JPH0772585A - Polyester substrate - Google Patents

Abstract

PURPOSE:To reduce the yellowing of the substrate, to enhance the adhesion of the substrate to the emulsion layer and back layer and to obtain a substrate which is hardly curled by specifying the intensity ratio of the photoelectron emitted from the 1s orbit of oxygen atom to the photoelectron emitted from the 1s orbit of carbon atom. CONSTITUTION:The intensity ratio of the photoelectron emitted from the 1s orbit of oxygen atom (O1s) to the photoelectron emitted from the 1s orbit of carbon atom (C1s) obtained by photoelectron spectrography (XPS) is controlled to 1.0 to 3.0. Namely, the polyester is surface-treated so that the area ratio of the XPS spectra is controlled to 1.0 to 3.0, when the photoelectrons from the O1s/C1s are measured. The O1s/C1s ratio of the aromatic polyester is t 1.0. The oxygen content of the polymer surface is increased and its hydrophilicity is enhanced when the surface treatment is intensified and the O1s/C1s intensity ratio is increased. The substrate surface is frequently coated with a hydrophilic polymer, and the hydrophilicity is essential to improve adhesion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material including a support having excellent adhesion between an emulsion layer and the support and being hard to curl.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials include sheet-like forms such as X-ray films, plate-making films and cut films, and roll-like forms. A typical roll film is a color film or a black-and-white negative film, which is stored in a patrone with a width of 35 mm or less and which is loaded into a general camera and used for photographing.

It is difficult to increase the adhesive strength of the polyester support to the emulsion layer and the back layer, and it is known to carry out a surface modification treatment for this purpose. For example, JP-A-5
9-56430, U.S. Pat. Nos. 3,761,299, 4,072,769, and JP-B-53-
794, JP-A-53-129262, British Patent 891,409, JP-A-50-11357.
8 gazette, the same 47-15625 gazette, the same 51-417.
The method described in Japanese Patent Publication No. 70 is known. However, in any of these methods, the polyester support was easily colored yellow (yellowing) with these treatments.

In a photographic light-sensitive material using a curled curled support, when it is used in a roll state, scratches are generated and defocusing occurs in a printing process such as a printing step for forming an image on photographic printing paper after development. However, problems such as jamming during transportation will occur. On the other hand, the applications of photographic light-sensitive materials have been diversified, and the speed of film transport at the time of photographing, the high magnification of photographing, and the downsizing of photographing apparatus have been remarkably advanced. In that case, the support for the photographic light-sensitive material is required to have properties such as strength, dimensional stability and thinning.

In the conventional 135 system, if the winding diameter of the inside of the cartridge is reduced to 9 mm or less, a remarkable winding curl occurs and various troubles occur during the automatic developing process. PET film has been considered as an alternative to TAC because of its excellent productivity, mechanical strength, and dimensional stability, but it could not be used in the roll form because of strong residual curl. JP-A-1-244446
No. 4, JP-A-4-220329, and JP-A-4-23503.
No. 6, JP-A-4-235037 and the like have attempted to achieve curl recovery by making polyester water-absorbent, but it is inferior in dimensional stability to PET and has a strong trough curl. New problems such as transportability in the development processor and scratches in the camera occurred.

On the other hand, there is known a method of heat treating a polyester support as described in JP-A-51-16358 at a temperature of Tg or lower.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyester support having less yellowing of the support, excellent adhesiveness between the support and the emulsion layer and the back layer, and having less curling tendency. .

[0008]

These problems are caused by the 1s orbit (C1) of a carbon atom obtained by photoelectron spectroscopy (XPS).
1s of oxygen atom with respect to the amount of photoelectrons emitted from
The intensity ratio of the amount of photoelectrons emitted from the orbit (O1s) is 1.
Achieved with a polyester support of 0 to 3.0.

The present invention is a polyester support having an XPS spectrum area ratio of photoelectrons emitted from Ols and Cls of 1.0 to 3.0 as determined by photoelectron spectroscopy (XPS). That is, the present invention is Ols / C
Surface treatment is performed so that the area ratio of the XPS spectrum when the amount of photoelectrons emitted from Is is measured is 1.0 or more and 3.0 or less. This XPS analysis enables elemental analysis up to 5 nm from the surface of the substance. In the present invention, it was determined from the area of the photoelectron spectrum emitted from the ls orbit of oxygen and carbon by XPS analysis. With these values, the peak top of Cls is set to 284.6 eV, and after correcting the charge shift amount, Cls becomes 296 eV and 2
80 eV was connected by a straight line, and from the peak area appearing on it, Ols was calculated by connecting the 537 and 527 eV by a straight line and the peak area appearing on it. This Ols / Cls
The ratio is 1.0 or more and 3.0 or less, preferably 1.20 or more and 2.0 or less, and more preferably 1.25 or more and 1.8 or less. The aromatic polyester has an O1s / C1s ratio of less than 1.0. Usually, the surface treatment is strengthened and O1s /
The increase in the intensity ratio of C1s indicates that the amount of oxygen on the polymer surface is large and the hydrophilicity is high. In the case of photographic light-sensitive materials, a hydrophilic polymer typified by gelatin is often coated on these polyester supports, so that the surface of the support is hydrophilic in order to improve adhesion. Is. Therefore, in order to obtain sufficient adhesiveness, it is desirable that O1s / C1s is as high as possible. However, when the surface treatment is strengthened, in addition to the increase in the O1s / C1s ratio, the breaking of the molecular chain also progresses, the hydrogen atom is broken, and it easily pops out. Instead, a double bond is generated, and the visible-UV Absorption tends to extend to the long wavelength side. As a result, yellowing occurs. Therefore, even if the surface treatment is too strong, a problem occurs.

The surface energy (γ _B ) of the polyester support of the present invention is preferably 55 dyn / cm or more and 100 dyn / cm or less. These values can be controlled by the intensity of surface treatment, time, and treatment atmosphere. In order to obtain strong adhesiveness, it is desirable that this value is large, but if this value is made too large, scratch resistance decreases and yellowishness increases. Therefore, as a range that achieves both of these, 55 dyn / cm or more 10
It is 0 dyn / cm or less, more preferably 65 dyn / cm or more and 80 dyn / cm or less. The contact angle θ for obtaining the surface energy is a contact angle meter C manufactured by Kyowa Interface Science Co., Ltd.
Using the A-DT • A type, reading was performed 10 seconds after the liquid was dropped on the surface in the atmosphere of 25 ° C. and 60% RH.

Such surface treatment is achieved by glow discharge treatment or flame treatment. The glow discharge treatment conditions are generally such that the pressure is 0.005 to 20 Torr, preferably 0.1.
1-2 Torr is suitable. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow, sparks will easily occur, which is dangerous, and the base will easily become yellow. When the glow discharge treatment was performed under steam as in the present invention, the adhesiveness, yellowing and scratch resistance could be simultaneously improved. This is considered to be because water molecules react with the surface along with the glow discharge treatment, and hydroxyl groups are efficiently introduced into the surface. It is considered that this large amount of generated hydroxyl groups improves the affinity with the hydrophilic binder (eg, gelatin) coated on the surface. The introduction of water vapor into the glow discharge atmosphere is preferably such that the partial pressure is 10% or more and 100% or less, more preferably 40% or more. If the water vapor content is lower than this, sufficient adhesiveness cannot be obtained. Such glow discharge treatment under water vapor can be easily achieved by introducing water vapor into the discharge chamber.

Further, preheating the base before the glow discharge treatment seems to further promote the introduction of hydroxyl groups on the surface. This temperature is 35 ° C. or higher and Tg or lower. 5
At 0 ° C or lower, the adhesiveness does not improve, and at temperatures above Tg,
Significant blocking occurs. At the same time, damage to the glow discharge treatment causes the base to easily turn yellow, and at the same time, reduces scratch resistance. This yellowing and deterioration of scratch resistance are remarkable especially in the case of PEN. As a specific method for raising the polymer surface temperature in a vacuum as described above, there are heating by an infrared heater, heating by contact with a hot roll, and the like. For example, if you want to heat the film surface to 100 ℃, 1
It is sufficient to contact the film with a hot roll at 00 ° C. for at most 1 second. It goes without saying that the heating method is not limited to the above-mentioned method, and widely known heating methods can be used.

Such glow discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. Normally, within this pressure range, a stable steady glow discharge occurs between 500 and 5000V. A particularly suitable voltage range for improving the adhesion is 2000 to 4000V. As the discharge frequency, as seen in the prior art, from direct current to several 1000 MHz, preferably 50 Hz to
20 MHz is suitable. Regarding the discharge treatment strength, 0.01 KV · A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0.15 KV · A because the desired adhesive performance is obtained.
A · min / m ^{2 to 1} KV · A · min / m ² is suitable. The glow treatment may be of a batch type or a continuous type, and it is preferable to cool it immediately after the treatment.

Flame treatment includes natural rubber, liquefied propane gas,
Either city gas may be used, but the mixing ratio with air is important. This is because it is considered that the effect of surface treatment by flame treatment is brought about by plasma containing active oxygen, and the point is how much the plasma activity (temperature) and oxygen that are important properties of flame are. is there. These two are determined by the gas / oxygen ratio, and the energy density becomes the highest and the plasma activity becomes higher when the reaction is performed without excess or deficiency. In particular,
The preferred mixing ratio of natural gas / air is 1/6 to 1 by volume.
/ 10, preferably 1/7 to 1/9. In the case of liquefied propane gas / air, 1/14 to 1/22, preferably 1/16 to 1/19, and in the case of city gas / air, 1
/ 2 to 1/8, preferably 1/3 to 1/7. The amount of flame treatment is preferably 1 to 50 Kcal / m ² , more preferably 3 to 20 Kcal / m ² . The distance between the tip of the internal flame of the burner and the support is preferably 3 to 7 cm, more preferably 4 to 6 cm. The nozzle shape of the burner is
Flynn Burner (US) ribbon type, Wise (US) multi-hole type, Aerogen (UK) ribbon type, Kasuga Electric (Japan) staggered multi-hole type, Koike Oxygen (Japan) staggered type Hole type is preferable. The backup roll that supports the support in the flame treatment is a hollow roll, and it is preferable that the backup roll is water-cooled with cooling water and always treated at a constant temperature of 20 to 50 ° C.

In the case of the roll-shaped treatment, scratches are likely to occur due to squeaking of the outer peripheral surface during the surface treatment. As a countermeasure against this, the present invention kneaded optimal particles into a support to give unevenness to the surface, thereby preventing blemishes without increasing haze and obtaining scratch resistance. In addition, by performing the glow discharge treatment after performing the optimum knurling, it was possible to prevent the squeak and prevent scratching while minimizing the deformation of the base during winding the base. These conditions will be described in detail later. Furthermore, the conditions of glow discharge treatment were optimized, and it was possible to produce a base that is difficult to block and has excellent adhesiveness. Further, as described above, the conditions of the surface treatment were optimized, and it was possible to produce a base that is difficult to block and has excellent adhesiveness.

The polyester used in the present invention is a homopolymer such as polyethylene-2,6-dinaphthalate (PEN), polyarylylate (PAr) or polycyclohexanedimethanol terephthalate (PCT), and
2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), paraphenylenedicarboxylic acid (PPDC) as dicarboxylic acid, Ethylene glycol (EG), cyclohexanedimethanol (CHD
M), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), and parahydroxybenzoic acid (PHB) as hydroxycarboxylic acid.
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA) is copolymerized. More preferred among these are naphthalene dicarboxylic acid, terephthalic acid and ethylene glycol copolymers (mixing molar ratio of naphthalene dicarboxylic acid and terephthalic acid is preferably between 0.3: 0.7 and 1.00, 0.
It is more preferably 5: 0.5 to 0.8: 0.2. ), A copolymer of terephthalic acid, ethylene glycol, and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, more preferably 0.5: 0.5). Is preferably 0 to 0.9), isophthalic acid, paraphenylenedicarboxylic acid, and a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 0.1 when terephthalic acid is 1). 10.
0, 0.1 to 20.0, and more preferably 0.
2 to 5.0, preferably 0.2 to 10.0), naphthalene dicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.7: 0. 3 is preferable, and more preferably 0.9: 0.1 to 0.6: 0.
4) Copolymer of terephthalic acid, ethylene glycol and biphenol (The molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1: 0.9 to 0. 7: 0.3), a copolymer of para-hydroxybenzoic acid, ethylene glycol and terephthalic acid (molar ratio of para-hydroxybenzoic acid, ethylene glycol is 1: 0 to 0.1 :).
0.9 is preferable, and 0.9: 0.1 is more preferable.
0.2: 0.8) and other copolymers and PEN and PET
(A composition ratio of 0.3: 0.7 to 1.0: 0 is preferable, and 0.
5: 0.5 to 0.8: 0.2 is more preferable), PET
And PAr (composition ratio of 0.6: 0.4 to 0: 1.0 is preferable, and 0.5: 0.5 to 0: 0.9 is more preferable). Most preferred are polyesters containing at least 2,6-naphthalenedicarboxylic acid. PEN is a typical example among them.

These homopolymers and copolymers can be synthesized according to conventionally known methods for producing polyesters. For example, when the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, first, the transesterification reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, it can be synthesized. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. Regarding these polyester synthesis methods, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pp. 103-136.
Page, "Synthetic Polymer V" (Asakura Shoten, 1971), 18th
It can be performed with reference to the descriptions on pages 7 to 286. The preferred average molecular weight range for these polyesters is about 5,000 to 50,000.

The polymer blends of the polymers thus obtained are disclosed in JP-A-49-5482 and JP-A-64-5482.
4325, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779.
-82, 294, 807-14, it can be easily formed. Next, the polyester used in the present invention preferably has a Tg of 90 ° C. or higher and 200 ° C. or lower, and specific examples of this compound are shown below. Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C. PCT: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100) / 100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. Copolymer (() represents a molar ratio.) PBC-12,6- NDCA / TPA / EG (50/50/100) Tg = 92 ° C. PBC-2 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. PBC-3 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C. PBC-4 TPA / EG / BPA (100/50/50) Tg = 105 PBC-5 TPA / EG / BPA (100/25/75) Tg = 135 ° C. PBC-6 TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. PBC-7 IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C

PBC-8 NDCA / NPG / EG (100/70/30) Tg = 105 ° C. PBC-9 TPA / EG / BP (100/20/80) Tg = 115 ° C. PBC-10 PHBA / EG / TPA ( 200/100/100) Tg = 125 ° C. PBC-11 NDCA / TPA / EG (52/48/100) Tg = 93 ° C. PBC-12 NDCA / TPA / EG / BPA (50/50/75/25) Tg = 102 ° C. PBC-13 NDCA / TPA / EG (60/40/100) Tg = 103 ° C. PBC-14 NDCA / TPA / EG (48/52/100) Tg = 89 ° C. PBC-15 NDCA / TPA / EG (35 / 65/100) Tg = 87 ° C. Polymer blend (() indicates weight ratio.) PBB-1 PEN / PET (60/40) Tg 95 ° C PBB-2 PEN / PET (80/20) Tg = 104 ° C PBB-3 PAr / PEN (50/50) Tg = 142 ° C PBB-4 PAr / PCT (50/50) Tg = 118 ° C PBB-5 PAr / PET (60/40) Tg = 101 ° C. PBB-6 PEN / PET / PAr (50/25/25) Tg = 108 ° C.

As described above, the polyester support of the present invention preferably has irregularities on the surface in order to secure scratch resistance after the surface treatment, and the irregularities are expressed by surface roughness (Ra), and 0.001 It is preferable that the thickness is up to 0.05 μm.
If it is less than this range, sufficient scratch resistance cannot be obtained, and if it is more than this range, the support is more likely to be caught and conversely the scratch resistance is lowered. In addition, haze tends to increase and transparency tends to decrease.
The polyester support having such irregularities is generally used at any time during the reaction for forming the polyester, for example, during the transesterification reaction or the polycondensation reaction in the case of the polyester exchange method, or in the direct polymerization method. It can be produced by adding fine particles to the reaction system at the time. Preferably, it is added at the initial stage of the polycondensation reaction, for example, until the intrinsic viscosity reaches about 0.3.

The fine particles usable in the present invention are represented by the following formula f = V / D ^3, where V is the average volume (μm ³ ) per particle, and D is the average maximum particle size ( μm). The volume shape factor (f) defined by is larger than 0.2 and is π / 6 or less. In the above definition, D
The average maximum particle size of the particles should be understood to mean the distance having the maximum length of the distances between two points where an arbitrary straight line crossing the particles intersects with the circumference of the particles. The more preferable value of f of the fine particles in the present invention is 0.3 to π / 6, and the more preferable value of f is 0.4 to π / 6. A particle having a value of f of π / 6 is a true sphere. F smaller than the lower limit
The use of fine particles having a value tends to increase the film haze.

The spherical fine particles have an average particle size of 0.
05-3.0 μm, preferably 0.05-1.0 μm,
More preferably, it is 0.1 to 0.8 μm.

When the average particle diameter of silica particles (total sum of area-equivalent diameters of measured particles / number of measured particles) is 0.05 μm or less, sufficient squeak preventive property cannot be obtained, and as a result, scratches are likely to occur. On the other hand, if the average particle size exceeds 3.0 μm, protrusions on the surface of the film become high and the scratch resistance decreases, which is not preferable. The spherical silica particles preferably have a sharp particle size distribution, and the relative standard deviation representing the steepness of the distribution is 0.5 or less, more preferably 0.4 or less, and particularly preferably 0.3 or less. . This relative standard deviation is given by

[0024]

[Equation 2]

[0025]

[Equation 3]

Represents When fine particles having a relative standard deviation of 0.5 or less are used, a polyester support having a perfect spherical shape and an extremely sharp particle size distribution and having uniform protrusion height and excellent in scratch resistance and transparency can be obtained.

The amount of such fine particles added is required to be 0.001 to 0.8% by weight, preferably 0.005 to 0.6% by weight, more preferably 0.1 to 0.8% by weight, based on the polyester. It is 0.5% by weight. Addition amount is 0.001
If it is less than 10% by weight, squeaks tend to occur during winding and scratches tend to occur. On the other hand, when it exceeds 0.8% by weight, haze is increased, transparency is lowered, and scratch strength is lowered, which is not preferable. Such fine particles may be either organic matter or inorganic matter. As an example of the fine particles of inorganic matter, preferably a. Silicon dioxide; b. Alumina; c. Silicates containing 30 wt% or more of SiO ₂ (for example, amorphous or crystalline clay minerals, aluminosilicates (including baked products and hydrates), warm asbestos, zircon, fly ash, etc .; d. Zn, Zr and Ti oxides; e. Sulfates of Ca and Ba; f. Li, Ba and Ca phosphates (1
Hydrogen salts and dihydrogen salts are included); Benzoate salts of Li, Na and K; Terephthalates of Ca, Ba, Zn and Hn; Mg, Ca, Ba, Zn, Cd, Pb, S
r, Hn, Fe, Co and Ni titanates; Ba
And Pb chromate salts; Carbon (eg carbon black, graphite, etc.); Glass (eg glass powder, glass beads, etc.); Carbon salts of Ca and Mg;
F. Fluorite; and yo. ZnS is exemplified. More preferably, silicic acid anhydride, hydrous silicic acid, aluminum oxide,
Aluminum silicates (including calcined products, hydrates, etc.), 1 lithium phosphate, 3 lithium phosphate, sodium phosphate, calcium phosphate, barium sulfate, titanium oxide, lithium benzoate, double salts of these compounds (hydrates Glass powder, clay (including kaolin, bentonite, clay etc.),
Examples are talc, diatomaceous earth, calcium carbonate and the like. Particularly preferred are silicon dioxide and alumina calcium carbonate. Further, these fine particles may be organic substances, and for example, crosslinked polystyrene, crosslinked polymethylmethacrylate, etc. can be used. Alternatively, a silicone resin may be used. These fine particles may be used alone or as a mixture.

Further, an ultraviolet absorber may be kneaded into these polymer films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the amount thereof added is usually 0.5% by weight to 20% by weight based on the weight of the polymer film.
%, Preferably about 1 to 10% by weight. If it is less than 0.5% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. As the ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ', 4. Benzophenone-based compounds such as 4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2
(2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy 3 ', 5'-di-t-
Examples include benzotriazole-based UV absorbers such as butylphenyl) benzotriazole and 2 (2′-hydroxy-3′-di-t-butyl-5′-methylphenyl) benzotriazole; salicylate-based UV absorbers such as phenyl salicylate and methyl salicylate. To be

Further, one of the properties which poses a problem when the polyester film is used as a support for a photographic light-sensitive material is the problem of fogging caused by the high refractive index of the support. Polyester, particularly aromatic polyester, has a high refractive index of 1.6 to 1.7, while gelatin, which is the main component of the photosensitive layer coated on the polyester, has a refractive index of 1.50 to 1.55. Less than this value. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging). As a method of avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film, a method of adding a dye, and the like are known. The dye used for film dyeing is preferably gray dyeing due to the general properties of the light-sensitive material, and the dye preferably has excellent heat resistance in the film forming temperature range of the polyester film and has excellent compatibility with polyester. . From the above viewpoints, as the dye, it is possible to achieve the object by mixing commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more. Such a dye may be kneaded into the support together with the fine particles of the present invention.

Next, a method for forming a support film will be described.
In producing the biaxially oriented film of the present invention, spherical silica particles, or inert particles or internally precipitated particles with it in a polymerization vessel before or during the polymerization of the aromatic polyester, when pelletizing after the polymerization, extrusion, In the machine or when melt-extruding into a sheet, the aromatic polyester may be sufficiently kneaded in the extruder.

The polyester film of the present invention is obtained by melt-extruding an aromatic polyester at a temperature of, for example, a melting point (Tm: ° C.) to (Tm + 70) ° C. and an intrinsic viscosity of 0.45 to 0.
9. An unstretched film of No. 9 was obtained, and the unstretched film was uniaxially (longitudinal or transverse) (Tg-10) to (Tg + 7).
At a temperature of 0) ° C. (Tg: glass transition temperature of aromatic polyester) at a draw ratio of 2.5 to 5.0, and then in a direction perpendicular to the above-mentioned stretching direction (when the first stage stretching is in the longitudinal direction). Is in the transverse direction in the second stage stretching) to Tg (° C) to (T
It can be produced by stretching at a temperature of g + 70) ° C. at a draw ratio of 2.5 to 5.0 times. In this case, the area draw ratio is 9 to 2
It is preferably doubled, more preferably 12 to 22 times. The stretching means may be simultaneous biaxial stretching or sequential biaxial stretching.

Further, the biaxially oriented film has (Tg + 7
It can be heat-set at a temperature of 0) ° C. to Tm (° C.).
For example, a polyethylene-2,6-naphthalate film is preferably heat set at 190 to 250 ° C. The heat setting time is, for example, 1 to 60 seconds. When it is desired to further increase the elastic modulus, the heat setting temperature of these biaxially stretched films is (Tg + 20) ° C. to (Tg + 7).
0) ℃ and heat set, and then 10 to 10
Longitudinally or transversely at a temperature of 40 ° C. higher, and then further transversely or longitudinally at a temperature 20 to 50 ° C. higher than this temperature,
In the longitudinal direction, the draw ratio is 5.0 to 6.9 times, and in the transverse direction, the total draw ratio is 5.0 to 6.9 times. The stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. The number of times of stretching in the machine direction and the transverse direction is not limited.

The haze of the polyester thus formed is 3% or less and 0% or more, preferably 2% or less, and more preferably 1.5% or less. Haze is 3
When it is more than%, the sharpness of the photographic image becomes poor.
The polyester support of the present invention has a friction coefficient of 0.6 or more, preferably 0.7 or more, and more preferably 0.75 or more. If the coefficient of friction is less than 0.6, the rolls in the manufacturing process may slip and cause scratches. In addition, slippage occurs when winding a long film, which causes misalignment. The polyester of the present invention has a thickness of 50 to 100 μm. If it is thinner than this, it cannot withstand the contraction force of the emulsion and becomes a gutter-like curl, and if it is thicker than this, the camera and the cartridge cannot be made thin and small.

The surface roughness Ra of the support is 0.001.
˜0.05 μm is preferable. This value is 0.
If it is 001 or less, sufficient squeak preventing ability cannot be obtained, and as a result, scratches easily occur, and if it is 0.05 or more, scratching becomes large and scratch resistance is lowered again.

The knurling in the present invention is disclosed in Japanese Patent Publication No. 57-57.
It was carried out according to the method shown in No. 36129. The height of knurling was determined by measuring the thickness of the knurling portion and the portion without knurling. The height of knurling is
5 μm or more and 50 μm or less was preferable. If it is 5 μm or less, the squeak preventing effect is insufficient, while if it is 50 μm or more, there is a problem that winding misalignment tends to occur during winding.
Further, knurling is preferably applied to the end of the film from the viewpoint of product yield. Further, from the viewpoint of preventing winding deviation, it is preferable to attach the film to both ends.

As a means for solving the problem of curling curl, it is known that the curl is reduced by heating the film according to US Pat. No. 4,141,735. It is desirable to perform this heat treatment at a temperature slightly below the glass transition temperature in order to shorten the treatment time.
C. or higher and the glass transition temperature or lower, and more preferably, the temperature is 30 ° C. below the glass transition temperature or higher and the glass transition temperature or lower. On the other hand, when the heat treatment is performed under this temperature condition, the effect is recognized after 0.1 hour. On the other hand, at 1500 hours or more, the effect is almost saturated. Therefore, it is necessary to perform heat treatment for 0.1 hour or more and 1500 hours or less. Furthermore, in the method of heat-treating the polyester of the present invention, in order to shorten the time, it is previously heated to Tg or more for a short time (preferably 5 minutes to 3 times Tg of 20 ° C. or more and 100 ° C. or less).
It is preferable to process for time. In the heating method, the film roll may be left as it is in a heating warehouse for heat treatment, or the film may be conveyed by a heat roll or a heater and then heated to be wound at a high temperature and then heat treated. May be given. Furthermore, a long heating zone may be heat-treated during transportation. Further, the roll core used in the heat treatment preferably has a structure in which an electric heater is built in or a high-temperature liquid can be poured so that the film can be hollow or heated in order to efficiently propagate the temperature to the film. The material of the roll winding core is not particularly limited, but it is preferable that the material does not undergo strength reduction or deformation due to heat, and examples thereof include stainless steel and resin containing glass fiber.

When the polymer film thus formed is used as a support, (1) a method of performing surface treatment and then directly applying a photographic emulsion to obtain an adhesive force, (2) an undercoat first
In the layer, for example, a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethyleneimine, epoxy There is a method in which resin, grafted gelatin, nitrocellulose, etc. are used, and gelatin is mainly used in the second undercoat layer, (3) a single layer method by swelling the support and interfacial mixing with a hydrophilic undercoat polymer. . Examples of the hydrophilic undercoating polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose as a cellulose ester,
Hydroxyethyl cellulose and the like. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-resin. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Various gelatin hardeners can be used in the subbing layer of the present invention. As a gelatin hardening agent, chromium salts (chrome alum, etc.),
Aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin, etc. can be mentioned.

The subbing layer of the present invention comprises SiO ₂ , Ti.
O ₂ and inorganic fine particles such as a matting agent or polymethylmethacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent. In addition to this, the undercoat liquid may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is a well-known coating method such as dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by the extrusion coating method using the hopper described in the specification of 2,681,294. If desired, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be simultaneously coated by the method described in “Coating Engineering”, page 253 (1973, published by Asakura Shoten).

The binder for the back layer may be either a hydrophobic polymer or a hydrophilic polymer used in the subbing layer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a slip agent, a matting agent, a surfactant, a dye and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, and for example, as the anionic polymer electrolyte, carboxylic acid and carboxylic acid salt,
A polymer containing a sulfonate is disclosed in, for example, JP-A-48-220.
17, JP-B-46-24159, JP-A-51-30
725, JP-A-51-129216, JP-A-55-
It is a polymer as described in No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
3, JP-A-48-91165, JP-B-49-245.
No. 82 is available. Further, the ionic surfactant has anionic property and cationic property, and is disclosed in, for example, JP-A-49-85826 and JP-A-49-33630.
U.S. Pat. No. 2,992,108, U.S. Pat. No. 3,2
06, 312, JP-A-48-87826, JP-B-49
-11567, JP-B-49-11568, JP-A-5
The compound as described in 5-70837 etc. can be mentioned.

Most preferred as an antistatic agent for the back layer of the present invention
Preferred are ZnO and TiO₂, SnO₂, Al₂
O₃, In₂O₃, SiO₂, MgO, BaO, MoO
₃V ₂O_FiveAt least one crystalline gold selected from
It is a fine particle of a group oxide or a complex oxide of these.
Conductive crystalline oxide used in the present invention or composite thereof
Oxide particles have a volume resistivity of 10⁷Ωcm or less,
More preferably 10^FiveΩcm or less. Also its particles
The size is 0.002-0.7 μm, especially 0.005-
It is desirable to set it to 0.3 μm. The table mentioned above
Surface treatment, heat treatment, undercoat, back layer coating after surface treatment
If the undercoat and back layer are applied, the other order does not matter.
Any order is acceptable, and the following order is preferable. Heat treatment → Surface treatment → Undercoat, back layer coating Surface treatment → Heat treatment → Undercoat, back layer coating Surface treatment → Back layer coating → Heat treatment → Undercoat

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be any of black and white colors. Here, a color silver halide photographic light-sensitive material will be described. The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support, and a silver halide emulsion. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed according to the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-61 are used.
The couplers and DIR compounds as described in 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is usually used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, JP-A-57-112751.
No. 62-200350, No. 62-206541.
No. 62-206543, No. 56-25738,
62-63936, 59-202464, JP-B-55-34932, and 49-15495.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. (Additive type) (RD176439) (RD187169) 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to 24, page 648, right column, page 649, right Column 4 Whitening agent Page 24 5 Antifoggants and stabilizers 24 to 25 pages 649 Right column to 6 Light absorbers, filter dyes, UV absorbers 25 to 26 pages 649 Right column to 650 Left column 7 Stain prevention Agent page 25 right column page 650 left to right column 8 dye image stabilizer page 25 9 film hardening agent page 26 651 page left column 10 binder page 26 same as above 11 plasticizer, lubricant page 27 650 right column 12 coating aid, Surfactants, pages 26 to 27, page 650, right column Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503. React with, it is preferable to add a compound capable of immobilizing the photosensitive material.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. .

Since the photographic film using the polyester support of the present invention has a characteristic that it is difficult to curl, it can be stored in a cartridge or a film-integrated camera with a small inner diameter, but if the inner diameter is 3 mm or less. The photographic property is seriously deteriorated due to the pressure of the light-sensitive material, and cannot be practically used.
Therefore, in the present invention, the preferable inner diameter of the film in the camera is 3 mm or more, and the upper limit is preferably 12 mm, more preferably 5 mm to 11 mm, further preferably 6 m.
It is from m to 10 mm.

[0048]

【Example】

Example-1 The present invention will be further described with reference to the following examples. The present invention is not limited to this. Various terms, physical property values, and methods for measuring characteristics in the present invention are as follows. (1) Core set To wrap a film around a spool under specified conditions. (2) Core set curl A curl in the length direction attached by the core set. The degree of winding is Te of ANSI / ASC pH 1.29-1985.
It was measured according to st Method A and expressed in 1 / R [m] (R is the radius of the curl). (3) Glass transition temperature (Tg) Using a differential thermal analyzer (DSC), sample film 10
When mg is heated to 300 ° C once in helium at 20 ° C / min, then rapidly cooled, and when the temperature is raised again at 20 ° C / min, the temperature begins to shift from the baseline and returns to a new baseline. When an endothermic peak appears in the arithmetic mean temperature of temperature or Tg, the temperature shown at the maximum value of this endothermic peak is defined as Tg.

I. Evaluation of Fine Particles (1) Particle Diameter The following two methods are available for measuring the particle diameter. For internally precipitated particles, use method (2), otherwise use method (1). 1) When obtaining the average particle size, particle size ratio, etc. from spherical fine powder. 2) When obtaining the average particle size, particle size ratio, etc. of the fine powder particles in the film. 1) From spherical particle powder: Spherical fine powder is scattered on the electron microscope sample stand so that individual particles do not overlap as much as possible, and a gold thin film deposition layer is formed on this surface with a thickness of 200 to 300Å by a gold sputtering device. Observe at a magnification of 10,000 to 30,000 with a scanning electron microscope and at least 10 with a Luzex 500 manufactured by Nippon Regulator Co., Ltd.
The maximum diameter (Dli), the minimum diameter (Dsi) and the area circle equivalent diameter (Di) of 0 particles are obtained. Then, the number average value represented by the following equation represents the maximum diameter (Dl), the minimum diameter (Ds), and the average particle diameter (D ⁻ ) of the spherical fine powder particles.

[0050]

[Equation 4]

2) Spherical fine particles in the film: A small piece of the sample film was fixed on a sample stand for a scanning electron microscope, and a sputtering device (JFC-110 manufactured by JEOL Ltd.) was used.
The film surface is subjected to an ion etching treatment under the following conditions using a 0 type ion sputtering device). The conditions were as follows: the sample was placed in a bell jar, the degree of vacuum was raised to a vacuum state of about 10 ^-3 Torr, the voltage was 0.25 kV, and the current was 12.
Ion etching is performed at 5 mA for about 10 minutes. Further, the film surface was subjected to gold sputtering with the same device, and observed with a scanning electron microscope at a magnification of 10,000 to 30,000, and the maximum diameter (Dli) of at least 100 particles was measured with Luzex 500 manufactured by Nippon Regulator Co., Ltd. Minimum diameter (Dsi)
And the equivalent circle diameter (Di). Hereafter, the same procedure as the above (a) is performed.

(2) Relative standard deviation The difference particle size distribution is obtained from the integrated curve of the above item 1), and the relative standard deviation is calculated based on the following definition formula of relative standard deviation.

[0053]

[Equation 5]

II. Evaluation of Physical Properties after Film Forming Film and Surface Treatment (1) Film Surface Roughness (Ra) It is a value defined by JIS-BO601 as the center line average roughness (Ra). Stylus-type surface roughness meter (SURFCORDER SE-30C)
Is measured. The measurement conditions are as follows. (A) Stylus tip radius: 2 μm (b) Measuring pressure: 30 mg (c) Cut-off: 0.25 mm (d) Measuring length: 0.5 mm (e) How to put together data The same sample was repeatedly measured 5 times, The largest value is 1
Except for one, round off the fourth decimal place of the average value of the remaining four data, and display up to the third decimal place.

(2) Squeakiness Two films are stacked on a smooth glass plate, a rubber plate is further placed on the film, and a load is placed on the rubber plate, and the contact pressure between the two films is set to 2 g / cm ² and 20 mm / The film was slid at min and the frictional force was measured. The coefficient of friction was defined as the coefficient of kinetic friction at the point of 5 mm sliding, and this was used as an index of squeakiness. (3) Haze Measured according to ASTN-D 1003-52. (4) Scratch strength A sample film (35 mm x 1.8 m) was put in a 135 cartridge, and the film was rolled and loosened at 50 ° C for 24 hours.
Heat treatment was performed for an hour. This was taken out, and a diamond needle having a tip diameter of 25 μm was vertically placed on the back surface, and a continuous load was applied to scratch the needle at a speed of 60 cm / min. After removing the emulsion layer with antiformin, the emulsion layer was observed on a light table, and the load at which scratches started to be seen by transmitted light was taken as the scratch strength. (5) Evaluation of Yellowness of Support The absorbance (A) at 400 nm of the support after the glow discharge treatment was measured. The measurement was performed on the sample side with the surface-treated film and on the reference side with air. The absorbance (A ') of the film before surface treatment was measured by the same method, and (A) / (A') was taken as the increase in the yellowness of the film.

(6) Generation of scratches The support after the glow discharge treatment was applied with a tension of 20 kg / 1 m width for 3 times.
After winding at 0 m / min, this was wound and unwound, and the occurrence of scratches was examined with a reflection light source. No scratches visible to the naked eye in 5 cm square
.About.3 or less are indicated by .largecircle., 4 to 6 are indicated by .DELTA.

(7) Winding form 1 m wide base is 20 kg / 1 m wide with constant tension of 30 m /
When the maximum difference in the unevenness of the base end surface is 10 mm or less when the film is wound up for 3000 m at a speed of 10 minutes, ○, 10
Those with a diameter of 20 mm are indicated by Δ, and those with a diameter of 20 mm or more are indicated by a cross. (8) Ols / Cls intensity ratio The support immediately after the surface treatment was measured under the following conditions.・ Equipment: ESCA-750 type (manufactured by Shimadzu Corporation) ・ X-ray source: Mg Kα ray ・ Measurement speed: 0.5 sec / eV The method for determining the peak area and the method for charge shift are as described above. . (9) Surface Energy By the method described above, the contact angle of methylene iodide and water of the support immediately after the surface treatment was measured to calculate the surface energy.

III. Evaluation of Film after Coating of Photosensitive Layer (1) Rolled film (35 mm × 1.8 m) was conditioned at 25 ° C. and 60% RH for one night or more, and the humidity was adjusted under predetermined conditions (temperature). , Which was core-set on a spool of 8 mmφ for a night, and allowed to cool overnight, this was developed in Minilab (FP-550B: Fuji Photo Film Co., Ltd.), and troubles and curl values associated with the minilab treatment were measured ( ANSI / ASC pH 1.29-1
It was carried out using a curl plate according to 985 method A). The composition of the developing solution, the processing time, etc. are described in Japanese Patent Application No. 5-82.
This is the same as the method of the first embodiment.

(2) Adhesion Evaluation (2-1) Adhesion Evaluation Method During Drying A razor is used to make 6 cuts at intervals of 5 mm in length and width to make 25 squares, and an adhesive tape ( Attach Nitto tape manufactured by Nitto Denki Kogyo Co., Ltd. and quickly peel it off in 180 ° direction. In this method, 95% or more of the unpeeled portion is class A, 90% or more is class B, 60% or more is class C, and less than 60% is class D. Adhesive strength that can withstand practical use as a photographic material is one classified into Class A in the above four-stage evaluation.

(2-2) Adhesion Evaluation Method During Wetness In each of the following color development, fixing and stabilizing bath processing steps, the emulsion surface of the film is marked with an X mark to scratch the emulsion surface of the film with a writing brush. This was rubbed 5 times strongly with a fingertip with a rubber sack, and the maximum peeling width peeled along the line X was used to evaluate the adhesion. Class A when the emulsion layer does not peel more than scratches,
When the maximum peel width is within 2 mm, it is classified as B class, when the maximum peel width is within 5 mm, it is classified as C class, and the others are classified as D class. Adhesive strength that can withstand practical use as a photographic material is one classified into Class A in the above four-stage evaluation.

1. Film formation of support Intrinsic viscosity of 0.60 containing fine particles under the conditions shown in Table 1
Polyethylene-2,6-naphthalate and its derivatives were synthesized by a transesterification method, and the polyethylene terephthalate pellets were dried at 170 ° C. for 4 hours and then T
-After melt-extruding from the die, it was stretched 3.4 times in the longitudinal direction and 4 times in the transverse direction to prepare a biaxially stretched film having a thickness of 85 µm. Extrusion temperature is 300 ° C, longitudinal stretching temperature is 140
C., and the transverse stretching temperature was 130.degree. The biaxially stretched film thus prepared was heat set at 250 ° C. for 6 seconds.
Haze, scratch strength, friction coefficient, and surface roughness of the film thus formed were measured and shown in Table 1. 2. Knurling This film was knurled as shown in Table 1. 3. Heat treatment of the support According to the levels 1-1 to 37 in Table 1, the surface to be coated with the photosensitive layer is wound around a winding core having a diameter of 150 mm, and 110
Heat treatment was performed for 24 hours in a constant temperature air bath at ℃.

4. Surface Treatment of Support 4-1) Glow Discharge Treatment The support after the above heat treatment was subjected to glow discharge treatment on both sides of the film under the conditions shown in Table 1. In the glow discharge treatment device used here, four aluminum rod electrodes having a diameter of 30 mm and a length of 400 mm were fixed on an insulating plate at intervals of 10 cm, and a position 150 mm away from the electrode surface was for 2 seconds. The treatment was carried out by passing through the support. In addition, the temperature of the base is adjusted by using a heat roll installed immediately before the glow discharge electrode.
The contact was performed for 2 seconds. Further, a cooling roll (25 ° C.) was placed immediately after the electric discharge treatment and then wound. After that, XPS measurement, surface energy measurement, and blocking property, winding shape, and yellowness were evaluated. 4-2) Flame treatment Using a frame processing device manufactured by Kasuga Electric Co., Ltd., surface treatment was performed on the front and back surfaces of the support under the following conditions. -City gas / air ratio: 1 / 5-Flame treatment amount: described in Table 1-Distance between inner flame and support 5 cm-Roll temperature at which the support is in contact during flame treatment: 35
C. After that, XPS measurement, surface energy measurement, blocking appearance, and yellowness were evaluated. 5. Coating of undercoat layer The following undercoat liquid was applied to a support of a level subjected to glow discharge treatment, dried at 115 ° C for 2 minutes and then wound up.
The coating amount was 10 ml / m ² . Gelatin 1 part by weight Water 1 〃 Methanol 50 〃

[0063]

[Chemical 1]

For the flame-treated support,
The following undercoat liquid was applied, dried at 115 ° C. for 2 minutes, and then wound. The coating amount was 10 ml / m ² . Gelatin 1.0 parts by weight Water 1.0 〃 Acetic acid 1.0 〃 Methanol 50.0 〃 Ethylene dichloride 50.0 〃 p-Chlorophenol 4.0 〃 6. Application of Back Layer A back layer having the following composition was applied to the surface opposite to the side provided with the undercoat layer of the above-mentioned level of the support after undercoating. 6-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were added to 300 parts of ethanol.
It was dissolved in 0 part by weight to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish average particle size of 0.1.
A fine powder of tin oxide-antimony oxide composite having a size of μm was obtained. The specific resistance of this fine particle powder was 25 Ω · cm.

A mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0 and roughly dispersed with a stirrer, and then a horizontal sand mill (trade name: Dynomill; WILLYA.BA).
CHOFENAG) and dispersed until the residence time reached 30 minutes.

6-2) Preparation of back layer: the following formulation [A]
To a dry film thickness of 0.3 μm,
And dried for 60 seconds. The following coating solution (B) for coating layer was further applied onto this so that the dry film thickness was 1 μm.
It was dried at 5 ° C for 3 minutes. [Formulation A] 10 parts by weight of the conductive fine particle dispersion liquid 1 part by weight gelatin 1 part by weight water 27 parts by weight methanol 60 parts by weight resorcin 2 parts by weight polyoxyethylene nonylphenyl ether 0.01 part by weight [coating layer coating solution (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-Chlorophenol 4 parts by weight Silica particles (average particle size 0.2 μm) 0.01 parts by weight Polysiloxane 0.005 parts by weight C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (8/2 weight ratio) 0.01 parts by weight Dispersion (average particle size 20 nm)

7) Coating of Photosensitive Layer On the support obtained by the above-mentioned method, each layer having the same composition as in Example 1 of Japanese Patent Application No. 5-82 was coated in multiple layers to prepare a multilayer color photosensitive material. These were evaluated for adhesiveness and curl.

8) Evaluation results The results are shown in Tables 1 and 2.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

[Table 5]

[0075]

[Table 6]

[0076]

[Table 7]

[0077]

[Table 8]

(1) Ols / Cls, surface energy Examples 1-1 to 21, 23, 24, 27 subjected to glow discharge treatment and flame treatment within the XPS Ols / Cls intensity ratio, surface energy range of the present invention. , 28, 31, 32,
34-36, 38-43 and O1s / within the scope of the invention
Flame treated within the range of C1s ratio and surface energy 2
Regarding Nos. 2 and 3, both good adhesion and little yellowness could be achieved. These are glow processing vacuum degree 0.0
05 Torr or more, 20 Torr or less, water vapor content 10
% Or more and 100% or less, voltage between electrodes 500 V or more 500
At 0 V or less, at a base temperature of 35 ° C. and at Tg or less, the flame treatment was achieved by carrying out a treatment intensity of 1.0 to 50 Kcal / m ² . In the case of glow discharge treatment, when the vacuum degree is outside this range, as shown in Examples 1-26 and 29, Ols /
Cls ratio and surface energy are low, and sufficient adhesion cannot be obtained. When the water vapor content is below this range, the water vapor content of Examples 1-3
As shown in 7, the Ols / Cls ratio and the surface energy were low and the adhesive strength was insufficient. In the range below this range, as shown in Example 1-30, the Ols / Cls ratio and the surface energy are low, and the adhesive strength is insufficient, while above this range,
As in Example 1-33, the yellowness was remarkably increased and it was NG. When the base temperature was below this range, the adhesive strength was insufficient as shown in Example 1-22. On the other hand, even if it is over this range, as shown in Example 1-25, the yellowness increases and the N
It was G. Similarly, in the flame treatment, the treatment strength was insufficient, and the O1s / C1s ratio and the surface energy were small.
As shown in -1, the adhesiveness was lowered, and on the other hand, when the treatment strength was too strong and O1s / C1s and the surface energy were too large, scratches were likely to occur and yellowness increased.

(2) Surface Roughness of Support, Fine Particles Added, Haze Further, by carrying out the contents described in claims 3 to 8 of the present invention, scratches are further reduced, scratch strength is excellent, and haze is excellent. We were able to make a support with less winding and good winding appearance. Fine particles having a particle size level of 1-2 have a poor squeaking property, and scratches are generated during winding.
G, on the other hand, Levels 1-5 using the ones larger than this had a significant decrease in scratch strength and were NG. Level 1 within this range
-3 and 1-4 were good in both scratch generation and scratch strength. Amount of fine particles added Level 1-7 has poor squeakiness and scratches occur during winding.
G, and the levels 1 and 9 higher than this were NG with haze of 3% or more. On the other hand, the levels within this range 1-6, 1-
The sample No. 8 had a small haze and a few scratches, and was good. Volume Shape Factor of Fine Particles At the low level 1-11, the haze increases to 3% or more and N
It was G. On the other hand, in the level 1-10 within this range, the haze was low and good. At the relative standard deviation level 13 of the fine particles, the scratch strength decreased and the result was NG. On the other hand, level 12 within the range was OK. Fine particle material Silica (Level 1-1), Cross-linked polystyrene (Level 1-3)
6) and silicone (1-37) were used, but there was no problem in either case. The surface roughness of level 1-15 was NG and scratches were generated, and the level of level 1-17 above this range was significantly poor in scratch strength. On the other hand, within this range 1-14, 1-1
No. 6 was good in both scratch resistance and scratch strength.

(3) Knurling By applying knurling to the support before the glow discharge treatment, it was possible to reduce the occurrence of scratches and prevent the winding from slipping. Knurling thickness At level 1-19, scratches were generated and NG was found, and at 1-21, which was larger than this range, winding deviation was found and NG. On the other hand, 1-20 and 1-18 within this range were OK.

(4) Heat Treatment of Base For the levels 1-1 to 35 and 1-37 to 44 obtained by subjecting the polyester base to heat treatment at a temperature not higher than Tg and not lower than 35 ° C., a forced core corresponding to about 3 years in natural time Curling is sufficiently small under the set conditions (50 ° C 24hr),
No trouble occurred in the minilab. On the other hand, with respect to the level 1-36 which was not subjected to this heat treatment, the curl value was large and a trouble (breaking of the rear end) occurred in the minilab.

(5) Base species Naphthalenedicarboxylic acid content 50 mol of naphthalenedicarboxylic acid in dicarboxylic acid component
% Level of 1-39 to 41, it becomes difficult to curl by applying heat treatment at 35 ° C to Tg, and 50 ° C2
Under the core setting condition of 4 hours, all of the workability of the minilab was OK, and no trouble occurred even under the stronger core setting condition of 80 ° C. for 2 hours. On the other hand, when the level is less than 50 mol% and the level is 1-42 to 43, a trouble occurs during transportation in the minilab under the core set condition of 80 ° C. for 2 hours. Tg Tg is 35 in the level 1-39 to 41 of 90 ° C or higher.
The combination of -Tg heat treatment makes it difficult to curl, and there are no problems in the minilab under the core setting conditions of 50 ° C for 24 hours and 80 ° C for 2 hours. On the other hand, 1-42, 43, and 44 having a Tg of less than 90 ° C. had no problem at 50 ° C. for 24 hours, but had a problem under the core setting condition of 80 ° C. for 2 hours.

[0083]

EFFECTS OF THE INVENTION By carrying out the present invention, it is possible to provide a photographic light-sensitive material containing a support with excellent productivity such as excellent adhesion, less curling, less yellowing and less scratches. .

Claims (11)

[Claims] 1. The intensity ratio of the amount of photoelectrons emitted from the 1s orbit (O1s) of oxygen atom to the amount of photoelectrons emitted from the 1s orbit (C1s) of carbon atom, which is determined by photoelectron spectroscopy (XPS), is 1 A polyester support having a ratio of 0.0 to 3.0. 2. The polyester support according to claim 1, wherein the glass transition point of the polyester support is 90 ° C. or higher and 200 ° C. or lower. 3. The dicarboxylic acid of the polyester,
The polyester support according to claim 1, which contains at least naphthalenedicarboxylic acid. 4. The polyester support according to claim 2 or 3, wherein at least 30 mol% of the dicarboxylic acid of the polyester is naphthalenedicarboxylic acid. 5. The polyester is polyethylene-2,
The polyester support according to claim 4, which is 6-naphthalate. 6. The surface energy of at least one surface of the polyester support is 55 dyn / cm or more and 100 dyn / cm.
The polyester support according to any one of claims 1 to 5, wherein: 7. The T of the polyester support at 35 ° C. or higher.
The polyester support according to any one of claims 1 to 6, which has been heat-treated to a temperature of not more than g. 8. The surface roughness Ra of the polyester support is 0.001 μm or more and 0.05 μm or less, and the haze is 3% or less, according to claim 1. Polyester support. 9. The volume shape factor is 0.2 to π / 6, and the relative standard deviation of the particles defined by the following formula is 0.
Fine particles having a particle diameter (D) of 0.05 to 3 μm are characterized in that the particle diameter is 0.001 to 0.
8 wt% is contained, Claim 1- Claim 8 characterized by the above-mentioned.
The polyester support described in 1. [Equation 1] 10. A polyester support having a knurled thickness of 5 to 50 μm thicker than an average non-knurled thickness, and a non-knurled portion of the polyester support having a thickness of 60 to 50 μm.
It is 100 micrometers, It is characterized by the above-mentioned.
The polyester support described in 1. 11. A silver halide photographic light-sensitive material comprising at least one photosensitive layer on a polyester support, wherein the polyester support is the polyester support according to any one of claims 1 to 10. A silver halide photographic light-sensitive material characterized by: