JPH06167776A - Manufacture of photographic support - Google Patents

Abstract

PURPOSE:To obtain a photographic support small in occurrence of core set curl and good in cleavability and superior in transparency and mechanical characteristics. CONSTITUTION:This photographic support is characterized by being made of a copolymerized polyester derived from terephthalic acid derivative and 2,6- naphthalenedicarboxylic acid as aromatic dicarboxylic acid and as a diol, mainly, ethylene glycol, and having a glass transition point (Tg) of >=90 deg.C measured by a differential scanning calorimeter and a melting point of >=200 deg.C, and biaxially stretched and, after heat fixing, heat treated (anealed) at a temperature lower than Tg by 5-40 deg.C for 0.1-100hr.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolyester film, which is particularly useful as a photographic support, is less likely to cause core set curl, has good cleavage, is excellent in transparency and mechanical properties. It relates to a method for producing a polyester film.

[0002]

Photographic light-sensitive materials are generally prepared by coating at least one photographic light-sensitive layer on a plastic film support. As the plastic film, generally, a fiber-based polymer represented by triacetyl cellulose (hereinafter referred to as "TAC") and a polyester-based polymer represented by polyethylene terephthalate (hereinafter referred to as (PET)) are used. There is.

Conventionally, PET films have been excellent in productivity,
It has been considered to be a substitute for TAC film because of its mechanical strength and dimensional stability, but in the roll form widely used as a photographic light-sensitive material, curling curls strongly remain, so that after development processing Although it has poor handleability and has the above-mentioned excellent properties, its range of use has been limited.

Generally, as a photographic light-sensitive material, a sheet-shaped material such as a film for X-ray, a plate-making film and a cut film, and a typical roll film has a width of 35 m / m or less. It is a color or black-and-white negative film that is stored in a cartridge and is loaded into a general camera and used for shooting.

On the other hand, the most important feature of the TAC film, which is mainly used for roll films, as a photographic support is that it has poor optical anisotropy and high transparency.
Another feature is that it has excellent properties in decurling after development. That is, the characteristic of the molecular structure of the TAC film is that it has a relatively high water absorbing property as a plastic film. Therefore, the curling curl that occurs over time in the situation of being wound as a roll film causes the molecular chain to be absorbed by water absorption in the developing process. The molecular chains that flow and become immobilized with the time of winding undergo rearrangement.

As a result, it has an excellent property that the curling curl once formed is eliminated. TA like this
A photographic light-sensitive material using a film that does not have curl curl recovery such as C film, when used in a roll state, may be scratched during a printing step for forming an image on photographic printing paper after development. Problems such as occurrence, defocusing, and jamming during transportation occur.

By the way, in recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film transportation at the time of photographing, the high magnification of photographing, and the miniaturization of photographing apparatus have been remarkably advanced. In that case, as the support for the photographic light-sensitive material,
Properties such as strength, dimensional stability, and thinning are required.

However, in the above-mentioned TAC, since the film formed by the rigid molecular structure has a weak film quality and cannot be used for these purposes, the roll curling becomes a problem even after the development processing. In the film field, PET film has a problem that it cannot be used although it has excellent mechanical properties.

Such a problem of curling is a serious problem even in a color or black-and-white film contained in a patrone, which has been conventionally used. However, in a novel patrone system as described below, a more serious problem is caused. Becomes This is because such a Patrone system makes it easy to load the camera into the camera, and at the same time, the motor inside the camera rotates the core of the Patrone to automatically load the film inside. In order to do this, it is necessary that the film is tightly wound and stored in the patrone, which makes the system easier to curl than the conventional patrone. This is because

[0010]

In order to solve such a problem, as a method for modifying a PET film used as a photographic support, for example, in JP-A-1-24446, a polyester film as a photographic light-sensitive material is used. A copolyester film containing an aromatic dicarboxylic acid component having a metal sulfonate group and an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms has been proposed. Although this method can certainly increase the water absorption rate than the PET film, it is still insufficient and the level of curl elimination is TAC.
It is far behind the film. Therefore, an object of the present invention is to provide a process for producing a photographic support comprising a copolyester film which is excellent in core set curl without curling curl, transparency and mechanical strength.

[0011]

The present invention is directed to terephthalic acid (hereinafter referred to as TPA) and 2,6-naphthalenedicarboxylic acid (hereinafter referred to as 2,6-ND) as an aromatic dicarboxylic acid.
CA) as a main component and ethylene glycol (hereinafter referred to as “EG”) as a diol as a main component, which has a glass transition point (Tg) of 90 ° C. or higher as measured by a differential scanning calorimeter (DSC). The biaxially stretched film having a melting point of 200 ° C. or higher measured by a melting point measuring device and obtained from the copolyester is 0.1 to 100 at 5 ° C. to 30 ° C. lower than its Tg after heat setting. The present invention relates to a method for producing a photographic support having excellent curl property and cleavage property, which is characterized by performing a heat treatment (annealing) for a time.

The terephthalic acid derivative used in the present invention is preferably terephthalic acid represented by the general formula (I), terephthalic acid dimethyl ester, terephthalic acid diethyl ester or the like, and the 2,6-naphthalenedicarboxylic acid derivative is represented by the general formula (II ) 2,6-naphthalenedicarboxylic acid represented by
2,6-naphthalenedicarboxylic acid dimethyl ester,
2,6-naphthalenedicarboxylic acid diethyl ester and the like are preferable. In addition, ethylene glycol is a diol represented by HOCH ₂ CH ₂ OH.

[0013]

[Chemical 1]

In order to obtain a copolyester having a Tg of 90 ° C. or higher in the present invention, the content of 2,6-naphthalenedicarboxylic acid component relative to the terephthalic acid component must be 40 mol% or higher, and the melting point is 200 ° C. or higher. To make it a copolyester, the terephthalic acid component
The 6-naphthalenedicarboxylic acid component needs to be 60 mol% or more, and therefore, to satisfy both Tg and melting point, therefore, the 2,6-naphthalenedicarboxylic acid component in the terephthalic acid component is 60 mol% or more and 95 mol% or less. . At this time, Tg is 90 ° C to 115 ° C, and the melting point is 20.
It was 0 ° C to 263 ° C.

The copolyester obtained in the present invention is dried and melt-extruded at a temperature of 290 ° C. to 320 ° C. to form an amorphous base, and then simultaneously stretched at 100 ° C. to 150 ° C. by 2.5 to 4.5 times. Alternatively, it is sequentially stretched to obtain a biaxially stretched film. The biaxially stretched film thus obtained has a melting point of the polyester of 5 ° C to 40 ° C.
Heat set at a temperature lower by 0.degree. C., preferably at a temperature lower than 10.degree. C. to 30.degree. C. for 0.5 minutes to 5 minutes, preferably 1 minute to 3 minutes, and 5.degree.
Heat treatment (annealing) is carried out at a temperature lower by 0 ° C., preferably 10 ° C. to 30 ° C. lower than 0.1 hour to 100 hours, preferably 10 to 30 hours. By such heat-setting and annealing treatment, the copolyester film becomes tough and becomes a photographic support having no core set curl, improved cleavage and excellent transparency.

In the present invention, the core set curl test is conducted as follows.
The film is wound on a core of 11 mm and heat-treated at 80 ° C. for 2 hours. If the Tg measured by DSC is 90 ° C. or more, a winding habit is formed and the film cannot be used satisfactorily. In addition, polyethylene-2,6-naphthalate (hereinafter referred to as PEN) that does not copolymerize TPA
The film has a problem of cleavage during cutting, and improvement has been demanded. According to the present invention, a high Tg that can sufficiently achieve the object is obtained, and a copolyester film having an excellent core set curl property and improved cleavage property can be obtained.

The production of the copolyester as referred to in the present invention may be carried out continuously or batchwise, and may be carried out by a transesterification reaction method or a direct esterification reaction method, whereby the desired copolyester can be obtained. An example thereof will be given below, but the present invention is not limited thereto. For example, dimethyl terephthalate, 2,6-naphthalenedicarboxylic acid dimethyl ester, and ethylene glycol are charged into a reaction vessel equipped with a stirrer, an N ₂ inlet pipe, and a rectification column, and manganese known as a transesterification reaction catalyst is used. , Calcium or magnesium compounds can be selected and used. For example, manganese acetate is 100 pp as manganese metal.
Add an amount of m 2 and heat to 200 ° C. While removing methanol generated by the reaction from the rectification column, the mixture is heated for 1 hour, further heated to 225 ° C for 1 hour, and then heated to 250 ° C. The transesterification reaction ends when the theoretical amount of methanol flows out.

The reaction completed liquid was transferred to a polycondensation reaction tank equipped with a stirrer, a distillation pipe and an N ₂ introduction pipe and heated at 290 ° C. to prepare an antimony, germanium or titanium compound known as a polycondensation reaction catalyst. You can choose from and use it. For example, antimony triacetate is used as antimony metal 2
The amount of 00 ppm is added, and the reaction system is evacuated. Gradually raise the vacuum to 1.5 torr. The end point of the polycondensation reaction is judged by the torque value of the stirrer, but it takes about 3 hours. At the end of the polycondensation reaction,
Pressurize to about 1 kg / cm ² with N ₂ pressure, slide out the polymer from the bottom of the kettle, and cut into pellets while cooling with water. The pellets are dried at 290 ° C to 320
Melt-extruded at 0 ° C. and used as an amorphous base at 100 ° C. to 150 ° C. in the longitudinal and transverse directions at the same time, or sequentially stretched to form a biaxially stretched film, then heat set at a temperature higher than Tg, and further The target film is obtained by heat treatment (annealing) at a temperature 5 ° C. to 40 ° C. lower than Tg for 0.1 to 100 hours. The heat setting is 20
The range of 0 ° C. to 250 ° C. is preferable, and the range of 0.5 minutes to 1 hour is preferable.

The photographic support of the present invention may contain a copolymerization component other than the above components within the range not changing their properties. As components other than the above, examples of dicarboxylic acid components include adipic acid, sebacic acid, phthalic acid,
Cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, or the like can contain, as the glycol component, for example, propylene glycol, hexamethylene glycol, polyethylene glycol, etc., but is not limited thereto. Also, from the transesterification reaction or the direct esterification reaction to the polycondensation reaction at an appropriate time T
Lubricants such as inorganic inert particles such as i, Ca, Si and Al and organic particles such as crosslinked styrene; 2,6-di-t-butyl-p-gresol and 2,2′-methylene-bis- (4 −
Antioxidants such as methyl-6-t-butylphenol) can be added. Further, other polymer, dye or the like may be added during melt extrusion.

The thickness of the photographic support film used in the present invention can be appropriately set depending on the field of application of the photographic film, and is preferably 25 to 250 μm, but preferably 4
It is 0 to 200 μm. The film obtained by the present invention has excellent transparency and mechanical strength, has a Tg of 90 ° C. or higher, is excellent in core set curl property, and is excellent in cleavage. The film haze is 2.5% (at a thickness of 100 μm) or less, and the breaking strength is 20 to 30 kg / mm.
² , the initial elastic force is 400 to 600 kg / mm ² .
The most preferable photographic layer of the photographic light-sensitive material of the present invention is
It is a silver halide photographic light-sensitive material, and examples thereof include a silver halide color negative film, a color positive film, a color reversal, and a black and white negative film. For the structure and manufacturing method of the photographic layer, see JP-A-1-24444.
As detailed in 46, this can be used as it is.

[0021]

EXAMPLES Examples of the present invention are shown below, but the present invention is not limited to these examples. "Parts" in Examples means "parts by weight" unless otherwise specified. In the present invention, Tg, transparency, haze, mechanical strength (breaking strength, initial elastic modulus), core set curl property, and cleavage property are measured as follows. (Glass transition point; Tg) It was measured at a temperature rising rate of 10 ° C./min using DSC. (Transparency (haze)) The haze of the film is determined by ASTM-D.
It was measured according to 1003-52.

(Break strength and initial elastic modulus) JIS-Z
According to 1702-1976, width 10mm, length 100mm
The strip speed is 30 and the pulling speed is 30 when measuring the breaking strength.
The base length at break was 0 mm / min, and the initial elastic modulus was 20 mm / min. (Cleavability) Light load tear strength tester (Toyo Seiki Co., Ltd.)
Manufactured by K.K.) and the cleavage of 13 mm incision with a sample size of 51 × 64 mm and the remaining 51 mm was torn apart was observed.

(Core set curl property) Sample size 1
Wrap a 2 cm x 35 mm film around a 10 mm diameter core, and
Treatment at 0 ° C. × 30% RH × 72 hours, then release from the core and measure the winding diameter (curvature radius) of the sample,
It was evaluated by the ANSI curl value. ANSI curl value = 1 /
(Radius of curvature (m))

Examples 1-3 1.94 kg of dimethyl terephthalate and 22.0 kg of 2,
Dimethyl 6-naphthalenedicarboxylate and 14.3 kg of ethylene glycol were charged into a reaction vessel equipped with a stirrer, a N ₂ introduction tube and a rectification column, and manganese acetate as an ester exchange catalyst was adjusted to 80 ppm as manganese metal. Is added and heated to 200 ° C. The methanol produced by the reaction is heated for 1 hour while being removed from the rectification column, and further heated to 225 ° C for 1 hour and then to 250 ° C. The transesterification reaction ends when the theoretical amount of methanol flows out. The reaction-terminated liquid is transferred to a polycondensation reaction container heated to 290 ° C., antimony trioxide as a polycondensation reaction catalyst is added in an amount of 200 ppm as antimony metal, and the reaction system is evacuated. The degree of vacuum was gradually increased to finally 1.2 Torr. The polycondensation reaction was terminated when a predetermined stirring torque value was reached. The obtained polymer was taken out from the bottom of the kettle in the form of strands, cooled in water, and then cut into pellets. After drying this pellet, 3
An amorphous base was prepared by melt-extruding at 20 ° C., and this was stretched at 130 ° C. in the longitudinal direction by 3.6 times each to obtain a biaxially oriented film having a thickness of 100 μm. This film was heat-set at 230 ° C. for 1 minute and further annealed at 100 ° C. for 24 hours to obtain a target copolyester film. Table 1 shows the characteristics of Examples 1 to 3.

Comparative Example 1 24.4 kg of dimethyl 2,6-naphthalene cycarboxylate and 14.3 kg of ethylene glycol were charged into the reaction vessel used in Examples 1 to 3, and any ester of Examples 1 to 3 was used. A polyethylene naphthalate film having a thickness of 100 μm was obtained through the exchange reaction, polycondensation reaction, film formation, and heat treatment process. The characteristics are shown in Table 1.

Comparative Example 2 19.4 kg of dimethyl terephthalate and 14.3 kg of ethylene glycol were charged into the reaction vessel used in Examples 1 to 3, and manganese acetate was used as a transesterification reaction catalyst in an amount of 80 ppm as manganese metal. Add and 160 ℃
Heat to. The methanol produced by the reaction is heated for 1 hour while being removed from the rectification column, and further heated to 200 ° C. for 1 hour and then to 230 ° C. The transesterification reaction ends when the theoretical amount of methanol flows out. The reaction completion is transferred to a polycondensation reaction tank heated to 280 ° C., antimony trioxide as a polycondensation reaction catalyst is added in an amount of 200 ppm as antimony metal, and the reaction system is evacuated. The degree of vacuum was gradually increased to finally 1.2 Torr. When the predetermined stirring torque value was reached, the polycondensation reaction was terminated. The obtained polymer was taken out from the bottom of the kettle as a strand, cooled with water, and then cut into pellets. The pellets were dried, melt-extruded at 280 ° C. to form an amorphous base, and then stretched 3.6 times in the longitudinal and transverse directions to obtain a biaxially oriented film having a thickness of 100 μm. This film was heat set at 230 ° C for 1 minute and then 65 ° C.
Annealed for 24 hours. The characteristics are shown in Table 1.

[0027]

[Table 1]

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[Procedure amendment]

[Submission date] January 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

[0010]

In order to solve such a problem, as a method for modifying a PET film used as a photographic support, for example, in JP-A-1-24446, a polyester film as a photographic light-sensitive material is used. A copolyester film containing an aromatic dicarboxylic acid component having a metal sulfonate group and an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms has been proposed. Although this method can certainly increase the water absorption rate than the PET film, it is still insufficient and the level of curl elimination is TAC.
It is far behind the film. Therefore, an object of the present invention is to provide a process for producing a photographic support comprising a copolyester film which is excellent in core set curl with no curl curl due to its high Tg and which is excellent in transparency and mechanical strength. is there.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

[0011]

According to the present invention, a terephthalic acid derivative and a 2,6-naphthalenedicarboxylic acid derivative are main components as an aromatic dicarboxylic acid, and ethylene glycol (hereinafter referred to as EG) is a main component as a diol. A copolymerized polyester having a glass transition point (Tg) of 90 ° C. or higher as measured by a differential scanning calorimeter (DSC) and a melting point of 200 ° C. or higher as measured by a melting point measuring device, and obtained from the copolymerized polyester. The axially stretched film is heat-set, and then heat-treated (annealed) at a temperature 5 ° C to 30 ° C lower than its Tg for 0.1 to 100 hours. For core set curl and cleavability. It relates to a method for manufacturing a support.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

The reaction completed liquid was transferred to a polycondensation reaction tank equipped with a stirrer, a distillation pipe and an N ₂ introduction pipe and heated at 290 ° C. to prepare an antimony, germanium or titanium compound known as a polycondensation reaction catalyst. You can choose from and use it. For example, antimony triacetate is used as antimony metal 2
The amount of 00 ppm is added, and the reaction system is evacuated. Gradually raise the vacuum to 1.5 torr. The end point of the polycondensation reaction is judged by the torque value of the stirrer, but it takes about 3 hours. At the end of the polycondensation reaction,
Pressurize to about 1 kg / cm ² with N ₂ pressure, slide out the polymer from the bottom of the kettle, and cut into pellets while cooling with water. The pellets are dried at 290 ° C to 320
Melt-extruded at 0 ° C. and used as an amorphous base at 100 ° C. to 150 ° C. in the longitudinal and transverse directions at the same time, or sequentially stretched to form a biaxially stretched film, then heat set at a temperature higher than Tg, and further The target film is obtained by heat treatment (annealing) at a temperature 5 ° C. to 40 ° C. lower than Tg for 0.1 to 100 hours. The heat setting is 20
The range of 0 ° C to 250 ° C is preferable, and the range of 0.5 minutes to 5 minutes is preferable.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

The photographic support of the present invention may contain a copolymerization component other than the above components within the range not changing their properties. As components other than the above, examples of dicarboxylic acid components include adipic acid, sebacic acid, phthalic acid,
The cyclohexanedicarboxylic acid or the like may contain, as the glycol component, for example, propylene glycol, hexamethylene glycol, polyethylene glycol or the like, but is not limited thereto. In addition, lubricants such as inorganic inert particles such as Ti, Ca, Si and Al and organic particles such as cross-linked styrene at an appropriate time from transesterification reaction or direct esterification reaction to polycondensation reaction,
2,6-di-t-butyl-p-gresol and 2,2'-
Antioxidants such as methylene-bis- (4-methyl-6-t-butylphenol) can be added.
Further, other polymer, dye or the like may be added during melt extrusion.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027]

[Table 1]

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Claims (1)

[Claims] 1. A differential scanning calorimeter (DS) comprising a copolymerized polyester containing a terephthalic acid derivative and a 2,6-naphthalenedicarboxylic acid derivative as main components as an aromatic dicarboxylic acid and ethylene glycol as a main component as a diol.
The glass transition point (Tg) measured in C) is 90 ° C. or higher, the melting point measured by a melting point meter is 200 ° C. or higher, and the biaxially stretched film obtained from the copolymerized polyester is , 5 ° C to 4 from its Tg
A process for producing a photographic support, which comprises subjecting to heat treatment (annealing) at a temperature lower by 0 ° C. for 0.1 to 100 hours.