JP3242739B2 - Film for photographic photosensitive materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for a photographic light-sensitive material, and more particularly, to a biaxially stretched copolymer (1,4-) having excellent curl removability, scratch resistance and transparency. The present invention relates to a film for a photographic light-sensitive material comprising a cyclohexanedimethylene-2,6-naphthalenedicarboxylate) film.

[0002]

2. Description of the Related Art Triacetate films have been widely used as base films used in photographic tourism materials.

[0003] Triacetate films have safety and environmental issues due to the use of organic solvents in the manufacturing process. There are also problems such as limitations on mechanical strength and dimensional stability.

For this reason, a polyethylene terephthalate film has been used as an alternative material in some cases. However, in a roll form widely used as a photographic light-sensitive material, a curled curl remains strongly. Is poor in handling, and its use range has been limited.

On the other hand, JP-A-53-146773 and JP-A-1-244446 propose a modified polyethylene terephthalate film in which the water vapor permeability and the water content are improved. However, although these proposals are effective in reducing curling due to curling, they have drawbacks such as deterioration of dimensional stability due to moisture absorption and deformation of the film end face due to lowering of glass transition temperature. It was inadequate.

In particular, in recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film transport during photographing and the miniaturization of photographing apparatuses have been advanced. In addition to resolvability, performance such as strength, dimensional stability, and adaptability to thinning is required. In response to this demand, neither triacetate film nor modified polyethylene terephthalate film can sufficiently cope with the demand, and a film for a photographic light-sensitive material having excellent characteristics has been desired.

[0007]

SUMMARY OF THE INVENTION The inventors of the present invention have made intensive studies to solve such problems and to develop a film suitable for a photographic light-sensitive material. As a result, the biaxially stretched copolymer (1,4) was obtained. (Cyclohexanedimethylene-2,6-naphthalenedicarboxylate) film has excellent properties and can solve the above-mentioned problem.

Accordingly, it is an object of the present invention to provide a biaxially stretched polyester film having excellent curl removability, scratch resistance, transparency or deformation resistance.

[0009]

According to the present invention, there is provided , according to the present invention, 2,6-naphthalenedicarboxylic acid as an acid component, 50-95 mol% of cyclohexanedimethanol as a glycol component and ethylene glycol. The copolymerized poly (1,4-) substantially consisting of 5 to 50 mol%
(Cyclohexane dimethylene-2,6-naphthalenedicarboxylate) film having a glass transition temperature of 90 ° C. or higher.

[0010] Copolymerization of poly (1,4-cyclohexane dimethylene-2,6-naphthalene dicarboxylate) film of the present invention, 2,6-naphthalenedicarboxylic acid as acid components, cyclohexanedimethanol and ethylene as grayed recall component Polyester film using glycol , that is, 2,6-naphthalenedicarboxylic acid,
Cyclohexanedimethanol and ethylene glycol?
It is a polyester film substantially consisting of here
2,6-naphthalenedicarboxylic acid, cyclohexane
Consists essentially of dimethanol and ethylene glycol
Means 2,6-naphthalenedicarboxylic acid, cyclohexa
Copolysynthesis other than dimethanol and ethylene glycol
Minutes are based on moles of 2,6-naphthalenedicarboxylic acid
Means 20 mol% or less.

In the present invention, cyclohexanedimethanol as a glycol component may be any of a trans-form, a cis-form, and a mixture thereof, but the copolymerization ratio is based on 2,6-naphthalenedicarboxylic acid component, which is a main acid component. It is 50 to 95 mol%, preferably 60 to 80 mol%.

When the copolymerization ratio is less than 50 mol%, the crystallinity becomes low and the dimensional stability and the like are insufficient, and when it exceeds 90 mol%, the film surface is apt to be scratched. Since the transparency of the film is reduced, the quality is reduced.

[0013] The copolymer polyester film used in the present invention, further comprising an acid component having a sulfonate group and / or
Alternatively, a copolymer obtained by copolymerizing a glycol component is preferable from the viewpoint of improving curl elimination.

Examples of the acid component having a sulfonate include 5-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, sodium sulfosuccinic acid, and sodium such as potassium,
Compounds substituted with lithium, phosphonate, and the like can be given.

The glycol component having a sulfonate includes, for example, a lower alcohol oxide adduct (I) or (II) of a sulfobisphenol compound and a lower alkylene oxide adduct (III) of a sulfohydroquinone.
And the like.

[0016]

Embedded image

(Where X is hydrogen or an alkyl group having 2 to 5 carbon atoms, k + m = 2 to 50, Y = —CH ₂ , —C
(CH ₃ ) ₂ , —SO ₂ or none. M is an alkali metal,
Indicates alkaline earth or phosphonium. )

The copolymerization ratio of the acid component and / or the glycol component having a sulfonate is preferably 10 mol% or less from the viewpoint of maintaining the transparency of the film.

The copolymerized polyester film used in the present invention may be one obtained by further copolymerizing another acid component or glycol component as long as the transparency and mechanical properties are not impaired. For example, the acid component includes terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, adipic acid, sebacic acid and the like. Glycol components include propylene glycol, tetramethylene glycol, neopentyl glycol, diethylene glycol, bisphenol A
-Glycol adducts, polyethylene glycol, polytetramethylene glycol and the like can be mentioned. When polyethylene glycol or polytetramethylene glycol is copolymerized, the molecular weight is 600 to
Preferably it is 5000.

Such 2,6-naphthalenedicarboxylic
Acid, cyclohexane dimethanol and ethylene glycol
Copolymerization proportion of the copolymer component composed of component other than Le from haze and the glass transition temperature of the polyester film, rather it is determined the appropriate value, 2,6-naphthalene dicarboxylic acid
20 mol% or less, preferably 1 mol, based on the number of moles
5 mol% or less.

The haze of the copolyester film of the present invention is preferably 5% or less, more preferably 3% or less, and preferably 2% or less.
The following are particularly preferred.

If the haze is too high, the transparency of the film decreases, which is not preferable as a base film for a photographic material. Therefore, it is necessary to consider the film haze in the copolymerization ratio of the copolymer component.

The glass transition temperature of the copolymerized polyester film of the present invention is 90 ° C. or higher, preferably 100 ° C.
° C, particularly preferably 110 ° C or higher. If the glass transition temperature is too low, the edge portion of the roll-shaped film is deformed, and it is easy to generate wakame-shaped flatness defects, which is not preferable as the base film. Therefore, it is necessary to consider the glass transition temperature in the copolymerization ratio of the copolymer component.

The water content of the copolymerized polyester film of the present invention is preferably 2% or less, more preferably 1% or less. If the water content is too high, the dimensional stability tends to deteriorate due to moisture absorption, and the lower the water content, the better. In addition,
The moisture content was measured by adjusting the humidity of the film at 23 ° C. and 30% RH for 3 hours, immersing the film in distilled water at 23 ° C. for 15 minutes, and then drying the film at a drying temperature of 15 ° C. using a trace moisture meter.
Perform at 0 ° C.

Further, the water content is influenced by the composition of the copolymer component. For example, it can be adjusted by a method of reducing the copolymerization amount of dicarboxylic acid having a metal sulfonate to 10 mol% or less, a method of optimizing the copolymerization amount of polyethylene glycol, and the like.

The copolymerized polyester film of the present invention comprises:
It is also possible to impart lubricity according to the application. The means for imparting smoothness is not particularly limited,
Incorporation of inert particles or application of a lubricating agent is used as a general technique.

As a method for containing inert particles, S
Examples thereof include a method in which iO ₂ , BaSO ₄ , CaCO ₃ , alumina silicate, crosslinked organic particles, and the like are externally added, and a method in which a catalyst or the like is precipitated during a polymerization reaction of a copolymerized polyester. From the viewpoint of securing the transparency of the film, when added from the outside, the particles preferably have a refractive index close to that of the copolymerized polyester. For example, BaSO ₄ , aluminosilicate, crosslinked organic particles (crosslinked polystyrene) Etc.).

Further, in the case where inert particles are contained, in order to obtain transparency of the film, a layer containing inert particles is formed on at least one surface of a copolymer ester film substantially containing no particles. A method of laminating thinly is also preferable. As this means, for example, a co-extrusion method using a plurality of extruders and a feed block or a multi-manifold die is mentioned as an effective means.

The polyester film of the present invention has various hues (blue, green,
(Red, gray, etc.) and flame retardant with phosphorus compounds.

The raw material polymer for the copolymerized polyester film of the present invention can be synthesized according to a conventionally known polyester manufacturing method. For example, the ester component of the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, a transesterification reaction with the glycol component is performed, followed by heating under reduced pressure to remove the excess glycol component, thereby obtaining a polymer Can be obtained.

The polyester film of the present invention is not limited by the production method. For example, the raw material polymer is cooled and molded into granules, dried and melt-extruded to obtain an unstretched sheet; or, after the raw material polymer is produced, extruded in a molten state to form an unstretched sheet, and then subjected to biaxial stretching and heat treatment. The desired film can be produced.

The biaxial stretching may be either vertical or horizontal sequential stretching or simultaneous stretching, and the stretching ratio is usually 2 to 5 times. Further, if necessary, after the stretching in the longitudinal and transverse directions, the film may be further stretched in one or both of the longitudinal and transverse directions.

Further, the polyester film of the present invention comprises:
The refractive index in the thickness direction is preferably 1.495 or more, more preferably 1.500 or more, from the viewpoint of preventing delamination of the film. The Young's modulus in both the vertical and horizontal directions is 700 kg / mm ² or less, and the difference between the values is 100 kg / mm ^2.
/ Mm ² or less is preferred from the viewpoint of preventing delamination of the film and improving dimensional stability.

Further, the thickness of the copolymerized polyethylene naphthalate film of the present invention can be appropriately selected depending on the mode of use as a photographic light-sensitive material.
50 μm is preferred.

It is preferable to heat-treat the copolymer film of the present invention after the film is formed, in order to improve the curl removability. The heat treatment is preferably performed at a temperature 5 to 30C lower than the glass transition temperature of the film for 1 to 500 hours. The state of the film in the heat treatment is not particularly limited, such as a state in which the film is wound into a roll or a state in which the film is formed into a flat sheet.

The film for a photographic light-sensitive material of the present invention has excellent curl curl removability and edge deformation resistance. As a film for photographing, a roll film for a still photograph, a roll film for a movie, an X-ray film It can be applied to a wide range of applications such as film for film making and film for plate making.

[0037]

The present invention will be further described below with reference to examples. In the examples, "parts" represents parts by weight. The measurement of each characteristic value was performed according to the following method.

(1) Curl recovery rate A film sample was cut into a size of 120 mm × 35 mm.
After winding in the longitudinal direction around a core with a diameter of 10 mm,
After time treatment, release from the core. Thereafter, the sample is immersed in distilled water at 40 ° C. for 15 minutes, and then the sample is dropped vertically in the longitudinal direction, and dried in an air thermostat at 55 ° C. under a load of 5 g for 3 minutes. Subsequently, the distance (Amm) between the upper end and the lower end of the film is obtained except for the load.

The curl recovery rate is represented by the following equation.

[0040]

(Equation 1)

(2) Scratch resistance After mounting the film on a Haydon-14 type measuring machine (Shinto Chemical Co., Ltd.), the surface of the film is run with a diamond needle to evaluate the scratched state. ：: The film is good without scratches. ：: The film surface is slightly scratched but endurable. △: The film surface is scratched. ×: The film surface is deeply scratched and defective.

(3) Glass transition temperature Differential calorimeter (Du Pont DSC2100)
The glass transition peak temperature is determined at a heating rate of 20 ° C./min.

(4) Film haze Measured with a commercially available haze meter according to JIS K-6714. ：: good at haze 2% or less △: good haze 2 to 5% ×: use limited at haze 5% or more

[0044]

Example 1 100 parts of dimethyl 2,6-naphthalenedicarboxylate, 33 parts of cyclohexanedimethanol, and 35 parts of ethylene glycol were added to manganese acetate tetrahydrate 0.04
After transesterification as usual with the part as catalyst,
0.06 parts of trimethyl phosphate, 0.0 of antimony trioxide
3 parts were added. Thereafter, a polycondensation reaction was carried out in a usual manner under a high temperature and a vacuum to obtain a copolyester having an intrinsic viscosity of 0.60 and a glass transition temperature of 118 ° C.

Further, the obtained polyester was dried at 160 ° C., extruded on a cooling drum by an extruder, cooled and solidified to form a sheet, and then tripled at 135 ° C. in the longitudinal direction and continuously at 140 ° C. in the horizontal direction. Stretched 3.3 times at a thickness of 75
A μm film was obtained.

Thereafter, the film was heat-treated at 100 ° C. for 2 days and various evaluations were performed. As a result, as shown in Table 1,
It had good characteristics.

[0047]

[Table 1]

[0048]

Examples 2 to 5 and Comparative Examples 1 to 3 As shown in Table 1, a polyester film was obtained in the same manner as in Example 1 except that the composition and the amount of the raw materials were changed.

Those satisfying the conditions of the present invention exhibited excellent characteristics, but the others exhibited some disadvantages.

Continuation of the front page (56) References JP-A-2-54254 (JP, A) JP-A-5-158188 (JP, A) JP-A-5-170889 (JP, A) JP-A-5-170890 (JP) JP-A-6-306192 (JP, A) JP-A-6-308665 (JP, A) JP-A-5-105748 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) G03C 1/795

Claims (3)

(57) [Claims] (1) 2,6-naphthalenedicarboxylic acid as an acid component, 50 to 95 mol% of cyclohexanedimethanol and 5 to 5% of ethylene glycol as a glycol component.
A copolymerized poly (1,4-cyclohexanedimethylene-2,6-naphthalenedicarboxylate) film consisting essentially of 50 mol% and having a glass transition temperature of 9
A film for a photographic light-sensitive material, wherein the temperature is 0 ° C. or higher. 2. The film according to claim 1, wherein an acid component having a sulfonate and / or a glycol component is copolymerized. 3. The film has a glass transition temperature of 5-30.
3. The film for a photographic light-sensitive material according to claim 1 or 2, which has been heat-treated at a temperature lower by a temperature of ° C.