JPH10115891A - Support for photosensitive material and, photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a support for photosensitive material low in curling tendency even in the case of being stored in the form of a roll, and improved in flatness by increasing a Vh component through heat treatment. SOLUTION: The expression: 1.5<Vh(b)/Vh(a)<20 is satisfied and preferably, the expression: 1.5<Vv(b)/Vv(a)<20 is also satisfied, where Vh(b) is a dispersion intensity in the Vh direction measured with a polarization dispersion device after stripping a photosensitive layer and Vh(a) is a dispersion intensity in the Vh direction measured with the polarization dispersion device by heat treating a sample at 14 deg.C held flat after stripping the photosensitive layer. Vv(b) is a dispersion intensity in the Vv direction measured with the polarization dispersion device after stripping the photosensitive layer and Vv(a) is a dispersion intensity in the Vv direction measured with the polarization dispersion device by heat treating a sample at 14 deg.C held flat after stripping the photosensitive layer. It is preferred to form at least one photosensitive layer on the support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a roll-shaped photosensitive material, and more particularly, to a support for a photosensitive material which has good flatness, hardly forms a curl even when stored in a roll, and has good dimensional stability. The present invention relates to a photosensitive material using the same.

[0002]

2. Description of the Related Art In recent years, photosensitive materials have been used in large quantities, but the number of photosensitive materials conventionally used in the form of sheets and shipped in roll form has increased. This is because the size of the preference differs depending on the user, and it has been cut on the user side. For this reason, since the photosensitive material is stored for a while in the state of being rolled, the problem of curling that accompanies nature has become apparent. This is due to the problem that, when a plastic film such as a PET film is placed in a roll state for a long time, the curl becomes large and jamming occurs during automatic conveyance or conveyance to an automatic machine. .

Accordingly, it has been desired to reduce the curl of a plastic film for a photosensitive material represented by a PET film.

[0004] From such a viewpoint, in the world of silver halide photographic light-sensitive materials, Japanese Patent Application Laid-Open No. S51-16358 discloses a method of reducing the curl of a polyester film by rolling a thermoplastic resin film at Tg-5 ° C. ~ Tg-30 ° C
For 0.1 to 1500 hours. Further, JP-A-6-35118 discloses that after a polyester film having a Tg of 90 ° C to 200 ° C is drawn,
A method of performing heat treatment at 50 ° C. to Tg for 0.1 to 1500 hours has been proposed.

[0005]

The thermoplastic resin film is heated at Tg-5 ° C to Tg-30 ° C for 0.1 to 1500 hours.
Heat treatment methods include PET film and polyethylene naphthalate film (hereinafter referred to as PEN film),
The effect of reducing the curl of a crystalline or semi-crystalline thermoplastic resin was considered effective. However, such a long-time heat treatment at a relatively low temperature has a problem that the quality of the photosensitive material is significantly impaired.

That is, the photosensitive material is adjusted to a temperature of 50 ° C. to Tg of 0.1%.
The method of heat treatment for up to 1500 hours is in principle exactly the same as the method described in JP-A-51-16358. In this case, a curl improvement treatment is performed before coating the photosensitive layer due to problems such as prevention of fogging of the photosensitive layer, and then the photosensitive layer is coated. In other words, there is no problem if the worker applies the photosensitive layers one by one, but in view of productivity efficiency, the curl improvement treatment is performed with a certain long roll shape. . Generally, such an annealing treatment is a method in which a roll-shaped film cooled to room temperature is raised in a furnace to a desired temperature, treated for a desired time, and then cooled to room temperature. In this case, the problem is the thermal expansion of the plastic film. In other words, heat treatment of a tightly wound roll-shaped film is in the direction of overall elongation, but because it is fixed in all directions, it is broken at the part where it is distorted and pushed, and the photosensitive layer etc. is applied. This is due to coating failure at the time.

The reason why such a failure occurs is that heat treatment at Tg or lower cannot be carried out while being transported on a production line because heating for a long time is required.

[0008]

Means for Solving the Problems Normally, a plastic film is manufactured and takes a certain form in its outer shape, but a newly manufactured one is still in an unstable state from a microscopic viewpoint. Therefore, it is expected that the molecules will gather together and the free volume will decrease over time. Therefore, a habit is formed based on the shape of the film.
Prior art annealing at Tg or lower consists in accelerating this time to make the plastic film remember a flat state habit. This means that an endothermic peak, which was not observed immediately after production, appeared near the Tg in the DSC of a film that took a long time or a film that had been annealed below Tg, and this increased with the heat treatment time. It can be inferred from the fact that when these substances are exposed to a temperature higher than Tg, this peak disappears.

The present inventors proceeded with structural analysis of polymers,
The above structure was able to be captured by a polarization scattering measurement device.

In a polarized light scattering device, polarized light is applied to a sample,
The Vv component and Vh component of the transmitted light are measured. The measurement of the polarized light scattering was performed according to the method described in P.K. 50-1
21 and Stein R. S. and Wilson
P. R. , J. et al. Appl. PHYS. , 33, 191
4 (1962).

Here, in order to facilitate understanding of the present invention, FIG. 1 shows a simple schematic diagram of the polarization scattering measurement, and a brief description is given below.

As the incident light, a highly parallel beam of monochromatic light is used. Generally, a He-Ne gas laser (wavelength 632.8 nm) is most often used. The incident light passes through one polarizing plate a and is given linearly polarized light, and then irradiates the sample 2 vertically. The light scattered from the sample 2 is two polarizing plates b
, A scattered image is projected on the image receiving unit 4. As a method of recording and analyzing scattered images, place a photographic film on the image receiving unit,
A method of analyzing the degree of blackening after exposure and development has been used for a long time.In recent years, however, a method of scanning the photomultiplier tube on the image receiving unit to record the intensity distribution, and receiving a scattered image with a photodiode array or a CCD camera The method of recording by recording is the mainstream.

The angle θ between the scattered light and the incident optical axis is the scattering angle,
The angle μ formed by the scattered light with the polarization direction of the polarizing plate a is called an azimuth angle, and the scattered image is recorded and analyzed as a function of the scattering angle and the scattering intensity with respect to the azimuth angle. The scattering light intensity distribution in the scattering angle direction reflects the size of the scattering unit present in the sample, and the scattered light intensity distribution in the azimuthal direction reflects the optically anisotropic scattering unit (crystal ) Is known to reflect the shape and orientation. The scattering image when the polarizing directions of the polarizing plate a and the polarizing plate b are orthogonal to each other is generally called a Vh scattering image or an Hv scattering image, and is a scattering unit (crystal) of optical anisotropy existing in the sample.
It is known that the fluctuation of the optical axis orientation reflects the scattering intensity.

The scattering image when the polarization directions of the polarizing plates a and b are parallel is generally called a Vv scattering image, and together with the fluctuation of the optical axis orientation, the fluctuation of the density in the sample causes the scattering intensity to decrease. It is known to reflect.

In brief, the density unevenness and the crystal affect the Vv scattering image, and only the crystal affects the Vh component.

Normally, a crystalline plastic film such as PET is partially crystallized to be whitened when completely crystallized. It is said that about 40% of PET is crystallized. That is, when measured by this method, the structure of the crystal part can be measured by the Vh component, and the amorphous and crystal parts can be measured by the Vv component.

According to this measurement, the annealed PET is compared with the untreated PET,
Although the Vh component did not change, it was observed that the Vv component increased. That is, although the crystal does not change, it is observed that the amorphous portions are gathered.

This is because the free volume of a molecule is reduced by annealing or leaving it naturally.

That is, the present inventors have made intensive studies and as a result,
It has been found that when the Vh component is increased by the heat treatment, the curl becomes hard to stick.

That is, the object of the present invention has been achieved by the following constitution.

(1) A support for a photosensitive material satisfying the following relational expression (I).

1.5 <Vh (b) / Vh (a) <20 (I) where Vh (b) is measured by a polarization scattering device after the photosensitive layer is peeled off. Scattering intensity in the Vh direction Vh (a); 14
Scattering intensity in the Vh direction measured by a polarization scattering device on a sample that has been heat-treated at 0 ° C. for 2 minutes. (2) A support for a photosensitive material which further satisfies the following relational expression (II) in the support described in (I) above.

1.5 <Vv (b) / Vv (a) <20 (20) where Vv (b) is measured by a polarization scattering device after the photosensitive layer is peeled off. Scattering intensity in Vv direction Vv (a); 14
Scattering intensity in the Vv direction measured by a polarization scattering device on a sample that has been heat-treated at 0 ° C. for 2 minutes. (3) A photosensitive material having at least one photosensitive layer on the support described in (1) or (2) above.

In these polarized light scattering measurements, the measurement is performed under the following conditions.

The incident light is a He-Ne laser (632.8).
The azimuth angle is an angle at which the scattering intensity is maximized. The scattering intensity is an average value in the range of a scattering angle of 2 to 3 ° in the azimuth direction.

The present invention will be described in more detail.

The plastic used as a support in the present invention includes syndiotactic polystyrene and polyester. Among them, polyester is
This is preferable in terms of excellent mechanical and optical performance and relatively low cost.

The polyester of the present invention is not particularly limited, but is preferably a polyester having a film-forming property containing a dicarboxylic acid component and a diol component as main components.

The main components of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2,6-
Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid,
Examples thereof include cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketonedicarboxylic acid, and phenylindanedicarboxylic acid. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexane dimethanol,
2,2-bis (4-hydroxyphenyl) propane,
Examples thereof include 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, and cyclohexanediol.

Among the polyesters containing these as main components, from the viewpoints of transparency, mechanical strength, dimensional stability and the like, terephthalic acid as a dicarboxylic acid component, ethylene glycol and / or 1,4-
Polyesters containing cyclohexanedimethanol as the main constituent are preferred. Among them, polyesters having polyethylene terephthalate as a main component, copolymer polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters as main components Polyester is preferred.

When the content of the ethylene terephthalate unit is at least 70% by weight based on the polyester, a film having excellent transparency, mechanical strength and dimensional stability can be obtained.

As long as the effects of the present invention are not impaired, the polyester constituting the biaxially stretched polyester film of the present invention may be further copolymerized with other copolymer components or mixed with other polyester. It may be.
Examples of these include the above-mentioned dicarboxylic acid component and diol component, and polyesters composed thereof.

The polyester used in the present invention may contain an antioxidant. In particular, the effect is remarkable when the polyester contains a compound having a polyoxyalkylene group. The type of the antioxidant to be contained is not particularly limited, and various antioxidants can be used. For example, hindered phenol compounds,
Antioxidants such as phosphite compounds and thioether compounds can be mentioned. Above all, an antioxidant of a hindered phenol compound is preferable in terms of transparency.

The content of the antioxidant is usually from 0.01 to 2% by weight, preferably from 0.1 to 2% by weight, based on the polyester.
0.5%. By setting the content of the antioxidant in this range, it is possible to prevent the so-called fogging phenomenon in which the density of the unexposed portion of the photographic light-sensitive material is increased, and the haze of the film can be suppressed to be low, so that a photograph having excellent transparency can be obtained. Support is obtained. In addition, these antioxidants may be used alone or in combination of two or more.

The biaxially stretched polyester film of the present invention can be provided with lubricity as required. The means for imparting lubricity is not particularly limited, but a method of adding external particles for adding inert inorganic particles to the polyester, a method of depositing internal particles for depositing a catalyst to be added at the time of synthesis of the polyester, or a method such as a surfactant is used. A method of applying the composition to the surface is generally used. Among these, an internal particle precipitation method that can control the particles to be deposited relatively small is preferable because lubricity can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but it is particularly preferable to use Ca and Mn because high transparency can be obtained. One of these catalysts may be used, or two or more of them may be used in combination.

The method for synthesizing the polyester as a raw material of the biaxially stretched polyester film of the present invention is not particularly limited, and it can be produced according to a conventionally known method for producing polyester. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first using a dialkyl ester as a dicarboxylic acid component,
A transesterification method can be used in which a transesterification reaction is carried out between this and a diol component, and this is heated under reduced pressure to remove excess diol component and thereby polymerize.
At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. In addition, in each process during the synthesis, a coloring inhibitor, an antioxidant, a crystal nucleating agent, a slipping agent, a stabilizer, an antiblocking agent, an ultraviolet absorber, a viscosity modifier, an antifoaming agent, a clarifying agent, an antistatic agent, A pH adjuster, a dye, a pigment, and the like may be added.

The thickness of the biaxially stretched polyester film of the present invention is not particularly limited. What is necessary is just to set so that it may have required intensity | strength according to the use purpose.

That is, when used for a photosensitive material, 5
It is preferably from 0 to 300 μm, particularly preferably from 60 to 200 μm.

The haze of the biaxially stretched polyester film of the present invention is preferably 3% or less. More preferably, it is 1% or less. The haze is ASTM
-Measured according to D1003-52.

The Tg of the biaxially stretched polyester film of the present invention is preferably 60 ° C. or higher. Tg is determined as an average value of a temperature measured by a differential scanning calorimeter at which a baseline starts to be shifted and a temperature at which the baseline returns to a new baseline. When the Tg is at least this value, a photosensitive material having no deformation of the film in the drying step of the developing machine and having a small curl after development can be obtained.

Next, a method for producing the polyester film of the present invention will be described.

A method for obtaining an unstretched sheet and a method for uniaxially stretching in the longitudinal direction can be performed by a conventionally known method. For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled, solidified, and unstretched. Get a sheet. Next, the obtained unstretched sheet is subjected to Tg + 100 from the glass transition temperature (Tg) of the polyester through a plurality of roll groups and / or a heating device such as an infrared heater.
This is a method in which the film is heated in the range of ° C. and stretched longitudinally in one step or multiple steps. The stretching ratio is usually in the range of 2.5 to 6 times, and it is necessary to make the subsequent transverse stretching possible. When the sheet has a multilayer structure, the setting of the stretching temperature is preferably based on the Tg of the polyester of the thickest layer among the Tg of the polyester of each constituent layer.

At this time, when the polyester is laminated,
A conventionally known method may be used. For example, a plurality of extruders and a co-extrusion method using a feed block type die or a multi-manifold type die, melt extrusion of a single layer film constituting a laminate or other resin constituting a laminate on a laminate film from an extruder, cooling Examples include an extrusion lamination method of cooling and solidifying on a drum, and a dry lamination method of laminating a single-layer film or a laminated film constituting a laminate via an anchor or an adhesive as necessary. Among them, a co-extrusion method that requires a small number of production steps and has good adhesion between the layers is preferable.

Next, the polyester film uniaxially stretched in the machine direction obtained as described above was treated with Tg to Tm-2.
In a temperature range of 0 ° C., the film is stretched in the transverse direction and then heat-set. The transverse stretching ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse stretching ratios is determined by measuring the physical properties of the obtained biaxially stretched film and appropriately adjusting the film to have preferable characteristics. In the case of the present invention, the elastic modulus in the width direction is made larger than the elastic modulus in the longitudinal direction. It may be changed according to the purpose of use. At this time, the temperature difference in the stretched region divided into two or more is 1 to 50.
It is preferable to carry out transverse stretching while sequentially increasing the temperature in the range of ° C because the distribution of physical properties in the width direction can be reduced. Further, it is preferable to hold the film after the transverse stretching at a temperature of not higher than the final transverse stretching temperature and at a temperature of at least Tg-40 ° C. for 0.01 to 5 minutes, because the distribution of physical properties in the width direction can be further reduced.

The heat setting is at a temperature higher than its final transverse stretching temperature,
Heat fixing is usually performed for 0.5 to 300 seconds within a temperature range of Tm-20 ° C or lower. At this time, it is preferable to heat-set while sequentially increasing the temperature in a range of 1 to 100 ° C. in the two or more divided regions.

The heat-fixed film is usually cooled to Tg or less, cut off the clip gripping portions at both ends of the film, and wound up. At this time, in the temperature range of not more than the final heat setting temperature and not less than Tg, 0.1 in the width direction and / or the longitudinal direction.
It is preferable to perform a relaxation treatment of 10% to 10%. In addition, cooling
100 ° C to 10 ° C per second from the final heat setting temperature to Tg
It is preferable to gradually cool at a cooling rate of. The means for cooling and relaxing treatment is not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to perform these treatments while sequentially cooling in a plurality of temperature regions from the viewpoint of improving the dimensional stability of the film. The cooling rate is a value determined by (T1−Tg) / t, where T1 is the final heat setting temperature and t is the time required for the film to reach Tg from the final heat setting temperature.

Since the most optimal conditions of the heat setting, cooling and relaxation treatment conditions differ depending on the polyester constituting the film, the physical properties of the obtained biaxially stretched film are measured and adjusted appropriately so as to have preferable characteristics. It may be determined by doing so.

In the production of the film, a functional layer such as an antistatic layer, a lubricating layer, an adhesive layer and a barrier layer may be applied before and / or after stretching. At this time, various surface treatments such as corona discharge treatment and chemical treatment can be performed as necessary. Further, for the purpose of improving the strength, stretching used for known stretched films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal-lateral stretching, and horizontal / longitudinal stretching can also be performed. Of course, the clip gripping parts at both ends of the cut film are pulverized, or subjected to granulation, depolymerization, repolymerization, etc. as necessary, as raw materials for the same type of film or different types May be reused as a film raw material.

Next, the silver halide photographic light-sensitive material will be described.

Examples of the photosensitive material to be used include a silver halide photographic material, a lithographic printing photosensitive material, a relief photosensitive material, and a color proofing photosensitive material.

The silver halide emulsion for the photosensitive layer used in the present invention and the method for preparing the same are described in detail in
Disclosure (Research Disclo
Sure) 176 No. 17643, pp. 22-23 (197
(December 2008) or in the literature cited.

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

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. .

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion according to the present invention. As gelatin, acid-processed gelatin may be used in addition to lime-processed gelatin, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. Other hydrophilic colloids can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like.

For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile,
Olefin, styrene, etc., alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, etc. A polymer as a body component can be used.

In the present invention, the following compounds are preferably contained in the constituent layers of the silver halide photographic material.

(1) Solid Dispersion Fine Particles of Dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111]
(7) Nucleation accelerator: JP-A-7-114126, page (32) [0158]
(8) Tetrazolium compound JP-A-6-208188, page (8), [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556 (5) page [0028] to
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) Compound described on page About the above-mentioned additives and other known additives,
For example, Research Disclosure No. 17643
No. (December 1978). 18716 (1979
No.) and the same No. 308119 (December 1989
Month). The following table shows the types and locations of the compounds shown in these three research disclosures.

Additive RD-17643 RD-18716 RD-308119 page classification page classification page classification Chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IVA desensitizing dye 23 IV 998 IVB dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Is preferably subjected to photographic processing by an automatic developing machine having at least four processes of developing, fixing, washing (or stabilizing bath) and drying after exposure.

In the present invention, an automatic developing machine having the following method and mechanism can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column.

(2) Washing water regeneration purifying agent and apparatus: JP-A-6-250352, page (3) “0011” to page (8) “0058”.

(3) Waste liquid treatment method: JP-A-2-6463
No. 8, 388 (2) lower left column to 391 (5) lower left column.

(4) Rinse bath between the developing bath and the fixing bath: JP-A-4-313949, page (18), “0054” to (2)
1) Page "0065".

(5) Water replenishment method: JP-A-1-28144
No. 6, page 250 (2), lower left column to lower right column.

(6) Method for controlling the drying air of an automatic developing machine by detecting the outside air temperature and humidity: JP-A-1-315745
6 (2) lower right column to 501 (7) lower right column and JP-A-2-108051, 588 (2) lower left column to 589
(3) The lower left column of the page.

(7) Method for recovering silver from fixing waste liquid:
No. 27623, page (4) “0012” to page (7) “0”
071 ".

Next, other photosensitive materials will be described.

These include a photosensitive layer containing a photopolymerizable compound and a binder, a photosensitive layer containing an o-quinonediazide compound and a binder, a photosensitive layer containing a photoconductive compound and a binder, and a near infrared light absorber. It comprises a photosensitive layer containing a binder, and can be used as a non-silver salt photosensitive material by laminating this photosensitive layer in the present invention. In addition to these photosensitive layers, it is generally known that a metal deposited layer of aluminum or the like, a hydrophilized layer, a colored layer, an image receiving layer, an antistatic layer and the like are laminated and used as required.

In the color proofing material, the photosensitive layer containing a near-infrared light absorber and a binder, or the photosensitive layer containing a photopolymerizable compound and a binder, or an o-quinonediazide compound and a binder may be used as the support of the present invention. When laminated on a resin layer to be laminated, it is generally widely used in the field of printing as a color proof material.

Examples of the color proofing material comprising a photosensitive layer containing a near-infrared absorbing agent and a binder include a recording material having a heat-meltable coloring material layer or a coloring material layer containing a heat sublimable dye on a support and an image receiving material. And a thermal transfer recording system using a laser beam as a heat source (Japanese Patent Laid-Open No. 49-15437).
Nos. 49-17743, 57-87399, 61-112665, etc.).

Hereinafter, typical recording materials and image receiving materials will be described.

The ink layer to be laminated on the resin layer of the present invention as a recording material may be a transfer layer comprising a colorant, a photothermal conversion agent and a binder, or a transfer layer comprising a colorant and a binder; A non-transferable light-to-heat conversion layer composed of

First, the case where the ink layer is a transfer layer capable of converting light to heat will be described.

Examples of the coloring material include pigments such as inorganic pigments and organic pigments, and dyes.

Examples of the inorganic pigment include titanium dioxide, carbon black, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium, and calcium.

Examples of the organic pigment include azo-based, thioindigo-based, anthraquinone-based, anthranthrone-based, triphenedioxazine-based pigments, vat dye pigments, phthalocyanine pigments (eg, copper phthalocyanine) and derivatives thereof.
And quinacridone pigments. Examples of the organic dyes include acid dyes, direct dyes, disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes, and sublimable dyes.

As a coloring material, for example, Lionol Blue FG-
7330, Lionol Yellow No. 1206, No.
1406G, Lionol Red 6BFG-4219X
Pigments such as (all manufactured by Toyo Ink) can be used.

The content of the coloring material in the ink layer is not particularly limited, but is usually in the range of 5 to 70% by weight, preferably 10 to 60% by weight.

As the photothermal conversion agent, any conventionally known photothermal conversion agent can be used. In a preferred embodiment of the present invention, heat is generated by irradiation with a semiconductor laser beam. Therefore, when a color image is formed, a near-infrared light absorbing agent showing an absorption maximum in a wavelength band of 700 to 3000 nm and having no or small absorption in a visible region is used. preferable. When a monochrome image is formed, carbon black or the like having absorption in the visible to near infrared region is preferable.

Examples of the near-infrared light absorbing agent include organic compounds such as cyanine, polymethine, azurenium, squarium, thiopyrylium, naphthoquinone, and anthraquinone dyes, and phthalocyanine, azo, and thioamide organic metal complexes. And the like. Specific examples thereof are described in JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, and JP-A-1-280750.
-293342, 2-2074, 3-2659
No. 3, No. 3-30991, No. 3-34891, No. 3
-36093, 3-36094 and 3-3609
No. 5, 3-42281, 3-97589, 3
And the compounds described in JP-A-103476.

These can be used alone or in combination of two or more.

Examples of the binder for the ink layer include a heat-meltable substance, a heat-softening substance, and a thermoplastic resin. The heat-fusible substance is generally a solid or semi-solid substance having a melting point in the range of 40 to 150 ° C. measured using Yanagimoto MJP-2. Specifically, carnauba wax, wood wax,
Vegetable waxes such as ouricure wax and Espal wax; animal waxes such as beeswax, insect wax, shellac wax, spermaceti wax; petroleum waxes such as paraffin wax, microcrystal wax, polyethylene wax, ester wax, acid wax; Waxes such as mineral waxes such as ozokerite and ceresin; and besides these waxes and the like, higher fatty acids such as palmitic acid, stearic acid, margaric acid and behenic acid; palmityl alcohol;
Higher alcohols such as stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, and eicosanol; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate, and myricyl stearate; acetamide, propionamide, palmitamide; Amides such as stearic acid amide and amide wax; and stearylamine;
And higher amines such as behenylamine and palmitylamine.

Examples of the thermoplastic resin include ethylene copolymer, polyamide resin, polyester resin, polyurethane resin, polyolefin resin, acrylic resin, vinyl chloride resin, cellulose resin, rosin resin, Resins such as polyvinyl alcohol resin, polyvinyl acetal resin, ionomer resin, petroleum resin;
Natural rubber, styrene butadiene rubber, isoprene rubber,
Elastomers such as chloroprene rubber and diene copolymer; rosin derivatives such as ester gum, rosin maleic acid resin, rosin phenol resin and hydrogenated rosin; and phenol resin, terpene resin, cyclopentadiene resin, aromatic hydrocarbon resin and the like High molecular compounds and the like can be mentioned.

By appropriately selecting the above-mentioned heat-fusible substance and thermoplastic substance, a thermal transfer layer having a desired heat-softening point or heat-melting point can be formed.

Next, a case where the ink layer has a two-layer structure of a transferable color material layer and a photothermal conversion layer will be described. By having a two-layer structure of a color material layer and a light-to-heat conversion layer, a light-to-heat conversion agent having absorption in the visible region can be used, which is advantageous in color reproduction especially when a color image is formed.

As the photothermal conversion agent in the photothermal conversion layer,
The above-mentioned light-to-heat convertible ink layers can be used. However, the photothermal conversion layer has a thickness of 700 to 1000 nm.
In the near-infrared light region, the absorption for the wavelength of the light source is at least 0.25 or more, preferably 0.5 or more. When an infrared absorbing dye is used, it has an absorption coefficient per unit weight as compared with a pigment such as carbon black, so that the thickness of the light-to-heat conversion layer can be reduced, and high sensitivity can be achieved.

As the binder in the light-to-heat conversion layer,
Resins with high glass transition point and high thermal conductivity, such as gelatin, polyvinylpyrrolidone, polyester, polyparabanic acid, polymethyl methacrylate, polycarbonate, polystyrene, ethylcellulose, nitrocellulose, polyvinyl alcohol, polyvinyl chloride, polyamide, polyimide, polyether General heat-resistant resins such as imide, polysulfone, polyethersulfone, and aramid can be used.

The thickness of the light-to-heat conversion layer is preferably from 0.1 to 3 μm.
Usually, the absorbance at the wavelength of the light source used for image recording is 0.3
It can be determined to be 3.0.

The light-to-heat conversion layer can also be formed as a vapor-deposited film in addition to carbon black, gold, silver, aluminum, chromium, nickel, antimony, tellurium described in JP-A-52-20842. , Bismuth, selenium and other metal black deposited layers. Note that the photothermal conversion agent may be the coloring material itself of the ink layer, and is not limited to the above, and various substances can be used.

Next, the image receiving material will be described.

The image receiving material receives the ink layer peeled imagewise from the recording material to form an image. Usually, the image receiving material has a support and an image receiving layer, and may be formed of only the support.

The image receiving layer comprises a binder and various additives and a matting agent which are added as required. In some cases, it is formed only with a binder.

Examples of the image receiving layer binder having good image receiving properties include:
Adhesives such as polyvinyl acetate emulsion adhesive, chloroprene adhesive, epoxy resin adhesive, natural rubber,
Adhesives such as chloroprene rubber, butyl rubber, polyacrylate, nitrile rubber, polysulfide, silicon rubber, rosin, vinyl chloride, petroleum resin and ionomer resin, recycled rubber, SBR, polyisoprene, Polyvinyl ether and the like can be mentioned.

When the image formed on the image receiving layer is retransferred to another recording medium by heating and / or pressurizing, a resin having a relatively small polarity (small SP value) is used as the image receiving layer. Is particularly preferred. For example, polyethylene, polypropylene, ethylene-vinyl chloride copolymer, polybutadiene resin, ethylene-acrylic copolymer, vinyl chloride resin, various modified olefins, and the like.

The thickness of the image receiving layer is usually from 10 to 100 μm, but is not limited to the case where the support of the present invention is used as an image receiving material. As the cushion layer, a cushioning intermediate layer described in the recording material can be used. Further, the film thickness when re-transferring to another recording medium is preferably 30 to 50 μm. Other undercoat layer, back coat layer,
In some cases, an antistatic layer or the like may be provided.

When the photosensitive layer contains an o-quinonediazide compound, any one can be used as long as it can function as a photosensitive agent.

Specifically, for example, 1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride,
Naphthoquinonediazide-5-sulfonyl chloride,
A compound obtained by condensing 1,2-naphthoquinonediazide-6-sulfonyl chloride with a compound containing a hydroxyl group and / or an amino group is preferably used. Preferably, it is a compound having a sulfonyl chloride group at the 4-position, and is a condensed compound with 1,2-naphthoquinonediazido-4-sulfonyl chloride.

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, dihydroxyanthraquinone, bisphenol A, phenol novolak resin, resorcinbenzaldehyde condensation resin, pyrogallol acetone condensation resin and the like. Examples of the amino group-containing compound include aniline, p-aminodiphenylamine,
Examples include p-aminobenzophenone, 4,4'-diaminodiphenylamine, and 4,4'-diaminobenzophenone.

With respect to the quinonediazide compounds, including those described herein, see also J. Am. Koser (J. Kosa)
r) "Light Sensitive System" (Light
Sensitive System (New York City, John Wiley & Sons, 1965), and Nagamatsu, Inui co-authored "Photosensitive Polymers" (Kodansha, 1
977) can be used.

When a photopolymerizable compound is contained in the photosensitive layer, specifically, for example, as the photopolymerizable compound, generally used compounds can be arbitrarily used.
For example, at least one compound selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters can be used. Examples include, but are not limited to, ethylene glycol diacrylate, glycerin triacrylate, polyacrylate, ethylene glycol dimethacrylate, and the like.

The photosensitive layer can contain a photopolymerization initiator. The photopolymerization initiator in this case is optional,
Those having less absorption in the visible region are more preferable, and examples of such compounds include the following compounds.
However, it is not limited to these. That is, benzophenone, Michler's ketone [4 ', 4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone,
Aromatic ketones such as phenanthraquinone and other aromatic ketones, benzoin ethers, methyl benzoin, ethyl benzoin and other benzoins,
And 2- (o-chlorophenyl) -4,5-diphenylimidazole duplex, 2- (o-chlorophenyl)
-4,5- (m-methoxyphenyl) imidazole duplex, 2- (o-fluorophenyl) -4,5-diphenylimidazole duplex, 2- (o-methoxyphenyl)
-4,5-diphenylimidazole dimer, 2- (p-
Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Weight,
2- (p-methylmercaptophenyl) -4,5-diphenylimidazole duplex and U.S. Pat.
185, 2,4,5-triacrylimidazole duplexes, such as similar duplexes described in GB 1,047,569 and U.S. Pat. No. 3,784,557. .

As other photopolymerizable compounds, 2,4-
Thioxanthones such as diethylthioxanthone can also be used. In this case, a compound known as a photopolymerization accelerator, for example, isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, N-methyldiethanolamine, bisdiethylaminobenzophenone and the like can be used.

As a binder, a known polymer compound,
It can contain a synthetic resin, and preferably contains, for example, a polymer compound having a carboxylic acid vinyl ester polymerization unit represented by the following formula in the molecular structure.

[0105]

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In the formula, R ₁₀ represents an alkyl group which may have a substituent.

Any polymer compound having the structure described above can be used arbitrarily. Examples of the vinyl carboxylate monomer for constituting the polymerized unit represented by the above formula include vinyl acetate and vinyl propionate. , Vinyl butyrate, vinyl laurate, vinyl versatate (shown below) and the like.

[0108]

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R ₁₁ and R ₁₂ are alkyl groups, and the total number of carbon atoms is 7. That is, R ₁₁ + R ₁₂ = C ₇ H ₁₆ .

The polymer compound may be a polymer obtained by polymerizing one kind of vinyl carboxylate, a polymer obtained by copolymerizing two or more kinds of vinyl carboxylate, or a polymer obtained by copolymerizing vinyl carboxylate with the same. It may be a copolymer in any component ratio with other possible monomers.

Examples of the monomer unit which can be used in combination with the polymerization unit represented by the above formula include ethylenically unsaturated olefins such as ethylene and propylene, styrenes, acrylic acids such as acrylic acid and methacrylic acid, and the like. Maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, diesters of unsaturated dicarboxylic acids such as diethyl maleate, α-methylene aliphatic monocarboxylic esters such as methyl acrylate, nitriles such as acrylonitrile, Amides such as acrylamide, anilides such as acrylanilide, vinyl ethers such as methyl vinyl ether, vinyl chloride, vinylidene chloride,
Vinylidene cyanide, for example, ethylene derivatives such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, For example, there are vinyl monomers such as N-vinyl compounds such as N-vinyl pyrrole and N-vinyl carbazole. These monomer units are present in the polymer compound in a structure in which the unsaturated double bond is cleaved.

Particularly preferred as the polymer compound to be used are those having a vinyl acetate polymerized unit in the molecular structure. Among them, those having 40 to 95% by weight of vinyl acetate polymerized units and having a number average molecular weight (MN) of 1,000
~ 60,000, weight average molecular weight (MW) of 50
Those having 0 to 150,000 are preferred.

More preferably, a polymer compound having a vinyl acetate polymerized unit (particularly 40 to 95% by weight) and a carboxylic acid vinyl ester polymerized unit having a longer chain than vinyl acetate is preferable, and a number average molecular weight (MN) is particularly preferable. Is 2,000
0-60,000, weight average molecular weight (MW) of 10,000
It is preferably from 00 to 150,000.

In this case, the monomer constituting the polymer compound having a vinyl acetate polymerized unit by copolymerizing with vinyl acetate is arbitrary as long as it can form a copolymer. For example, vinyl acetate-ethylene, Vinyl acetate-vinyl chloride, vinyl acetate-vinyl stearate, vinyl acetate-
It can be arbitrarily selected from the above monomers such as vinyl versatate and vinyl propionate-vinyl versatate.

A dye and / or a pigment is added to the photosensitive layer as a colorant. Especially when used for color proofing,
Pigments and dyes having the same colors as those required for ordinary colors, that is, yellow, magenta, cyan, and black are required, but other metal powders, white pigments, and fluorescent pigments are also used.

When a colorant is used, the ratio of the colorant / components other than the colorant in the colored photosensitive layer is determined by a method known to those skilled in the art in consideration of the target optical density and the removability of the colored photosensitive layer in a developing solution. Can be determined by For example, in the case of a dye, the content is preferably 5% to 75% by weight, and in the case of a pigment, the content is preferably 5% to 90% by weight.

The thickness of the colored photosensitive layer is determined by a method known to those skilled in the art according to the target optical density, the type of coloring agent (dye, pigment, carbon black) used in the colored photosensitive layer and its content. However, as long as the thickness of the colored photosensitive layer is as small as possible, the resolution becomes higher and the image quality is good. Thus, the membrane thickness is preferably usually being used in the range of ^{0.1g / m 2 ~5g / m 2} .

In addition, if necessary, a plasticity or coating property improving agent may be added to the layer components of the transfer material and the image receiving material.

Examples of the plasticizer include various low molecular weight compounds such as phthalates, triphenyl phosphates, and the like.
Examples of the maleic acid esters and the coatability improver include surfactants such as fluorine surfactants and nonionic surfactants represented by ethylcellulose polyalkylene ether.

The photosensitive layer can be divided into two layers, a colored layer composed of a colorant and a binder, and a photosensitive layer composed of a photosensitive composition. In this case, either layer may be arranged on the support side.

The protective layer used if necessary may be any known one, but its gas permeability is preferably selected appropriately according to the type of the photosensitive composition used. That is, it is preferable to provide a protective layer having a high gas permeability in the case of a photosensitive composition which generates a gas at the time of exposure to o-quinonediazide or the like, and in the case of using a photopolymerizable photosensitive composition, it is preferable to provide a protective layer. It is preferable to provide a protective layer having low permeability. Further, those which are soluble in a developing solution during development, in particular, a water-soluble polymer such as polyvinyl alcohol and cellulose, having a thickness of about 0.01 to 5 μm, particularly 0.0
Those having a size of about 3 to 1 μm are preferred.

The material used for these photosensitive layers and other layer constitutions is not only a color proof material but also a lithographic printing material and a relief printing photosensitive material, wherein a binder is a novolak resin or a vinyl-based material having a phenolic hydroxyl group. It can be widely used by changing to a polymer.

As a color proofing material containing a photopolymerizable compound and a binder, and an o-quinonediazide compound and a binder, there is a method of forming a multicolor transfer image using a color sheet, for example, as described in JP-A-47-41830. Direct transfer of colored images to final receiving paper
97140 and 61-189535, JP-A-3-13-1
No. 07852, an indirect transfer system for temporarily transferring a colored image onto a temporary image receiving sheet.
Generally, a method of transferring the colored photosensitive layer described in No. 7 to an image receiving paper and thereafter forming an image is repeated.

The method of performing the heat treatment of the present invention is not particularly limited, but a method capable of uniformly heating the film in as short a time as possible is preferable. Such methods include, for example,
The film is transported continuously by gripping both ends of the film with pins or clips, or by roll transport by multiple roll groups or air transport that blows air to the film and floats it, etc., from multiple slits A method in which heated air is blown onto one or both surfaces of the film, a method using radiant heat from an infrared heater or the like, a method in which the heated air is brought into contact with a plurality of heated rolls, or a combination of a plurality of methods is used for heat treatment.

A method for keeping the film flat is as follows.
Although there is no particular limitation, for example, the above-described pin and clip transfer method, air transfer method, roll transfer method, and the like can be used. The roll transport method is not perfectly flat because the roll is transported with a wrap angle with the film, but
Since the film is alternately contacted with the roll on the front and back, and the winding direction of the film does not become one direction, the film can be regarded as substantially flat.

The step of applying the heat treatment as described above may be any step from the production of the film to the cutting and packaging of the final product. Heating at the above temperature for more than 30 minutes will diminish its effect. In particular, care must be taken when the temperature is equal to or higher than Tc, since the effect disappears in a very short time. Of course, even if the effect is once lost, the effect of reducing the original curl can be obtained by performing the heat treatment again.

The heat treatment may be performed in one stage or may be performed in two or more zones with a temperature difference.

After applying and drying the photosensitive layer, it is preferable to subsequently carry out a heat treatment.

The heat-treated base thus obtained is:
Since it is higher than Tg, it is cooled to room temperature.

[0130]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Preparation of Supports 1 to 16 To 100 parts by weight of dimethyl terephthalate and 65 parts by weight of ethylene glycol, 0.05 part by weight of magnesium acetate hydrate was added as a transesterification catalyst, followed by a conventional method. A transesterification reaction was performed according to the following. To the obtained product, 0.05 parts by weight of antimony trioxide, trimethyl phosphate 0.0
3 parts by weight were added. Next, gradually raise the temperature and reduce the pressure,
Polymerization is performed at 280 ° C. and 0.5 mmHg, and the intrinsic viscosity is set to 0.1.
As a result, 65 polyethylene terephthalates were obtained.

Further, this polyethylene terephthalate was vacuum-dried at 150 ° C. for 8 hours, and then dried using an extruder.
It was melt-extruded at 85 ° C., adhered to a 30 ° C. cooling drum while applying static electricity, cooled and solidified to obtain an unstretched sheet.
The unstretched sheet is rolled at 90 ° C. using a roll-type longitudinal stretching machine.
And stretched 3.2 times in the machine direction. The temperature difference between the front and back surfaces was within 5 ° C.

The obtained uniaxially stretched film was stretched by a tenter type transverse stretching machine in a first stretching zone at 95 ° C. by 50% of the total transverse stretching ratio, and further in a second stretching zone at 100 ° C. by a total transverse stretching ratio of 3. The film was stretched so as to be doubled. Then 70
Heat treatment at 2 ° C. for 2 seconds, and first heat fixing zone 160 ° C.
For 5 seconds and a second heat set zone at 220 ° C. for 15 seconds. Next, a biaxially stretched polyethylene terephthalate film 1 having a thickness of 100 μm was obtained. The Tg of the polyethylene terephthalate film 1 was 75 ° C.

(Preparation of Supports 1 to 11)
Is subjected to a corona discharge treatment of 8 W / (m ² · min) on one surface thereof, and the following undercoat layers A-1 and A-2 are formed thereon.
Coating was performed so that the dry film thickness became 0.8 μ and 0.1 μ, respectively. Further, on the other surface, 8 W / (m ² ·
min), and the following undercoat layers B-1 and B-2 each having a dry film thickness of 0.8 μm.
After coating so as to have a thickness of 1.0 μm, a heat treatment was carried out while being conveyed in a heat treatment oven having a film conveyance device (zone length 100 m) composed of a plurality of roll groups. At this time, the set temperature and dew point temperature in the oven were changed as shown in Table 1. The heat treatment time is 10 minutes (line speed 10 minutes).
m / min).

(Preparation of Supports 12 to 16) After the above-mentioned undercoating A-1 and A-2 were applied to the film 1, the film was once wound into a roll, and in this state, the temperature and dew point temperature shown in Table 1 were measured. Heat treatment was performed in a constant temperature bath under the conditions. Thereafter, the undercoat layers B-1 and B-2 were applied.

A support 16 was prepared in the same manner except that the above heat treatment was not performed.

-Coating of Emulsion Layer and Back Layer-The following (emulsion layer) and (back layer) were coated on A-2 and B-2, respectively, on the obtained supports 1 to 16 to obtain a silver halide. Photographic material samples 1 to 16 were prepared.

<Undercoat Coating Solution A-1> A copolymer latex solution (solids: 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate) 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml <Undercoating coating solution B-1> Butyl acrylate 40% by weight, styrene 20 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished with water 1000 ml <Undercoating coating solution A-2> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Finished with water 1000 ml <Undercoat coating solution B-2> Water-soluble conductive polymer (UL-4) 60 g Compound (UL) Latex liquid containing -5) as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g Hardener (UL-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish with water 1000 ml

[0139]

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[0140]

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<Coating of Emulsion Layer / Backing Layer> The following (emulsion layer) and (backing layer) were coated on A-2 and B-2, respectively, on Samples Nos. 1 to 16 to prepare Sample No. 1 which is a silver halide photographic material. 1 to 16 were prepared. Incidentally, gelatin coating amount at this time, the emulsion layer side is 2.7 g / m ^2, including gelatin in the emulsion, as gelatin total amount to be 5.0 g / m ² Backing layer side in 2.7 g / m ² Was applied.

(Preparation of Emulsion) A rhodium hexachloride complex was added to a silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide at 8 ×.
The solution added so as to be 10 ⁻⁵ mol / Agmol was
A cubic crystal containing 0.13 μm in particle size and 1 mol% of silver bromide was added simultaneously to the gelatin solution while controlling the flow rate and desalting.
A monodispersed silver chlorobromide emulsion was obtained. This emulsion was sulfur sensitized by a conventional method, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer.
The following additives were added to prepare an emulsion coating solution.

(Preparation of Emulsion Coating Solution) Gelatin 1.0 g / m ² Compound (a) 1 mg / m ² NaOH (0.5 N) Adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² saponin (20% aqueous solution) 0.5 ml / m ² sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e) 10 mg / m ² compound ( f) 6 mg / m ² latex (m) 1.0 g / m ² Styrene-malenic acid copolymerized aqueous polymer (thickener) 90 mg / m ² (emulsion protective layer coating solution) Gelatin 0.5 g / m ² compound (g) ) (1% aqueous solution) 25 cc / m ² compound (h) 120 mg / m ² spherical monodisperse silica (8 μm) 20 mg / m ² spherical monodisperse silica (3 μm) 10 mg / m ² compound (i) 100 mg / m ² latex (m) 0.5 g / m ² Citric acid Adjusted to pH 6.0.

(Coating solution for backing layer) Gelatin 0.8 g / m ² Compound (j) 100 mg / m ² Compound (k) 18 mg / m ² Compound (l) 100 mg / m ² Saponin (20% aqueous solution) 0.6 cc / m ² latex (m) 300 mg / m ² 5-nitroindazole 20 mg / m ² styrene - maleic acid copolymer aqueous polymer (thickener) 45 mg / m ² glyoxal 4 mg / m ² (backing protective layer coating solution) gelatin 0. 5 g / m ² compound (g) (1% aqueous solution) ² cc / m ² spherical polymethyl methacrylate (4 μ) 25 mg / m ² sodium chloride 70 mg / m ² glyoxal 22 mg / m ² Compound (n) 10 mg / m ² latex (m ) 0.5 g / m ²

[0145]

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[0146]

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[0147]

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Light-sensitive material samples 1 to 16 prepared as described above
Was evaluated as described below, and the results are shown in Table 1.

(Evaluation Method) <Measurement of Scattering Intensity> The emulsion layer and the backing layer of the photosensitive material sample were peeled off using pancreatin.
Light scattering was measured on the support from which the undercoat layer was peeled off using acetone under the following conditions.

Model: Light scattering measurement device POLYME
R DYNAMICS ANALYZERDYNA-1
00 (manufactured by Otsuka Electronics Co., Ltd.) Optical system: two types of Hv (polarizer direct) pattern and Vv (parallel polarizer) pattern Scattering angle: 0 ° to 20 ° Azimuth angle: 45 ° (however, support Measurement temperature: 23 ° C., 140 ° C. The light scattering intensity was defined as the value of the maximum peak measured within the above scattering angle.

The measured value was obtained by measuring the scattering intensity at 23 ° C. as Hv.
(B) After measuring Vv (b), the same sample is heated on a temperature stage and subjected to heat treatment at 140 ° C. for 2 minutes, and the measured values are defined as Hv (a) and Vv (a).

<Curse> 35 mm wide and 210 mm long
After humidifying a photographic photosensitive material having the following dimensions under a condition of 23 ° C. and 55% RH for one day, fix the photographic photosensitive layer with the photographic photosensitive layer side inward so that the photographic photosensitive material is not wound back around a 2 inch (50 mm) core. I do. Then, in this state, put in an aluminum barrier bag and heat-treated at 55 ° C. and 20% RH for 4 hours.
Furthermore, it is left to cool for 1 hour under the conditions of 23 ° C. and 55% RH.
Thereafter, the film was released from the winding core, and the heights of the four corners rising with the convex portions of the film facing down were measured, and the average value was obtained. The unit is mm.

This is referred to as the rising curl of the film obtained by the above method. The stronger the curling, the larger the amount. If the rising curl is too large, it will cause poor transportability and workability on an automatic machine, and it is usually preferable that the curl is 40 mm or less.

<Glass Transition Temperature Tg> 10 mg of a film or pellet was placed in a nitrogen stream at 300 cc / min.
Melt at 00 ° C and immediately quench in liquid nitrogen. This quenched sample was used as a differential scanning calorimeter (manufactured by Rigaku
8230), and the temperature is raised at a rate of 10 ° C./min in a nitrogen stream at 100 cc / min to detect Tg.
Tg was defined as the average value of the temperature at which the baseline began to be skewed and the temperature at which it returned to the new baseline. Note that the measurement start temperature is a temperature lower than the measured Tg by 50 ° C. or more.

<Transportability of Automatic Developing Machine> A photographic light-sensitive material sample was wound around a 2.8-inch paper core with the emulsion side wound inside.
After heat treatment at 40 ° C. for 72 hours (corresponding to a self-release time of 2 years), the film was transferred to an automatic developing machine to evaluate transportability as follows.

：: No jamming occurred even when 100 sheets were passed. Δ: Jamming of 10 sheets out of 100 sheets ×: Jamming of 50 or more sheets out of 100 sheets <Evaluation of flatness of support>
The sample was cut out to a size of × 100 cm (width × length), placed on a table having excellent flatness, and visually evaluated for unevenness of the base.

：: Good flatness and tightly adhered to the table △: The base is distorted in some places ×: The base is entirely undulating.

[0158]

[Table 1]

As is clear from Table 1, when a support having a light scattering intensity ratio within the range of the present invention is used, the curl is improved and the flatness of the support is also improved. I understand.

[0160]

According to the present invention, it is possible to provide a support for a photosensitive material which is hardly curled even when stored in a roll and has improved flatness.

[Brief description of the drawings]

FIG. 1 is a simple schematic diagram of a polarization scattering measurement.

[Explanation of symbols]

 Reference Signs List 1 polarizing plate a 2 polarizing plate b 3 sample 4 image receiving unit

Claims (3)

[Claims] 1. A support for a photosensitive material, characterized by satisfying the following relational expression (I). 1.5 <Vh (b) / Vh (a) <20 (I) Vh (b): Vh (b) in the Vh direction measured by a polarization scattering device after peeling the photosensitive layer Scattering intensity Vh (a): 14
Scattering intensity in the Vh direction measured by a polarization scattering device on a sample that has been heat-treated at 0 ° C. for 2 minutes. 2. The support according to claim 1, wherein the following relational expression (II) is satisfied. 1.5 <Vv (b) / Vv (a) <20 (20) where Vv (b) is the value in the Vv direction measured by a polarization scattering device after the photosensitive layer is separated. Scattering intensity Vv (a); 14
Scattering intensity in the Vv direction measured by a polarization scattering device on a sample heat-treated at 0 ° C. for 2 minutes. 3. A light-sensitive material comprising at least one light-sensitive layer on the support according to claim 1.