it is possible to polymerize by the method described in JP-A-62-117708, and for other polymers, JP-A-1-46
It can be obtained by polymerizing by the method described in Nos. 912 and 1-178505.

For the main chain chain, ¹³ C-NM
It is general and highly accurate to quantify as pentad tacticity by measuring the carbon at the 1-position of the benzene ring using R.

In the present invention, the racemo chain is two chains.
It is preferably 85% or more, 75% or more in 3 chains and 50% or more in 5 chains.

The polymer constituting the syndiotactic polystyrene-based composition includes styrene, alkylstyrene, halogenated alkylstyrene,
It is a polymer containing alkoxy styrene, vinyl benzoate, etc. as main components.

The polystyrene resin having a syndiotactic structure of the present invention is described in (a) (a) on pages 4 to 10 of JP-A-5-320448, using the above raw material monomers as a catalyst for polymerization. ) A compound containing a transition metal compound and (b) an aluminoxane as a main component, or (b) containing a compound capable of reacting with a transition metal compound (a) and a transition metal compound (c) to form an ionic complex as a main component It can be produced by polymerizing the same.

Although there are various transition metal compounds of the above-mentioned component (a), the compound of the general formula (III) M ¹ R is preferred.
² ... ^RK (III) [wherein, M ¹ represents Ti, Zr, Cr, V, Nb, Ta or Hf,
R ^{2 to} R ^k are each a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms, an alkylaryl group or arylalkyl. Group; acyloxy group having 1 to 20 carbon atoms, allyl group, substituted allyl group, acetylacetonato group, substituted acetylacetonato group, substituent containing silicon atom, carbonyl, oxygen molecule, nitrogen molecule,
A ligand such as Lewis base, chain unsaturated hydrocarbon or cyclic unsaturated hydrocarbon, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group,
A tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown.
Further, K represents a valence of a metal and usually represents an integer of 2 to 5].

Examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group and tetra. Methylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group Group, a trimethylsilylcyclopentadienyl group, and the like. Also, R ²
The ligands of to R ^k may form a crosslinked body by a covalent bond between the ligands. Specific examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom; carbon number 1
As the alkyl group of ~ 20, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, octyl group,
Examples of the alkoxy group having 1 to 20 carbon atoms such as 2-ethylhexyl group are an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group and phenoxy group. Is a phenyl group, a tolyl group, a xylyl group, a benzyl group, etc., an acyloxy group having 1 to 20 carbon atoms, a heptadecylcarbonyloxy group, etc., a substituent containing a silicon atom, a trimethylsilyl group, a (trimethylsilyl) methyl group. Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as benzonitrile, trimethylamine, triethylamine, and tributylamine. N, N-dimethylaniline, pyridine; amines such as 2,2'-pipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; chain unsaturated hydrocarbons such as ethylene, butadiene, 1 -Pentene, isoprene,
Examples of cyclic unsaturated hydrocarbons such as pentadiene, 1-hexene and derivatives thereof include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the covalent cross-link include methyl cross-link, dimethylmethylene cross-link, ethylene cross-link, dimethylsilylene cross-link, dimethylstannylene cross-link, and the like.

Specific examples of titanium compounds include tetramethoxy titanium, tetraethoxy titanium, titanium tetrachloride, titanium trichloride, cyclopentadienyltrimethyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl tripropyl titanium, 1 , 2-Dimethylcyclopentadienyl trimethyl titanium, pentamethyl cyclopentadienyl triethyl titanium, pentamethyl cyclopentadienyl tributyl titanium, cyclopentadienyl methyl titanium dichloride, pentamethyl cyclopentadienyl methyl titanium dichloride, cyclopentadi Phenyl dimethyl titanium monochloride; cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium triphenoxide, pentamethyl cyclopentadienyl titanium triethoxide Sid, pentamethylcyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethyl cyclopentadienyl titanium trichloride, pentamethyl cyclopentadienyl methoxy titanium dichloride, indenyl titanium trimethoxide, indenyl trimethyl Examples include titanium.

Of the transition metal compounds represented by the general formula (III), specific examples of zirconium compounds in which M ¹ is zirconium include dicyclopentadienyl zirconium dichloride, tetrabutoxy zirconium, zirconium tetrachloride, Tetraphenylzirconium, cyclopentadienylzirconium trimethoxide, pentamethylcyclopentadienyltribenzylzirconium, bisindenylzirconium dichloride, zirconium dibenzyldichloride, tributoxyzirconium chloride, triisopropoxyzirconium chloride,
(Pentamethylcyclopentadienyl) trimethylzirconium, (Pentamethylcyclopentadienyl) triphenylzirconium, (Cyclopentadienyl) trichlorozirconium, (Methylcyclopentadienyl) trichlorozirconium, (Methylcyclopentadienyl) Dimethyl (methoxy) zirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dihydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis ( Methylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) hydridomethylzirconium, ethylenebis ( Ndenyl) dimethyl zirconium, dimethyl silylene bis (cyclopentadienyl) dimethyl zirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9 -Fluorenyl)
Examples thereof include (cyclopentadienyl) dimethylzirconium, cyclobutyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, and dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium.

Specific examples of the hafnium compound include cyclopentadienyl hafnium trimethoxyimide, pentamethylcyclopentadienyl hafnium trimethoxyside, pentamethylcyclopentadienyl tribenzyl hafnium, hafnium dibenzyl dichloride, hafnium tetraoxide. , Dicyclopentadienyl hafnium dichloride and the like. Specific examples of vanadium include vanadium trichloride, vanadyl trichloride,
Vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopenta Dienyl vanadium dichloride, dicyclopentadienylmethyl vanadium and the like can be mentioned. Specific examples of the niobium compound include niobium pentachloride, tetrachloromethylniobium, dichlorotrimethylniobium, dicyclopentadienylniobium dichloride, dicyclopentadienylniobium trihydride, pentabtoxiniob, and the like. Specific examples of tantalum compounds include tantalum pentachloride, dichlorotrimethyltantalum, dicyclopentadienyltantalum trihydride, pentabtoxniobium, and the like, and specific examples of chromium compounds include chromium trichloride, tetrabutoxychromium, and tetramethyl. Examples include chromium, dicyclopentadienyl chromium, and dibenzene chromium.

Further, as other transition metal compounds,
It is possible to use the transition metal compound supported on a carrier such as a magnesium compound or a silicon compound,
It is also possible to use the above transition compound modified with an electron donating compound. Particularly preferable among these transition metal compounds are titanium compounds and zirconium compounds. For the catalyst (a), aluminoxane (b) is used together with the transition metal compound (a). This aluminoxane is obtained by contacting an organoaluminum compound with a condensing agent, and has the general formula (IV)

[0035]

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[In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, and p represents a number of 0 to 50, preferably 5 to 30. ] Chain aluminoxane represented by the general formula (V)

[0037]

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[Wherein R ³ is the same as above and q is 2
-50, preferably 5-30. ] Cyclic aluminoxane represented by Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, etc. Among them, trimethylaluminum is preferable. Further, as the condensing agent, water can be mentioned as a typical one, but in addition to this, various substances such as trialkylaluminum that undergoes a condensation reaction, such as copper sulfate pentahydrate, water adsorbed to inorganic or organic substances, etc. There are things.

Generally, the contact product of an organoaluminum compound such as trialkylaluminum with water is a mixture of unreacted trialkylaluminum and various condensation products together with the above-mentioned chain alkylaminoxane and cyclic alkylaluminoxane, Furthermore, these are molecules intricately associated with each other, and various products are formed depending on the contact conditions of these trialkylaluminums and water as a condensing agent. At this time, the method of contacting the alkylaluminum compound and water is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization and water is added later, and further, a metal salt is contained. There is a method of reacting water of crystallization, water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound. The water may contain up to about 20% of ammonia, amine such as ethylamine, sulfur compound such as hydrogen sulfide, phosphorus compound such as phosphite. Although this reaction proceeds in the absence of a solvent, it is preferably carried out in a solvent, and suitable solvents include aliphatic hydrocarbons such as hexane, heptane, and decane, or aromatic hydrocarbons such as benzene, toluene, and xylene. Can be mentioned.

This aluminoxane (for example, alkylaluminoxane), after the above-mentioned catalytic reaction, when a hydrous compound or the like is used, the solid residue is filtered off, and the filtrate is heated under normal pressure or reduced pressure at a temperature of 30 to 200 ° C. Preferably 40-150 ℃
What was heat-treated while distilling off the solvent at the temperature of 20 minutes to 8 hours, preferably 30 minutes to 5 hours is preferable. In this heat treatment, the temperature may be appropriately determined according to various situations, but it is usually performed in the above range. Generally, 30 ° C
If the temperature is less than 200 ° C., the effect is not exhibited, and if it exceeds 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, which is not preferable. Then, the reaction product is obtained as a colorless solid or a solution state depending on the treatment conditions of the heat treatment. The product thus obtained can be used as a catalyst solution after being diluted with a hydrocarbon solvent, if necessary.

A suitable example of an aluminoxane, particularly an alkylaluminoxane, which is a contact product of an organoaluminum compound used as such a catalyst component and a condensing agent is aluminum observed in a proton nuclear magnetic resonance spectrum.
-The high magnetic field component in the methyl proton signal region based on the methyl group (Al-CH ₃ ) bond is 50% or less.
That is, when the proton nuclear magnetic field resonance ( ¹ H-NMR) spectrum of the above contact product is observed in a toluene solvent at room temperature, the methyl proton signal based on “Al—CH ₃ ” is a tetramethylsilane (TMS) standard. At 1.0 to −0.5 pp
Found in the m range. TMS proton signal (0pp
Since m) is in the methyl protons observation area based on the "Al-CH _3", the methyl proton signal based on the "Al-CH _3", a high magnetic field is measured based on the methyl proton signal 2.35ppm toluene in TMS standard Component (i.e., -0.1
~ -0.5ppm) and other magnetic field components (ie 1.0-0.1ppm)
When the high magnetic field component is 50% or less, preferably 45 to 5%, the high magnetic field component can be suitably used as the catalyst component.

As the (b) catalyst, a compound capable of reacting with the (c) transition metal compound to form an ionic complex is used together with the (a) transition metal compound. The compound is not particularly limited, but the compound consisting of a cation and an anion in which a plurality of groups are bound to an element, that is, the compound (c) is IIIB group, VB group, VIB group, VIIB group, VII group of the periodic table.
A cation containing an element selected from Group I, Group IA, Group IB, Group IIA, Group IIB, Group IVA, and Group VIIA, and multiple groups of VB in the periodic table
Tribe, VIB, VIIB, VIII, IB, IIB, IIIA, IV
A compound composed of an anion bonded to an element selected from Group A and Group VA, particularly a coordination complex compound composed of a cation and an anion bonded to an element of a plurality of groups can be preferably used. For example, general formula (VI) or (VII) ([L ¹ −R ⁴ ] ^{u +} ) _V ([M ² Z ¹ Z ²・ ・ ・ Z ^e ) ^(ef)- ) _W (VI) or ([L ² ] ^{u +} ) _V ([M ³ Z ¹ Z ²・ ・ ・ Z ^e ) ^(ef)- ) _W (VII) (However, L ² is M ⁴ , R ⁵ R ⁶ M ⁵ , R ⁷ ₃ M ⁵ or R ⁸ M ⁵ is a) wherein, L ¹ is a Lewis base, VB group M ² and M ³ are each the periodic table, VIB group, VIIB group, VIII group, IB group, IIB group, II
Elements selected from IA group, IVA group and V group, M ⁴ and M ⁵ are IIIB group, IV group, V group, VIB group and VIIB of the periodic table, respectively.
An element selected from Group I, Group VIII, Group I, Group IB, Group IIA, Group IIB and Group VIIA, Z ^{1 to} Z ^e are each a hydrogen atom, a dialkylamino group, an alkoxy group, an alkoxy group having 1 to 20 carbon atoms, Aryloxy group having 6 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, carbon number 1-20 acyloxy group, organometalloid group or halogen atom, Z ¹ to Z ^e may form a ring of two or more thereof with each other. R ⁴
Is hydrogen atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Represents an aryl group, an alkylaryl group or an arylalkyl group, wherein R ⁵ and R ⁶ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ⁷ is an alkyl group having 1 to 20 carbon atoms. Represents a group, an aryl group, an alkylaryl group or an arylalkyl group. R ⁸ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. f is the valence of M ² and M ³ , an integer of 1 to 7, e is an integer of 2 to 8, and u is [L ¹ −
The ionic valences of R ⁴ ] and [L ² ] are integers of 1 to 7, v is an integer of 1 or more, and w = (v × u) / (ef). ] It is a compound represented by these.

Specific examples of the Lewis base represented by L ¹ include amines such as ammonia, methylamine, aniline, dimethylamine, diethylamine, diphenylamine, trimethylamine, triethylamine, N, N-dimethylaniline and phenanthroline. , Phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran dioxane, thioethers such as diethylthioether and tetrahydrothiophene, esters such as ethylbenzoate, acetonitrile, benzo Examples thereof include nitriles such as nitrile.

Specific examples of M ² and M ³ include B,
Specific examples of M ⁴ , such as Al, Si, P, As, and Sb, include Li and N.
Specific examples of M ⁵ , such as a, Ag, Cu, Br, I, and I ₃ , include M
Examples include n, Fe, Co, Ni and Zn. Specific examples of Z ^{1 to} Z ^e include, for example, a dimethylamino group and a diethylamino group as the dialkylamino group; a methoxy group, an ethoxy group, an n-butoxy group, and a carbon number of 6 to 20 as the alkoxy group having 1 to 20 carbon atoms. Phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as the aryloxy group, and methyl group, ethyl group as the alkyl group having 1 to 20 carbon atoms,
n-propyl group, iso-propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms, phenyl group as alkylaryl group or arylalkyl group, p-tolyl group, Benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4- Dimethylphenyl group, 2,3-dimethylphenyl group, 1,2-dimethylphenyl group, p-as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms
Fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group,
Pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, halogen atoms such as F, C, I, Br,
I: Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron group. Specific examples of R ⁴ and R ⁷ are the same as those mentioned above. Specific examples of the substituted cyclopentadienyl group for R ⁵ and R ⁶ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. To be Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected by an integer of 1 to 4.

Among the compounds represented by the above general formulas (VI) and (VII), those in which M ² and M ³ are boron are preferable. Among the compounds of the general formulas (VI) and (VII), the following compounds can be used particularly preferably. For example, as the compound of the general formula (VI), triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, tetraphenylborate Methyltriphenylammonium borate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, trimethylsulfonium tetraphenylborate, triphenylammonium tetra (pentafluorophenyl) borate, tetraethyl tetra (pentafluorophenyl) borate Ammonium, methyl diphenylammonium tetra (pentafluorophenyl) borate, tetra (pentane) Motor-fluorophenyl) borate dimethyl diphenyl ammonium, tetra (pentafluorophenyl) borate dimethylanilinium tetra (pentafluorophenyl methyl)
Dimethyl borate (p-bromoanilinium), tetra (pentafluorophenyl) pyridinium borate, tetra (pentafluorophenyl) borate (N-benzylpyridinium), tetra (pentafluorophenyl) borate benzyldimethylsulfonium, tetra (pentafluorophenyl) Examples thereof include tetrafelphosphonium borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, and triethylammonium hexafluoroarsenate.

On the other hand, as the compound of the general formula (VII),
Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, decamethylferrocenium tetra (pentafluorophenyl) borate, formylferrocenium tetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, tetra (Pentafluorophenyl) sodium borate, tetra
Examples thereof include (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate, and silver hexafluoroantimonate. And as compounds other than the general formulas (VI) and (VII), for example, tri (pentafluorophenyl) boric acid, tri [3,5-di (trifluoromethyl) phenyl] boric acid, triphenylboric acid, etc. are also used. be able to.

In the present invention, an organometallic compound may be used as the component (d) together with the catalyst (a) or the catalyst (b), if desired. Examples of the (d) organometallic compound which is optionally used in combination include compounds represented by the general formula (VI
II) The compound represented by M ⁶ (R ⁹ ) _r (VIII) is used. In this general formula (VIII), R ⁹ is an alkyl group having 1 to 20 carbon atoms and 2 carbon atoms.
A alkenyl group having 20 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, for example, a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group,
Examples thereof include i-butyl group, hexyl group, 2-ethylhexyl group and phenyl group. M ⁶ represents lithium, sodium, potassium, magnesium, zinc, cadmium, aluminum, boron, gallium, silicon or tin. Further, r represents the valence of M ⁶ . General formula (V
There are various compounds represented by III).
Specifically, alkyllithium compounds such as methyllithium, ethyllithium, propyllithium, and butyllithium, alkylmagnesium compounds such as diethylmagnesium, ethylbutylmagnesium, dinormalbutylmagnesium, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc. Dialkyl zinc compounds, such as
Examples thereof include alkylgallium compounds such as trimethylgallium, triethylgallium and tripropylgallium, alkylboron compounds such as triethylboron, tripropylboron and tributylboron, and alkyltin compounds such as tetraethyltin, tetrapropyltin and tetraphenyltin. Further, there are various compounds when M ⁶ is aluminum. Specific examples thereof include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum and trioctylaluminum.

The proportion of each component used in the catalyst is not particularly limited, but in the catalyst (a),
The molar ratio of component (a) to component (b) is 1:20 to 1: 1000.
Both components may be used in an amount of 0, preferably 1: 100 to 1: 2000. On the other hand, in (b) catalyst, (a)
It is preferable to use both components so that the molar ratio of the component to the component (c) is 1: 0.01 to 1: 100, preferably 1: 1 to 1:10. In this ratio, the component (a) and the component (c) may be contacted in advance and the contact-treated product may be separated and washed before use, or may be contacted in the polymerization system. In the catalyst (a) or the catalyst (b), the amount of the component (d) used as desired is usually 0 to 1 mol of the component (a).
It is selected in the range of 100 mol. By using this component (d), the polymerization activity can be improved, but even if it is used in too large an amount, the effect equivalent to the amount added is not exhibited. The component (d) may be used by contacting it with a contact-treated product of the component (a), the component (c) or the component (a) and the component (c). This contact may be made in advance,
It may be added to the polymerization system one after another and contacted. Further, the use ratio of the styrene-based monomer and the catalyst is not particularly limited, but usually the styrene-based monomer / transition metal compound molar ratio is in the range of 10 to 10 ⁹ , preferably 10 ² to 10 ⁷ . Chosen to be.

To produce the styrenic polymer of the present invention, the styrenic monomer is first polymerized in the presence of any of the above catalysts. At this time, the polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent, etc. may be appropriately selected. Usually, the polymerization is carried out at a temperature of −50 to 200 ° C., preferably 30 to 100 ° C. for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in the solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane, and octane may be used alone or in combination. It can be used in combination.
In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. In addition, the molecular weight control and composition control of the polymer are
It may be performed by a commonly used method. The molecular weight can be controlled by, for example, hydrogen, temperature, monomer concentration and the like.

The molecular weight of the SPS film of the present invention is not limited as long as it is formed, but the weight average molecular weight is preferably 10,000 to 3,000,000, and particularly preferably 3000.
Those of 0 to 150,000 are preferable. The molecular weight distribution (number average molecular weight / weight average molecular weight) at this time is preferably 1.5 to 8. This molecular weight distribution can be adjusted by mixing different molecular weights.

Further, to the extent that the effects of the present invention are not impaired,
It does not matter to copolymerize another monomer copolymerizable therewith.

<< Example of Polymerization >> SP according to JP-A-3-31843
S pellets were made. The process from the adjustment of the catalyst to the polymerization reaction was carried out under a stream of dry argon. Copper sulphate pentahydrate (CuSO ₄ / 5H ₂ O) 17.8 g (71
(mmol) Purified benzene (200 ml) and trimethylaluminum (24 ml) were added, and the mixture was stirred at 40 ° C for 8 hours to adjust the catalyst. This was filtered through a No. 3 glass filter under an argon stream, and the filtrate was freeze-dried. Take this out, 2l
The mixture was placed in a stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein and heated to 90 ° C.

1 liter of purified styrene was put into this, and the polymerization reaction was continued at this temperature for 8 hours. Thereafter, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added with further stirring to deactivate the catalyst. The contents were gradually dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and then dried. This was pelletized with an extruder and then dried at 130 ° C.

The SPS film of the present invention is preferably SPS made of styrene alone, but as a film further containing SPS, a styrene-based polymer having an isotactic structure in which the main chain is a meso chain is added to SPS. The crystallization rate can be controlled by mixing the combined (IPS) (forming a so-called stereo complex), and a stronger film can be obtained.

When SPS and IPS are mixed, the ratio depends on the high stereoregularity of each other, but from 30:70 to
99: 1, preferably 50:50 to 98: 2.

The film may contain inorganic fine particles, an antioxidant, a UV absorber, an antistatic agent, a dye and the like for the purpose of imparting functionality within a range not impeding the object of the present invention.

As the polyester resin laminated on both sides of the SPS film of the present invention, any polyester resin in which dicarboxylic acid and glycol are condensed can be used.

The dicarboxylic acid component of the polyester resin according to the present invention includes terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid (for example, naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,
7-dicarboxylic acid, etc.), sulfoisophthalic acid (eg 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, etc.), 1,1′-
Diphenylethane-4,4'-dicarboxylic acid, diphenyl ether-4,4-dicarboxylic acid, 1,1'-diphenyl sulfone-
4,4'-dicarboxylic acid, 1,1'-diphenyl ketone-4,4'-
Dicarboxylic acid, adipic acid, sebacic acid, maleic acid,
Although fumaric acid, 1,4-cyclohexyldicarboxylic acid and the like can be mentioned, terephthalic acid, naphthalene dicarboxylic acid and sulfoisophthalic acid are preferable.

Examples of the glycol component of the polyester resin according to the present invention include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (for example, a polymerization degree of 4 to 6,000), polypropylene glycol (for example, a polymerization degree of 2 to 2). 5,000), cyclohexanedimethanol, hydroquinone, resorcin, 2,2-bis (4-hydroxyphenyl) propane, 1,4-dihydroxymethylbenzene and the like, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, Polyethylene glycol is preferred.

Polyester resins obtained from these dicarboxylic acids and glycols have a low glass transition point (for example, -20 to 40 ° C) and a high glass transition point (for example, 40 to 40 ° C).
120 ° C), and higher one is preferable. When laminating a polyester resin having a low glass transition point with SPS, it is better that the thickness of the polyester resin layer is thin, 0.5-1
0 μm is suitable, and preferably 1 to 5 μm. When the glass transition point is high, the film thickness of the polyester resin layer is appropriately 1 to 50 μm, preferably 5 to 20 μm.

The properties of these polyester resins with respect to water, for example, the degree of hydrophilicity also differ. The more hydrophilic polyester resin reduces the film thickness to 0.5-10 μm.
Is suitable, and preferably 1 to 5 μm. In the case of a more hydrophobic polyester resin, 1 to 50 μm is suitable, and 5 to 20 μm is preferable.

The polyester resin constituting the laminated structure with SPS of the present invention has a higher glass transition point (preferably 50 ° C. or higher), is hydrophobic and has low water absorption (water vapor permeability is preferably 30 g / m ⁻² (24 h / 0.1 mm) or less) and a high tensile elastic modulus (preferably 400 kg / mm ² or more as a film). The reason for this is by stacking
This is because it does not affect the properties of the SPS film. From this point of view, as the polyester resin constituting the laminate, PET or polyethylene naphthalate, especially polyethylene-2,6-naphthalate (hereinafter PE
(Abbreviated as N) is more preferable. Commercially available PET resins and PEN resins can be used, but photographic grade resins are preferably used.

The polyethylene naphthalate resin (PEN) according to the present invention is obtained by condensing a naphthalene polycarboxylic acid as a dicarboxylic acid component and a glycol component. As the naphthalene component, naphthalene having two carboxyl groups is preferable, and among them, naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid and the like are preferable.
Further, the glycol component is preferably the above-mentioned one.

Among the polyester resins constituting the laminated structure with the SPS resin of the present invention, hydrophilic ones having a glass transition point of 50 ° C. or more and a tensile elastic modulus of 30 as a film.
It is preferably 0 kg / mm ² or more, and a dicarboxylic acid and glycol selected from terephthalic acid, naphthalene-2,6-dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid and ethylene glycol, and polyethylene glycol (polymerization degree 5 to 3,000). A modified polyester consisting of is suitable. A modified polyester composed of terephthalic acid, 5-sodium sulfoisophthalic acid, ethylene glycol and polyethylene glycol is particularly preferable.

The SPS and polyester laminating method of the present invention will be described. Preferred examples are SPS resin and PET
A method of laminating with a resin will be described.

The lamination method according to the present invention comprises a PET resin and
SPS resin is dried in two separate vacuum dryers, three separate extruders with two PET resins, one with SPS
After the resin is charged, melted and extruded, each molten resin is introduced into one conduit so that the upper, middle, lower, and three layers are formed, and three layers of molten resin form a laminar flow in the conduit to form one layer. Extruded from the extrusion die of a die with slits onto a cooling drum to form one unstretched sheet or, alternatively, three melted polymers are introduced into one die to create three separate slits. From the extrusion die that it has, or from the extrusion die that allows three slits to be combined into one slit in the die, extrude the three laminar layers onto the cooling drum to form one sheet. After being formed and cooled and solidified on a cooling drum to obtain an unstretched film, it is longitudinally stretched by a longitudinal stretching machine, then laterally stretched by a horizontal stretching machine, and then heat-set in the same machine. Biaxially stretched film heat set in the zone A method of laminating a molten state that is a useful method for the present invention. As another method, another position film forming method in which three kinds of molten polymers are separately extruded onto a cooling drum and cooled and solidified is also useful in the present invention. These are also called coextrusion methods.

In addition to this, there is a method of laminating and laminating an SPS film and two PET films which are separately formed. That is, SPS and PET are separately formed into an unstretched film or a uniaxially stretched film, and after coating them with an anchor agent, an adhesive, etc., these films are laminated and laminated, and then biaxially stretched and heat-treated. It is a method of fixing. However, this method is not practical in terms of quality because the process is complicated, the equipment cost is too high, and the coextrusion method is preferable because of its simplicity.

The temperature at which the SPS resin and the polyester resin (eg PET) in the coextrusion method are melted in the extruder is 26.
A range of 0 to 340 ° C is used. Preferably, the core SPS resin and the outer layer PET resin melt at 280 to 330 ° C. at the same temperature.

The stretching conditions of the laminated film according to the present invention are not particularly limited, but generally the glass transition temperature (Tg)
The high temperature resin is biaxially stretched in the temperature range of Tg to Tg + 100 ° C. At this time, the following methods A, B, and C can be adopted in the same manner as the stretching method of the polyethylene terephthalate layer. The stretching ratio is preferably in the range of 4 to 16 times in area ratio. The heat setting can be performed in the temperature range of 150 to 250 ° C.

(A) A method in which an unstretched sheet is first stretched in the longitudinal direction and then stretched in the transverse direction (B) A method in which an unstretched sheet is stretched in the transverse direction first and then in the longitudinal direction (C) Unstretched A method in which a sheet is stretched in the longitudinal direction in one or multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction.

The term "polyester layer" as used herein means
A film having a certain thickness of a resin as a support, which is distinguished from layers such as an undercoat layer, an antistatic layer, an emulsion layer and a back layer.

The total thickness of the laminated structure film according to the present invention is not particularly limited and can be arbitrarily determined according to the application, but is usually 40 to 250 μm, and particularly preferably 65 to 180 μm.

In the polyester layer of the present invention, calcium carbonate, titanium oxide, silicon dioxide, kaolin and the like may be blended to such an extent that the transparency is not impaired in order to improve the slipperiness of the obtained film.

The laminated structure, which is a feature of the present invention, has a high degree of dimensional stability comparable to that of an SPS film, and a polyester layer on which a subbing layer for adhering a photographic photosensitive layer can be easily provided for photographic support. To have on the surface layer of the body. Therefore, all the undercoating techniques for polyester, especially PET film, can be applied to the photographic support of the present invention.

The subbing on PET can be carried out in any of the processes before stretching during film formation, after uniaxial stretching, after biaxial stretching and before heat setting, or after biaxial stretching and heat setting. PET
Oriented crystallization is completed after heat setting after biaxial stretching,
It becomes relatively difficult for an upper object such as an emulsion layer to adhere. Therefore,
An undercoating agent is generally applied before the completion of oriented crystals. In order to apply the undercoating agent before heat setting, the following known undercoating agents and undercoating methods can be used. For example, US Pat.
852,378, 358,608, 3,630,741, 2,62
7,088, 2,698,235, JP-A-51-135991, JP-B-5
2-48312, Belgian Patent Nos. 721,469, 742,769 and the like, vinyl halogenoester-containing copolymers or vinylhalogenoester-containing copolymers and vinyl chloride and / or vinylidene chloride-containing copolymers, JP-B-58
-58661, JP-B-58-55497, JP-A-52-108114, copolymers containing diolefins as monomers,
61-204242, Acrylic polymers described in JP-A-61-204241, JP-B-57-971, JP-A-61-204240, JP-A-60-2482
31, polyester-based polymers described in JP-A-3-265624 and the like can be mentioned.

After the biaxially stretched heat setting, the undercoating is applied by an organic solvent-based undercoating method or a so-called etching solvent (eg, phenol, cresol, resorcin, hydrate) for etching PET to bond the undercoating material by the anchoring effect. There is also a method of applying an organic solvent-based or water-based undercoat liquid containing chloral, chlorophenol, etc.). This is because PET has a regular structure that is difficult to adhere, and this surface structure is loose or chemically changed. For this purpose, surface activation treatment such as mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone treatment and the like is preferable. Good adhesive strength can be obtained by directly coating the photographic emulsion after the above treatment, but in order to further strengthen the adhesive strength, a further subbing layer may be provided and a photographic emulsion layer may be formed on the undercoating layer. A good film is obtained. Even with a water-based undercoating agent, the adhesiveness can be easily improved by utilizing the above various treatments as a pretreatment. For example, a quaternary copolymer latex composed of n-butyl methacrylate: t-butyl methacrylate, styrene and 2-hydroxyethyl methacrylate according to the method described in JP-A-55-67745, JP-A-59-19941 and the like, an interface Adhesion is achieved by coating with an aqueous subbing solution consisting of an activator and a curing agent, drying, then corona discharge treatment again, and then applying an aqueous gelatin solution such as an antihalation layer or emulsion layer to the photographic emulsion layer side. A photosensitive material having good properties can be obtained. Further, on the opposite side of the antistatic layer, after the same treatment or undercoat layer is applied, the antistatic composition is directly applied, and the antistatic layer binder such as cellulose diacetate is applied in advance and then the antistatic composition is applied. A desired photographic light-sensitive material can be finished by applying the product as an organic solvent system liquid.

It is preferable to provide a hydrophilic binder layer called the second undercoat layer on the undercoat layer in order to strengthen the adhesion of the photosensitive layer and the like.

The second subbing layer is preferably a hydrophilic resin layer which sticks well to the photographic emulsion layer. As the binder constituting the hydrophilic resin layer, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethyl cellulose, hydroxyethyl cellulose,
Examples thereof include water-soluble polymers such as the following, a combination of a poly (thrylene sulfonic acid sodium copolymer) and a hydrophobic latex, and gelatin is preferable.

It is preferable to increase the film strength by using a hardening agent in this layer. Examples of such hardening agents include aldehyde type, aziridine type, isoxazole type, epoxy type, vinyl sulfone type, Acryloyl-based, carbodiimide-based, triazine-based, polymer-based, other maleimide-based, acetylene-based, and methanesulfonic acid ester-based hardening agents can be used alone or in combination.

The second subbing layer preferably contains inorganic fine particles such as silicon dioxide and titanium dioxide, and an organic matting material (1 to 10 μm) such as polymethylmethacrylate. In addition to this, if necessary, various additives, for example,
Antistatic agents, antihalation agents, coloring dyes, pigments,
A coating aid can be included.

Among these, it is preferable to include an antistatic agent. Preferred antistatic agents include non-photosensitive conductors and / or semiconductor fine particles.

The non-photosensitive conductor and / or semiconductor fine particles used in the present invention are those exhibiting conductivity due to charge carriers existing in the particles, such as cations, anions, electrons and holes. It may be an organic material, an inorganic material, or a composite material of both. Preferably, it is a compound exhibiting electronic conductivity, and organic materials include polymer fine particles such as polyaniline, polypyrrole, and polyacetylene, and inorganic materials include oxygen-deficient oxides, metal-excess oxides, and metal-deficiency. Examples thereof include metal oxide fine particles that easily form nonstoichiometric compounds such as oxides and oxygen-excess oxides. If it is a charge transfer complex or an organic-inorganic composite material, a phosphazene metal complex or the like can be mentioned. Among these, the most preferable compound for the present invention is metal oxide fine particles which can be manufactured by various methods. Further, in the present invention, a conductor having a volume resistivity of 10 ³ Ω · cm or less is defined as a conductor and a semiconductor having a volume resistivity of 10 ¹² Ω · cm or less is defined as a conductor and a semiconductor, respectively.

A preferred method for producing conductive fine particles will be exemplified below.

(Preparation of Semiconductor Fine Particle Solution) 65 g of stannic chloride hydrate was dissolved in 2000 cc of water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The formed precipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed, and after confirming that there is no reaction with chloride ions, 1000 ccwo of distilled water is added to bring the total volume to 2000 cc. further
40 cc of 30% aqueous ammonia was added and heated in a water bath to obtain a colloidal gel dispersion. This colloidal gel dispersion is designated as dispersion A-1.

The coating liquid concentration of the undercoat layer composition is usually 20% by weight or less, preferably 15% by weight or less. The coating amount is preferably 1 to 30 g, and more preferably 5 to 20 g in terms of coating liquid weight per 1 m ² of the film.

As a coating method, various known methods can be applied. For example, a roll coating method, a gravure roll coating method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method, a curtain coating method or the like can be applied alone or in combination.

In the laminated film of the present invention, various photosensitive materials can be produced by providing at least one photosensitive hydrophilic colloid layer above the subbing layer, for example, at least one silver halide emulsion layer. The photographic light-sensitive material provided may be mentioned.

The light-sensitive material of the present invention is for radiography,
It can be used for various purposes such as printing plate making, general photography, and direct viewing.

The crystal form of silver halide used in the light-sensitive material of the present invention may be any of a tetradecahedron, an octahedron, an irregular plate and a cubic crystal, and a high-sensitivity tabular grain or a high-hardness cubic crystal grain is preferable. The silver halide composition is AgBr, AgC
l, AgClBr, AgClBrI, AgBrI, AgClBrI, etc. can be arbitrarily used, but for high speed emulsions, AgBr rich AgBrI
Is preferred. For rapid processing, a silver chloroiodobromide emulsion rich in AgCl and low in iodine is preferable. When used as a medical sensitive material, the silver halide grain size is preferably 0.01 μm to 1 μm,
0.05μ to 0.5μ is commonly used. 0.05μ for printing materials
~ 0.2μ is often used.

Tabular grains are described in US Pat. No. 4,439,520,
No. 4,425,425, No. 4,414,304 and the like, the intended tabular grains can be easily obtained. The tabular grains can be formed by epitaxially growing silver halide having a different composition on a specific surface site or by shelling. Further, in order to control the photosensitive nuclei, it is preferable to provide a transition line on the surface or inside of the tabular grains. In order to have a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodide ions.

When tabular grains are used in the present invention, the tabular grains are preferably 50% or more of the total projected area of all grains of the emulsion layer in which the tabular grains are used or have an aspect ratio of 2 or more. . In particular, the proportion of tabular grains is 60% to 70%,
It is more preferable to increase to 80%. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of tabular grains and the distance between two parallel planes. In the case of medical sensitive material, the aspect ratio is preferably 3 or more and less than 20, and in the case of printing sensitive material, the aspect ratio is preferably 1.5 to 8.
For the tabular grains rich in silver chloride component, the method described in US Pat. No. 5,320,938 can be referred to.

The presence of 0.001 mol% or more and less than 10% high silver iodide sites or the presence of silver nuclei in the silver halide grains is preferable for improving the pressure resistance of the grains. The larger the aspect ratio, the flatter the plate. The preferred thickness of tabular grains is
Although it becomes 0.01 to 0.5 μ, it can be arbitrarily selected by setting the aspect ratio and the average volume particle diameter. The distribution of tabular grain diameters is a coefficient of variation that is often used (a value S / the standard deviation S when the projected area is approximated by a circle divided by the diameter D /
It is preferably a monodisperse emulsion having 100% of D) of 30% or less, particularly 20% or less. Further, two or more kinds of tabular grains and normal crystal grains can be mixed. For the preparation of particles, an acidic method, an intermediate method, an ammonia method, or the like can be appropriately selected.
When the metal is doped, it is particularly preferable to form particles under acidic conditions of pH 2-4.

In order to control grain growth during formation of tabular grains, it is possible to use, for example, ammonia, thioethers, thiourea compounds and thione compounds as silver halide solvents. As a thioether compound, 3,6,9,15,18,21-hexoxa-12-thiatricosane, 3,9,15-trioxa-6,12-dithiaheptadecane described in German Patent No. 1,147,845; 1 , 17-Dioxy-3,9-15-trioxa-6,12-dithiaheptadecane-4,14-dione; 1,20-dioxy-3,9,12,18-
Tetroxa-6,15, -dithiaeicosan-4,17-dione; 7,1
0-dioxa 4,13-dithiahexadecane-2,15-dicarboxamide. Oxathioether compounds described in JP-A-56-94347 and JP-A-1-121847, JP-A-63-259653
No. 63-301939, and cyclic oxathioether compounds. Especially as thiourea, JP-A-53-824
Those described in No. 08 specification are useful. Specifically, tetramethylthiourea, tetraethylthiourea,
Dimethylpiperidinothiourea, dimorpholinothiourea;
1,3-dimethylimidazole-2-thione; 1,3-dimethylimidazole-4-phenyl-2-thione; tetrapropylthiourea and the like.

Further, during physical aging or chemical aging, zinc,
Metal salts such as lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can be made to coexist. Doping iridium in an amount of 10 ^-9 to 10 ^-3 mol per mol of silver halide in order to obtain a high illuminance property, and similarly doping rhodium to obtain a high-contrast emulsion with γ = 10 or more, is to use silver halide. Commonly used in emulsions. Ruthenium, osmium and rhenium doping can be used instead of rhodium doping. The ruthenium, osmium and rhenium compounds are preferably added during the formation of silver halide grains. As the addition position, there are a method of uniformly distributing in the particles, and a method of forming a core-shell structure and localizing a lot in the core portion or the shell portion. It is often better to have more in the shell. In addition, a method of increasing the existing amount may be used as it is continuously outside the particles, in addition to localizing in a discontinuous layer structure. The addition amount can be appropriately selected within the range of 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide.

Specific examples of the compound used are shown below, but the invention is not limited thereto.

[Ru (NO) Cl ₅ ] ^-2 , [Ru (NO) Br ₅ ] ^-2 [Ru (NO) I ₅ ] ^-2 , [Ru (NO) F ₅ ] ^-2 [Ru (CN) Cl ₅ ] ^-2 , [Ru (CN) Br ₅ ] ^-2 [Ru (CN) I ₅ ] ^-2 , [Ru (CN) F ₅ ] ^-2 [Ru (SCN) Cl ₅ ] ^-2 , [Ru (SCN) Br ₅ ] ^-2 [Ru (SCN) I ₅ ] ^-2 , [Ru (SCN) F ₅ ] ^-2 [Ru (SeCN) Cl ₅ ] ^-2 , [Ru (SeCN) Br ₅ ] ^-2 [Ru (SeCN) I ₅ ] ^-2 , [Ru (SeCN) F ₅ ] ^-2 [Ru (TeCN) Cl ₅ ] ^-2 , [Ru (TeCN) Br ₅ ] ^-2 [Ru (TeCN) I ₅ ] ^-2 , [Ru (TeCN) F ₅ ] ^-2 [Ru (CO) Cl ₅ ] ^-2 , [Ru (CO) Br ₅ ] ^-2 [Ru (CO) I ₅ ] ^-2 , [Ru (CO) F ₅ ] ^-2 [Ru (NH ₃ ) Cl ₅ ] ^-2 , [Ru (NH ₃ ) Br ₅ ] ^-2 [Ru (NH ₃ ) I ₅ ] ^-2 , [Ru (NH ₃ ) F ₅ ] ^{- 2} [RuCl _6] ^-2, [RuBr _6] ^-2 [RuI _6] ^-2, [RuF _6] ^-2 _{[Ru (NO) Cl 2 (H} 2 O) 2 ] ^-1, [Ru (NO) Br ₂ (H ₂ O) ₂ ] ^-1 [Ru (NO) F ₂ (H ₂ O) ₂ ] ^-1 , [Ru (NO) I ₂ (H ₂ O) ₂ ] ^-1 [Ru (NO) Cl ₄ (CN)] ^-2, _{[Ru (NO) Br 4 (SCN} ) ] ^-2 _{[Ru (NO) Cl 4 (SeCN} ) ] ^-2, _{[Ru (NO) Br 4 (SeCN} ) ] ^-2 _{Ru (NO) Cl 3 (CN} ) 2 ] ^-2, _{[Ru (NO) Br 3 (CN} ) 2 ] ^-2 [Ru (NO) Cl _5] ^-4, [Ru (NO) Br _5] ^-4 [ Ru (NO) I ₅ ] ^-4 , [Ru (NO) F ₅ ] ^-4 [Ru (CN) Cl ₅ ] ^-4 , [Ru (CN) Br ₅ ] ^-4 [Ru (CN) I ₅ ] ^{- 4} , [Ru (CN) F ₅ ] ^-4 [Ru (SCN) Cl ₅ ] ^-4 , [Ru (SCN) Br ₅ ] ^-4 [Ru (SCN) I ₅ ] ^-4 , [Ru (SCN) F _5] ^-4 [Ru (SeCN) Cl _5] ^-4, [Ru (SeCN) Br _5] ^-4 [Ru (SeCN) I _5] ^-4, [Ru (SeCN) F _5] ^-4 [Ru (TeCN ) Cl ₅ ] ^-4 , [Ru (TeCN) Br ₅ ] ^-4 [Ru (TeCN) I ₅ ] ^-4 , [Ru (TeCN) F ₅ ] ^-4 [Ru (CO) Cl ₅ ] ^-4 , [ Ru (CO) Br ₅ ] ^-4 [Ru (CO) I ₅ ] ^-4 , [Ru (CO) F ₅ ] ^-4 [Ru (NH ₃ ) Cl ₅ ] ^-4 , [Ru (NH ₃ ) Br ₅ ] ^-4 [Ru (NH ₃₎ I _5] ^-4, [Ru (NH ₃₎ F _5] ^-4 [RuCl _6] ^-4, [RuBr _6] ^-4 [RuI _6] ^-4, [RuF _6] ^-4 [Ru (NO) Cl ₄ (CN)] ^-4 , [Ru (NO) Cl ₄ (SCN)] ^-4 [Ru (NO) Cl ₄ (SeCN)] ^-4 , [Ru (NO) Br ₄ (SeCN)] ^-4 _{[Ru (NO) Cl 3 (CN} ) 2 ] ^-4 _{[Ru (NO) Br 3 (CN} ) 2 ] ^-4 [Ru (NH _{3) 6]} Cl _3, [Ru (NH ₃ ) ₆ ] Br ₃ For other metals such as osmium and rhenium, as well as rhodium, iridium, palladium and platinum, the Ru part is replaced by Os.
I omit it because it can be expressed by substituting with Re, Rh, Ir, Pa, Pt, but the hexadentate transition metal compound is disclosed in JP-A Nos. 2-2082, 2-20853, and 2-20854. , Ibid 2-2085
No. 5 specification can be referred to. As the alkali complex salt, general sodium salt and potassium salt can be selected, but in addition to this, primary, secondary, and tertiary amine salts may be used. For example, K ₂ [RuCl ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₄ [Ru ₂
Cl ₁₀ O] XH ₂ O, K ₂ [RuCl ₅ (H ₂ O)], etc.

The silver halide can be sensitized with a noble metal salt such as a sulfur compound or a gold salt. Further, selenium sensitization or reduction sensitization can be performed, and these methods can be combined for sensitization. When sensitizing with a noble metal salt, the presence of a sensitizing dye described below can enhance the sensitizing effect. When these are added to the emulsion, the sensitizing effect can be further enhanced by adding them in the form of fine particles and dispersing them. When AgI fine particles are dispersed and added at the time of chemical sensitization, AgI is formed on the particle surface, and the effect of dye sensitization can be enhanced. When forming tabular grains AgI, the contribution of the transition line portion ranging from 0 to 1000 is often utilized.

As the sensitizing dye, cyanine, carbocyanine, merocyanine, hemicyanine, etc. are used.
As the merocyanine, those having an oxazole ring and a thiohydantoin ring of JP-B-4-73860 are preferable.

The above silver halide is applied by being dispersed in a hydrophilic colloid medium, for example, gelatin.

Crosslinking of hydrophilic colloidal medium such as gelatin or carboxylic acid, polymers having hydroxy group or amino group is carried out by aldehydes such as glyoxal or mucochloric acid, sodium 2,4, -dichloro-6-hydroxy-s-triazinate. Cyanuric acid chlorides such as salts, aziridine such as bis (aziridineacetamido) hexane and bis (aziridineacetamido) butane, or 1,2-bis (sulfonylacetamido) ethane, 1,3-bis (vinylsulfonyl) -2-propanolethane And a vinyl sulfone-based hardener such as bis (vinylsulfonyl) methyl ether.

Particularly preferred hardeners are represented by the general formula R ₁ —N (R ₂ ) —CO-pyridinium, where the pyridinium ring is R ₃ and / or L—X—S.
It is replaced by O ₃ H.

In the formula, R ₁ and R ₂ represent an alkyl group or an aryl group, and R ₁ and R ₂ may form a ring. R ₃
Represents a hydrogen atom or a substituent. L represents a single crystal or two groups. X represents a single bond or a divalent group. X represents a single bond or _{-O -, - N (R 4} ) - is R ₄ represents a hydrogen atom or an alkyl group, an aryl group.

When the light-sensitive material of the present invention is applied for printing plate making, a hydrazine compound as a contrast-increasing agent, an amine compound as a contrast-increasing aid, or a redox compound which releases a development inhibitor by oxidation can be used. .

When the light-sensitive material of the present invention is applied to a light-sensitive material for printing, a desensitizing dye can be used for controlling sensitivity and safelight property.

The light-sensitive material of the present invention has at least one light-sensitive emulsion layer on a support. A protective layer can be provided on the photosensitive emulsion layer. The emulsion layer and the protective layer can be further divided into two or more layers. Further, by disposing an intermediate layer between the protective layer and the emulsion layer, it is possible to control the diffusion of additives and the transmission of light, and to suppress the chemical or physical influence of the adjacent layers. A filter dye may be fixed to the protective layer to block out safety light. For immobilization, fine particles can be used, an anion-cation ionic bond can be used, or a redox reaction that decomposes by oxidation or reduction can be used. Fixing the dye in the lower layer of the emulsion layer or on the side opposite to the support for preventing halation is good for improving image quality. The antihalation layer is preferably provided below the emulsion layer. In the case of X-ray silver halide photographic elements with emulsions on both sides, the filter dye is fixed as a transverse light blocking layer. When two or more emulsion layers are provided, the emulsion having high photosensitivity and development may be provided closer to the support side or may be provided farther. Since light reaching the side closer to the support is less and the penetration of the developing solution is delayed, providing an emulsion layer with high sensitivity and high developability improves the image quality, so it is preferably applied to medical and printing sensitive materials. You can Since the difference in developability becomes large in the latter stage of development, a redox compound releasing a development inhibitor can be used for speed control. In order to enhance the effect of the development inhibitor released from the redox compound, it is preferable that the layer in which the redox compound is present is adjacent to the emulsion layer via the intermediate layer. The specific layer structure is from the support / adhesive layer / transverse light blocking layer or antihalation layer / emulsion layer / intermediate layer /
The order is redox-containing layer / protective layer. Also, from the support / adhesive layer / transverse light blocking layer or antihalation layer /
It can also be used in the order of redox-containing layer / intermediate layer / emulsion layer / protective layer. The gelatin used in these layers can be swollen with a known cross-linking agent, but in order to cross-link each layer, it is preferable to adjust the molecular weight or use a cross-linking accelerator.
The amount of gelatin used in each layer is usually 0.1 g to 2.0 g / m ² . The cross-linking agent is preferably used at 0.01 mmol to 1 mmol per gram gelatin. In addition to gelatin, a hydrophilic polymer such as dextrin, starch, grape or the like or a hydrophobic latex can be introduced into each layer to control the degree of swelling. The degree of swelling is generally 120 to 200. For drying each layer, the temperature and time are adjusted according to the evaporation rate of water. A temperature of 25 ° C to 200 ° C and a time of 0.1 second to 200 seconds are generally applied. The degree of swelling can be measured by immersing in water and measuring with a microscope, or by a swelling degree meter. As the degree of swelling, the ratio (Lw / Ld) of the dry film thickness = Ld (film thickness after humidity conditioning at 23 ° C. and 50% relative humidity for 24 hours) to the swollen thickness Lw in water at 23 ° C. is 100. The value multiplied by can be used as an index.

In order to accelerate development, at least one layer of the hydrophilic colloid layer may contain the following developing agent used in the developing solution. Also, as a mildew-proofing agent
-Isothiazol-3-one, N-methyl-isothiazol-5-
It is possible to use chloro-3-one, N-methyl-isothiazol-4,5-dichloro-3-one, 2-nitro-2-bromo-3-hydroxypropanol, 2-methyl-4-chlorophenol, etc. it can.

A plurality of constituent layers of 3 to 10 layers are provided at a rate of 30 per minute.
U.S. Pat.No. 3, for simultaneous application at high speeds of ~ 1000 meters
The known slide hopper method described in Nos. 636,374 and 3,508,947, or curtain coating can be used. In order to reduce unevenness during coating, it is preferable to use a hydrophilic polymer capable of lowering the surface tension of the coating liquid and imparting thixotropic properties in which the viscosity is reduced by shearing force.

The silver halide photographic light-sensitive material of the present invention may have a backing layer. When a backing layer is provided, it is common to provide an adhesive layer / antistatic layer / dye-containing layer / protective layer on a support.

The backing layer contains an inorganic filler such as colloidal silica for dimensional stability, silica for preventing adhesion, a methyl methacrylate matting agent, a silicone-based slipping agent or a release agent for controlling transportability, and the like. Can be made. As the backing dye, a benzylidene dye or an oxonol dye is used. These alkali-soluble or decomposable dyes can be fixed in the form of fine particles. The concentration for preventing halation is preferably 0.1 to 2.0 at each photosensitive wavelength.

The light-sensitive material of the present invention is preferably dried at a moisture content of 300% or less based on the dry weight of the binder at 25 ° C. under a relative humidity condition of 50% or less, and stored at 25 ° C. and a relative humidity of 50% or less. It is desirable to be in an atmosphere that is a quantity.

The processing solution for developing the light-sensitive material includes hydroquinones such as hydroquinone, sodium hydroquinone sulfonate and chlorohydroquinone as developing agents, as well as 1-phenyl-3-pyrazolidone and 1-phenyl-4,4-dimethyl-. 3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-3
-Can be used in combination with pyrazolidones such as pyrazolidone and super-additive developing agents such as N-methylparaaminophenol sulfate. Further, ascorbic acid or isoascorbic acid may be used in combination with the above-mentioned super-additive developing agent without using hydroquinone. Sodium sulfite or potassium sulfite as a preservative, sodium carbonate or potassium carbonate as a buffer, and ED as a chelating agent.
5-methylbenzotriazole, such as TA, EDTA / 2Na, EDTA / 4Na, as a fog inhibitor or silver sludge inhibitor,
2-mercaptobenzothiazole, 1-phenyl-5-mercaptotetrazole, 6-nitrobenzimidazole, 1- (4
-Phenylcarboxylate) -5-mercaptotetrazole, 1-
(Phenyl 4-sulfonate) -5-mercaptotetrolazole, 2-mercaptobenzimidazole, 2-mercapto-5
-Sulfonic acid-benzimidazole, and development accelerators such as diethanolamine, triethanolamine, and diethylaminopropanediol may be contained. The antifoggant can be added to photographic element layers such as an emulsion layer and an emulsion protective layer to improve not only fog suppression but also sharpness and bright reproducibility. The developing solution can be adjusted to a pH range of 9 to 12 with an alkaline agent such as sodium hydroxide or potassium hydroxide. Adjustment of pH is generally used in the range of 10 ± 0.5, which has good storage stability, but pH of 11 ± 0.5 can also be used for rapid processing. The development processing can be carried out under processing conditions of 20 ° C. to 40 ° C. and 1 second to 90 seconds. In addition, a development accelerator or a sensitizer is used to replenish the developer or fixer with a replenishment rate of 5 cc to 21 m ² per m ² .
It can be in the 6cc range or less. Replenishment amount reduction is particularly effective by reducing the amount of silver halide grains used by the emulsion sensitization technique, and can be achieved in combination with the development acceleration technique.

[0112]

【Example】

Example 1 << Preparation of Subbed Substrates D-2 for Comparison >><Preparation of SPS Film> The SPS pellets obtained by the polymerization example were melt extruded at 320 ° C. in an extruder. The molten polymer was extruded through a pipe into an extrusion die. Then, the film thickness is reduced to 1000 by extruding and cooling while applying electrostatically to the casting drum cooled from the die slit.
A μm SPS unstretched sheet was obtained.

The obtained sheet was preheated at 110 ° C. and then stretched 3.3 times in the machine direction, further preheated to 130 ° C. in a stenter and stretched 3.3 times in the transverse direction. After heat-setting at 230 ℃ while relaxing a little further in the lateral direction, heat-relax at 170 ℃ for about 5 minutes, cool to 100 ℃, and cool at 80 ℃ for about 10 minutes.
It heat-processed for a minute and produced the support body D-1.

On top of this, the following undercoat processing liquid was added to give a dry film thickness of 0.
A subbing support D-2 for comparison was prepared by applying it to a thickness of 7 μm and drying at 100 ° C. for 5 minutes.

<Preparation of subbing processing liquid> According to JP-A-3-31843, aqueous gelatin solution (5 wt%) 7 parts by weight Formalin aqueous solution (4 wt%) 1 part by weight Finished with pure water to 100 parts by weight.

<< Preparation of Undercoated Substrates A, B and C of the Present Invention >><Preparation of Laminated Unstretched Sheet> The SPS pellets obtained in the polymerization examples were melt extruded at 330 ° C. in one extruder. Further, polyethylene terephthalate having an intrinsic viscosity of 0.62 was melt-extruded at 310 ° C. by the other extruder and divided into two directions. Pipe these molten polymers through pipes
It was extruded through an extrusion die consisting of layers. That is PET /
SPS / PET = 1/8/1 is extruded to form a three-layer structure, combined and laminated in a die, and extruded while being electrostatically applied to a casting drum cooled from a die slit to cool the film to a thickness of 1000 μm. A laminated unrolled sheet was obtained.

<Preparation of First Subbing Liquid 1> Styrene-Butadiene Latex (Nippole Lx432 manufactured by Zeon Corporation) 25 parts by weight Methylcellulose (10 wt aqueous solution) 10 parts by weight Silica-based matting agent (average particle size 3.0 μm) 0.5 parts by weight Part Hardener (2.4-dichloro-6-hydroxy-S-triazine sodium) 0.5 parts by weight Make up to 100 parts by weight with pure water.

<Preparation of First Undercoating Processing Liquid 2> Acrylic latex (solid content 30%) (butyl acrylate / styrene / hydroxyethyl methacrylate = 2/1/1 weight ratio) 12.3 parts by weight Anionic surfactant ( C ₉ H ₁₉ -C ₆ H ₆ -O (CH ₂ CH ₂ O) ₁₂ SO ₃ Na) 1.8 parts by weight Hardener (hexamethylene-1,6-bis (ethyleneurea)) 1.2 parts by weight 100 with pure water Finish to the weight part.

<Preparation of First Undercoat Processing Liquid 3> Water-dispersible polyester (WD size: manufactured by Eastman Kodak Co.) 12.3 parts by weight Anionic surfactant (C ₉ H ₁₉ —C ₆ H ₄ —O (CH ₂ CH ₂ O) ₁₂ SO ₃ Na) 1.8 parts by weight Hardener (hexamethylene-1,6-bis (ethylene urea)) 1.2 parts by weight Finish with pure water to 100 parts by weight.

<Preparation of Second Undercoating Liquid 1> Aqueous gelatin solution (10 wt%) 20 parts by weight Ammonium sulfate 0.5 parts by weight Semiconductor fine particles A-1 40 parts by weight Made up to 100 parts by weight with pure water and using zirconia beads with a sand grinder Dispersed for about 8 hours. Immediately before coating, 1.2 parts by weight of a curing agent (mucochromic acid) was added.

<Preparation of Second Undercoating Liquid 2> Gelatin aqueous solution (10 wt%) 20 parts by weight Hardener (mucochromic acid) 1.2 parts by weight Anionic surfactant (C ₉ H ₁₉ —C ₆ H ₄ —O ( CH ₂ CH ₂ O) ₁₂ SO ₃ Na) 1.8 parts by weight Make up to 100 parts by weight with pure water.

<< Preparation of Substrate Substrate A-2 >> The laminated unstretched sheet was preheated at 115 ° C., then stretched 3.3 times in the machine direction and further preheated to 130 ° C. in a stenter and stretched 3.3 times in the transverse direction. After further relaxing the heat in the lateral direction at 225 ° C, heat relax at 170 ° C for about 5 minutes to 100 ° C.
Cooled to 80 ° C and heat treated for about 10 minutes to obtain support A-1
It was created.

After subjecting this film to corona discharge on each side, the first undercoating liquid 1 was dried at 140 ° C.
It was coated so as to have a thickness of μm.

Corona discharge was applied to the support so that the backing layer surface side was provided with the second undercoating processing liquid 1 and the photographic emulsion layer surface side was provided with the second undercoating processing solution 2 so that the dry film thickness was 0.1 μm. After being applied, it was dried at 140 ° C. and sequentially laminated to prepare an undercoated support A-2.

<< Preparation of Subbed Substrate B-2 >> The subbed support B is prepared in the same manner as the subbed support A-2 except that the first subbing solution 1 is changed to the first subbing solution 2. -2 was created.

<< Preparation of Substrate Substrate C-2 >> The laminated unstretched sheet was preheated at 115 ° C. and then stretched 3.3 times in the machine direction. After applying corona discharge on both sides, the first undercoating liquid 3 is extruded and applied on both sides with a coater and 100 in the stenter.
It was dried during preheating at ℃ and further stretched 3.3 times in the transverse direction at 130 ℃. After heat fixing at 225 ° C. while slightly relaxing in the lateral direction, heat relaxing at 170 ° C. for about 5 minutes, cooling to 100 ° C., and heat treatment at 80 ° C. for about 10 minutes to prepare a support C-1. ..

On this support, the second undercoating liquid 1 was applied to the backing layer surface side, and the second undercoating liquid 2 was applied to the photographic emulsion layer surface side so that the dry film thickness was 0.1 μm. After that, it is dried at 140 ° C. and sequentially laminated to form an undercoat support C.
-2 was created.

<< Preparation of Photosensitive Material >> An antistatic layer and an antihalation layer were applied to each of the obtained supports, and then a photographic constituent layer and a backing layer having the following constitution were formed by a curtain coater to prepare a photosensitive material. . The emulsion used here was composed of silver chlorobromide having a silver chloride content of 60 mol%, and tabular grains in which iridium and rhodium were doped at 10 ⁻⁶ mol per mol of silver. Sensitization was performed using 8.2 mg of sodium thiosulfate pentahydrate, 163 mg of potassium thiocyanate, 5.4 mg of chloroauric acid, and 2.0 mg of diphenylpentafluorophenyl selenide per mole. The emulsion in the high-sensitivity emulsion layer has an average grain size of 0.13 μm and the aspect ratio = 1.5, and the emulsion in the low-sensitivity emulsion layer has an average grain size of 0.14 μm and the aspect ratio =
2. The difference in sensitivity between the high-speed emulsion and the low-speed emulsion was 32%.

<< Photographic layer >> First layer Reflected light absorption layer (absorbance at 500 nm = 0.36) Gelatin 0.3 g / m ² matting agent (average particle size 2 μm) 0.02 g / m ² solid disperse dye B (average particle size 0.06 μm) 0.03 g / m ²

[0130]

Embedded image

Thickener to polystyrene sulfonic acid (MW = 500,000) 0.1 g / m ² Styrene-maleic acid copolymer 0.1 g / m ² Polyvinylpyrrolidone 0.1 g / m ² Second layer High-sensitivity emulsion layer Silver halide ( 1.5 g / m ² gelatin 1.0 g / m ² poly (ethyl methacrylate-butyl acrylate) copolymer latex 0.5 g / m ² solid dispersion contrast agent (average particle size 0.12 μm) ~ 1-formyl-2- {4- [2- (2,4-Di-tert-pentylphenoxy) butyramide] phenyl} hydrazine 0.02 g / silver 1 mol Sensitizing dye-5- [3- (4-sulfobutyl) -5-chloro-2- Oxazolidene] -1-hydroxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt 1 × 10 ⁻³ mol / silver 1 mol Thickener to polystyrene sulfonic acid (MW = 500,000) 0.1 g / m ² Styrene - maleic acid copolymer 0.1 g / m ² polyvinyl pyrrolidone 0.1 g / m ² the third layer intermediate layer Zera Down 0.3 g / m ² thickener - polystyrene sulfonic acid (MW = 500,000) 0.1g / m 2 4th layer low-sensitivity emulsion layer the silver halide (in terms of silver) 1.5 g / m ² Gelatin 1.0 g / m ² poly ( Ethyl methacrylate-butyl acrylate) Copolymer latex 0.5 g / m ² Solid dispersion Hardening agent (average particle size 0.12 μm) ~ 1-formyl-2- {4- [2- (2,4-di-tert-pentyl] Phenoxy) butyramide] phenyl} hydrazine 0.02 g / silver 1 mol Solid dispersion redox compound (average particle size 0.12 μm) ~ 1- (5-nitroindazol-1-yl) -2- {4- [2,4-di- tert-Pentylphenoxy) butylamido] phenyl} hydrazine 0.02 g / silver 1 mol Hardening agent-bis (1-piperidinotriethyleneoxaside) thioether 0.2 g / silver 1 mol Nonylphenoxydocosaethylene oxide sulfonate-sodium salt 0.2 g / Silver 1 mole antifoggant Hide Quinone monosulfonate 12 mg / silver 1 mol Hydroquinone aldoxime 12 mg / silver 1 mol 1- (p-carboxyphenyl) -5-mercaptotetrazole 12 mg / silver 1 mol Benzotriazole 12 mg / silver 1 mol 1-butanesulfonic acid-2,3 -Dithiacyclohexane 12 mg / silver 1 mol Adenine 12 mg / silver 1 mol Butyl gallate 12 mg / silver 1 mol Sensitizing dye-5- [3- (4-sulfobutyl) -5-chloro-2-oxazolidene] -1-hydroxy Ethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt 1 × 10 ^-3 mol / silver 1 mol Thickener to polystyrene sulfonic acid (MW = 500,000) 0.1 g / m ² Styrene-maleic acid copolymer 0.1 g / m ² Polyvinylpyrrolidone 0.1 g / m ² Fifth layer Protective layer lower layer Gelatin 0.5 g / m ² Thickener to polystyrene sulfonic acid (MW = 500,000) 0.1 g / m ² Styrene-maleic acid copolymer 0.1 g / m ² polyvinylpyrrolidone 0.1 g / m ² ethyl methacrylate - butyl acrylate copolymer latex 0.2 g / m ² Matting agent - silicon dioxide (average particle size 4μm) 0.03g / m ² Solid dispersion safelight dye (average particle size 0.06 .mu.m) 4, 4 ′ -Bis [1- (4-carboxyphenyl) -3-carboxyethylpyrazol-5-one] heptamethine 60 mg / m ² Alkali-soluble solid dispersion development inhibitor (average particle size 0.07 μm) 4-nitroindazole 60 mg / m ² Sixth layer Protective layer Upper layer Gelatin 0.5 g / m ² Thickener to polystyrene sulfonic acid (MW = 500,000) 0.1 g / m ² Styrene-maleic acid copolymer 0.1 g / m ² Polyvinylpyrrolidone 0.1 g / m ² Ethyl methacrylate -Butyl acrylate copolymer latex 0.2 g / m ² matting agent to silicon dioxide (average particle size 4 μm) 0.03 g / m ² solid dispersion safelite dye (average particle size 0.06 μm) 4,4′-bis [1- ( 4-carboxyphenyl) -3- Rubokishiechiru pyrazol-5-one] heptamethine 60 mg / m ² alkali-soluble solid dispersion development inhibitor (average particle size 0.07 .mu.m) 4-nitroindazole 60 mg / m ² In addition, pyrrolidinopyridine carbamoyl pyridine ethane hardener in reflected light absorbing layer Sulfonic acid 0.3% for all layers of gelatin
The coating was performed by adding so that the amount would be mmol / g gelatin.

<< Backing Layer >> The backing layer coating liquid (backing layer coating liquid BC-1) and the backing protective film layer coating liquid prepared by the following methods were used as gelatin coating amounts of 1.8 g / m ² and 0.5 g / m, respectively. Layer-coating was applied so as to be ² .

[Preparation of Backing Layer Coating Liquid] The following additives were added and mixed, and then adjusted with pure water so that the total amount was 895 ml, to prepare a backing layer coating liquid BC-1.

Gelatin 32.4 g Pure water 696 ml Dye C 6% (W / V) aqueous solution 64 ml Dye D saponin 33% (W / V) aqueous solution 6.6 ml Polymer latex 20% (W / V) emulsion 33.6 ml (average) Cyclohexyl-methacrylate, isononyl acrylate, glycidyl-acrylate and styrene-isoprene sulfonic acid copolymer with a particle size of 0.10 μm) 10% of zinc oxide (W / V) solid fine particle dispersion (average particle size 0.15 μm) 10 ml of compound N Solid fine particles 16% (W / V) dispersion (average particle size 0.1 μm) 10 ml Citric acid 7% (W / V) aqueous solution 3.8 ml Sodium styrene sulfonate 4% (W / V) aqueous solution 23 ml [For backing protective film layer Preparation of Coating Liquid] The following additives were added and mixed, and then adjusted with pure water so that the total amount was 711 ml to prepare a coating liquid for a backing protective layer.

Gelatin 24.9 g Pure water 605 ml Methyl methacrylate (average particle size 7 μ) 2% (W / V) dispersion 72 ml 1-decyl-2- (3-isopentyl) succinate-2-sulfonate 4% ( W / V) Aqueous solution 11 ml Glyoxal 4% (W / V) aqueous solution 4 ml [Preparation of hardener liquid for in-line addition of backing layer] Pure water 27.22 ml Methanol 1.5 ml Hardener H1 1.28 ml NaCl 0.005 g (In addition, above addition The backing layer in-line addition hardener solution prepared by mixing the agents was added and mixed in line with the protective layer coating solution immediately before coating.)

[0136]

[Chemical 4]

<< Performance Evaluation >> A line drawing original of the prepared photosensitive material sample was photographed with a camera and developed, fixed, washed with water and dried using an automatic processor, the following developing solution and fixing solution. Development is temperature
28 ° C 6 seconds, fixing temperature 28 ° C 6 seconds, water washing 25 ° C 6 seconds, drying temperature
The temperature was set to 60 ° C for 6 seconds.

For the adhesion, the pick-off number of the emulsion layer per A-3 size film after development was counted.

The evaluation of the extracted character quality was carried out by placing a 7-point Mincho character line-drawing original on the original imaged at 175 lines per inch on the staking base, and further placing the silver halide of the present invention. The emulsion surface side of the light-sensitive material was brought into close contact and returned, and the reproducibility of line drawing characters on 50% halftone dots was visually observed and evaluated in 5 grades with a 10 times magnifier. The case where the boundary between the blackened image area and the non-image area of the character is sharp and the silver density is sufficiently high is ranked as 5, and the character image is blurred and the density is 1.0 or lower.

As for the storability, the extracted character quality was evaluated after conditioning the humidity at 23 ° C. and 50% relative humidity for 24 hours and then allowing it to stand at 55 ° C. for 72 hours. The results are shown in Table 1.

<Developer composition> 1-phenyl-3-pyrazolidone 1.5 g hydroquinone 30 g 5-nitroindazole 0.250 g 5-methylbenzotriazole 0.06 g potassium bromide 3.0 g sodium sulfite 50 g potassium hydroxide 30 g boric acid 10 g Water was added. The pH was adjusted to 10.20.

<Composition of fixer> Ammonium thiosulfate (72.5% W / V) aqueous solution 240 ml Sodium phosphite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Acetic acid (90% W / V V aqueous solution) 13.6 ml sulfuric acid (50% W / V aqueous solution) 4.7 g aluminum sulfate (Al ₂ 0 ₃ in terms of content by adding 8.1% aqueous solution of W / V) 26.5 g water to 1 liter pH was adjusted to 5.0 .

[0143]

[Table 1]

As is clear from Table 1, the use of the support of the present invention makes it possible to obtain a photographic light-sensitive material excellent in photographic performance and adhesive performance which cannot be obtained by SPS alone.

After exposing the entire surface of these light-sensitive materials to the above developing solution and rubbing them with a rubber glove for 30 seconds, sample Nos. 1 to 3 (supports A to C) showed no problem, but sample N
In the sample of o.4 (Support D), the coating film was peeled off entirely when touched.

Example 2 Preparation of Photosensitive Material 1-1 Photosensitive Material 1-1 of Example 1 (support: PET / SPS /
(PET = 1/8/1 stack).

Preparation of Light-Sensitive Material 2-2 Instead of PET (intrinsic viscosity 0.62), PEN (intrinsic viscosity 0.
68, prepared in the following manner) except that the photosensitive material 1-1 was used.
In the same manner as in Photosensitive material 2-2 (support is PEN / SP
S / PEN = 1/8/1 stack) was prepared.

<Preparation of PEN> 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 56 parts by weight of ethylene glycol were used as a transesterification catalyst and calcium acetate monohydrate 0.1.
By weight part, transesterification reaction was carried out by a conventional method. Thereafter, the obtained product was added with antimony trioxide 0.04
Parts by weight and 0.1 parts by weight of phosphoric acid trimethyl ester were added, then the temperature was gradually raised and the pressure was reduced, and polymerization was carried out under conditions of 285 ° C. and 0.5 mmHg to obtain a PEN chip having an intrinsic viscosity of 0.68.

Preparation of Photosensitive Material 2-3 Instead of PET (intrinsic viscosity 0.62), M-PET (modified polyester, intrinsic viscosity 0.57, prepared as described below) was used (slightly reduced, described below or in Table 2). Other than the above, in the same manner as the light-sensitive material 1-1, the light-sensitive material 2-3 (support is M-
PET / SPS / M-PET = 0.5 / 9 / 0.5) was prepared.

<Preparation of M-PET (modified polyester)> To 100 parts by weight of terephthalic acid and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added, and an esterification reaction was carried out by a conventional method. The obtained product was 28 parts by weight of ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight) (5 mol% / total acid content), polyethylene glycol (number average molecular weight 3000). 8.1 parts by weight (7% by weight / polymer),
0.05 parts by weight of antimony trioxide and 0.13 parts by weight of trimethyl phosphate were added. Then gradually raise the temperature and reduce the pressure,
Polymerized at 280 ℃, 0.5mmHg and having an intrinsic viscosity of 0.57 M-
PET (modified polyester) was obtained.

Preparation of Photosensitive Material 2-4 SPS Single Layer Support (Same as Support D-1, film thickness 100 μm)
In the same manner as in the photosensitive material 1-1 except that the photosensitive material 2 is used,
-4 (support is SPS single layer) was prepared.

Preparation of Light-Sensitive Material 2-5 A light-sensitive material 2-5 was prepared in the same manner as Light-sensitive Material 1-1 except that a PET single-layer support (intrinsic viscosity 0.62, film thickness 100 μm) was used. )created.

Regarding these samples, the coefficient of humidity expansion of the support (measured by JIS K 705) and the humidity were 55% RH and 65% RH.
The dimensional change (dimensional stability) of the light-sensitive material was measured and evaluated.

<Measurement / Evaluation Method of Dimensional Stability> Registration marks are placed on a glass dry plate at intervals of 560 mm. After the humidity of the photographic light-sensitive material was adjusted to 55% RH, the above-mentioned glass dry plate was used as an original and was contact-exposed and baked with a printer, and then developed. When the humidity of this sample was adjusted in a room at 55% RH for one day, the dimensional deviation (μm) between the sample and the glass plate was measured. Next, the humidity was controlled for one day in a room of 65% RH, and the dimensional deviation (μm) from the glass plate was measured. These deviations (μm) for the 560 mm distance of the glass plate were expressed as dimensional stability. Table 2 shows the above results.

[0155]

[Table 2]

As is clear from Table 2, the support (film) of the present invention has a humidity expansion coefficient much smaller than that of the conventional PET support (F-1), and is further improved as a light-sensitive material. However, it can be seen that the dimensional stability is very excellent.

[0157]

According to the present invention, it is possible to provide a photographic support for a silver halide photographic light-sensitive material which is highly excellent in dimensional stability and has adhesiveness to a light-sensitive layer and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08L 67/03 LPD

Claims (5)

[Claims] 1. A support for a silver halide photographic light-sensitive material, which has a structure in which a polyester resin layer is laminated on both sides of a film containing syndiotactic polystyrene as a main component. 2. The polyester resin layer is a polyethylene terephthalate resin layer.
A support for a silver halide photographic light-sensitive material as described above. 3. A support for a silver halide photographic light-sensitive material according to claim 1, wherein the polyester resin layer is a polyethylene naphthalate resin layer. 4. The support for a silver halide photographic light-sensitive material according to claim 1, wherein the polyester resin layer is a modified polyester resin layer. 5. The modified polyester resin layer is formed by condensation of at least one selected from terephthalic acid, naphthalene dicarboxylic acid and 5-sodium sulfoisophthalic acid and at least one selected from ethylene glycol and polyethylene glycol. A support for a silver halide photographic light-sensitive material according to claim 4.