JPH06295014A - Film for photographic sensitive material - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a modified polyester film for a photographic light-sensitive material, which has excellent curl curl elimination property, scratch resistance and transparency. [Composition] Naphthalenedicarboxylic acid 50 to 50 as an acid component
Copolymerized poly (95% by mole), 5 to 50% by mole of one or more dicarboxylic acids selected from the group of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, and cyclohexanedimethanol as a glycol component. 1,
A film for a photographic material, which is a 4-cyclohexanedimethylene-2,6-naphthalene dicarboxylate) film having a glass transition temperature of 90 ° C. or higher.

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 specifically to a biaxially stretched copolymer poly (1,4--) having excellent curl-curling decurling property, scratch resistance and transparency. The present invention relates to a film for a photographic light-sensitive material, which comprises a cyclohexanedimethylene-2,6-naphthalene dicarboxylate) film.

[0002]

2. Description of the Related Art A triacetate film has been widely used as a base film used for a photographic tourism material. This triacetate film has safety and environmental problems because it uses an organic solvent in its manufacturing process. In addition, there is a problem that mechanical strength and dimensional stability are limited.

Therefore, a part of polyethylene terephthalate film has come to be used as an alternative material. However, in a roll form widely used as a photographic light-sensitive material, curling curl strongly remains, so that after development processing. Is not easy to handle and its range of use has been limited.

On the other hand, JP-A-53-146773
Japanese Patent Application Laid-Open No. 1-244446 proposes a modified polyethylene terephthalate film having improved water vapor permeability and improved water content. However, although these proposals are effective in reducing curling curl, they have drawbacks such as deterioration in dimensional stability due to moisture absorption and increase in deformation of the end surface of the film due to decrease in glass transition temperature. It was something.

In particular, in recent years, the applications of photographic light-sensitive materials have been diversified, and the speed of film transport at the time of shooting has been increased and the size of photographic devices has been reduced. As a film for photographic light-sensitive materials, excellent curl curl In addition to resolvability, performance such as strength, dimensional stability, and adaptability for thinning is required. In response to this demand, neither a triacetate film nor a modified polyethylene terephthalate film can be sufficiently dealt with, and a film for a photographic light-sensitive material having excellent properties has been desired.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made diligent studies to solve such problems and develop a film suitable for a photographic light-sensitive material. As a result, biaxially stretched copolymer poly (1,
The inventors have found that the 4-cyclohexanedimethylene-2,6-naphthalene dicarboxylate) film has excellent properties and can solve the above problems, and have reached the present invention.

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

[0008]

The object of the present invention is to:
According to the present invention, 50 to 95 mol% of naphthalene dicarboxylic acid as an acid component and 5 to 50 mol% of at least one dicarboxylic acid selected from the group of aromatic dicarboxylic acids, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids. And a copolymerized poly (1,4-cyclohexanedimethylene-) consisting of cyclohexanedimethanol as the main glycol component.
2,6-naphthalene dicarboxylate) having a glass transition temperature of 90 ° C.
This is achieved by a film for a photographic light-sensitive material having the above characteristics.

The copolymerized polyester film of the present invention contains 50 to 9 of 2,6-naphthalenedicarboxylic acid as an acid component.
It is contained in an amount of 5 mol%, preferably 60 to 85 mol%. If the content is less than 50 mol%, the crystallinity is insufficient and dimensional stability is insufficient, and curl curl desolvability is insufficient, and if it exceeds 95 mol, the film surface is scratched. However, there is a problem in that the transparency of the film is deteriorated in addition to the tendency to enter.

The copolymerized polyester film of the present invention is
As the acid component, in addition to the 2,6-naphthalenedicarboxylic acid, at least one dicarboxylic acid selected from the group of aromatic dicarboxylic acids, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids is contained as a copolymerization component.

Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, orthophthalic acid, 2,7
-Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and other aliphatic and alicyclic dicarboxylic acids. it can.

The copolymerization ratio of the dicarboxylic acid component is 5
.About.50 mol%, preferably 20 to 40 mol%,
When an aliphatic dicarboxylic acid component is copolymerized, it is important to select a copolymerization ratio that maintains the glass transition temperature at 90 ° C. or higher because the glass transition temperature tends to decrease.

The copolymerized polyester film of the present invention comprises:
Those obtained by copolymerizing a dicarboxylic acid component having a sulfonate are preferable from the viewpoint of improving the curl eliminating property.

Examples of the dicarboxylic acid component having a sulfonate include 5-sodium sulfoisophthalic acid, 4
-Sodium sulfo-2,6-naphthalenedicarboxylic acid, sodium sulfosuccinic acid and compounds obtained by substituting these sodium with potassium, lithium, phosphonate and the like can be mentioned.

The copolymerization ratio of the dicarboxylic acid component having a sulfonate is 1 from the viewpoint of maintaining the transparency of the film.
It is preferably 0 mol% or less.

The copolyester film of the present invention contains cyclohexanedimethanol as a glycol component. Cyclohexanedimethanol may be any of trans isomer, cis isomer and a mixture thereof.

The copolymerized polyester film of the present invention may be copolymerized with a glycol component other than cyclohexanedimethanol as a glycol component in an amount of less than 10 mol%. Examples of the glycol component include ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, diethylene glycol,
Examples thereof include triethylene glycol, polyethylene glycol, polytetramethylene glycol, and an alkylene oxide adduct of bisphenol A. When polyethylene glycol and polytetramethylene glycol are copolymerized, the molecular weight is preferably 600 to 5000.

An appropriate value for the copolymerization ratio of the glycol component may be determined from the transparency and the glass transition temperature of the copolymerized polyester film, but it is less than 10 mol%, preferably 5 mol% with respect to the main glycol component cyclohexanedimethanol. It is not more than mol%.

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

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

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

The water content of the copolyester 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. The water content was measured by adjusting the humidity of the film in an atmosphere of 23 ° C. and 30% RH for 3 hours, immersing the film in distilled water of 23 ° C. for 15 minutes, and then using a trace moisture meter to obtain a drying temperature of 150. Perform at ℃.

The water content is influenced by the composition of the copolymerization component, and, for example, a method of optimizing the copolymerization amount of the dicarboxylic acid component having a metal sulfonate, a method of optimizing the polyethylene glycol copolymerization amount and the like can be adopted. it can.

The copolyester film of the present invention is
It is also possible to impart slipperiness according to the application. The means for imparting slipperiness is not particularly limited,
Incorporation of inert particles or coating of a slipperiness agent is generally used.

As a method of incorporating the inert particles, S
Examples thereof include a method of externally adding iO ₂ , BaSO ₄ , CaCO ₃ , alumina silicate, crosslinked organic particles and the like, and a method of depositing a catalyst and the like during the polymerization reaction of the copolyester. From the viewpoint of ensuring the transparency of the film, when externally added, the particles preferably have a refractive index close to that of the copolyester, for example, B
Examples include aSO ₄ , aluminosilicate, and crosslinked organic particles (crosslinked polystyrene, etc.).

Further, in the case of containing the inert particles, in order to maintain the transparency of the film, a layer containing the inert particles on at least one surface of the copolymer ester film substantially containing no particles. It is also preferable to thinly laminate. Examples of effective means include a co-extrusion method using a plurality of extruders and a feed block or a multi-manifold die.

The polyester film of the present invention is
Various hues (blue, green,
It is also possible to color it in red, gray, etc. and to make it flame-retardant with a phosphorus compound or the like.

The raw material polymer for the copolymerized polyester film of the present invention can be synthesized by a conventionally known polyester production method. For example, by directly esterifying the acid component with the glycol component, or when using a dialkyl ester as the acid component, transesterification reaction with the glycol component, and then heating under reduced pressure to remove the excess glycol component, to obtain be able to.

The polyester film of the present invention is not limited by its manufacturing method. For example, the raw material polymer is cooled, molded into granules, dried, and melt-extruded to obtain an unstretched sheet. Alternatively, the target film can be obtained by extruding the raw material polymer in a molten state in the molten state into an unstretched sheet, followed by biaxial stretching and heat treatment.

Biaxial stretching may be either longitudinal or transverse sequential stretching or simultaneous stretching, and a suitable stretching ratio is usually 2 to 5 times. In addition, if necessary, after longitudinal and transverse stretching, further longitudinal,
It may be re-stretched in either or both of the transverse directions.

Further, the polyester film of the present invention is
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 the longitudinal direction and the transverse direction is 700 kg / mm ² or less, and the difference between the values is 100 kg / mm ^2.
Prevents delamination of the film if the condition is less than mm ² .
It is preferable in terms of improving dimensional stability.

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, but is 25 to 250 μm, and further 50 to 1
50 μm is preferable.

It is preferable that the copolymer film of the present invention is subjected to heat treatment after film formation in order to improve curling and curl elimination. The heat treatment is preferably performed at a temperature 5 to 30 ° C. 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 flat sheet.

The film for a photographic light-sensitive material in the present invention has excellent curl curl elimination and deformation resistance at the edge portion. As a photographic film, a still photographic roll film, a movie roll film, an X-ray film. It can be widely used as a film for film or a film for plate making.

[0035]

EXAMPLES The present invention will be further described below with reference to examples. In addition, "part" in an Example represents a weight part. Moreover, the measurement of each characteristic value followed the following method.

(1) Curl recovery rate A film sample was cut into 120 mm × 35 mm,
After winding it around the core of 10mm diameter in the longitudinal direction,
After the time treatment, the core was released. After that, the sample was soaked in distilled water at 40 ° C. for 15 minutes, and then the sample was hung vertically in the longitudinal direction and dried for 3 minutes in a constant temperature air bath at 55 ° C. under a load of 5 g. Subsequently, the load was removed, and the distance (A mm) between the upper end and the lower end of the film was obtained.

The curl recovery rate is expressed by the following formula.

[0038]

[Equation 1]

(2) Scratch resistance After mounting the film on a Haydon-14 type measuring machine (Shinto Kagaku), the film surface is run with a diamond needle to evaluate the scratched state. ⊚: The film is not scratched and is good. ◯: The film surface is slightly scratched but withstands use. Δ: The film surface has scratches. ×: Deep scratches are formed on the film surface and the film is defective.

(3) Glass transition temperature differential thermal analyzer (DSC2100 type manufactured by Du Pont)
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 with haze 2% or less Δ: Haze 2-5% x: Use is limited with haze 5% or more.

[0042]

Example 1 50 parts of dimethyl 2,6-naphthalenedicarboxylate, 33 parts of dimethyl isophthalate and 70 parts of cyclohexanedimethanol were mixed with 0.04 part of manganese acetate tetrahydrate.
After transesterification was carried out in the usual manner with 1 part as a catalyst, trimethyl phosphate 0.06 part and antimony trioxide 0.0
3 parts were added. After that, polycondensation reaction is performed under a high temperature vacuum in a usual manner to obtain an intrinsic viscosity of 0.60 and a glass transition temperature of 100.
A copolyester of ℃ was obtained.

Further, the obtained polyester was dried at 160 ° C., then extruded on a cooling drum by an extruder to be cooled and solidified to form a sheet. 3.3 times to obtain a film having a thickness of 75 μm.

After that, the film was heat-treated at 100 ° C. for 2 days and then various evaluations were carried out. As shown in Table 1, the film had good properties.

[0045]

[Table 1]

[0046]

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 of raw materials and the addition amount were changed.

Those satisfying the conditions of the present invention showed excellent characteristics but had some other defects.

Claims (3)

[Claims] 1. Naphthalenedicarboxylic acid 5 as an acid component
0 to 95 mol%, 5 to 50 mol% of at least one dicarboxylic acid selected from the group of aromatic dicarboxylic acids, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, and cyclohexanedimethanol as the main glycol component Copolymerized poly (1,4-cyclohexanedimethylene-
2,6-naphthalene dicarboxylate) having a glass transition temperature of 90 ° C.
A film for a photographic light-sensitive material having the above characteristics. 2. The film for a photographic light-sensitive material according to claim 1, wherein a dicarboxylic acid component having a sulfonate is copolymerized. 3. The film has a glass transition temperature of 5 to 30.
The film for a photographic light-sensitive material according to claim 1 or 2, which is heat-treated at a temperature lower by ° C.