JPH06301147A - Film for photosensitive material - Google Patents

Abstract

PURPOSE:To provide a film having excellent curl resolving property, size stability, deformation resistance, and scratch resistance by using the polyethylene naphthalene carboxylate film copolymerized specific glycol and having the glass transition temperature of a specific value or above. CONSTITUTION:A polyethylene naphthalene carboxylate film is copolymerized with the glycol of 0.1-20mol% expressed by the formula I and/or the formula II, and its glass transition temperature is 80 deg.C or above, where R1, R2 indicate the alkyl group having the hydrogen or carbon number of 1-5, M1, M2 indicate the alkyl group having the carbon number of 1-5, R3, R4 indicate the alkyl group having the carbon number of 1-5, M3, M4 indicate the alkyl group having the carbon number of 2-5, and n1, (m) indicate integers of 1-10. This film is mainly made of 2, 6-naphthalene dicarboxylic acid as the acid component and ethylene glycol and the glycol expressed by the formula I and the formula II as the glycol component.

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 polyethylene having excellent curl curl decurling property, deformation resistance of engine part and scratch resistance. The present invention relates to a film for a photographic light-sensitive material made of a naphthalate film.

[0002]

2. Description of the Related Art Conventionally, a triacetate film has been widely used as a base film used in a photographic light-sensitive material.

The 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.

For this reason, polyethylene terephthalate film has come to be partially 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, JP-A-1-244446 and the like propose a modified polyethylene terephthalate film which has improved water vapor permeability and water content. However, although these proposals are effective in reducing curling curl, they have drawbacks such as deterioration of dimensional stability due to moisture absorption and increase in deformation of the end surface of the film due to a decrease in glass transition temperature. It was enough.

In particular, in recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film transport at the time of photographing and the downsizing of photographing devices have been advanced. 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.

[0007]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have made extensive studies to solve such problems and develop a film suitable for a photographic light-sensitive material, and as a result, biaxially stretched copolymerized polyethylene naphthalene dicarboxylate. The present invention has been accomplished by finding that a film (hereinafter abbreviated as polyethylene naphthalate) has excellent characteristics as a base film for photographic use and can solve the above-mentioned problems.

Therefore, an object of the present invention is to provide a film for a photographic light-sensitive material comprising a biaxially stretched polyethylene naphthalate, which has excellent curl curl eliminating property, dimensional stability, deformation resistance and scratch resistance.

[0009]

According to the present invention, such an object of the present invention is as follows: (I) and / or (I)
I) A polyethylene naphthalate film obtained by copolymerizing 0.1 to 20 mol% of a glycol represented by the structure, and having a glass transition temperature of 80 ° C. or higher. .

[0010]

[Chemical 2]

The copolymerized polyethylene naphthalate film according to the present invention contains 2,2 as an acid component as a main component.
6-naphthalenedicarboxylic acid, ethylene glycol as a glycol component and a specific glycol.

The above-mentioned specific glycol component is a glycol represented by the following (I) and / or (II).

[0013]

[Chemical 3]

Specific names of glycol components are as follows:
The glycol having the structure (I) is, for example, neopentyl glycol, 2,2-diethyl-1,3-propanediol,
2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol and the like can be mentioned. The glycol having the structure (II) is, for example, an ethylene oxide adduct of bisphenol A or bisphenol A.
Propylene oxide adduct, bisphenol A isobutylene oxide adduct, 2,2-bis (4'-oxyphenyl) butane ethylene oxide adduct, 2,2-
Examples thereof include an ethylene oxide adduct of bis (4′-oxyphenyl) 3 methylbutane and an ethylene oxide adduct of 2,2-bis (4′-oxyphenyl) -3,3-dimethylbutane.

The copolymerization ratio of the glycol component is 0.1 to 20 mol%, preferably 1 to 15 mol%, more preferably 3 to 10 mol based on 2,6-naphthalenedicarboxylic acid which is the main acid component. Mol%. When the copolymerization ratio is less than 0.1 mol%, scratches are likely to be formed on the film surface, and the decurling property is insufficient, and when it exceeds 20 mol%, the dimensional stability of the film decreases.

The copolymerized polyethylene naphthalate film used in the present invention can be copolymerized with other acid component or glycol component as long as the transparency and mechanical properties are not impaired. Examples of the acid component include terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, adipic acid, sebacic acid and the like. Also,
Examples of the glycol component include propylene glycol, tetramethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol and polytetramethylene glycol. When polyethylene glycol or polytetramethylene glycol is copolymerized, the molecular weight is 600 to 500.
It is preferably 0.

The copolymerization ratio of the copolymerization component is as follows.
The suitable value may be determined from the haze and glass transition temperature of the polyester film, but it is 20 mol% or less, preferably 15 mol% or less, with respect to 2,6-naphthalenedicarboxylic acid as the main acid component.

The haze of the copolymerized polyethylene naphthalate film of the present invention is preferably 5% or less, and particularly preferably 3% 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 polyethylene naphthalate film of the present invention must be 80 ° C. or higher,
The temperature is preferably 90 ° C or higher, particularly preferably 100 ° C or higher. If the glass transition temperature is too low, the edge portion of the roll-shaped film is deformed, and wakame-shaped poor 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 copolymerized polyethylene naphthalate film of the present invention is preferably 1% by weight or less, more preferably 0.1 to 0.5% by weight. 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 conditioning the film at 23 ° C. in an atmosphere of 30% RH for 3 hours, immersing the film in distilled water at 23 ° C. for 15 minutes, and then using a trace moisture meter to obtain a drying temperature of 150. Perform at ℃.

Since the water content is affected by the composition of the copolymerization component, it is advisable to adjust the polyethylene glycol copolymerization amount to make it appropriate.

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,
The application of a slippery agent containing inert particles 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 a polymerization reaction of copolymerized polyethylene naphthalate. From the viewpoint of ensuring the transparency of the film, when added from the outside, the particles preferably have a refractive index close to that of copolymerized polyethylene naphthalate, and BaSO ₄ , aluminosilicate, crosslinked organic particles (crosslinked polystyrene). Etc.) are mentioned as a preferable example.

Further, in the case of containing the inert particles, in order to obtain transparency of the film, a layer containing the inert particles on at least one surface of the copolymerized polyethylene naphthalate film which does not substantially contain the particles. It is also preferable to thinly laminate. As this means, for example, a co-extrusion method using a plurality of extruders and a feed block or a multi-manifold die can be cited as an effective means.

The copolymerized polyethylene naphthalate film of the present invention can be colored in various hues (blue, green, red, gray, etc.) with dyes, pigments or the like depending on the application.

The raw material polymer for the copolymerized polyethylene naphthalate film of the present invention can be synthesized by a conventionally known method for producing polyester. 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 excess glycol component A polymerized polyethylene naphthalate film can be obtained.

The copolymerized polyethylene naphthalate film of the present invention is not limited by its production method. For example, cooling the raw material polymer and molding it into granules,
After drying, melt extrusion is performed to obtain an unstretched sheet, or after production of a raw material polymer, extrusion is performed in a molten state to obtain an unstretched sheet, which is biaxially stretched and heat treated to obtain a target film.

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

The thickness of the copolymerized polyethylene naphthalate film of the present invention can be appropriately selected according to the mode of use as a photographic light-sensitive material, but is 25 to 250 μm, 40 to 40 μm.
150 μm is more preferable.

The copolymerized polyethylene naphthalate film of the present invention is preferably 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 may be a state in which the film is wound in a roll shape or a state in which it is a flat sheet, and the winding state is not limited.

The film for photographic light-sensitive material of the present invention has excellent curl curl eliminating property and deformation resistance at the edge portion, and is used as a photographic film for still photographic roll film, movie roll film, X-ray film. It can be applied to a wide range of applications such as film for film or film for plate making.

[0033]

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, release from the core. Then, after soaking in distilled water at 40 ° C. for 15 minutes, the sample is 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. Then, the load is removed and the distance (Amm) between the upper end and the lower end of the film is determined. The curl recovery rate is expressed by the following formula.

[0035]

[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 is resistant to use. Δ: The film surface is scratched. ×: Deep scratches are not formed on the film surface.

(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.

[0038]

Example 1 100 parts of 2,6-naphthalenedimethyl, 45 parts of ethylene glycol and neopentyl glycol 4
Using 0.04 part of manganese acetate tetrahydrate as a catalyst, the parts were transesterified in the usual manner, and 0.06 part of trimethyl phosphate and 0.03 part of antimony trioxide were successively added. Then, polycondensation reaction was carried out in a usual manner under high temperature vacuum to obtain a copolymerized polyethylene naphthalate having an intrinsic viscosity of 0.60 and a glass transition temperature of 116 ° C.

Further, the obtained polyester was dried at 180 ° C., formed into a sheet by an extruder, stretched at a temperature of 130 ° C. in the longitudinal direction by 3.0 times, and subsequently at 135 ° C. in a lateral direction of 3.3 times. The film was stretched to obtain a film having a thickness of 75 μm.

The obtained film was heat-treated at 100 ° C. for 2 days and then evaluated variously. As a result, it had good properties as shown in Table 1.

[0041]

Examples 2 to 4 and Comparative Examples 1 to 3 As shown in Table 1, copolymer films were 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 those other than that had some drawbacks.

[0043]

[Table 1]

Claims (2)

[Claims] 1. A polyethylene naphthalene dicarboxylate film obtained by copolymerizing 0.1 to 20 mol% of a glycol represented by the following (I) and / or (II) structure, and having a glass transition temperature of 80 ° C. or higher. A film for a photographic light-sensitive material, characterized in that [Chemical 1] 2. The film has a glass transition temperature of 5 to 30.
The film for a photographic light-sensitive material according to claim 1, which is heat-treated at a temperature lower by ° C.