JPH1010676A - Photographic support and its preparation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photographic support small in dimensional variation after heat development processing and high in lamination accuracy, and its preparation method. SOLUTION: This photographic support has a heat dimensional variation of 0.001-0.04% at 120 deg.C for 30sec. It is heat treated by conveying it at 80 deg.C-200 deg.C in a tension of 0.04-600kg/cm<2> , or winding it in a tension of 0.1-20kg/cm<2> around a roll and heat treating it at 80 deg.C-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photographic support and a method for preparing the same.

[0002]

2. Description of the Related Art In a photosensitive material using a heat development method, 80 to 80% is used.
It is often thermally developed at 150 ° C., and the dimensional change of the photosensitive material after thermal development is larger than that of a conventional photosensitive material of wet development.
This was a practical problem. As a method of improving a dimensional change due to heat, a method of relaxing after heat fixing during a film forming process as described in JP-A-61-235608 or JP-A-3-275332 is known. But,
Such a support has a large heat shrinkage after the undercoating, and as a result, the image quality of the photosensitive material is remarkably deteriorated.

[0003]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a photographic support having an undercoat layer, which has a small dimensional change after heat development, has high overlay accuracy, and has excellent adhesion between the support and the photosensitive layer. It is to provide a preparation method.

[0004]

According to the present invention, there is provided a photographic support having a thermal dimensional change rate at 120 ° C. for 30 seconds of 0.001% or more and 0.04% or less. .04kg / cm
^A method for preparing a photographic support, wherein the support is heat-treated while being conveyed at a tension of ^{2 to} 6 kg / cm ² , and the support is rolled at a tension of 0.1 kg / cm ^{2 to} 20 kg / cm ^2. After winding, 80 ° C in roll state
A method of preparing a photographic support, wherein the heat treatment is performed at a temperature of 200 ° C. or lower.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the absolute value of the thermal dimensional change at 120 ° C. for 30 seconds is 0.001% or more and 0.04% or less, more preferably 0.002% or more and 0.03% or less.
More preferably, it relates to a support of 0.003% or more and 0.02% or less. It is necessary that the thermal dimensional change rate satisfies both the longitudinal direction (MD) and the width direction (TD).

The present inventors have surprisingly found that the tension during the heat treatment of the support, preferably during the application of the undercoat layer, is an important factor. When the undercoat layer is applied, the support may be dried at a high temperature of 100 to 200 ° C. In this step, the support is stretched by tension and becomes a support having a large residual stress again. The term "after undercoat" as used herein refers to the entire process after the undercoat layer is provided on at least one surface of the support. The tension at the time of heat treatment and preferably at the time of applying the undercoat layer is 0.04 kg / cm ² or more and 8 kg /
cm ² or less, more preferably 0.2 kg / cm ² or more 6
kg / cm ² or less, more preferably 1 kg / cm ² or more and 5 kg / cm ² or less. Incidentally, the tension of the present invention,
The value was obtained by dividing the force applied to the support by the cross-sectional area (width × thickness) of the support. Such adjustment of the tension can be easily achieved by adjusting the torque of the winding motor and / or the feeding motor. Also, set up a dancer roll,
It can be easily achieved by adjusting the load applied thereto. Further, in order to control the low tension, it is also preferable to measure the amount of heat shrinkage of the support in advance and reduce the winding amount by an amount corresponding to this amount. By the above method, the tension generated by the heat shrinkage stress is also controlled, so that the treatment with a weaker tension is possible. Further, it is preferable that the width direction is not restricted by a clip or the like, and the support is freely contracted. In order to convey the support with such low tension, it is preferable to use air levitation conveyance other than roll conveyance as much as possible. This is to prevent the occurrence of scratches caused by the reduced roll hold force.

The heat treatment temperature or drying temperature is 70 ° C. to 2
20 ° C, more preferably 80 ° C to 200 ° C, 90 ° C to
190 ° C. is more preferred. The adjustment of the drying temperature may be performed by using a panel-like heater incorporating a nichrome heater or the like, by using a heat source such as a halogen lamp or an IR heater, or by sending hot air. A temperature sensor is installed in the drying zone to monitor the temperature at various places and adjust the output of these heat sources to control the temperature. For this reason, it is preferable that these heat sources are divided into several parts and have a structure that can be individually controlled in order to suppress temperature non-uniformity. It is preferable to surround the casing for performing the drying treatment with a heat insulating material such as glass wool in order to eliminate temperature unevenness. The drying time is preferably from 1 minute to 30 minutes, more preferably from 2 minutes to 20 minutes, even more preferably from 3 minutes to 15 minutes.

After the above steps, the following heat treatment is carried out, that is, (1) heat treatment for transportation and / or (2) heat treatment in a roll form. The heat treatment may be performed subsequently to the first step, but is more preferably performed after winding once. This is because, although the mechanism is unknown, there is an unexpected synergistic effect that the thermal dimensional change rate becomes smaller. In addition, a long drying heat treatment zone is required to carry out these steps continuously, which increases equipment costs.

(1) Heat treatment for transportation 0.04 kg / cm after undercoating the support^TwoMore than 6
kg / cm^TwoHeat-treat while transporting at temperature with the following tension
You. Preferred tension is 0.04 kg / cm^Two6kg /
cm^TwoOr less, more preferably 0.2 kg / cm^Twothat's all
5.5kg / cm ^TwoHereinafter, more preferably, 1 kg / c
m^TwoMore than 5kg / cm^TwoIt is as follows. Tension falls within this range
If it exceeds, the dimensional change after thermal development becomes large.
If it falls below this, it will be held on the transport roll during transport of the support.
And abrasion easily occurs.

The temperature at this time is 80 ° C. or more and 200 ° C. or less,
More preferably 90 ° C or more and 180 ° C or less, still more preferably
Or 100 ° C. or more and 150 ° C. or less. Heat treatment time is 1
Min to 60 min, preferably 2 min to 40 min
More preferably, the time is 3 minutes or more and 30 minutes or less. This
After the heat treatment, a post-heat treatment is further performed. Post heat treatment
Subsequent to the above heat treatment, a temperature of 15 ° C or more and 70 ° C or less, more preferably
It is preferably at least 20 ° C and not more than 60 ° C, more preferably at least 2 ° C.
Heat treatment is performed at 5 ° C. or more and 50 ° C. or less. Processing time is 1 second or more
5 minutes or less, preferably 5 seconds or more and 3 minutes or less
It is more preferably from 10 seconds to 1 minute. After this heat treatment
It is preferable to carry out the treatment while transporting it after the heat treatment of the present invention.
Preferably, the preferred tension is 0.04 kg / cm^TwoMore than 6k
g / cm^TwoOr less, more preferably 0.2 kg / cm^TwoLess than
5.5kg / cm above^TwoHereinafter, more preferably, 1 kg /
cm ^TwoMore than 5kg / cm^TwoIt is as follows.

(2) Roll heat treatment After undercoating the support, 0.1 kg / cm ² or more
0 kg / cm ² or less, more preferably 0.2 kg / cm
² or more and 18 kg / cm ² or less, more preferably 0.5
b In kg / cm ² or more 15 kg / cm ² or less tension - after wound Le, 80 ° C. or higher, 200 ° C. or less, and more preferably not 90 ° C. or higher 180 ° C. or less, more preferably 10
Heat treatment is performed at a temperature of 0 ° C. or more and 150 ° C. or less. Then, after the heat treatment, the cooling temperature up to 75 ° C. is −0.1 ° C./hour or more, −10 ° C./hour, more preferably −0.3 ° C./hour or more, −8 ° C./hour, and still more preferably −0.5 ° C./hour. Cooling at -5 ° C / hour or more at ℃ / hour does not decrease the adhesion between the support and the undercoat interlayer.

In the present invention, the tension at the time of applying the undercoat layer is 1 kg.
/ Cm ² or more 5 kg / cm ² was less dried at 90 ° C. to 190 ° C., (1) conveying a heat treatment and / or (2) B - is an example of a most preferred embodiment is a method of Le heat treatment.

The term "undercoat" as used herein refers to a layer other than the photosensitive layer, which is provided immediately above the support, and may be provided on at least one of the photosensitive layer side and the back layer side. In addition to adhesiveness, the undercoat layer can be provided with antistatic properties, antihalation properties, crossover cut properties, dyeing properties, ultraviolet cut properties, matte properties, scratch resistance, and the like.
As the undercoat layer provided with adhesiveness, a layer (hereinafter, abbreviated as the first undercoat layer) that adheres well to the support is provided as the first layer, and the first undercoat layer and the photographic layer are further formed thereon as the second layer. There are a so-called multi-layer method in which a layer to be adhered (hereinafter, abbreviated as a second undercoat layer) is applied, and a single-layer method in which only a single layer is adhered to the support and the photographic layer.

The first undercoat layer in the multilayer method is selected from, for example, vinyl chloride, vinylidene chloride, butadiene, vinyl acetate, styrene, acrylonitrile, methacrylic acid ester, methacrylic acid, acrylic acid, itaconic acid, and maleic anhydride. Copolymer starting from the obtained monomer, epoxy resin, gelatin, nitrocellulose,
Polyvinyl acetate or the like is used. Also, if necessary,
Triazine-based, epoxy-based, melamine-based, isocyanate-based including blocked isocyanate-based, aziridine-based, oxazaline-based crosslinking agents, colloidal silica and other inorganic particles, surfactants, thickeners, dyes, preservatives, etc. Is also good. (For these, see EHImmergut "Polymer
Handbook "VI187-231, Intersciense Pub.New Y
ork 1966 and JP-A-50-39528 and 50-47.
196, 50-68881, 51-133526,
JP-A 64-538, JP-A 63-174698, JP-A 1-2
40965, 2-184844, JP-A-48-898
70, 48-93672, etc.). In the second layer of the undercoat, gelatin is mainly used.

In the single-layer method, adhesion is obtained by swelling the support and mixing it with the undercoat polymer at the interface. Undercoat polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch,
Water-soluble polymers such as polyvinyl alcohol, polyacrylic acid copolymer and maleic anhydride copolymer, cellulose esters such as carboxymethylcellulose and hydroxyethylcellulose, vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, and acrylic acid ester-containing Latex polymers such as copolymers, vinyl acetate-containing copolymers and vinyl acetate-containing copolymers are used. Preferred is gelatin. As the gelatin, any of those generally used in the art such as so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, and modified gelatin can be used. Among these gelatins, lime-treated gelatin and acid-treated gelatin are most preferably used. The drying temperature in the single-layer method and the multi-layer method is 50 ° C. or more and 150 ° C. as described above.
The point is to perform the process at a temperature of not more than ° C.

It is also preferable to provide a back layer for imparting scratch resistance, slipperiness, curl compensation and antistatic ability to the back surface. This layer may be applied directly on the support and used as an undercoat layer, or may be applied on the adhesive undercoat layer. The back layer may use a hydrophilic colloid as a binder or a hydrophobic polymer as a binder. The most preferred hydrophilic colloid is gelatin. As the gelatin, any one generally used in the art such as so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivative, and modified gelatin can be used. Among these gelatins, lime-processed gelatin is most preferably used,
Acid-treated gelatin. Hydrophilic colloids other than gelatin include colloidal albumin, proteins such as casein, agar, sodium alginate, sugar derivatives such as starch derivatives, cellulose compounds such as carboxymethylcellulose and hydroxymethylcellulose, polyvinyl alcohol, poly-N-vinylpyrrolidone, and polyacrylamide. And the like. In the case of a synthetic hydrophilic compound, other components may be copolymerized. These hydrophilic colloids may be used alone or in combination of two or more. Examples of the binder for the hydrophobic polymer layer include (meth) acrylate polymers such as polymethyl methacrylate and ethyl acrylate, olefin polymers such as polyethylene, styrene polymers,
Rubber polymers such as vinylidene chloride, urethane polymers and butadiene are used. This layer can be one layer or two
It may be more than layers. A polymer latex may be further added to the back layer. The polymer latex used in the present invention is an aqueous dispersion of a water-insoluble polymer having an average particle size of 20 μm to 200 μm.
The dry weight ratio is preferably from 0.01 to 1.0, particularly preferably from 0.1 to 0.8. Preferred examples of the polymer latex used in the present invention include acrylic acid alkyl ester, hydroxyalkyl ester or glycidyl ester, or methacrylic acid alkyl ester, hydroxyalkyl ester, or glycidyl ester as a monomer unit and have an average molecular weight of 10 It is more than 10,000, particularly preferably 300,000 to 500,000.
Specific examples include polyethyl acrylate, poly-n-butyl acrylate, poly-n-propyl methacrylate, n-butyl acrylate / glycidyl methacrylate copolymer, ethylene / 2-hydroxypropyl methacrylate and ethyl acrylate / acrylic acid copolymer Can be shown.

Further, a conductive crystalline gold oxide is used for the back layer.
Alternatively, the surface resistivity is adjusted to 10 by adding the composite oxide fine particles.
¹²It is preferable to set the following. Conductive crystalline oxide or
Has a volume resistivity of 10 as fine particles of the composite oxide. ⁷
Ωcm or less, more preferably 10^FiveΩcm or less is desirable
New The particle size is 0.01 to 0.7 μm,
It is preferably 0.02 to 0.5 μm. The present invention
Conductive crystalline metal oxide or complex acid used for
Japanese Patent Application Laid-Open No. Sho 56-143 discloses a method for producing fine particles of a compound.
No. 430 is described in detail. That is,
First, metal oxide fine particles are produced by Akashiri to improve conductivity.
Heat treatment in the presence of heteroatoms to improve, secondly
Conductivity when producing metal oxide fine particles by firing
Method of coexisting heterogeneous atoms for improvement, third firing
Oxygen concentration in the atmosphere when producing metal fine particles
It is easy to reduce the temperature and introduce oxygen vacancies. metal
Examples including atoms include ZnO, Al, In, etc.
iO_TwoFor Nb, Ta, etc._TwoFor S
b, Nb, a halogen element and the like. Addition of hetero atoms
The addition amount is preferably in the range of 0.01 to 30 mol%, but is preferably 0.1 to 30 mol%.
It is particularly preferable if it is 1 to 10 mol%. Of these
SnO with Sb added_TwoComposite metal oxide particles are most preferred
Good.

Further, a dyed non-photosensitive hydrophilic colloid layer (hereinafter, referred to as a dyed layer) may be provided for the purpose of preventing halation, improving safelight safety, and improving front / back discrimination. These are described in detail in U.S. Pat. Nos. 3,455,693 and 2,548,564 described in the following patents.
Nos. 4,124,386 and 3,625,694
And JP-A-47-13935 and JP-A-55-33172.
No. 56-36414, No. 57-161853,
No. 52-29727, No. 61-198148, No. 6
1-177447, 61-217039, 61
A method of adsorbing a dye to a mordant described in JP-A-219039, JP-A-61-213839, JP-A-63-2088
No. 46, No. 63-296039, JP-A-56-126
No. 39, No. 55-155350, No. 55-15535
No. 1, 63-27838, 63-197943
No., EP No. 15,601, No. 274,723, No. 27
6,566, 299,435, WO88 / 047
No. 94, JP-A-2-264936, etc., and a method using a water-insoluble dye solid. Among these methods, the method of dispersing the dye in a solid state is preferable because the residual color after the development processing is small. In addition to these, a matting agent, a slipping agent, a surfactant, a crosslinking agent, and the like may be added to the binder of the back layer, if necessary.

It is also preferable to provide a back compensation layer. For this purpose, a hydrophilic polymer typified by gelatin, as described in JP-A-7-128770, on which a water vapor permeable polymer coating is applied is preferably used.

The application of the undercoat and the back layer is as follows.
Commonly known coating methods such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or the method described in U.S. Pat. No. 2,681,294. It can be applied by an extrusion coating method using a hopper or the like. Also, if necessary, U.S. Patent Nos. 2,761,791, 3,508,947,
2,941,898 and 3,526,528, Yuji Harazaki, “Coating Engineering”, p. 253 (197
Two or more layers can be applied simultaneously by the method described in Asakura Shoten for 3 years. Such a back undercoat or back layer may be a single layer or a multi-layer, and each layer after drying has a thickness of 0.02 to 10 μm, more preferably 0.1 to 10 μm.
It is preferable to apply the coating so that the total thickness of these layers is 0 to 7 μm.

It is also preferable to perform a surface treatment prior to the undercoating in order to improve the adhesiveness. Preferred surface treatments include glow discharge treatment, corona treatment, ultraviolet irradiation treatment, and flame treatment. In the glow treatment, the most excellent bonding effect can be obtained particularly when steam is introduced into the atmosphere. The water vapor partial pressure is preferably from 10% to 100%, more preferably from 40% to 90%. The gas other than water vapor is air composed of oxygen, nitrogen and the like. Further, if the glow treatment is performed in a state where the support to be surface-treated is heated, the adhesiveness is improved in a short time. The preheating temperature is preferably from 50 ° C. to Tg, more preferably from 60 ° C. to Tg, and even more preferably from 70 ° C. to Tg. The degree of vacuum during the glow treatment is 0.005 to 20 Torr
It is preferred that More preferably, 0.02 to 2 To
rr. The voltage is preferably between 500 and 5000V. More preferably, it is 500-3000V.
The discharge frequency used is from DC to several 1000 MHz, preferably 50 Hz to 20 MHz, more preferably 1 KH.
z to 1 MHz. The discharge treatment intensity is 0.01 KV
Preferably A · min / m ² ～5KV · A · min / m ^2, more preferably 0.15KV · A · min / m ² ～1KV · A · min / m ²
, A desired adhesive performance is obtained.

The discharge frequency of the corona treatment is 50 Hz to 50
00 kHz, preferably 5 kHz to several 100 kHz, is appropriate. Regarding the processing strength of the processing object, 0.001
KV · A · min / m ² ~5KV · A · min / m ^2, preferably is 0.01 kV · A · min / m ² ~1KV · A · min / m ² suitably. The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm.

UV treatment is described in JP-B-43-2603,
It is preferably carried out by the processing methods described in JP-B-43-2604 and JP-B-45-3828. The mercury lamp is a high-pressure mercury lamp or a low-pressure mercury lamp formed of a quartz tube, and preferably has a wavelength of ultraviolet light of 180 to 380 nm. Regarding the method of irradiating the ultraviolet rays, if the mercury lamp is a high-pressure mercury lamp having a main wavelength of 365 nm, the irradiation amount is 20 to 10000 (m
J / cm ² ), more preferably 50 to 2000 (m
J / cm ² ). In the case of a low-pressure mercury lamp having a main wavelength of 254 nm, the irradiation light amount is 100 to 10,000 (mJ).
/ Cm ² ), more preferably 200 to 1500 (m
J / cm ² ).

The method of flame treatment may be natural gas or liquefied propane gas, but the mixing ratio with air is important. In the case of propane gas, a preferable mixing ratio of propane gas / air is 1/14 to 1/22, preferably 1/16 to 1/19 by volume ratio. In the case of natural gas, the ratio is 1/6 to 1/10, preferably 1/7 to 1/9. Flame treatment is 1~50Kcal / m ^2, more preferably performed in the range of 3~30Kcal / m ^2. Further, it is more effective if the distance between the tip of the internal flame of the burner and the support is less than 4 cm. As the processing device, a frame processing device manufactured by Kasuga Electric Co., Ltd. can be used. The backup roll supporting the support during the flame treatment is a hollow roll, which is preferably cooled at a constant temperature by passing through cooling water.

The support used in the present invention preferably uses a polymer having a high Tg. Examples of such polymer materials include polyester-based polymers, polycarbonate (PC) -based polymers, polyarylate (PAr) -based polymers, polyetherimide (PEI) -based polymers, and polysulfone (PSF) -based polymers. , Polyethersulfone (PES) -based polymers, syndiotactic polystyrene (SPS) -based polymers, and the like. Of these, polyester-based polymers, polycarbonate-based polymers, and polyarylate-based polymers are more preferred, and polyester-based polymers are more preferred. Polyester is synthesized by condensation polymerization of dicarboxylic acid and diol. Preferred dicarboxylic acids are terephthalic acid (TPA), isophthalic acid (IPA), and naphthalenedicarboxylic acid (NDC).
A) and the like. These are dicarboxylic acids,
These lower alcohol esters may be used as raw materials in any form. Preferred diols include ethylene glycol (EG), diethylene glycol (DEG), bisphenol A (BPA)), cyclohexane dimethanol (CHDM) and the like. Each of these dicarboxylic acids and diols may be used alone and in the form of a homopolymer.
Alternatively, at least one of them may be used as a mixture of two or more copolymers. In addition, the above homopolymer was
It is also preferable to mix more than one species and use them as a polymer blend. Among these, PET composed of TPA and EG, PEN composed of NDCA and EG, and NDCA are more preferable.
PET is particularly preferred as a copolymer composed of PET and TPA and EG. This is because the photosensitive material for printing has an ultraviolet transmittance necessary for printing on a PS plate. Polyethylene naphthalate (PEN) has the advantage of high glass transition temperature and small thermal dimensional change,
UV transmittance is inferior to PET.

These homopolymers and copolymers can be synthesized according to a conventionally known polyester production method. These polyester synthesis methods are described, for example, in Polymer Experimental Studies, Vol. 5, “Polycondensation and Polyaddition” (Kyoritsu Shuppan, 1980), pp. 103-136, “Synthetic Polymer V” (Asakura Shoten, 1971). Years) 187-286
Page description and JP-A-5-163337,
See -290722, 61-241316 and the like. The polymer thus polymerized is
The intrinsic viscosity measured at 35 ° C. in orthochlorophenol is preferably from 0.40 to 0.9, more preferably from 0.45 to 0.70.

Preferred examples of the specific compounds of the polyester used in the present invention are shown below, but the present invention is not limited thereto. Polyester homopolymer Example HP-1: Polyethylene terephthalate (PET) {terephthalic acid (TPA) / ethylene glycol (EG) (100/100)} (PET) Tg = 69 ° C HP-2: polyethylene naphthalene -(PEN) [2,6-Naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] (PEN) Tg = 119 ° C

Polyester copolymer example (numbers in parentheses indicate molar ratio) CP-1: 2,6-NDCA / TPA / EG (10/90/100) Tg = 73 ° C. CP-2: 2,6- NDCA / TPA / EG (80/20/100) Tg = 105 ° C. CP-3: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C. CP-4: TPA / EG / BPA (100/50/50) Tg = 105 ° C. CP-5: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 110 ° C.

PB-1: PEN / PET (20/80) Tg = 79 ° C. PB-2: PEN / PET (60/40) Tg = 95 ° C PB-3: PEN / PET (80/20) Tg = 104 ° C PB-4: PAr / PET (15/85) Tg = 89 ° C PB-5: PAr / PC / PET (10/10/80) Tg = 77 ° C PB-6: PEN / PET / PAr (10/65/25) Tg = 105 ° C

Examples of the polycarbonate (PC) polymer include the following specific examples. The polycarbonate resin has an average molecular weight of preferably from 8,000 to 100,000, more preferably from 10,000 to 50,000, still more preferably from 15,000 to 35,000. PB-1 (PC) 50 wt% + (PAr) 50 wt% Tg = 170 ° C. PB-2 (PC) 70 wt% + (PAr) 30 wt% Tg = 160 ° C. PB-3 (PC) 90 wt% + (PAr) 10 wt% Tg = 150 ° C. PB-4 (PC) 50 wt% + (PES) 50 wt% Tg = 185 ° C. PB-5 (PC) 70 wt% + (PES) 30 wt% Tg = 170 ° C. PB-6 (PC) 90 wt% + ( PES) 10 wt% Tg = 160 ° C

The polyarylate (PAr) -based polymer is bisphenol-A (2,2-bis (4-
(Hydroxyphenyl) propane) and at least 50 mol% or more of a polycondensate of terephthalic acid as a dicarboxylic acid. The molecular weight of the polyarylate is from 5,000 to 100,000, more preferably from 10,000 to 50,000. Of these, more preferred is bispheno-
It is composed of ru-A and terephthalic acid as constituent units. These polymers may be used alone or in a mixture (polymer
(Blend).

These polymers include inorganic fine particles such as silica, talc, titania, alumina, calcium carbonate, calcium oxide, calcium chloride, and mixtures thereof;
It is also preferable to add organic fine particles such as cross-linked polystyrene and cross-linked polymethyl methacrylate. The average particle diameter of the preferred fine particles is preferably 0.01 μm or more and 3 μm or less,
0.03 μm or more and 1 μm or less are more preferable, and 0.05
More preferably, it is not less than μm and not more than 0.5 μm. The addition amount is preferably from 0 ppm to 300 ppm, more preferably from 0 ppm to 100 ppm, and more preferably from 0 ppm to 10 ppm.
The following are more preferred.

When a film is made of a material containing inert inorganic particles or a dye to which a dye is added in order to prevent the so-called light piping phenomenon (edge fringing), the color tone is preferably gray dyeing due to the general properties of the light-sensitive material. Specific examples of the dye include Diaresin manufactured by Mitsubishi Kasei and Kaya manufactured by Nippon Kayaku.
Dyes commercially available as set or the like can be mixed. Anthraquinone dyes can also be preferably used. For example, dyes described in JP-A-7-13299 can be used. The addition amount is preferably such that the spectral transmittance is 65% to 98% in the wavelength range of 400 nm to 700 nm, and more preferably 70% to 95%. Further, the difference between the maximum value and the minimum value of the spectral transmittance in this wavelength range is preferably 0% or more and 15% or less, more preferably 2% or more and 10% or less.

For improving the stability, it is also preferable to add a phosphate ester. The added amount is preferably 0 ppm to 300 ppm in terms of phosphorus atom, more preferably 10 ppm to 100 ppm. Further, an ultraviolet absorber may be added to the polymer for the purpose of imparting stability over time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the amount of the ultraviolet absorber is usually about 0.5% to 20% by weight, preferably about 1% to 10% by weight based on the weight of the polymer film. It is. Specific examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Benzophenones such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole,
(2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'
-Di-t-butyl-5'-methylphenyl) benzotriazole and the like; and salicylic acid-based ultraviolet absorbents such as phenyl salicylate and methyl salicylate.

Next, a method for forming these polymer films will be described. These are generally produced by a melt film forming method. In this case, the polymer is first formed into pellets and then at a temperature of 100 ° C to 200 ° C for 0.1 hour to 100 hours, more preferably at 120 ° C to 180 ° C for 1 hour to 24 hours.
After drying for a period of time, using a single-screw or multi-screw extruder, heating and melting the material between its melting temperature and the pyrolysis temperature, filtering using a filter as necessary, and then opening a predetermined gap. It is extruded from a holding die and cooled and solidified on a smooth band or drum. At this time, the temperature of the band or drum is 0 ° C. or higher and Tg or lower, more preferably room temperature or higher, Tg−5 ° C. or lower, still more preferably 40 ° C. or higher.
It is preferably carried out at a temperature of not higher than g-20 ° C. At this time, it is preferable to use an electrostatic application method in order to secure better flatness. The applied voltage at this time is preferably 2 kV to 20 kV, more preferably 4 kV to 15 kV.

The unstretched support from which the cooled and solidified film is peeled off is formed into a film according to the following classification. (1) Amorphous polymer A polymer having a crystal melting peak calorie of 10 J / g or more measured by a differential thermal analyzer (DSC) according to the following method. A sample (10 mg) was set in a DSC and placed in a nitrogen stream.
The temperature is raised to 350 ° C. at 0 ° C./min. The largest peak exceeding 200 ° C. and appearing on the endothermic side is defined as a crystal melting peak. The base line on the high-temperature side of the crystal melting peak is interpolated by a straight line on the low-temperature side, and the endothermic amount is calculated from this line and the area formed by the crystal melting peak. This value is defined as the heat of crystal fusion.
Representative amorphous polymers include PC, PAr, PSF, and the like. It is preferable that these polymers are used by winding without stretching.

(2) Crystalline polymer A polymer other than an amorphous polymer.
ET, PEN and the like can be mentioned. These polymers are preferably formed by simultaneously or successively biaxially stretching, heat setting, and relaxing the unstretched film to form a film. The number of stretchings in the vertical and horizontal directions is not limited. Specifically, the unstretched film is uniaxially (longitudinal or transverse) at a temperature of (Tg-10) to (Tg + 70) ° C (where Tg: glass transition temperature) is 2.5 to 5.0 times. The film is stretched at a draw ratio, and then at a temperature of Tg (° C.) to (Tg + 70) ° C. in a direction perpendicular to the above stretching direction (when the first stage stretching is a longitudinal direction, the second stage stretching is a transverse direction). ~
It can be manufactured by stretching at a magnification of 5.0 times. Preferably, the longitudinal stretching is 3.2 to 4.8 times, more preferably,
3.3 to 4.5 times, the transverse stretching is preferably 3.3 to 4.
It is 8 times, more preferably 3.5 to 4.7 times. Further, the biaxially oriented film is formed by melting the (Tg + 30) ° C. to melting temperature (Tm), more preferably Tg + 40 ° C. to Tm−
10 ° C, more preferably Tg + 60 ° C to Tm-20
It is preferred to heat set at a temperature of ° C. In addition, Tm indicates a low temperature rising temperature of the crystal melting peak. The processing time at this time is preferably from 3 seconds to 120 seconds, more preferably from 5 seconds to 60 seconds, even more preferably from 10 seconds to 40 seconds. Further, it is also preferable to relax in the width direction at the end of the heat fixing. The preferred amount of relaxation is 1% or more 1
0% or less, more preferably 2% or more and 8% or less, still more preferably 3% or more and 6% or less. The thickness of these supports thus obtained depends on the amorphous polymer,
In any of the crystalline polymers, the thickness is from 80 μm to 250 μm, more preferably from 90 μm to 220 μm, and still more preferably from 95 μm to 200 μm.

A photosensitive layer is provided on the support having the undercoat layer and heat-treated as described above. The photosensitive layer may or may not contain silver halide.

Finally, the measuring method used in the present invention will be described. (1) Thermal dimensional change rate Sampling: Sample film (film after undercoating, film after application of photosensitive material), three pieces each in the longitudinal direction (MD) and transverse direction (TD) at the center and both ends of the raw film Sample each. The sample is a rectangle of 5 cm × 25 cm, and when measuring a dimensional change in the MD direction, 25 mm is required.
When measuring a dimensional change in the TD direction with a piece of cm parallel to the MD direction, a piece of 25 cm is sampled parallel to the TD direction. Measurement of dimensional change: Two holes are made in the center of the sample at intervals of 20 cm. This is measured using a pin gauge after moisture conditioning at 25 ° C. and 60% RH for 12 hours or more. (This length is defined as L ₁ ) Then, the plate is pressed on a smooth stainless steel plate having a thickness of 10 mm and heated to 120 ° C. for 30 seconds. After this 25
After conditioning for 12 hours or more at 60 ° C. and 60% RH, the length is measured again using a pin gauge. (This length is defined as L ₂ ) The thermal dimensional change rate is determined based on the following equation. Thermal dimensional change rate (%) = ｛100 × (L ₁ −L ₂ ) /
Absolute value of L ₁こ れ This is measured at each of the measurement points (M at the center
The average value is calculated for each of the two directions of D and TD (total of 6 points), and the largest value among these 6 points is reported.

[0040]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples. Example-1 (1) Preparation of support (1-1) Preparation of PET support Using terephthalic acid and ethylene glycol, IV = 0.66 (phenol / tetrachloroethane = 6) according to a conventional method.
/ 4 (measured at 25 ° C. in a weight ratio). This was pelletized and dried at 130 ° C. for 4 hours.
After being melted at ℃, the mixture was extruded from a T-die and then rapidly cooled to prepare an unstretched film having a thickness such that the film pressure after heat setting became 100 μm. This is done using rolls with different peripheral speeds, 3.3
The film was stretched twice in length and then stretched in 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the horizontal direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling was performed on both ends and wound at 4 kg / cm ² . Thus, a roll having a width of 2.4 m, a length of 5000 m, and a thickness of 100 μm was obtained. (1-2) Preparation of PEN support Starting from 2,6-naphthalenedicarboxylic acid dimethyl ester and ethylene glycol as raw materials, 50 ppm of spherical silica particles having an average particle diameter of 0.3 μm were added, and polyethylene-polyester was transesterified by a conventional method. 2,6-Naphthalate was polymerized according to a conventional method. IV = 0.56 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.). After drying the pellet at 170 ° C. for 4 hours, 3
After being melted at 00 ° C., it was extruded from a T-die and then rapidly cooled to prepare an unstretched film having a thickness such that the film pressure after heat setting became 100 μm. This was longitudinally stretched 3.0 times and then transversely stretched 3.3 times. The temperatures at this time were 140 ° C. and 130 ° C., respectively. Then, after heat-setting at 250 ° C. for 20 seconds, it was relaxed by 3% in the lateral direction. This was wound at 4 kg / cm ² in the same manner as in PET. Thus, the width 2.4 m, the length 5000 m, the thickness 10
A roll of 0 μm was obtained. (1-3) Production of Polymer Blend Support PET and PEN produced by the above method were made into a polymer blend using the twin screw kneading extruder at the following ratio. PB-1: PEN / PET (20/80: weight ratio) Tg = 79 ° C. This was dried under the same conditions as the PET support, stretched 3.4 times vertically at 120 ° C., and then 4.2 times at 140 ° C. It was stretched twice. After this, heat setting was performed at 245 ° C. for 20 seconds, and then 5
% Relaxed. This is made 4 kg /
It was wound up in cm ² . Thus, a roll having a width of 2.4 m, a length of 5000 m and a thickness of 100 μm was obtained.

(1-4) Preparation of Polycarbonate (PC) Support A 2,2′-bis (4-hydroxyphenyl) propane polycarbonate resin having a degree-average molecular weight of 28,000 was polymerized according to a conventional method. The Tg of this resin was 140 ° C. This was dried at 130 ° C. for 3 hours, melted at 310 ° C., filtered and extruded from a T-die. This is electrostatically applied at 50 ° C
After being cooled and solidified on a casting drum of No. 1, it was stripped off, knurled (thickened) at both ends, and wound up. After solidifying at a cooling rate under the conditions shown in the above with a thickness of 100 μm, it was stripped off under the tension shown in Table 1, knurled (thickened) at both ends, and wound up. Thus, width 2.4m, length 5000m, thickness 100μm
Got a roll.

(2) Coating Layer A coating layer selected from the following was provided on the support as shown in Table 1.

[0043]

[Table 1]

(2-1) A adhesive layer The following surface treatment was performed prior to application. Using a solid state corona treatment machine 6KVA model manufactured by Pillar Co., both surfaces of the support are treated at room temperature at 20 m / min. From the current and voltage readings at this time, 0.375
Processing of kV · A · minute / m ² is performed. The processing frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. The following 2
An adhesive layer consisting of layers was applied. 1st layer The undercoating solution of the following composition was applied at 6 ml / m using a wire bar.
^{2 was} applied and dried at 120 ° C. for 2 minutes. Butadiene-styrene copolymer latex 13 ml (solid content 43%, butadiene / styrene weight ratio = 32/68) 2,4-dichloro-6-hydroxy-S-triazine sodium 7 ml 8% aqueous solution sodium laurylbenzenesulfonate 1% Aqueous solution 1.6 ml Distilled water 80 ml Second layer Onto the above-mentioned first undercoat layer, an undercoat solution having the following composition was applied at 9 ml / m ² using a wire bar, and dried at 185 ° C. for 5 minutes. Gelatin 0.9 g Methyl cellulose (Metroose SM15 substitution degree 1.79-0.1 g 1.83) Acetic acid (concentration 99%) 0.02 ml Distilled water 99 ml

(2-2) B adhesive layer Adhesive I solution The following undercoat solution I was directly applied on the support without surface treatment.
After adjusting the pH to 6 using 0% KOH, the film was coated on both sides of the support by bar coating so that the film thickness after drying was 0.1 μm, and dried at 120 ° C. for 2 minutes. Vinylidene chloride latex solution 15 wt% 2,4-dichloro-6-hydroxy-S-triazine sodium salt 0.15 wt% Silica fine particles (average particle size 0.1 μm) 0.2 wt% Add distilled water to 100 wt% The vinylidene chloride polymer was obtained by copolymerizing vinylidene chloride (VdC), methyl methacrylate (MMA), methacrylic acid (Ma) and acrylonitrile (AN), and was prepared in the form of a latex liquid. PVd
The composition of C is shown in Table 1. Assuming that the composition of VdC is X wt%, the compositions of MMA, Ma and AN are (100-
X) The value obtained by multiplying wt% by 0.8, 0.05, and 0.15 (wt
%). These can be prepared, for example, by referring to Synthesis Example 1 of JP-A-3-141346. The solid content concentration of the obtained latex solution was 50%, and the average particle size was 0.16 μm. Adhesion II solution An undercoat solution II having the following composition was further applied on both sides of the support so that the film thickness after drying was 0.1 μm.
Dry at 0 ° C. for 5 minutes. Gelatin 1.0 wt% C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.05 wt% Methyl cellulose 0.05 wt% Distilled water is added to 100 wt%

(2-3) Conductive Layer A liquid having the following composition was applied and dried at 40 ° C. for 5 minutes. SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ² (composite metal oxide) Gelatin (Ca ²⁺ content 3000 ppm) 77 {compound-117} sodium dodecylbenzenesulfonate 10 {Sodium dihexyl-α-sulfosuccinate 40} Sodium polystyrene sulfonate 9 (2-4) Protective layer A solution having the following composition was applied and dried at 40 ° C. for 5 minutes. Gelatin (Ca ²⁺ content: 30 ppm) 3.6 g / m ² Compound-11 3 mg / m ² Polymethyl methacrylate fine particles (average particle size: 3.4 μm) 50 {Compound-1240} Compound-1340 {Compound-1480ナ ト リ ウ ム sodium dodecylbenzenesulfonate 75 ナ ト リ ウ ム sodium dihexyl-α-sulfosuccinate 20 化合物 compound 155 〃 N-perfluorooctanesulfonyl-N-propyl 7 〃 sodium glycinepotadium sulfate 50 ナ ト リ ウ ム sodium acetate 85 １，２ 1,2 -Bis (vinylsulfonylacetamido) ethane 150

[0047]

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(2-5) A liquid having a composition equal to or less than the dye layer is wetted to a thickness of 1
It is applied so as to be 00 μm. Polyvinyl butyral # 4000-2 (produced by Denki Kagaku Kogyo KK) 10% isopropyl alcohol solution 60 g isopropyl alcohol 10 g 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (produced by Wako Pure Chemical Industries, Ltd.) Dye S-1 is added to a solution of 8 g or more of an 8% solution of ethyl acetate in ethyl acetate. Dye S-10.
A solution of 2 g dissolved in 10 g of methanol + 20 g of acetone is added so that the absorption at 633 nm becomes 0.8.

[0049]

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(2-6) Curl Compensation Layer First Layer A solution having the following composition was prepared and adjusted to pH 5.7 with 1N hydrochloric acid. This was applied using a wire bar. Gelatin 2.5 g / m ² Polymethyl methacrylate fine particles (particle size 3 μm) 7.2 mg / m ² N, N′-ethylenebis- (vinylsulfoneacetamide) 25 mg / m ² Sodium dodecylbenzenesulfonate 2.1 mg / m over ² acetate 74.5 mg / m ² second layer the first layer to prepare a liquid of the following composition was applied with a wire bar. (Methyl methacrylate / styrene / 2-ethylhexyl / hydroxyethyl acrylate / methacrylic acid) copolymer latex (59/9/26/5/1: molar ratio) 2 g / m ² benzyl alcohol 160 mg / m ² dodecylbenzene sulfonic acid Sodium 1.3 mg / m ² C ₈ F ₁₇ SO ₃ K 2.5 mg / m ²

(3) Heat treatment A heat treatment was performed according to the procedure shown in Table 1 by selecting from the following methods. (3-1) Heat treatment for conveyance Heat treatment Heat treatment was performed at a conveyance speed of 20 m / min through a heat treatment zone having a total length of 200 m set at the temperature and tension shown in Table 2 of the support after undercoating. Post-heat treatment After the heat treatment, post-heat treatment was performed at the temperature and for the time shown in Table 2, and the film was wound. The winding tension at this time is 1
It was 0 kg / mm ² . (3-2) Roll Heat Treatment After passing the undercoated support through a heat treatment zone set to the temperature shown in Table 2, the support was heated under the temperature atmosphere.
And wound on a core having a diameter of 30 cm under the tension described in (1). Thereafter, it was cooled to room temperature at -1 ° C / hour while rotating at 0.2 rotation / hour. (4) Evaluation of undercoat support After coating these layers, the dimensional change after the undercoat was measured by the above-described method.

[0052]

[Table 2]

Further, the dimensional stability and the adhesiveness of the photosensitive material provided with the silver halide photosensitive layer were good.

Example 2 (1) Preparation of Support The PET support of Example 1 was used. (2) Coating Layer The various coating layers (BC-side adhesive layer, BC-side conductive layer, and protective layer) described in Example 1 were dried while being transported at the tension and temperature shown in Table 3. (3) Heat treatment / Post heat treatment Heat treatment: At the tension and temperature shown in Table 3, at a conveying speed of 20 m
Per minute using a 200 m processing zone. Post heat treatment: 1 at 40 ° C. at the tension and temperature shown in Table 3.
Heat treatment was performed for 5 seconds. (4) Dimensional change rate after undercoating Each level was measured in the same manner as in Example 1 for a sample wound immediately before application of the photosensitive material. (5) Results It was more effective to heat up after winding once after the undercoating step, since the rate of dimensional change could be made smaller than in the case of continuous application. Further, the effect was more remarkable when the tension at the time of coating and drying was reduced. Further, the dimensional stability and the adhesiveness of the photosensitive material provided with the diazo photosensitive layer were good.

[0055]

[Table 3]

[0056]

According to the present invention, a photographic support having surprising performance with almost no dimensional change and a method for preparing the same can be realized.

Continued on the front page (72) Inventor Naohiro Nakayama 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd.

Claims (11)

[Claims] 1. The thermal dimensional change rate at 120 ° C. for 30 seconds is 0.
A photographic support characterized by being at least 001% and at most 0.04%. 2. The photographic support according to claim 1, wherein the support is provided with an undercoat layer. 3. The method according to claim 1, wherein the temperature is between 0.0.degree.
A method for preparing a photographic support, wherein heat treatment is performed while transporting the film under a tension of 4 kg / cm ² or more and 6 kg / cm ² or less. 4. The method for preparing a photographic support according to claim 3, wherein an undercoat layer is provided on the support before the heat treatment. 5. A method for preparing a photographic support, wherein the post-heat treatment is carried out at a temperature of 15 ° C. to 70 ° C. for 1 second to 5 minutes following the heat treatment according to claim 3 or 4. 6. The coating of the undercoat layer is performed at 0.04 kg / cm.
^TwoMore than 6kg / cm ^TwoIt is characterized by performing with the following transport tension
A method for preparing a photographic support according to claim 4 or 5. 7. The heat treatment and / or post heat treatment according to claim 4 or 5, wherein after the undercoat layer is applied, the film is wound up on a roll and then sent out again from a winding roll. A method for preparing a support for a photographic light-sensitive material according to the above. 8. A support having a weight of 0.1 kg / cm ² or more and 20 k or more
A method for preparing a photographic support, comprising: winding a film on a roll with a tension of not more than g / cm ² , and performing a heat treatment in a roll at a temperature of from 80 ° C. to 200 ° C. 9. The method for preparing a photographic support according to claim 8, wherein an undercoat layer is applied to the support before the heat treatment. 10. The photographic support according to claim 1, which is prepared by the method according to claim 3. Description: 11. The photographic support according to claim 1, wherein the photographic support is a polyester support.