JP3345624B2 - Photographic support - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic support,
More specifically, the present invention relates to a photographic support having excellent strength, excellent roll recovery, preventing light piping, and obtaining a good photograph when printed on photographic paper.

[0002]

2. Description of the Related Art Printed photographs are widely used in general because of their high image quality and the convenience of being easily enjoyed whenever it is desired to stick them directly to an album or the like.

However, a complicated process such as a film development process and a subsequent printing process for forming an image on a photographic printing paper is required from photographing to obtaining a print photograph, so that it takes too much time. In order to solve this problem, a large amount of various processing devices are being processed at high speed.

[0004] At this time, the support is required to have enough strength to withstand the transport load accompanying high-speed processing.

By the way, as a plastic used for a conventional photographic support, triacetyl cellulose (T
AC) and polyethylene terephthalate (PET) are typical.

[0006] The TAC film has the property that it has no optical anisotropy and high transparency.
After developing a photographic light-sensitive material using a C film as a photographic support, it has an excellent property that curls can be quickly removed. However, the TAC film originally has a disadvantage of low mechanical strength.

On the other hand, PET films have excellent productivity, mechanical strength, dimensional stability and the like, and are therefore mainly used for sheet-like films such as X-ray films. However, in a roll form widely used as a photographic light-sensitive material, there is a problem of fogging that occurs because the PET film has a high refractive index. PE
The refractive index of T film is about 1.6
The film is as small as 1.5. On the other hand, the refractive index of gelatin usually used for the undercoat layer and the photographic emulsion layer is 1.50 to 1.55,
In a PET film, when light enters from the edge of the film, the light is easily reflected at the interface between the base and the emulsion layer, causing a so-called light piping phenomenon (edge fogging).

As a method of preventing the light piping phenomenon, there is a method of adding a gray dye to a film. For this purpose, a polyester film is excellent in heat resistance in a film forming temperature range and is compatible with polyester. For example, a method of dyeing Diaresin (manufactured by Mitsubishi Kasei Co., Ltd.) so that the color density in the visible light region becomes 0.01 or more is known.

However, in order to prevent the light-piping phenomenon by using a conventionally known gray (or black) dye, it is actually necessary to increase the amount of the dye added to the film. Therefore, there is a problem that the transparency of the film is reduced. If the transparency of the film is reduced, the overall color density is reduced when printed on photographic printing paper, resulting in an image of poor photographic quality, which is not preferable. In addition, there is a method of solving the decrease in transparency by extending the exposure time during printing, but this method cannot be adopted because a large amount and high-speed processing cannot be performed.

Accordingly, it is an object of the present invention to provide a photographic support having excellent strength, excellent roll-up recovery, preventing the light piping phenomenon, and obtaining good photographs when printed on photographic paper. It is in.

[0011]

To achieve the above object of the SUMMARY OF THE INVENTION The present invention, according to a first aspect of the invention, less as a dye
Both Macrolex Green G 30-300ppm
Containing aromatic dicarboxylic acid having a metal sulfonate group
From copolymerized polyester containing acid as copolymer component
A photographic support comprising: 400
Spectral transmittance in the wavelength range of nm to 700 nm is 60%
Within the range of not less than 85% and not more than 600 nm.
Located photographic support the difference between the maximum value and the minimum value of the spectral transmittance in the wavelength range of 700nm to said der Rukoto within 10%, the invention of claim 2, wherein the polyester, 2. The photographic material according to claim 1, wherein the laminate comprises at least one polyester layer and at least one layer of a copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component. Ru support near.

The polyester used in the photographic support of the present invention has a spectral transmittance of 60% in a wavelength range of 400 to 700 nm.
The difference between the maximum value and the minimum value of the spectral transmittance in the wavelength range of 600 nm to 700 nm is within 10%, and the transmission in the wavelength range of 600 to 700 nm is preferable. The difference between the maximum value and the minimum value of the ratio is within 5%.

The spectral transmittance is 60 in the wavelength range of 400 to 700 nm.
%, The transparency is inferior, and when printed on photographic paper, the overall color density will decrease, resulting in an undesirable photo.
If it exceeds 85%, the light piping phenomenon cannot be prevented.

Further, even if the spectral transmittance is within the above range,
If the difference between the maximum value and the minimum value of the spectral transmittance in the wavelength range of 600 to 700 nm exceeds 10%, an unfavorable photograph having poor photographic quality results.

Therefore, by using a polyester film having a spectral transmittance within the range of the present invention for a photographic support, the light piping phenomenon can be prevented, and a better photograph can be obtained.

The polyester used for the photographic support of the present invention is a polyester having an aromatic dibasic acid and glycol as main components. Examples of the dibasic acid include terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. There are acids and the like, and glycols include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, p-xylylene glycol and the like. Among them, polyethylene terephthalate containing terephthalic acid and ethylene glycol as main components is preferable.
Further, as long as the excellent properties inherent in polyester are not impaired, a copolymer having 75 mol% or more of these main repeating units may be used, or another polymer may be blended.

The copolymer polyester used in the photographic support of the present invention is a copolymer containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymer component and an aromatic dibasic acid and a glycol as main components. Polyester is a preferred example.

Examples of the aromatic dibasic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and the like. Examples of the glycol include ethylene glycol, propylene glycol, butanediol, and the like.
Neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol and the like can be mentioned. Of these, terephthalic acid is preferred as the aromatic dibasic acid, and ethylene glycol is preferred as the glycol.

Examples of the aromatic dicarboxylic acid having a metal sulfonate group include 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, and 4-sodium sulfo-2,6.
-Naphthalenedicarboxylic acid, or an ester-forming derivative thereof, and a compound obtained by replacing sodium with another metal such as potassium or lithium.

In the present invention, the copolymerized polyester having an aromatic dicarboxylic acid having a metal sulfonate group as a copolymer component is an amount of the aromatic dicarboxylic acid having a metal sulfonate group, which is detected by hydrolyzing the polyester. In order to sufficiently recover the curl of the photographic film and obtain good flatness, the content is 2 to 7 mol% based on the total ester bond units.

The copolymerized polyester in the present invention is:
As long as it has an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and does not inhibit the object of the present invention, polyalkylene glycol and / or
Alternatively, it is preferable to further contain an aliphatic dicarboxylic acid having 4 to 20 carbon atoms as a copolymerization component.

As the polyalkylene glycol,
Examples include polyethylene glycol and polytetramethylene glycol. Of these, polyethylene glycol is preferred. The molecular weight is not particularly limited, but is preferably from 200 to 20,000, more preferably
Desirably, it is between 400 and 5,000, more preferably between 1,000 and 5,000.

It is preferable that the amount of the polyalkylene glycol is usually 3 to 10% by weight based on the total weight of the reaction product.

Examples of the aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, adipic acid, sebacic acid and the like, of which adipic acid is preferred.

In the present invention, when the copolymerized polyester having an aromatic dicarboxylic acid having a metal sulfonate group and diethylene glycol as a copolymerizable component further contains an aliphatic dicarboxylic acid as a copolymerizable component, The amount of the aliphatic dicarboxylic acid detected by hydrolyzing is preferably 3 to 15 mol% based on all ester bonds.

When the polyalkylene glycol and the aliphatic dicarboxylic acid as monomer units are contained in the copolymerized polyester so that the amounts of the polyalkylene glycol and the aliphatic dicarboxylic acid are within the above-mentioned ranges,
The curl of the photographic film can be easily eliminated.

Further, the polyester used for the photographic support of the present invention preferably contains an antioxidant.

The type of the antioxidant is not particularly limited with respect to its type, and specific examples thereof include a hindered phenol compound, an allylamine compound, a phosphite compound, and a thioester antioxidant. . Among these, hindered phenol compounds are preferred.

The content of the antioxidant is usually from 0.01 to 2% by weight, preferably from 2 to 10% by weight, based on the weight of the copolymerized polyester in order to maintain the effect of the photographic performance and suppress the turbidity of the polyester.
0.1 to 0.5% by weight. These antioxidants can be used alone or in a combination of two or more.

The polyester used in the photographic support of the present invention contains phosphoric acid, phosphorous acid and esters thereof and inorganic particles (eg, silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.) in the polymerization step. And the polymer may be blended with inorganic particles after polymerization. Further polymerization stage,
At any stage after the polymerization, a dye, an ultraviolet absorber or the like may be appropriately added.

The polyester used in the photographic support of the present invention is not particularly limited with respect to the production method. For example, after transesterification of a dicarboxylic acid component and a glycol component, the polyester is subjected to polymerization at high temperature and reduced pressure. It is suitably produced by a condensation method.

In particular, when a polyalkylene glycol is used as a copolymer component, it may be added before, during, or after transesterification, but it can be obtained up to the initial stage of transesterification. Since the polyester may be colored, it is preferably added after the transesterification.

The intrinsic viscosity of the polyester thus obtained is not particularly limited, but is preferably in the range of 0.35 to 1.0, and more preferably in the range of 0.45 to 0.70.

The polyester constituting the photographic support of the present invention is preferably a laminate having at least one copolymerized polyester layer in order to increase the strength while maintaining the curl removability.

When the polyester constituting the photographic support of the present invention is a laminate of at least one polyester layer and at least one copolymerized polyester layer, the number of the polyester layer and the copolymerized polyester layer is as follows. In general, two or three layers are preferable from the viewpoint that the production equipment becomes complicated, although they may be stacked. In the case of three layers, the inner layer may be a polyester layer and the outer layer may be a copolymerized polyester layer, or the inner layer may be a copolymerized polyester layer and the outer layer may be a polyester layer.

In particular, it is preferable to form a polyester layer on the inner layer and a copolymerized polyester layer on both sides thereof.

The thickness of each layer is used but may be appropriately determined by polyesters and copolyesters, preferably the ratio is 0.7 ≦ d ₂ of the sum d ₂ of the thickness of the copolyester layer to the sum d ₁ of thickness of the polyester layer / D ₁
≦ 3, more preferably 1 ≦ d ₂ / d ₁ ≦ 2, and the thickness of one polyester layer is preferably 50 μm or less, more preferably 40 μm or less.

The thickness of the photographic support of the present invention is not particularly limited as long as necessary strength and the like can be obtained according to the intended use, and is, for example, preferably from 30 to 200 μm, particularly preferably from 40 to 120 μm. .

Further, it is preferable to curl the multilayer film by changing the ratio of the thickness of each layer in order to further improve the removability of winding.

The thickness ratio varies depending on the layer structure and the composition of the polyester and copolymerized polyester used, and thus cannot be unconditionally determined. However, the case where a copolymerized polyester layer is laminated on both sides of the polyester layer will be described as an example. And the ratio of the thickness of the copolyester layer of both outer layers is preferably 1.5 or more and 4 or less.

The polyester film of the present invention is blended with a coloring agent such as a dye and / or a pigment for the purpose of preventing the light piping phenomenon.

The colorant is not particularly limited, but any colorant may be used as long as it has excellent heat resistance in the polyester film formation temperature range and excellent compatibility with the polyester. For example, anthraquinone or perinone chemical dyes And the like.

It is difficult to obtain the polyester film of the present invention with a generally known gray (or black) dye, and in particular, with the polyester film of the present invention, 700
dyes with absorption near nm (for example, Bayer M
(ACROLEX GREENG) is preferably blended in the range of 30 to 300 ppm.

The method of adding the colorant is not particularly limited, and the colorant may be added and colored at any stage from the polymerization of the polyester to the melt extrusion. A method in which so-called master pellets are prepared, and then appropriately diluted and extruded.

The method for producing the polyester film of the present invention is not particularly limited. The polymer is dried under dehumidified hot air or vacuum, melt-extruded from an extruder, cooled and solidified on a cooling drum, and then unoriented (stretched). ) Get the sheet.
Then, it is biaxially oriented (stretched) and heat set.

The stretching conditions vary depending on the type of the polyester, and thus cannot be determined unconditionally. Usually, the stretching ratio is 2.5 to 6.0 times in the biaxial direction in the temperature range from the glass transition temperature (Tg) to Tg + 100 ° C. It is preferable to be carried out within the range. Heat setting can be carried out at a temperature not higher than the crystalline melting point of the polyester, usually in the range of 150 to 240 ° C.

As a method of laminating a polyester film, for example, a polyester and a copolymerized polyester are melt-extruded from separate extruders, and then bonded and extruded in a laminar flow form in a conduit of a molten polymer or an extrusion die.
A co-extrusion method of cooling and solidifying on a cooling drum, obtaining an unstretched (oriented) film, then biaxially stretching (orienting), and heat-setting.
Alternatively, an unstretched (oriented) film obtained by melt-extruding a polyester from an extruder and solidified by cooling on a cooling drum, or a uniaxially oriented film obtained by uniaxially stretching (orienting) the unstretched (oriented) film, and, if necessary, an anchoring agent. There is an extrusion lamination method in which a copolyester is extrusion-laminated thereon after coating with an adhesive or the like, and then heat-fixed after completing biaxial stretching (orientation). The method is preferred.

Further, a functional layer such as an antistatic layer, a slippery layer, an adhesive layer, and a barrier layer may be provided in any step before and / or after the completion of the biaxial orientation.

At this time, various surface treatments such as a corona discharge treatment and a chemical solution treatment can be performed as required.

The polyester film thus obtained is particularly suitable as a support for a photographic film used in a roll form.

The photographic film has the following layer constitution using the photographic support of the present invention.

That is, the photographic film has at least one silver halide emulsion layer on at least one surface of the photographic support of the present invention. In other words, at least one silver halide emulsion layer may be provided on one side of the photographic support, or at least one silver halide emulsion layer may be provided on both sides of the photographic support. The silver halide emulsion can then be coated directly on a photographic support, or can be coated via another layer such as a hydrophilic colloid layer containing no silver halide emulsion, A hydrophilic colloid layer as a protective layer may be provided on the silver halide emulsion layer. Further, the silver halide emulsion layers may be separately applied to silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between the silver halide emulsion layers. That is, an intermediate layer made of a hydrophilic colloid may be provided as necessary. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, and a backing layer may be provided between the silver halide emulsion layer and the protective layer.

As the silver halide used in the silver halide emulsion, those having an arbitrary composition can be used.
For example, silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide, silver iodobromide and the like can be mentioned.

The silver halide emulsion may contain a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener, and the like.

To develop a photographic film using the photographic support of the present invention, for example, T.I. H. James al., The Theory of The Photographic Process, 4th edition (The Theory of The Photogra ph ic Pro
cess, Forth Edition) pp. 291-334 and Journal of the American Chemical Society, 73.
Vol. 3, page 100 (1951).

[0056]

【Example】

(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 according to a conventional method.

28 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight) and 8 parts by weight of polyethylene glycol (number average molecular weight: 3000) were added to the obtained product. , 0.05 parts by weight of antimony trioxide, trimethyl phosphate
0.13 parts by weight, 0.2 parts by weight of Irganox 1010 (manufactured by Ciba-Geigy) and 0.04 parts by weight of sodium acetate were added. Then, gradually raise the temperature and reduce the pressure, 280 ° C, 0.5mmH
Polymerization was carried out with g to obtain a copolymerized polyester having an intrinsic viscosity of 0.55.

A dye manufactured by Bayer was kneaded with the copolymerized polyester at the following mixing ratio to prepare a master pellet having a dye concentration of 2000 ppm. Macrolex Orange 3G1 Macrolex Red 5B1 Macrolex Violet B0.5 Macrolex Green G0.5

The copolymerized polyester and the master pellet were blended at a ratio of 9: 1, and dried at 150 ° C. under vacuum.
It was melt-extruded at 0 ° C. and quenched and solidified on a cooling drum to produce an unstretched sheet. This unstretched (oriented) sheet is heated at 80 ° C.
Stretches 3.3 times in the vertical direction at, then at 90 ° C in the horizontal direction
After stretching 3.3 times, heat set at 180 ° C for 30 seconds to a thickness of 10
A photographic support comprising a 0 μm biaxially oriented (oriented) polyester film was obtained.

Comparative Example 1 A biaxially oriented (oriented) polyester film having a thickness of 100 μm was prepared in the same manner as in Example 1 except that the copolymerized polyester and the master pellet were blended in a ratio of 19: 1. A photographic support consisting of

Comparative Example 2 A biaxially oriented (oriented) polyester film having a thickness of 100 μm was prepared in the same manner as in Example 1 except that the copolymerized polyester and the master pellet were blended at a ratio of 4: 1. A photographic support consisting of

Comparative Example 3 The procedure of Example 1 was repeated, except that a master pellet having a dye concentration of 3000 ppm was prepared using the dye Sumiplasut Black H3B manufactured by Sumitomo Chemical Co., Ltd. A photographic support comprising a biaxially oriented (oriented) polyester film was obtained.

Comparative Example 4 To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out according to a conventional method. The reaction was performed.

To the obtained product were added 32 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight), 0.05 parts by weight of antimony trioxide, and 0.13 parts of trimethyl phosphate.
Parts by weight and 0.05 parts by weight of sodium acetate were added. Subsequently, the temperature was gradually increased and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg, to obtain a copolymerized polyester having an intrinsic viscosity of 0.50.

The copolymerized polyester was added to Mitsubishi Kasei Co., Ltd.
Knead Dye Diaresin Black B, dye concentration 3000
A master pellet of ppm was prepared.

A photographic support comprising a biaxially oriented (oriented) polyester film having a thickness of 100 μm was obtained in the same manner as in Example 1 using the above-mentioned copolymerized polyester and master pellets.

Example 2 Using the copolymerized polyester of Example 1, a dye manufactured by Bayer was kneaded at the following mixing ratio.
A master pellet having a dye concentration of 2000 ppm was prepared, and the copolymerized polyester and the master pellet were blended at a ratio of 9: 1. Macrolex Red EG1 Macrolex Violet B1 Macrolex Green G1

On the other hand, a master pellet was prepared in the same manner as described above using commercially available polyethylene terephthalate (intrinsic viscosity: 0.65), and polyethylene terephthalate and the master pellet were blended at a ratio of 9: 1.

After each was vacuum dried at 150 ° C., it was melt-extruded at 285 ° C. using three extruders, and was joined in layers in a T-die so that both outer layers were made of copolymerized polyester and the central layer was made of polyethylene terephthalate. Then, the mixture was quenched and solidified on a cooling drum to obtain a laminated unstretched sheet . At this time, the extrusion rate of each material was adjusted so that the thickness ratio of each layer was 4: 3: 2. After stretching this unstretched sheet 3.3 times in the vertical direction at 85 ° C. and further stretching 3.3 times in the horizontal direction at 95 ° C.,
It was heat-set at 10 ° C. for 30 seconds to obtain a photographic support composed of a biaxially oriented (oriented) polyester film having a thickness of 100 μm.

Example 3 To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out according to a conventional method. The reaction was performed.

To the obtained product, 32 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight), 0.05 parts by weight of antimony trioxide, 0.13 parts by weight of trimethyl phosphate And 0.04 parts by weight of sodium acetate. Subsequently, the temperature was gradually increased and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg, to obtain a copolymerized polyester having an intrinsic viscosity of 0.55.

Using this copolymerized polyester, a dye manufactured by Bayer K.K. is kneaded at the following mixing ratio, and a dye concentration of 2500 ppm
Was prepared, and the copolymerized polyester and the master pellet were blended at a ratio of 9: 1. Macrolex Red EG 2 Macrolex Green 5B 2 Macrolex Green G 1

On the other hand, a master pellet was prepared in the same manner as described above using commercially available polyethylene terephthalate (intrinsic viscosity: 0.65), and polyethylene terephthalate and the master pellet were blended at a ratio of 9: 1.

After that, in the same manner as in the second embodiment,
m was obtained.

(Evaluation Method) The biaxially stretched films (Examples 1 to 3 and Comparative Examples 1 to 4) obtained as described above were evaluated as described below, and the results are shown in Table 3. Was.

<Spectral Transmittance> Using a Hitachi spectrophotometer U-3200, the wavelength was changed between 400 and 700 nm, and the transmittance at each wavelength was measured.

From the measurement results, it was evaluated whether or not the transmittance was within the range of 60% to 85% in the wavelength range of 400 to 700 nm. (Evaluation 1) Settled... Not settled... × Next, the largest value and the smallest value of the transmittance in the wavelength range of 600 to 700 nm were obtained, and the difference was calculated. (Evaluation 2)

<Recoverability of roll-up> Sample size 12 cm × 35
mm film on a 10mm diameter core, 55 ℃, 20% RH
Under the conditions of 3 days, and roll. Thereafter, the core is released from the core, immersed in pure water at 38 ° C. for 15 minutes, and dried with a hot air dryer at 55 ° C. for 3 minutes under a load of 50 g. The load was removed, the sample was hung vertically, the distance between both ends of the sample was determined, and the degree of recovery from the original distance of 12 cm was evaluated. The evaluation was performed according to the following criteria. ◎: 70% or more ：: 50% or more and less than 70% ×: less than 50% Note that a level of ○ or more is a level that does not pose any practical problem.

<Photo Quality> A photographic support of a biaxially stretched polyester film was prepared according to the method described below, and the color reproducibility was evaluated by the following method.

The following four scenes were photographed by loading the film photosensitive material into the camera. After the film was developed in accordance with the processing conditions described below, the film was printed on a commercially available color paper by an automatic print baking processor to obtain a color print for evaluation through a print processing step. The obtained print image was presented to 10 subjects, and as a comparison, an image obtained by similarly processing with a commercially available color film (TAC) was used to have a sensory evaluation from the viewpoint of color reproducibility. The poor score was given as 0 points, the ordinary score as 1 point, and the excellent score as 2 points, and a total score of 4 scenes was obtained for each. (1) Female portrait (2) Group photo (3) Mountain landscape photo (4) Amusement park landscape photo Relative color reproduction was evaluated in the following three stages. As a matter of course, a grade of ○ is required for color reproducibility. Grade ◎: 60 points or more ○: 40-60 points ×: Less than 40 points

<Light Piping Prevention> The photosensitive material obtained in the same manner as described above was packed in a patrone described in JIS K7519-1982, and the length from the tip of the slab of the photosensitive material to the tip of the film outlet of the patrone was reduced to 60 mm. The photosensitive material was pulled out, and exposed to light at 7000 Lux for 120 seconds using a Patrone Irradiator M-025 manufactured by Shinko Seisakusho Co., Ltd. The exposed photosensitive material was developed in the same manner as described above, and the exposed length L (mm) was measured. The value obtained by subtracting 60 mm from L was used as a measure of light piping prevention. The evaluation is performed according to the following criteria, and a level of ○ or more is required for practical use. ◎ 0-10mm ○ 10-15mm × 15mm

[Preparation Method of Photosensitive Material] A corona discharge treatment of 8 W / (m ² · min) was applied to both surfaces of the biaxially stretched polyester film, and the following undercoating was applied to one surface of the biaxially stretched polyester film. Liquid B-3 was dried to a thickness of 0.8 μm
To form a subbing layer B-3, and apply the following subbing coating solution B-4 to the other surface of the biaxially stretched polyester film to a dry film thickness of 0.8 μm. An undercoat layer B-4 was formed.

<Coating Liquid B-3> Copolymer latex liquid of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate (solid content: 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Water 1000 ml

<Coating liquid B-4> Copolymer latex liquid (solid content 30%) of butyl acrylate 40% by weight, styrene 20% by weight and glycidyl acrylate 40% by weight 270 g Compound (UL-1) 0.6 g Hexa Methylene-1,6-bis (ethylene urea) 0.8 g Water 1000ml

Further, a corona discharge of 8 W / m ² · min was performed on the undercoat layer B-3 and the undercoat layer B-4, and the undercoat layer B-3
On the undercoat layer B-5, the following coating solution B-5 was formed by applying the following coating solution B-5 so as to have a dry film thickness of 0.1 μm. 6 was applied to a dry film thickness of 0.8 μm to form an undercoat layer B-6 having an antistatic function.

<Coating Solution B-5> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles having an average particle diameter of 3 μm 0.1 g Water 1000 ml

<Coating liquid B-6> Water-soluble conductive polymer (UL-4) 60 g Latex liquid containing compound (UL-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g Curing agent (UL- 6) 12 g polyethylene glycol (weight average molecular weight 800) 6 g water 1000 ml The structures of the compounds used are summarized below.

A corona discharge of 25 W / m ² · min was applied to the undercoat layer B-5, and 8 W / m ² · mi was applied to the undercoat layer B-6.
n corona discharges were applied. The following emulsion layers and the like were sequentially formed on the surface of the undercoat layer B-5 from the photographic support side to prepare a multilayer color photographic light-sensitive material.

<Emulsion layer> First layer; Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Compound (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g

Second layer: Intermediate layer (IL-1) Gelatin 1.3 g Third layer: Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size: 0.3 μm) (Average iodine content: 2.0 Mol%) 0.4 g silver iodobromide emulsion (average particle size 0.4 μm) (average iodine content 8.0 mol%) 0.3 g sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.50 g Cyan coupler ( C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.55 g High boiling solvent (Oil-1) 0.55 g Gelatin 1.0 g

Fourth layer: high-sensitivity red-sensitive emulsion layer (R-H) silver iodobromide emulsion (average particle size 0.7 μm) (average iodine content 7.5 mol%) 0.9 g sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) ) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling solvent (Oil-1) 0.25 g Gelatin 1.0 g

Fifth layer: Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer: Low-sensitivity green-sensitive emulsion layer (G-1) Silver iodobromide emulsion (average grain size: 0.4 μm) (Average iodine content: 8.0 Mol%) 0.6 g silver iodobromide emulsion (average particle size 0.3 μm) (average iodine content 2.0 mol%) 0.2 g sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) Dye (S-5) 0.8 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D -3) 0.02 g High boiling solvent (Oil-2) 0.7 g Gelatin 1.0 g

Seventh layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average particle size 0.7 μm) (average iodine content 7.5 mol%) 0.9 g sensitizing dye (S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) ) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling solvent (Oil-2) 0.35 g Gelatin 1.0 g

Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling solvent (Oil) -2) 0.15 g gelatin 1.0 g

Ninth layer; low-sensitivity blue-sensitive emulsion layer (B-1) Silver iodobromide emulsion (average particle size 0.3 μm) (average iodine content 2.0 mol%) 0.25 g silver iodobromide emulsion (average particle size) 0.4 μm) (Average iodine content 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g gelatin 1.3 g

Tenth layer: high-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average particle size 0.8 μm) (average iodine content 8.5 mol%) 0.5 g sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g high Boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g

Eleventh layer; first protective layer (PRO-1) Silver iodobromide emulsion (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling solvent (Oil-1) 0.07 g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g

12th layer; 2nd protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: ethyl methacrylate: methacrylic acid = 3: 3 : 4 (weight ratio) copolymer (average particle size 3 μm) 0.13 g gelatin 0.5 g

—Preparation of Silver Iodobromide Emulsion— The silver iodobromide emulsion used in the tenth layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average particle diameter of 0.33 μm (iodobromide content: 2 mol%) as seed crystals.

A solution <G-1> having the following composition was heated at a temperature of 70 ° C.
Ag 7.8 and pH 7.0 were maintained, and a seed emulsion equivalent to 0.34 mol was added with good stirring.

(Formation of Internal High Iodine Phase-Core Phase) Thereafter, a solution <H-1> having the following composition and a solution <S-
1> and were added over 86 minutes at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) while maintaining a flow rate ratio of 1: 1.

(Formation of External Low Iodine Phase—Shell Phase) Subsequently, while maintaining pAg 10.1 and pH 6.0, <H-2> and <S-2> were accelerated at a flow ratio of 1: 1. It was added over 65 minutes at a flow rate (the flow rate at the end was 5.2 times the initial flow rate).

The pAg and the pH during the formation of the particles were controlled using an aqueous potassium bromide solution and a 56% acetic acid aqueous solution. After the formation of the particles, the particles were subjected to a water washing treatment by a conventional flocculation method, and then gelatin was added for redispersion, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The resulting emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ossein gelatin 100.0 g 10% by weight methanol solution of compound-I 25.0 ml 28% ammonia aqueous solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml

<H-1> Ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml

<S-1> Silver nitrate 309.2 g 28% ammonia aqueous solution equivalent Finish with water 1030.5 ml

<H-2> Ossein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finished with water 3776.8 ml

<S-2> Silver nitrate 1133.0 g 28% aqueous ammonia solution Equivalent to water 3776.8 ml

The silver iodobromide emulsion used in the emulsion layers other than the tenth layer also has the same method for changing the average grain size, temperature, pAg, pH, flow rate, addition time, and halide composition of the seed crystal. Thus, the above-mentioned emulsions having different average grain sizes and different silver iodide contents were prepared.

Each of them was a core / shell type monodisperse emulsion having a distribution area of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. ,
1-phenyl-5-mercaptotetrazole was added.

Incidentally, the above-mentioned light-sensitive material further comprises compounds Su-1, Su-2, a viscosity modifier, hardeners H-1, H-
2. Stabilizer ST-1, antifoggant AF-1, AF-2
(Weight average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1
(9.4 mg / m ² ).

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[Table 1] (Film development processing) In Table 1, the replenishment amount is a value per 1 m ² of the photographic light-sensitive material.

The color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenisher thereof were prepared as described below. <Color developer> Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N- Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20%
The pH was adjusted to 10.0.6 using sulfuric acid.

<Color developing replenisher> Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- ( β-Hydroxyethyl) aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and add potassium hydroxide or 20%
The pH was adjusted to 10.18 using sulfuric acid.

<Bleaching Solution> Water 700 ml 1,3-diaminopropanetetraacetate iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Add water to make 1 liter, add ammonia The pH was adjusted to 4.4 using water or glacial acetic acid.

<Bleaching replenisher> Water 700 ml 1/3 ammonium ferric (III) diaminopropanetetraacetate 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g using ammonia water or glacial acetic acid After adjusting the pH to 4.0, water was added to make up to 1 liter.

<Fixing solution> Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, water was added to make 1 liter. .

<Fixing replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Adjust the pH to 6.5 using ammonium water or glacial acetic acid, then add water to make up to 1 liter. did.

<Stable Solution and Stable Replenisher> 900 ml of water

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Embedded image Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (L-77 manufactured by UCC) 0.1 g Ammonia water 0.5 ml Add water to make 1 liter, then add ammonia water or 50%
The pH was adjusted to 8.5 using sulfuric acid.

(Printing process) The conditions of the printing process are as shown in Table 2.

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[Table 2]

<Color developing solution> Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Fluorescent brightening Agent (4,4'-diaminostilbenesulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water was added to adjust the total volume to 1 liter, and the pH was adjusted to 10.10.

<Bleaching and Fixing Solution> Ammonium ferric ethylenediaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to make a total volume of 1 liter. The pH was adjusted to 5.7 with potassium carbonate or glacial acetic acid.

<Stabilizing Solution> 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1- Diphosphonic acid 2.0 g o-Phenylphenol sodium 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g It was adjusted to 1 liter and adjusted to pH = 7.0 with sulfuric acid or potassium hydroxide.

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[Table 3] As is evident from Table 3, the photographic support comprising the biaxially stretched polyester film of the present invention having a spectral transmittance within the range of the present invention is excellent in roll recovery property, photographic quality and light piping prevention. And was useful as a photographic support.

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According to the present invention, the biaxially oriented polyester film used for a photographic support is provided with a spectral transmittance in a specific wavelength range, thereby preventing curling recovery and preventing light-piping phenomena, thereby improving photographic quality. Image was obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideyuki Kobayashi 1 in Sakura-cho, Hino-shi, Tokyo Konica Corporation (72) Inventor Hiromitsu Araki 1 in Sakura-machi, Hino-shi, Tokyo In Konica Corporation (72) Inventor Yoshioki Okubo 2-35-5 Soshacho, Hofu City, Yamaguchi Prefecture (72) Inventor Tetsutaro Hashimura 1751-15 Nitta, Hofu City, Yamaguchi Prefecture (72) Inventor Hiroshi Naito 2265-5, Okiyoshiki, Daiji, Yamaguchi City, Yamaguchi Prefecture (56) JP-A-55-734 (JP, A) JP-A-48-5425 (JP, A) JP-A-2-181139 (JP, A) JP-A-54-127319 (JP, A) JP-A-1 -244446 (JP, A) JP-A-60-19522 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/795

Claims (2)

(57) [Claims] (1) at least Macrolex
Containing 30 to 300 ppm of green G, metal sulfone
Aromatic dicarboxylic acid having a phosphate group as a copolymer component
A photographic support comprising a copolymerized polyester
Maximum I, the photographic support is a spectral transmittance in the wavelength range of 400nm~700nm is, in a range below 85% 60% or more, even the spectral transmittance in the wavelength range of 600nm~700nm photographic support the difference between the value and the minimum value, characterized in <br/> Oh Rukoto within 10%. 2. The method according to claim 1, wherein the polyester is a laminate comprising at least one polyester layer and at least one layer of a copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component. The photographic support according to claim 1.