JP2005062781A - Silver halide photographic sensitive material and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance performance to coat a laminated polyester support with an undercoat layer by etching a surface of a copolymerized polyester constituting both surface layers of the support, and to provide a silver halide photographic sensitive material which ensures improved adhesiveness to an undercoat layer and increases productivity. <P>SOLUTION: (1) In the silver halide photographic sensitive material having at least one silver halide emulsion layer on a support, the support is a laminated polyester support comprising mutually different polyester layers, wherein an angle of contact of a copolymerized polyester film surface with ion-exchanged water after surface treatment carried out before disposal of an undercoat layer on the support is ≤38°, or (2) in the silver halide photographic sensitive material, an undercoat layer coating speed after treatment of both surfaces of the support is ≥80 m/min. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

Detailed Description of the Invention

Industrial application fields

The present invention relates to a silver halide photographic light-sensitive material and a method for producing the same.

Silver halide photographic light-sensitive materials (hereinafter referred to as photographic light-sensitive materials) are generally cellulose fiber-based polymers represented by triacetylcellulose (hereinafter referred to as “TAC”), polyethylene terephthalate (hereinafter referred to as “PET”). It is manufactured by applying at least one photographic photosensitive layer on a plastic film support made of a polyester-based polymer typified by: In general, photographic photosensitive materials typically include a 35 mm width or less in a cartridge and a color or black-and-white negative film that is loaded into a camera and used for photographing, a bright room, a scanner, a facsimile, etc. Black and white photosensitive material film. TAC is mainly used as the support for roll film, but the greatest feature is that it has little optical anisotropy and high transparency. However, the TAC film is inferior in mechanical strength, and as a feature derived from its molecular structure, the plastic film has high water absorption and inferior in dimensional stability due to humidity. This is considered to be because, for example, the molecular chain moves due to water absorption during the development process, and the dimensional change increases.

On the other hand, PET film has been considered to be able to replace TAC because it has excellent mechanical properties, dimensional stability, and high productivity. However, when the roll is stored and the film is pulled out and used as necessary, it is relatively difficult to curl in a short period of time. Since it has a drawback that it cannot be solved, it has been demanded to be improved because it cannot be used as a photographic material.

That is, as a support for photographic light-sensitive materials, there is a long-awaited appearance of a support having excellent transparency and curl-resolving properties possessed by TAC film, and having excellent mechanical strength possessed by PET film. It had been.

As a result of intensive studies on such a film, the present inventors reached the laminated polyester support of the present invention as a photographic photosensitive material having at least one silver halide emulsion layer on the laminated polyester support as effective. Details thereof are described in JP-A-6-240020.

In general, in order to use a photographic light-sensitive material as a support, an emulsion layer is coated on one side and a backcoat layer is coated on the opposite side. In order to adhere the emulsion layer or the back coat layer to the support well, an undercoat layer is provided between the two layers to improve the adhesion. The laminated polyester support described in JP-A-6-240020 has the characteristics that TAC film has excellent transparency and curl resolving properties, and also has excellent mechanical strength that PET film has. Although it is promising as a support for photosensitive materials, the laminated polyester support of the present invention is poor in filming and poor in wettability when applying an undercoat layer, and does not increase production speed, both in terms of quality and production. I had a problem.

Problems to be solved by the invention

Therefore, the object of the present invention is to have excellent thermal, mechanical, physical, chemical, and optical properties, and particularly excellent in optical properties (light transmittance, haze, etc.) and curl elimination, An object of the present invention is to provide a silver halide photographic light-sensitive material comprising a laminated polyester support excellent in productivity with a film and a method for producing the same.

Means for solving the problem

The above object of the present invention can be achieved by the following constitution.

(1) A photographic material having at least one silver halide emulsion layer on a support, the support comprising a polyester layer comprising each other, and the polyester layer constituting both surface layers being a copolymer component As a laminated polyester support containing an aromatic dicarboxylic acid having a metal sulfonate group and a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid, it was applied before applying the undercoat layer of the support. A silver halide photographic light-sensitive material, characterized in that the contact angle with ion-exchanged water after the surface treatment of the copolyester film surface is 38 ° or less.

(2) The silver halide photographic light-sensitive material as described in (1), wherein the support has a contact angle with ion-exchanged water after both surface treatments of 33 ° or less.

(3) The silver halide photographic light-sensitive material as described in (1) or (2), wherein the coating speed of the undercoat layer after both surface treatments of the support is 80 m / min or more.

(4) The silver halide photographic light-sensitive material as described in (1) or (2), wherein the undercoat layer coating speed after both surface treatments of the support is 100 m / min or more.

(5) The method for producing a silver halide photographic light-sensitive material according to any one of (1) to (4) above.

The present invention is described in detail below.

The present invention relates to a photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the support is composed of different polyester layers, and the polyester layers constituting both surface layers are copolymerization components. As a laminated polyester support containing an aromatic dicarboxylic acid having a metal sulfonate group and a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid, copolymerization is carried out before applying the undercoat layer of the support. The present invention has been achieved by a silver halide photographic light-sensitive material characterized by subjecting a polyester film surface to a surface treatment and a method for producing the same. That is, by etching the surface of the copolyester constituting both surface layers composed of the laminated polyester support, the details are not clear, but the copolyester polymer crystal chain is cleaved, and the produced polymer crystal terminal amorphous chain is generated. And carboxyl groups improve wettability, improve coating performance of the undercoat layer, increase productivity, and incorporate polymer amorphous chains into the undercoat layer, and chemically bond with the undercoat layer. It can be estimated that the adhesiveness is greatly improved by such means.

By performing such surface treatment, the surface of the support is activated, and its wettability and adhesiveness can be relatively measured by measuring the contact angle with ion-exchanged water after the surface treatment of the support. It can be easily and quantitatively evaluated.

By the way, the contact angle with ion-exchanged water can be reduced by applying corona discharge treatment, plasma treatment or the like to the copolymer polyester surface of the laminated polyester support before applying the undercoat layer. The inventors have found that the smaller the contact angle is, the better the wettability and the adhesiveness, and that the undercoat layer can be applied at a high speed.

The contact angle between the copolyester surface of the laminated polyester support and the ion exchange water is preferably 38 ° or less. More preferably, it is 33 degrees or less. The lower limit of the contact angle is not particularly limited, but is about 2 °. If it is less than 2 °, the effect on wettability and adhesiveness will reach its peak, and very strong surface treatment conditions will be required.

The laminated polyester support of the present invention will be described in detail.

--- Material for forming the support-- The support of the present invention has a polyester layer and / or a copolyester layer.

--Polyester--The polyester as the material for forming the polyester layer is one having a repeating unit of a dicarboxylic acid and a diol as a main constituent, preferably a repeating unit of an aromatic dibasic acid and a glycol. Mention may be made of polyester as a constituent component.

Examples of the dibasic acid include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acids. Examples of the diol or glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol. And p-xylene glycol. Of these, polyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents and polyethylene-2,6-naphthalate containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents are preferable.

In addition, the main repeating unit may be a copolymer of 85 mol% or more, preferably 90 mol% or more, as long as the original excellent properties of the polyester are not impaired, and other polymers are blended. Also good. In addition, the polyester layer may be blended with about 50% by weight of the copolymer polyester constituting both surfaces of the present invention.

Although it does not specifically limit as intrinsic viscosity of preferable polyester, From a viewpoint of the drawability at the time of laminated polyester support preparation, 0.45-0.80 are preferable and 0.70 or less are especially preferable.

-Copolyester-Copolyester used to form the copolyester layer comprises an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, and the main component is a repeating unit of dicarboxylic acid and diol. As a component, a copolyester having an aromatic dibasic acid and glycol as main components can be mentioned. Furthermore, in the present invention, the polyester may be blended in the copolymerized polyester layer by about 30% by weight.

Examples of the dibasic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids, and examples of the glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, p -Xylene glycol and the like. As the copolymerized polyester, among them, a copolymerized polyethylene terephthalate containing terephthalic acid and ethylene glycol as main components, and a copolymerized polyethylene-2,6-naphthalate containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main components. Is preferred.

The intrinsic viscosity of the copolyester is not particularly limited, but is preferably 0.35 to 0.75, and particularly preferably 0.65 or less, from the viewpoint of stretchability when preparing a laminated polyester support.

The aromatic dicarboxylic acid containing a metal sulfonate group as a copolymerization component in the copolymerized polyester is 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoterephthalic acid, 4-sodium sulfo-2,6. -Naphthalenedicarboxylic acid or the following chemical formula

1

And compounds obtained by substituting these sodium with other metals such as potassium and lithium.

The copolymer polyester preferably contains a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid as a copolymer component as long as the effects of the present invention are not impaired.

Examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and derivatives thereof. The molecular weight of polyalkylene glycols that can be used is not particularly limited, but is preferably 300 to 20,000, more preferably 600 to 10,000, and particularly preferably 1,000 to 5,000. Polyalkylene glycol is particularly preferable, and among these, polyethylene glycol represented by the formula (a) is particularly preferable.

H (O-CH2CH2) n-OH (a)
Polyalkylene glycols include polyethyleneoxydicarboxylic acid represented by the formula (b) in which the terminal -H of polyethylene glycol is substituted with -CH2COOR (R: H or an alkyl group having 1 to 10 carbon atoms, n: positive The same effect can be obtained by using a polyether dicarboxylic acid (R ′: H or an alkylene group having 2 to 10 carbon atoms, n: a positive integer) as represented by the formula (c). .

ROOCCH2- (O-CH2CH2) n-OCH2COOR (b)
ROOCCH2- (OR ') n-OCH2COOR (C)
In any case of the compound represented by the formula (b) and the compound represented by the formula (c), the molecular weight is not particularly limited and is preferably 300 to 20,000, more preferably 600 to 10,000, particularly 1 5,000 to 5,000 are preferably used.

As the saturated aliphatic dicarboxylic acid, for example, an ester-forming derivative thereof is preferable, and adipic acid, dimethyl adipate, dimethyl sebacate and the like that are esters of adipic acid and sebacic acid are used. Preferred is dimethyl adipate.

In the copolymerized polyester used in the present invention, other components may be further copolymerized or other polymers may be blended as long as the effects of the present invention are not impaired.

-Production of polyester and copolymer polyester-Both polyester and copolymer polyester used in the present invention are phosphoric acid, phosphorous acid and esters thereof and inorganic particles (silica, kaolin, calcium carbonate, calcium phosphate, Titanium dioxide, etc.), organic crosslinked particles (polymethyl methacrylate, etc.) may be contained, and inorganic particles may be blended with the polymer after polymerization. Further, a pigment, an ultraviolet absorber, an antioxidant, or the like may be added as appropriate at any stage of polymerization or after polymerization.

In order to obtain a copolymerized polyester, the acid component and the glycol component may be transesterified, and then the above-described copolymerized component may be added to perform melt polymerization. Alternatively, the copolymerized component may be added before transesterification. Then, the melt polymerization may be performed after the ester exchange. Alternatively, a known synthesis method such as solid phase polymerization of a polymer obtained by melt polymerization can be employed.

Examples of the catalyst used in the transesterification include acetates, fatty acid salts, carbonates and the like of metals such as manganese, calcium, zinc, and cobalt. Of these, hydrates of manganese acetate and calcium acetate are preferable, and a mixture of these is preferable. It is also effective to add a hydroxide, a metal salt of an aliphatic carboxylic acid, a quaternary ammonium salt or the like within a range not to color the repolymer that has inhibited the reaction during the transesterification and / or polymerization. Sodium oxide, sodium acetate, tetraethylhydroxyammonium and the like are preferable, and sodium acetate is particularly preferable.

The polyester or copolymer polyester for forming the support of the present invention can contain various additives. For example, a mixture of dyes may be used.

-Layer structure of support-The support of the present invention contains a polyester layer and / or a copolyester layer as described above, and the layer structure includes two layers, three layers, four layers, and the like. Alternatively, a laminated structure in which an arbitrary number of layers are laminated may be used. The “layer” constituting the support of the present invention is limited to a layer having a thickness of 2 microns or more, and an undercoat layer having a thickness of less than 2 microns, for example, is not regarded as a “layer” constituting the support. .

--Support of laminated structure--When the support of the present invention has a laminated structure of two or more layers, generally, the thickness of each layer is appropriately determined according to the polyester and copolymer polyester to be used, depending on the application. Although it can be determined, the ratio of the total thickness d2 of the copolyester layer to the total thickness d1 of the polyester layer is preferably about 0.7 ≦ d2 / d1 ≦ 3.0.

The total thickness of the support in the laminated structure is not particularly limited, but is preferably about 6 to 250 μm.

Moreover, the laminated structure of a 4 layer or more including the case where the laminated structure in a support body is two layers and three layers may be sufficient.

In the support having a two-layer structure, since it is composed of a copolymer polyester layer and a copolymer polyester layer, the thicknesses of the layers may be the same as or different from each other. Moreover, it is preferable that the kind of main component of copolymer polyester in two layers, or content of the main component differ. As a copolymerization component in the copolymerized polyester layer, an aromatic dicarboxylic acid having a metal sulfonate group is preferably contained, and a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid is preferably contained. The content of the aromatic dicarboxylic acid having a metal sulfonate group is preferably 2 to 7 mol% based on the total ester bond, and the content of the polyalkylene glycol and / or the saturated aliphatic dicarboxylic acid It is preferably 3 to 10% by weight relative to the total weight of the product.

In the case of a support having a two-layer structure, the curl degree in the width direction of the support can be adjusted to a predetermined value by appropriately adjusting the above items.

In the support on which the copolyester layers are laminated, the curl degree in the width direction can be adjusted by appropriately adjusting the film thickness and the composition amount.

When two different types of copolyester layers are laminated, the copolyester layer having a high content of the copolymer component is usually concave and curled.

When the support of the present invention has a three-layer structure, both outer layers are a combination of copolymer polyester layers.

In the case of a three-layer structure, the thickness of the outer layer may be the same or different, but the thickness of the outer layer is preferably different. The thickness of the inner thick outer layer is dA, and the thickness of the thinner outer layer is dB. Then, the ratio dA / dB is preferably not particularly limited, but 1.1 ≦ dA / dB ≦ 5, preferably 1.3 ≦ dA / dB ≦ 3.

By varying the thickness of the outer layer, the curl or roll curl degree and recovery curl degree in the lateral direction can be adjusted to predetermined values.

In the case of a three-layer structure, the copolymer polyester constituting both surface layers of the laminated support is different in main component or main component amount, copolymer component or copolymer component amount, It is preferable that the intrinsic viscosities are different. In this case, as a copolymerization component in the copolymerized polyester to be used, aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 2 to 10 mol%, preferably 2 to 7 mol%, based on all ester bonds. Further, it is particularly preferable to contain polyalkylene glycols and / or saturated aliphatic dicarboxylic acids as copolymerization components in a proportion of 3 to 10% by weight based on the total weight of the reaction product.

In the case of three layers, by appropriately adjusting these items, it is possible to impart a width direction curl or curl degree or recovery curl degree to the laminated support. When it consists of three layers, both surface layers are composed of copolymerized polyester, so if the copolymerized component content or intrinsic viscosity of the copolymerized polyester constituting both surface layers is approximately the same, a copolymer with a large film thickness The polyester layer side becomes concave and curls. Further, when the thicknesses of the copolyester layers on both surface layers are substantially the same, the copolyester layer side having a large intrinsic viscosity or a high content of the copolymer component becomes concave and curls. When both surface layers are copolyester layers and their intrinsic viscosities are different, the difference ΔIV in intrinsic viscosities is 0.02 to 0.5, more preferably 0.05 to 0.4, especially 0.1 to 0.3. 3 is preferred. When the difference ΔIV in intrinsic viscosity is within the above range, when the film thicknesses of the two surface layers are not greatly different, the surface layer having a large intrinsic viscosity becomes concave and a preferable width curl can be realized. In addition, when both surface layers are the same copolyester layer, the central layer is also a copolyester layer, and when the copolymer component of the central layer contains more than the surface layer, the film thickness of both surface layers is small. The copolymer polyester layer side is usually concave and curls. When both surface layers of the center layer are copolymer polyester layers and the copolymer component of the center layer is contained less than the outer layer, the copolymer polyester layer side with the larger thickness of both surface layers is usually concave and curls. .

The support described in detail above can be applied to various currently known applications, and is particularly useful for a polyester support used for a roll-shaped support, and further useful for a photographic support. is there.

In the embodiment of the support having a laminate structure of three or more layers of the present invention, the aromatic dicarboxylic acid having a metal sulfonate group is used as a copolymerization component in an amount of 2 to 7 mol%, preferably 3 to 6 mol, based on the total ester bond. A copolymer polyester layer containing a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid in an amount of 3 to 10% by weight, preferably 4 to 8% by weight, based on the total weight of the reaction product. Both surfaces of the formed polyester layer are constituted.

The support of the present invention having a laminate structure of two or more layers can be produced as follows. That is, for example, polyester and copolymer polyester are melt-extruded from separate extruders, then extruded in a laminar flow in a molten polymer conduit or extrusion cap, extruded, and electrostatically applied on a cooling drum In this manufacturing method, after cooling and solidification to obtain an unstretched support, biaxial stretching and heat setting are performed.

When extruding, casting, for example, melting, extruding, cooling and solidifying a laminated polyester polymer to produce an unstretched support, a substantially non-oriented, amorphous polyester and / or copolymerized polyester raw material is formed into pellets. Then, it is dried and crystallized in an inert gas atmosphere such as air or nitrogen at 120 to 180 ° C. for 1 to 24 hours under vacuum or under normal pressure. The target moisture content is not particularly limited, but is 0.05% or less, preferably 0.01% or less, and most preferably 0.005% or less, from the viewpoint of preventing reduction in mechanical strength and the like due to hydrolysis. Melt and extrude at 260-340 ° C. It cools and solidifies on a 10-30 degreeC casting drum, and laminates polyester unstretched original fabric is produced.

If the cooling rate is 12 ° C./second or more, preferably 15 ° C./second or more, a transparent laminated polyester support having no difference in front and back and white turbidity can be obtained.

Next, the film forming conditions of this laminated polyester support will be described.

The polyester layer of any one of the different polyester layers contains an aromatic dicarboxylic acid having a metal sulfonate group and a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid as a copolymerization component. As the stretching method of the stretched support, a sequential biaxial stretching method in which longitudinal stretching and lateral stretching are sequentially performed is preferable, and the first stage stretching is performed at a magnification of 2.7 to 5.0 times in one direction. When the second-stage stretching is performed at a magnification of 1.2 to 5.0 times in a direction perpendicular to the stretching direction, the first-stage stretching temperature is set to one or both surfaces after the first-stage stretching. The refractive index in the direction perpendicular to the stretching direction in the support surface is selected to be 1.573 or less, and the second stage stretching temperature is set to the higher of the polyesters constituting the laminated polyester. Glass transition temperature Tg ° C. or higher, (Tg + 35) extends at ° C. or less, at Thereafter 150 to 240 ° C., is obtained from 3 seconds to fix 100 seconds heat.

Reason for selecting the first-stage stretching temperature so that the refractive index in the direction perpendicular to the stretching direction in the support surface of the copolyester support constituting one or both surfaces after the first-stage stretching is 1.573 or less. Is to actively maintain the orientation by the first-stage stretching to some extent or more.

That is, in the film formation of the laminated polyester in the longitudinal / transverse sequential biaxial orientation, from the knowledge of the longitudinal / transverse sequential biaxial orientation of the polyester homopolymer, the stretching conditions in which the longitudinal / lateral strength, Young's modulus, etc. are almost balanced ( Stretching ratio, stretching temperature, stretching speed, etc.) are employed. However, the longitudinal and lateral mechanical strength, Young's modulus, etc. of the obtained laminated polyester support of the present invention are more dominant in the lateral direction than that of the polyester homopolymer single membrane. It was revealed.

This means that the aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 2 to 7 mol% based on the total ester bond, and polyalkylene glycols and / or saturated aliphatic dicarboxylic acid is used as a copolymerization component in the total weight of the reaction product. It is apparent that the copolymer polyethylene terephthalate containing 3 to 10% by weight is predominantly stretched in the second stage as compared with homopolyethylene terephthalate.

That is, in the first-stage stretching of homopolyethylene terephthalate, if it is stretched in the longitudinal direction, it is oriented in the longitudinal direction. Subsequently, if it is stretched in the second stage in the direction perpendicular to the longitudinal direction, the orientation in the longitudinal direction is slightly weakened. However, the width direction orientation is also ensured. However, in the case of copolymerized polyethylene terephthalate, it is oriented in the longitudinal direction when it is stretched in the longitudinal direction in the first stage, but if it is subsequently stretched in the direction perpendicular to the longitudinal direction in the second stage, the longitudinal direction Is significantly weakened and the widthwise orientation is increased. This is because in the case of copolymer polyethylene terephthalate, the longitudinal orientation structure formed by the first stage stretching is destroyed by the second stage stretching, and an orientation structure oriented in the transverse direction is formed. Is reasonable. That is, the alignment structure formed by the previous stretching will be destroyed by the subsequent stretching, and a new alignment structure will be easily formed.

From the above viewpoint, when a laminated polyester support made of a combination of a homopolyester such as homopolyethylene terephthalate and a copolymerized polyester such as the above-mentioned copolymerized polyethylene terephthalate is formed from conventional knowledge, Although depending on the copolymerization ratio, the lamination thickness, the lamination ratio, etc., the orientation of the copolymer polyester in the longitudinal direction is lost, so the mechanical strength and Young's modulus in the longitudinal direction are smaller than expected. On the other hand, the orientation in the width direction is dominated by the copolyester, and the mechanical strength in the width direction and Young's modulus are relatively larger than those in the longitudinal direction. You will lose your thermal balance. This is synonymous with forming a support oriented in the second-stage stretching direction. Although this tendency tends to be seen weakly in polyester-based supports, the degree is greater than that of homopolyester, and the strength and Young's modulus retained during the first-stage stretching after the second-stage stretching. In other words, the orientation in the first-stage stretching direction is greatly eliminated. This departs from the purpose of forming a support having substantially the same longitudinal and lateral strength and Young's modulus, or maintaining both the longitudinal and lateral strength and Young's modulus in good balance.

Therefore, if the above-mentioned cooling rate is adopted for the laminated polyester support composed of the above-mentioned copolymer composition and combination, a laminated polyester support excellent in transparency and flatness can be obtained.

The thus obtained laminated polyester biaxially stretched heat-fixed support is usefully used for photographic photosensitive materials (color, X-ray, printing sensitive material, etc.). The thickness is not particularly limited, but it is useful for a laminated polyester biaxially stretched support having a thickness of 50 to 250 μm.

Next, the subbing treatment of the support before coating the hydrophilic colloid layer for silver halide photographic light-sensitive material will be described. When coating the undercoat layer, chemical treatment, mechanical roughening treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation It is essential to perform surface treatment such as treatment. The surface treatment and the undercoat layer application may be carried out continuously or separately. In the case of surface treatment with plasma, the atmosphere may be a vacuum, or may be a gas such as carbon dioxide, nitrogen, oxygen, or hydrogen alone, or a mixed gas atmosphere thereof. By these surface treatments, the contact angle of the copolyester film surface of the laminated polyester support with the ion-exchanged water is 38 ° or less 2 ° or more, preferably 33 ° or less 2 ° or more. If it is to be less than 2 °, it is necessary to make the processing conditions considerably strict (strong and intense), and it is almost meaningless to saturate at 2 ° or less. If this condition is satisfied, both wettability and adhesiveness during application of the undercoat layer are good.

In the corona treatment, the discharge frequency is 50 Hz to 5000 KHz, preferably 5 KHz to several hundreds KHz. If the discharge frequency is too low, stable discharge cannot be obtained, and pinholes are generated in the workpiece, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the price of the device and is not preferable. The treatment strength of the object to be treated is 5 to 20 Watt · min / m 2, preferably 6 to 15 Watt · min / m 2 with respect to the copolyester film surface of the laminated polyester support. Since the treatment strength is not strictly defined by the type of device (gap clearance between electrode and dielectric roll, discharge shape, discharge frequency, waveform, etc.), the contact angle between the support surface and ion-exchanged water is claimed in the claims. It is not limited to these values as long as the specified range is satisfied.

The ultraviolet treatment is preferably a high-pressure mercury lamp or low-pressure mercury lamp made of a quartz tube and having a spectrum of 180 to 380 nm. The ultraviolet treatment is preferably performed in the film forming step (stretching process, at the time of heat setting, after heat setting), particularly preferably in the latter half of the stretching step or at the time of heat setting. As a method of ultraviolet irradiation, an irradiation light amount of 100 to 1500 (mJ / m 2) is preferable for a high-pressure mercury lamp (a spectrum having a main wavelength of 365 nm is generated). In the case of a low-pressure mercury lamp (generating a spectrum having a main wavelength of 254 nm), the irradiation light quantity is preferably 200 to 1500 (mJ / m 2), and preferably 400 to 1300 (mJ / m 2). If it exceeds 1300 (mJ / m2), the effect is saturated. Since the treatment strength is not strictly defined by the type of apparatus, the contact angle between the support-treated surface and the ion-exchanged water is not limited to these values as long as it satisfies the specified range in the claims of the present invention. Absent.

For the undercoat layer, any material used in the industry may be used. The undercoat layer may be a single layer, but in order to obtain higher functionality and increase the adhesive strength, it is desirable that the undercoat layer be a multilayer. The subbing multi-layer method will be described below. In the multilayer method, the first subbing layer preferably adheres well to the support, and as materials, unsaturated carboxylic acids such as methacrylic acid and acrylic acid or esters thereof, styrene, vinylidene chloride, vinyl chloride, Examples thereof include polymers or copolymers obtained from such monomers, water-dispersed polyesters, polyurethanes, polyethyleneimines, and epoxy resins. Among these, preferred are copolymers having water-dispersible polyester and styrene polymer as constituent elements. A copolymer or composition comprising the water-dispersible polyester and styrene polymer as constituent elements will be described.

The water-dispersible polyester is a substantially linear polymer obtained by a polycondensation reaction between a polybasic acid or an ester-forming derivative thereof and a polyol or an ester-forming derivative thereof. The polybasic acid component of this polymer includes terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid A merit acid, a dimer acid, etc. can be illustrated. A small proportion of unsaturated polybasic acids such as maleic acid, fumaric acid and itaconic acid, and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used together with these components.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, trimethylolpropane, Examples thereof include poly (ethylene oxide) glycol and poly (tetramethylene oxide) glycol.

In order to impart water dispersibility and water solubility to the water dispersible polyester, introduction of a sulfonate, diethylene glycol, polyalkylene ether glycol or the like is an effective means. In particular, the dicarboxylic acid component having a sulfonate (dicarboxylic acid having a sulfonate and / or an ester-forming derivative thereof) is preferably contained in an amount of 5 to 15 mol% based on the total dicarboxylic acid component in the water-dispersible polyester. .

In the present invention, the dicarboxylic acid having a sulfonate used for the undercoat layer and / or its ester-forming derivative is particularly preferably one having an alkali metal sulfonate group, such as 4-sulfoisophthalic acid, 5- Alkali metal salts such as sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid, or ester-forming derivatives thereof are used. 5-sulfoisophthalic acid sodium salt or an ester-forming derivative thereof is particularly preferred. The dicarboxylic acid and / or ester-forming derivative thereof having these sulfonates is particularly preferably used in an amount of 6 to 10 mol% based on the total dicarboxylic acid component from the viewpoint of water solubility and water resistance.

In the present invention, the styrenic polymer monomer used in the undercoat layer may be styrene alone or copolymerized with, for example, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group); 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate Hydroxy-containing monomers such as 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-methylol methacrylamide, N-methylol Amyl group-containing monomers such as chloramide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide; amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylamino methacrylate; epoxies such as glycidyl acrylate and glycidyl methacrylate Group-containing monomers; monomers containing a carboxyl group such as acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof; styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, Monomers containing sulfonic acid groups such as potassium salts and ammonium salts) or salts thereof; carboxy such as itaconic acid, maleic acid, fumaric acid and their salts (sodium salt, potassium salt, ammonium salt) Monomer containing a group or a salt thereof; monomer containing an acid anhydride such as maleic anhydride, itaconic anhydride; vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, vinyl chloride, vinyl acetate, vinylidene chloride Etc. The above-mentioned monomers can be copolymerized using one kind or two or more kinds.

In order to modify the water-dispersible polyester into a vinyl polymer, a method of grafting by introducing an addition-polymerizable group into the terminal of the water-dispersible polyester and copolymerizing with a monomer of the vinyl copolymer, vinyl There is a method in which a reactive group is introduced and grafted when a water-dispersible polyester such as carboxylic acid, glycidyl group or amino group is subjected to polycondensation as a monomer by polymerizing a copolymer.

Examples of the polymerization initiator include ammonium persulfate, potassium persulfate, and sodium persulfate. Ammonium persulfate is preferably used.

Furthermore, the polymerization does not require a surfactant and can be reacted in a soap-free manner. However, for the purpose of improving the polymerization stability, a surfactant can be used as an emulsifier in the system, and either a general nonionic or anionic surfactant can be used.

The ratio of the water-dispersible polyester and the styrene copolymer to be modified is 99/1 to 5/95, preferably 97/3 to 50/50, and more preferably 95/5 to 80/20.

In the first undercoat layer, it is preferable to add an activator or a cellulose compound such as methylcellulose in order to improve coatability.

The undercoating treatment may be performed after the film formation, but if the undercoating composition can be stretched, before the longitudinal stretching, which is in the middle of film formation, between the longitudinal stretching and the lateral stretching, after the lateral stretching. It can be performed at any place such as before heat treatment. When stretching is not possible, for example, when using a polymer having a hydrophilic group, the interaction between the hydrophilic polymers is strong, and stretching may not be possible, but stretching under steam or polyglycerin as a stretching aid Stretching becomes possible by adding.

Preferable examples of the monomer having a hydrophilic group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride. From the viewpoint of water resistance, this content is preferably 1 to 10% by weight, more preferably 1 to 8% by weight, more preferably 1 to 6% by weight, and most preferably 1 to 4% by weight. is there. Further, as the fourth component of the copolymer, other copolymerizable monomers can be copolymerized in the range of 0 to 15% by weight, preferably 0 to 10% by weight, if necessary. Examples include alkyl-substituted styrenes such as methylstyrene, halogenated styrenes such as chlorostyrene and chloromethylstyrene, unsaturated nitrile compounds such as acrylonitrile, aliphatic acrylates such as methyl acrylate, methyl methacrylate, and t-butyl acrylate. And alicyclics such as cyclohexyl methacrylate, aromatic (meth) acrylic ester compounds such as benzyl acrylate, and rubber-modified compounds such as butadiene and isoprene.

The method for producing these copolymers is not particularly limited, and can usually be obtained by radical polymerization using a generally known radical initiator.

The weight average molecular weight in terms of standard polystyrene measured by the GPC method of the copolymer composed of these monomers is preferably 1500 to 700000, and more preferably 2000 to 500000.

The undercoat second layer is preferably a hydrophilic resin layer that adheres well to the photographic emulsion layer. As binders constituting the hydrophilic resin layer, gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethylcellulose, hydroxyethylcellulose and other water-soluble polymers, polystyrene sulfonate soda Examples include a combination of a copolymer and a hydrophobic latex, and gelatin is preferred.

In these subbing second layers, it is preferable to increase the film strength using a hardener. Examples of such a hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, U.S. Pat. No. 2,732, 303, 3,288,775, British Patents 974,723, 1,167,207 and the like, compounds having reactive halogen, ketone compounds such as diacetyl and cyclopentanedione, bis ( 2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1,3,5-triazine, divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, US Patent US Pat. Nos. 3,232,763, 3,635,718, British Patent 994,809, etc. Patents 3,539,644, 3,642,486, JP-B-49-13568, 53-47271, 56-48860, JP-A-53-57257, 61-128240, 62-4275, 63-53541, 63-264572, etc., vinyl sulfone compounds, N-hydroxymethylphthalimide, U.S. Pat. Nos. 2,732,316, 2,586,168, etc. N-methylol compounds, isocyanate compounds described in U.S. Pat. No. 3,103,437, aziridine compounds described in U.S. Pat. Nos. 2,983,611 and 3,107,280, U.S. Pat. No. 2,725,294 , Acid derivatives described in U.S. Pat. No. 2,725,295, carbodiimide compounds described in U.S. Pat. No. 3,100,704, U.S. Pat. Epoxy compounds described in allowed 3,091,537, etc., isoxazole compounds described in US Pat. Nos. 3,321,313 and 3,543,292, halogenocarboxaldehydes such as mucochloric acid, Organic hardeners such as dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride. Further, as a hardening agent having a relatively fast hardening action with respect to gelatin, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-59625, JP-A-62-262854, N-carbamoylpyridinium salts described in JP-A-62-264044 and JP-A-63-184741, acylimidazoles described in JP-B-55-38655, N-acyloxyimidazoles described in JP-B-53-22089, and JP-B-53 A compound having two or more N-acyloxyimino groups in the molecule described in JP-2208989, a compound having an N-sulfonyloxyimide group described in JP-A-52-93470, described in JP-A-58-11939 Compounds having a phosphorus-halogen bond, JP-A-60-225148, JP-A-6240240, Chloroform amidinium compounds are known as described in JP 3-41580.

This subbing second layer preferably contains inorganic fine particles such as silicon dioxide and titanium dioxide as a slip agent, and an organic mat material (1 to 10 μm) such as polymethyl methacrylate. In addition to this, various additives such as an antistatic agent, an antihalation agent, a coloring dye, a pigment, and a coating aid can be contained as necessary.

Among these, it is preferable to contain 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 for the undercoat layer in the present invention are those that exhibit conductivity by charge carriers present in the particles, such as cations, anions, electrons, holes, and the like. Organic materials, inorganic materials, or a composite material of both may be used. Preferably, it is a compound exhibiting electron conductivity, and examples of organic materials include polymer fine particles such as polyaniline, polypyrrole, and polyacetylene. Examples of inorganic materials include fine metal oxide particles that can easily form non-stoichiometric compounds such as oxygen-deficient oxides, metal-excess oxides, metal-deficient oxides, and oxygen-excess oxides. In addition, a phosphazene metal complex or the like can be used as long as it is a charge transfer complex or an organic-inorganic composite material. Among these, the most preferable compound for the undercoat layer of the present invention is metal oxide fine particles that can be produced by various methods. In the present invention, a conductor having a volume resistivity of 103 Ω · cm or less is defined as a conductor in the undercoat layer, and a semiconductor having a resistivity of 1012 Ω · cm or less is defined as a conductor and a semiconductor, respectively.

A preferable 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 a water / ethanol mixed solution to obtain a uniform solution. This was then boiled to obtain a coprecipitate. The produced precipitate is taken out by decantation, and the precipitate is washed several times with distilled water. Silver nitrate is dropped into distilled water from which the precipitate has been washed, and after confirming that there is no reaction of chlorine ions, 1000 cc of distilled water is added to make the total amount 2000 cc. Further, 40 cc of 30% aqueous ammonia was added and heated in a water bath to obtain a colloidal gel dispersion.

<< Preparation of Semiconductor Fine Particle Powder >> 65 g of stannic chloride hydrate and 1.5 g of antimony trichloride were dissolved in 1000 g of ethanol to obtain a uniform solution. To this solution, a 1N sodium hydroxide aqueous solution was added dropwise until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The resulting coprecipitate was allowed to stand at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. In order to remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated three times to remove excess ions. 100 g of colloidal precipitate from which excess ions have been removed are mixed with 50 g of barium sulfate having an average particle size of 0.3 μm and 1000 g of water, and sprayed into a baking furnace heated to 900 ° C. to give a bluish oxidation particle having an average particle size of 0.1 μm. A powder mixture consisting of distinous and barium sulfate was obtained.

The coating solution 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, more preferably 5 to 20 g in terms of the coating solution weight per 1 m 2 of film.

Various known methods can be applied as the coating method. For example, a roll coating method gravure roll coating method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method and a curtain coating method can be applied alone or in combination. If the contact angle with the ion-exchanged water after the surface treatment described in the claims of the present invention is satisfied, the coating can be performed without any problem at a coating speed of 80 m / min or more, preferably 100 m / min or more. The upper limit is 145 m / min at a contact angle of 38 to 2 ° with ion-exchanged water.

The silver halide photographic light-sensitive material according to the present invention is preferably subjected to photographic processing after exposure in an automatic processor having at least 4 processes of development, fixing, washing (or stabilizing bath) and drying.

A known developing agent can be used for the developer used in the present invention. Specifically, dihydroxybenzenes (for example, hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4) , 4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA) Iron salt, DTPA nickel salt, etc.) In combination it can be used. Among them, it is preferable to use a developer containing ascorbic acid and its derivatives. Ascorbic acid and its derivatives are known as developing agents. For example, those described in U.S. Pat. Nos. 2,688,548, 2,688,549, 2,302,168, 3,129,981, 4,975,354 and 5,326,816 can be used.

Furthermore, ascorbic acid and its derivatives developing agents and 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone) 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol) N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) and dihydroxybenzenes substituted with a hydrophilic group (for example, hydroquinone monosulfonate, hydroquinone monosulfonate sodium salt, potassium 2,5-hydroquinone disulfonate) (Salt etc.) Door is preferable. When used in combination, 3-pyrazolidones, aminophenols, and dihydroxybenzenes substituted with hydrophilic groups are usually used in an amount of 0.01 to less than 0.2 mol per liter of developer. Is preferred. In particular, a combination of ascorbic acid and its derivatives and 3-pyrazolidones, and a combination of ascorbic acid and its derivatives, 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

An alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (for example, carbonate, phosphate, borate, boric acid, acetic acid, succinic acid, alkanolamine, etc.) may be added to the developer. preferable. The pH buffer is preferably a carbonate, and the amount added is preferably 0.5 mol or more and 2.5 mol or less, more preferably 0.75 mol or more and 1.5 mol or less per liter. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazole, thiazoles, etc.), chelating agents (for example, ethylenediamine Acetic acid or alkali metal salts thereof, nitrilotriacetate, polyphosphate, etc.), development accelerators (eg, compounds described in US Pat. No. 2,304,025, JP-B 47-45541), hardeners (eg, Glutaraldehyde or its bisulfite adduct) Etc. may be added agent. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, the pH is 8.5 to 10.4.

As the fixing solution, a commonly used composition can be used. The fixer generally has a pH of usually 3-8. Fixing agents include organic thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate, and thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, as well as soluble stable silver complex salts. Any compound known as a fixing agent can be used.

A water-soluble aluminum salt that acts as a hardener, such as aluminum chloride, aluminum sulfate, potassium alum, aldehyde compounds (for example, glutaraldehyde, glutaraldehyde sulfite adduct, etc.), etc. can be added to the fixing solution.

If desired, the fixing solution may include a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, citric acid), a pH adjuster (eg, sulfuric acid), a chelating agent capable of softening water. Compounds can be included.

After the fixing process, it is washed with water and / or treated with a stabilization bath. As a stabilization bath, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (the film surface pH after processing to 3 to 8) for the purpose of stabilizing the image ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. ), Aldehydes (for example, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (for example, ethylenediaminetetraacetic acid or alkali metal salts thereof, nitrilotriacetic acid salts, polyphosphates, etc.), antibacterial agents (for example, phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, P-hy Loxybenzoic acid ester, 2- (4-thiazoline) -benzimidazole, benzisothiazoline-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro- 2'-hydroxydiphenyl ether, etc.), color tone adjusting agent and / or residual color improving agent (for example, nitrogen-containing heterocyclic compound having a mercapto group as a substituent; specifically, 2-mercapto-5-sulfonic acid sodium-benzimidazole) 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine and the like. Among them, it is preferable that a stabilizer is included in the stabilizing bath. These may be replenished in liquid or solid form.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and each of them may be adjusted separately.

When processing using an automatic processor due to the demand for shortening the development time, the total processing time (Dry to Dry) from when the film tip is inserted into the automatic processor until it comes out of the drying zone is 60 seconds or less and 10 seconds or more. Preferably there is.

The halogen composition of the silver halide in the silver halide emulsion is not particularly limited. However, when processing with a small replenishment amount or when performing rapid processing, silver chloride and a salt odor containing 60 mol% or more of silver chloride It is preferable to use a silver halide emulsion having a composition of silver halide and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is preferably 1.2 μm or less, particularly preferably 0.8 to 0.1 μm. The average particle diameter is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or particles that can approximate a sphere. When the particles are cubes, they are converted into spheres, and the diameter of the sphere is taken as the particle size. For details of the method for determining the average particle size, see Meas, James: The Theory of the Photographic Process (CE Mees & TH James: The theory of the photographic process), 3rd edition. 36-43 (1966 (published by McMillan "Mcillalan")).

The shape of the silver halide grains is not limited, and may be any of flat, spherical, cubic, tetradecahedral, regular octahedral and other shapes. A narrow grain size distribution is preferable, and a so-called monodispersed emulsion in which 90%, preferably 95% of the total number of grains falls within a grain size region of ± 40% of the average grain size is particularly preferred.

The silver halide emulsion and its preparation method are described in detail in the literature described or cited in Research Disclosure 176, 17643, pages 22-23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these methods may be used alone or in combination.

The light-sensitive material of the present invention can contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, many compounds known as antifoggants or stabilizers such as azoles, mercaptopyrimidines, mercaptotriazines, azaindenes, benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added. .

As the binder or protective colloid of the photographic emulsion, gelatin is advantageously used, but other hydrophilic colloids can also be used.

As gelatin, lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme-decomposed product can also be used.

An inorganic or organic hardener is added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer as a crosslinking agent for a hydrophilic colloid such as gelatin. These hardeners are described in Research Disclosure, 176, 17643 (issued December 1978), pages 26-26.

Various other additives are used in the photosensitive material. Examples include desensitizers, plasticizers, slip agents, development accelerators, oils, and the like.

Regarding the above-mentioned additives and other known additives, for example, Research Disclosure No. 17643 (December 1978), No. 18716 (November 1979) and And compounds described in 308119 (December 1989).

The light-sensitive material of the present invention can be used for various applications such as X-ray photography, printing plate making, general photography such as color or black-and-white negative film, and direct viewing.

Hereinafter, the present invention will be described in detail with reference to examples, but the embodiment of the present invention is not limited thereto.

Example 1 To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and a transesterification reaction was carried out by a conventional method. To the obtained product, 28 parts by weight (5 mol% / total ester bond) of ethylene glycol solution (concentration 35% by weight) of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (abbreviation: SIP), polyethylene glycol (Abbreviation: PEG) (number average molecular weight: 4,000) 11 parts by weight (8.5% by weight / total weight of reaction product), antimony trioxide 0.05 parts by weight, trimethyl phosphate 0.13 parts by weight Irganox 1010 (manufactured by CIBA-GEIGY) was added as an antioxidant so as to be 1% by weight based on the product polymer. Subsequently, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain copolymerized polyethylene terephthalate (abbreviated as modified PET) having an intrinsic viscosity of 0.55.

The modified PET and commercially available polyethylene terephthalate (inherent viscosity 0.64, abbreviated as homo-PET) were each dried at 150 ° C. for 4 hours under a nitrogen atmosphere, and then used in a T-die at 285 ° C. using three extruders. Bonded in layers, melt extruded, laminated in 3 layers so that modified PET / homo PET / modified PET = 0.5 / 1.0 / 1.5, and the support sheet was 15 by electrostatic application method. On the cooling drum maintained at ℃, cool and solidify quickly while applying cooling air from the non-contacting surface of the casting drum so that the difference in cooling speed between the surface in contact with the casting drum and the surface not in contact with the casting drum is minimized. An unstretched support having a thickness of about 1270 μm was prepared. The cooling rate at which the laminated molten polymer was rapidly cooled and solidified on a casting drum was 20 ° C./second. This unstretched support was stretched and stretched 3.2 times in the machine direction at 95 ° C. and 3.3 times in the transverse direction at 105 ° C., and heated at 220 ° C. for 10 seconds. The biaxially oriented laminated polyester support having a thickness of 120 μm was obtained.

(Example 2)
(1) Polymerization of copolymer polyester polymer In the same manner as in Example 1, a necessary amount of copolymer polyester polymer was secured.

(2) Film formation of laminated polyester support: Except that the molten polymer laminated in the same combination and proportion as in Example 1 was rapidly cooled and solidified on a casting drum so that the cooling rate was 15 ° C / second. In the same manner as in Example 1, a laminated polyester unstretched support having a thickness of about 1270 μm was produced. This unstretched support was formed into a film under the same conditions as in Example 1 to obtain a biaxially oriented laminated polyester support having a thickness of 120 μm.

(Example 3)
(1) Polymerization of copolymer polyester polymer In the same manner as in Example 1, a necessary amount of copolymer polyester polymer was secured.

(2) Film formation of laminated polyester support Example except that the same polymer combination as in Example 1 and the molten polymer laminated at a ratio were rapidly cooled and solidified on a casting drum, and the cooling rate was 12 ° C / second. In the same manner as in Example 1, a laminated polyester unstretched support having a thickness of about 1270 μm was produced. This unstretched support was formed into a film under the same conditions as in Example 1 to obtain a biaxially oriented laminated polyester support having a thickness of 120 μm.

(Comparative Example 1)
(1) Polymerization of copolymer polyester polymer In the same manner as in Example 1, a necessary amount of copolymer polyester polymer was secured.

(2) Film formation of laminated polyester support: Except that the molten polymer laminated at the same ratio and proportion as in Example 1 was rapidly cooled and solidified on a casting drum so that the cooling rate was 8 ° C / second. In the same manner as in Example 1, a laminated polyester unstretched support having a thickness of about 1270 μm was produced. This unstretched support was formed into a film under the same conditions as in Example 1 to obtain a biaxially oriented laminated polyester support having a thickness of 120 μm.

(Comparative Example 2)
(1) Polymerization of copolymer polyester polymer In the same manner as in Example 1, a necessary amount of copolymer polyester polymer was secured.

(2) Film Formation of Laminated Polyester Support Example except that the same polymer combination as in Example 1 and the molten polymer laminated at a ratio were rapidly cooled and solidified on a casting drum, and the cooling rate was 5 ° C./second. In the same manner as in Example 1, a laminated polyester unstretched support having a thickness of about 1270 μm was produced. This unstretched support was formed into a film under the same conditions as in Example 1 to obtain a biaxially oriented laminated polyester support having a thickness of 120 μm.

(1) Surface treatment Biaxially oriented laminated polyester roll film obtained as described above (this is the contact angle of ion-exchanged water on the untreated surface of the copolyester film constituting both surface layers of the laminated polyester support) The surface of the modified PET having a thin thickness of 42 ° (degrees) was subjected to corona treatment as shown in Table 1, and a laminated polyester film (support) F- with different contact angles was used. 1 to F-7 were obtained.

(2) Undercoat of laminated polyester film On the modified PET of the laminated polyester film subjected to the surface treatment described in (1) above, an undercoat layer having been subjected to antistatic treatment containing styrene-glycidyl acrylate and tin oxide fine particles was formed.

<< Preparation of Silver Halide Emulsion A >> Silver chlorobromide core grains having an average thickness of 0.05 μm and an average diameter of 0.15 μm made of silver chloride 70 mol% and the rest silver bromide were prepared using the simultaneous mixing method. At the time of mixing the core particles, 8 × 10 −8 mol of K 3 RuCl 6 was added per mol of silver. A shell was attached to the core particles using a simultaneous mixing method. At that time, K2lrCl6 was added at 3 × 10 −7 mol per mol of silver. The obtained emulsion was silver chloroiodobromide (90 mol% of silver chloride) having an average thickness of 0.10 μm and an average diameter of 0.25 μm of core / shell monodispersed (variation coefficient 10%) (100) plane as the main plane. Tabular grain emulsion comprising 0.2 mol% of silver iodobromide, the rest being silver bromide. Subsequently, desalting is performed using a modified gelatin described in JP-A-2-280139 (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-8 on page 287 (3) of JP-A-2-280139). did. The EAg after desalting was 190 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 −3 mol per mol of silver, and potassium bromide and citric acid were added to adjust the pH to 5.6. EAg was adjusted to 123 mv, 2 × 10 −5 mol of chloroauric acid was added, then 3 × 10 −6 mol of inorganic sulfur was added, and chemical aging was performed at a temperature of 60 ° C. until the maximum sensitivity was achieved. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was 2 × 10 −3 mol per mol of silver, 3 × 10 −4 mol of 1-phenyl-5-mercaptotetrazole and gelatin Added.

<< Preparation of Silver Halide Emulsion B >> Using the simultaneous mixing method, 60 mol% of silver chloride, 2.5 mol% of silver iodide, and the rest are silver bromide having an average thickness of 0.05 μm and an average diameter of 0.15 μm Silver iodobromide core grains were prepared. At the time of mixing the core particles, 2 × 10 −8 mol of K 3 Rh (H 2 O) Br 5 was added per mol of silver. A shell was attached to the core particles using a simultaneous mixing method. At that time, K2lrCl6 was added at 3 × 10 −7 mol per mol of silver. The obtained emulsion had an average thickness of 0.10 μm and an average diameter of 0.42 μm of core / shell monodisperse (variation coefficient 10%) silver chloroiodobromide (90 mol% of silver chloride, 0.5 mol of silver iodobromide) %, The rest consisting of silver bromide). Subsequently, desalting is performed using a modified gelatin described in JP-A-2-280139 (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-8 on page 287 (3) of JP-A-2-280139). did. The EAg after desalting was 180 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 −3 mol per mol of silver, and potassium bromide and citric acid were added to adjust the pH to 5.6. EAg was adjusted to 123 mv, 2 × 10 −5 mol of chloroauric acid was added, and then 3 × 10 −5 mol of N, N, N′-trimethyl-N′-heptafluoroselenourea was added and the temperature was the highest at 60 ° C. Chemical aging was performed until sensitivity was achieved. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was 2 × 10 −3 mol per mol of silver, 3 × 10 −4 mol of 1-phenyl-5-mercaptotetrazole and gelatin Added.

(3) Preparation of silver halide photographic light-sensitive material for printing plate making scanner for HeNe laser light source For each of the seven types of supports obtained in the above (2), a gelatin undercoat of the following formulation 1 was formed on one of the subbing layers. Further, the silver halide emulsion layer 1 of Formula 2 was further added so that the amount of gelatin was 0.5 g / m 2 and the amount of gelatin was 0.5 g / m 2. As an intermediate protective layer, a coating solution of the following formulation 3 is used as an intermediate protective layer so that the gelatin amount is 0.3 g / m 2, and a silver halide emulsion layer 2 of the formulation 4 is further formed thereon with a silver amount of 1.4 g / m 2 and gelatin. Further, a coating solution of the following formulation 5 was applied by simultaneous multilayer coating so that the amount of gelatin was 0.6 g / m 2 so that the amount was 0.4 g / m 2. On the other side of the undercoat layer, a backing layer of the following formulation 6 is coated with a hydrophobic polymer layer of the following formulation 7 on it so that the amount of gelatin is 0.6 g / m 2, and further a formulation of the following formulation 8 7 types of light-sensitive materials are prepared by simultaneously coating the backing protective layer of the emulsion layer side with the emulsion layer side so that the amount of gelatin is 0.4 g / m 2.

Formula 1 (gelatin subbing layer composition)
Gelatin 0.5g / m2
Solid dispersion fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m 2
Sodium polystyrene sulfonate 10mg / m2
S-1 (Sodium-iso-amyl-n-decylsulfo succinate) 0.4 mg / m 2
Formula 2 (composition of silver halide emulsion layer 1)
Silver Halide Emulsion A Solid dispersion fine particles of dye AD-8 (average particle size 0.1 μm) so that the silver amount is 1.5 g / m 2 20 mg / m 2
Cyclodextrin (hydrophilic polymer) 0.5g / m2
Sensitizing dye d-1 5 mg / m2
Sensitizing dye d-2 5mg / m2
Hydrazine derivative H-7 20 mg / m2
Redox compound: RE-1 20 mg / m 2
Compound e 100 mg / m2
Latex polymer f 0.5g / m2
Hardener g 5mg / m2
S-1 0.7 mg / m2
2-mercapto-6-hydroxypurine 5mg / m2
EDTA 30mg / m2
Colloidal silica (average particle size 0.05 μm) 10 mg / m 2
Formula 3 (interlayer composition)
Gelatin 0.3g / m2
S-1 2 mg / m2
Formula 4 (silver halide emulsion layer 2 composition)
Silver halide emulsion B Sensitizing dye d-1 3 mg / m2 so that the silver amount is 1.4 g / m2
Sensitizing dye d-2 3mg / m2
Hydrazine derivative H-20 20 mg / m2
Nucleation accelerator: Exemplified compound Nb-12 40 mg / m 2
Redox compound: RE-2 20 mg / m 2
2-mercapto-6-hydroxypurine 5mg / m2
EDTA 20mg / m2
Latex polymer f 0.5g / m2
S-1 1.7 mg / m2
Formula 5 (Emulsion protective layer composition)
Gelatin 0.6g / m2
Solid dispersion of dye AD-5 (average particle size 0.1 μm) 40 mg / m 2
S-1 12mg / m2
Matting agent: monodispersed silica having an average particle size of 3.5 μm 25 mg / m 2
Nucleation promoter: Exemplified compound Na-3 40 mg / m 2
1,3-vinylsulfonyl-2-propanol 40 mg / m 2
Surfactant h 1mg / m2
Colloidal silica (average particle size 0.05 μm) 10 mg / m 2
Hardener: K-1 30 mg / m2
Formula 6 (backing layer composition)
Gelatin 0.6g / m2
S-1 5mg / m2
Latex polymer f 0.3g / m2
Colloidal silica (average particle size 0.05 μm) 70 mg / m 2
Sodium polystyrene sulfonate 20mg / m2
Compound i 100 mg / m2
Formulation 7 (hydrophobic polymer layer composition)
Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m 2
Hardener g 6mg / m2
Formula 8 (backing protective layer)
Gelatin 0.4g / m2
Matting agent: monodisperse polymethyl methacrylate having an average particle diameter of 5 μm 50 mg / m 2
Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m 2
Surfactant h 1mg / m2
Dye k 20 mg / m2
H- (OCH2CH2) 68-OH 50 mg / m2
Hardener: K-1 20 mg / m2

The surface resistivity value on the backing side after coating and drying was 6 × 10 ¹¹ at 23 ° C. and 20% RH, the film surface pH on the emulsion side surface was 5.5, and the degree of swelling was 175.

<< Evaluation >> The wettability of the undercoat layer and the adhesiveness of the coating film were evaluated as follows.

<< Wettability of the undercoat layer >> The wettability of the undercoat layer was evaluated in five stages according to the following criteria.

The undercoat layer was applied at a coating speed of 80 m / min by the wire bar coating method, and was evaluated with the naked eye according to the following evaluation criteria.

(Evaluation criteria)
1. The wettability is very poor, and the vertical and horizontal stripes of the undercoat layer are very conspicuous and cannot be practically used. Even if the application speed was lowered, the target of muscle elimination was not found.
2. The wettability is poor, and the vertical and horizontal stripes of the undercoat layer are conspicuous, so it is not practical. The application speed was reduced to 50 m / min, and finally the goal of eliminating the streaks was obtained, but the productivity was remarkably impaired and it was not practical.
3. The wettability is slightly poor, and the vertical and horizontal stripes of the undercoat layer appear thin. Even if the emulsion layer is coated on the upper layer, it is not solved. Although the application speed was lowered to 65 m / min to obtain the goal of eliminating the streaks, the productivity was remarkably impaired and it was not practical.
4). Good wettability and no vertical or horizontal stripes in the undercoat layer. 30 days of continuous application was possible. The coating speed was increased to 100 m / min, and vertical and horizontal stripes were not generated in the undercoat layer application, and continuous application for 30 days was possible.
5). The wettability is very good, and the vertical and horizontal stripes of the undercoat layer are not visible at all. A continuous application for 30 days was possible at 100 m / min. The coating speed was increased to 145 m / min, and 30 days of continuous coating was possible.

<< Adhesiveness of coating film >> On the emulsion side of the silver halide photographic light-sensitive material obtained above, cuts are made in a lattice shape with a razor, and pressure-sensitive adhesive tape is pressure-bonded. ) Was evaluated in five stages.

(Adhesion evaluation criteria)
1. The adhesive strength is very weak, and 100% of the area peels completely.

2. An area of 50% or more and less than 100% peels off.

3. An area of 10% or more and less than 50% peels off.

4). Adhesive strength is strong, and an area of 5% or more and less than 10% peels off.

5). The adhesive strength is very strong, and the peeled area is less than 5% and hardly peels off.

(Adhesiveness)
1 to 3 are unusable levels; ×
4 is a level that can withstand practical use.
5 is a very good level;
Expressed in

The results are shown in Table 1.

As is clear from Table 1, Experiment No. 1-1 to 1-4 (invention) and Experiment No. From comparison with 1-5 to 1-7 (comparison), the contact angle with ion-exchanged water that satisfies the preferred ranges of wettability and adhesiveness is 38 ° or less 2 ° or more, preferably 33 ° or less 2 °. It is understood that the above is true.

Example 2
Wetability and adhesiveness were evaluated in the same manner as in Example 1 except that the corona treatment was changed to ultraviolet treatment of a low-pressure mercury lamp as shown in Table 2.

The results are shown in Table 2.

As is clear from Table 2, the experiment No. 2-1 to 2-4 (present invention) and Experiment No. From comparison with 2-5 to 2-7 (comparison), even if the surface treatment method is changed from corona treatment to low-pressure mercury lamp, the contact angle with ion-exchanged water that satisfies the preferred range of wettability and adhesiveness is 38 ° or less, 2 ° or more, and preferably 33 ° or less and 2 ° or more.

From the above results, the wettability of the undercoat layer of the silver halide photographic light-sensitive material of the present invention and the adhesiveness of the silver halide photographic light-sensitive material are in contact with ion-exchanged water after the surface treatment regardless of the surface treatment method. It can be understood that this can be achieved if the angle satisfies a specific angle, that is, 38 ° or less and 2 ° or more, preferably 33 ° or less and 2 ° or more. Moreover, it can be understood that the coating speed can be achieved by combining 80 m / min or more, preferably 100 m / min or more.

The invention's effect

According to the present invention, it has excellent thermal, mechanical, physical, chemical, and optical properties, particularly excellent in optical properties (light transmittance, haze, etc.), dimensional stability, and with good film. A silver halide photographic material excellent in productivity could be provided.

Claims (5)

A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the support is composed of different polyester layers, and the polyester layer constituting both surface layers is a metal sulfonate as a copolymerization component. A laminated polyester support comprising an aromatic dicarboxylic acid having a group, a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid, and a copolymerized polyester film applied before application of the undercoat layer of the support A silver halide photographic light-sensitive material, characterized in that the contact angle with ion-exchanged water after the surface treatment of the surface is 38 ° or less. The silver halide photographic light-sensitive material according to claim 1, wherein the support has a contact angle with ion-exchanged water after both surface treatments of 33 ° or less. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the coating speed of the undercoat layer after both surface treatments of the support is 80 m / min or more. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the coating speed of the undercoat layer after both surface treatments of the support is 100 m / min or more. A method for producing a silver halide photographic light-sensitive material according to any one of claims 1 to 4.