JP3387252B2 - Base film and photosensitive photographic material using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a base film having high dimensional stability, which is preferably used as a support for a base film for photographic film plate making, an original film for printed wiring boards, etc. The present invention relates to a base film which is excellent and has excellent light transmittance in the near ultraviolet region. The present invention further relates to a photosensitive photographic material using the base film.

[0002]

2. Description of the Related Art A base film (hereinafter sometimes simply referred to as a support) used as a support for a photographic film plate-making base film, a printed wiring board (PCB) original film, and the like has a relative humidity. A polyethylene terephthalate film having relatively good dimensional stability against (hereinafter sometimes abbreviated as humidity) and temperature changes is used. This is because in the case of a base film for photographic film plate making, if there is a shift in the exposure of the superposed films due to changes in humidity and temperature, image misalignment will occur when the four colors of cyan, magenta, yellow and black are superposed. Is. In the case of an original film for printed wiring boards, when the printed wiring boards obtained by exposing this film are laminated, if the image shift occurs due to changes in humidity and temperature, the circuit will be scraped when drilling through holes. Because of the reason. Among the polymer films, the polyethylene terephthalate film has a relatively small dimensional change with respect to humidity and temperature, but some dimensional change is unavoidable. Therefore, photographic film plate-making film, original film for printed wiring board, etc. are used in a room where humidity is controlled to about 55-60% RH and temperature is controlled to 20-27 ° C throughout the year. It is necessary to expose the film to its environment of use for a long time to control the humidity and temperature of the film itself. Therefore, the workability was considerably poor.

In Japanese Patent Laid-Open No. 5-289236,
SiOx (x is 1.2) on the hydrophobic polyester film
A photographic material comprising at least one hydrophilic image precurler layer on a support provided with a barrier layer consisting of Since the support has a barrier layer made of SiOx, the photographic material has a smaller dimensional change with respect to humidity as compared with a photographic material using a mere hydrophobic polyester film as the support. However, especially when using this photographic material in the PCB field, the longer the working time is, or if there is a gap between the use environment (especially humidity) when the image is formed by exposure and the use environment thereafter. As much as possible, the humidity dimensional stability obtained here is insufficient. The main reason for this is
One of the reasons is that a high barrier against water vapor cannot be obtained with a barrier layer consisting of SiOx alone (x represents a range of 1.2 to 1.8).

Further, there is a problem in the adhesion between SiOx (x represents a range of 1.2 to 1.8) and the hydrophobic polyester film, and it is exposed to severe conditions such as high humidity. Then, peeling occurred between the hydrophobic polyester film and the SiOx layer, which caused a problem as a photosensitive photographic film. When SiOx is laminated as a barrier layer on the hydrophobic polyester film, the laminated S
Since iOx itself has a considerably brown color, this base film has a low transmittance in the near ultraviolet region. Therefore, when a film obtained by exposing and developing a photosensitive photographic material using this brown substrate film as a support to a target pattern is used, near-ultraviolet light ( In the step of exposing at 350 nm, for example, the amount of transmitted light is small, and as a result, it is necessary to increase the output of the light source, and the exposure speed is slow, which causes a problem in productivity of printed wiring boards and the like.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is, in the field of base film for photographic film plate making, original film for printed wiring board, etc., particularly as a base film against temperature and humidity changes (particularly humidity changes). To provide a base film having high dimensional stability, further excellent adhesiveness between respective layers constituting the film, and particularly excellent light transmittance in the vicinity of 350 nm which is the near-ultraviolet region of the base film itself. is there. Another object of the present invention is to provide a photosensitive photographic material using the above-mentioned base film.

[0006]

The object of the present invention is to provide a SiO ₂ layer (B) on one side or both sides of a plastic film (A) by a vacuum thin film forming technique and to form a SiO ₂ layer (B) on one side or both sides by a vacuum thin film forming technique. , SiOx (where x is
Greater than 1.8 and less than 2.0) 98-80 mol% and
And 2 to 20 mol% of an alkaline earth metal fluoride
This can be achieved by forming a thin film layer (C) and using a base film having dimensional stability. An object of the present invention further by one or vacuum thin film forming technique on both surfaces of the plastic film (A), SiO ₂ layers of (B) is provided by a vacuum thin film forming technique on one or both sides, SiO
x (x is greater than 1.8 and less than 2.0) 97.5 to 8
0 mol%, fluoride of alkaline earth metal 2-19.5 m
% Of magnesium oxide and 0.5 to 18 mol% of magnesium oxide
It can be achieved by a base film formed by forming a thin film layer (C) .

The object of the present invention can be further achieved by a photosensitive photographic material obtained by laminating a photosensitive layer (D) on one side or both sides of the above-mentioned base film. In the present invention, the plastic film (A) is preferably a polyethylene terephthalate film having a relatively high dimensional stability among the polymer films, a fluorine film, or a film containing polystyrene as a main component. For example, polyethylene-2,6 -Naphthalate, triacetyl cellulose, polycarbonate, polyether sulfone and polyarylate are also applicable. Further, as the plastic film (A), a heat-fixed film, a biaxially stretched film or the like is desirable. Further, there is a film in which the dimensional stability is further improved by heat-treating (annealing) the biaxially stretched film once heat-set under appropriate conditions, but this is particularly desirable.

It is desirable that nothing be provided on the surface of this plastic film (A), but dimensional stability,
If the light transmittance is not impaired, apply an organic conductive agent such as a surfactant or polymer electrolyte or an inorganic conductive agent such as a conductive metal oxide, an easy-adhesive, or a polyvinylidene chloride-based barrier agent in advance. It does not matter if it is manufactured. The thickness of the plastic film (A) is not particularly limited and may vary depending on the application, but 50 to 500 μ is suitable. 75 to 250 when used as a support for a base film for photographic film plate making, an original film for printed wiring boards, etc.
μ is suitable. Particularly, 100 to 175 μ is suitable.

The SiO ₂ layer (B) must be in close contact with the plastic film (A) or the thin film layer (C). Among the vacuum thin film forming techniques, the method for obtaining the SiO ₂ layer (B) is limited to the sputtering method and the ion plating method, which have high adhesion energy to the substrate. The composition of this layer must be colorless and transparent.
₂ is preferred. The thickness of the SiO ₂ layer (B) is preferably 10 to 200 angstroms, particularly preferably 100 angstroms or less, from the viewpoint of adhesion to the plastic film (A) or the thin film layer (C) and light transmittance.

The SiO ₂ layer (B) may be provided on only one side of the plastic film (A), but is preferably provided on both sides. It is significant that the SiO ₂ layer (B) is interposed between the plastic film (A) and the thin film layer (C), and only when the thin film layer (C) is provided on only one side, this SiO ₂ layer (B) is formed. Must be provided on one side. The thin film layer (C) has good transparency from visible light to near-ultraviolet rays used when exposing the photosensitive layer, has a particularly high water vapor barrier property (that is, low water vapor transmission rate), has little expansion with respect to humidity, and It must be firmly adhered to the SiO ₂ layer (B). This thin film layer (C) is disclosed in JP-A-5-289236.
SiOx (x is 1.2 to
(Representing the range of 1.8), the water vapor barrier property is not very good, and the light transmittance in the near ultraviolet region is low.

According to the present invention, an alkaline earth metal fluoride is added to a thin film of silicon oxide (SiOx), or both an alkaline earth metal fluoride and a magnesium oxide are added. By laminating the thin film layer (C) and the SiO ₂ layer (B), the synergistic effect of the thin film layer / SiO ₂ layer / plastic film provides light transmittance in the near-ultraviolet region to the visible region and high water vapor barrier property. The adhesion of each layer is improved. SiOx x is greater than 1.8
Ku, and may be less than 2.0, x is closer rather watch containing oxides 2.0 to approach the SiO ₂ colorless transparent, the light transmittance of the resulting film layer (C) is increased.

The thin film layer (C) of the present invention will be described in more detail below. Examples of the alkaline earth metal fluoride forming the thin film layer (C) include magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride and the like. In particular, magnesium fluoride and calcium fluoride are excellent as fluorides of alkaline earth metals. Examples of magnesium oxides are magnesium oxide and magnesium oxide called forsterite or steatite. Examples thereof include oxides, composite compounds of magnesium oxide and fluorides of alkaline earth metals.

In the thin film layer (C), SiOx ( x is
Greater than 1.8 and less than 2.0 ) combined with an alkaline earth metal fluoride, or SiOx (where x is greater than 1.8).
(Less than 2.0 ), the alkaline earth metal fluoride and magnesium oxide are combined. That is, thin film layer (C)
Is SiOx ( x is greater than 1.8 and less than 2.0 )-
Alkaline earth metal fluoride compound, or SiOx
( X is greater than 1.8 and less than 2.0 ) -a fluoride of an alkaline earth metal-a compound of magnesium oxide. In the thin film layer (C) of the present invention, SiOx
( X is greater than 1.8 and less than 2.0 ) and an alkaline earth metal fluoride, or SiOx ( x is greater than 1.8).
Ku, although a 2.0 below) with the fluoride and magnesium oxide of an alkaline earth metal appears to be almost compound, depending on the manufacturing process, could contain those not part compound There is also.

SiOx ( x is greater than 1.8 and 2.0
Less than ) -The vapor-deposited layer of a fluoride compound of an alkaline earth metal is excellent in both dimensional stability and light transmittance, but is particularly excellent in light transmittance, and SiOx ( x is larger than 1.8, 2.0.
Less than ) -a vapor-deposited layer of an alkaline earth metal fluoride-magnesium oxide compound is also excellent in dimensional stability and light transmittance, but particularly excellent in dimensional stability. SiOx constituting the thin film layer (C) ( x is greater than 1.8 and less than 2.0 )
And the composition ratio of the alkaline earth metal fluoride are 9
In the range of 8 to 80 mol% and 2 to 20 mol%,
95-90 mol% and 5-10 mol% respectively
desirable. When it contains magnesium oxide, SiOx ( x is greater than 1.8 and less than 2.0 ),
The composition ratio of the alkaline earth metal fluoride and the magnesium oxide is 97.5 to 80 mol%: 2-1 respectively.
9.5 mol%: in the range of 0.5 to 18 mol%,
93-88 mol%: 5-10 mol%: 2-17 mol%
Range is desirable.

The thin film layer (C) laminated on the SiO ₂ layer (B) results in SiO x ( x is 1.8 when laminated).
Larger than less than 2.0 ) and fluoride of alkaline earth metal, or SiOx ( x is larger than 1.8, 2.0 or less )
Mitsuru) and it is sufficient that fluoride and magnesium oxide of an alkaline earth metal is compound, the raw material metal oxide thin film layer (C) laminated, fluoride of alkaline earth metals, metals, organometallic compounds Inorganic compounds such as, and organic compounds may be used alone or as a mixture. In particular, using a mixture of silicon oxide and a fluoride of an alkaline earth metal, or a mixture of silicon oxide, a fluoride of an alkaline earth metal and a co-oxide of silicon dioxide and magnesium oxide as a raw material, vacuum deposition, etc. The method of directly forming the thin film layer (C) on the plastic film by the method is desirable. The composition ratio of the raw materials is such that in the case of silicon oxide and fluoride of alkaline earth metal, silicon oxide: fluoride of alkaline earth metal = 98.
-70 mol%: The range of 2-30 mol% is desirable. Particularly preferably, silicon oxide: fluoride of alkaline earth metal = 95 to 85 mol%: 5 to 15 mol%.
In the case of a mixture of silicon oxide, an alkaline earth metal fluoride and a silicon dioxide-magnesium oxide co-oxide, silicon oxide: alkaline earth metal fluoride: silicon dioxide and magnesium oxide Cooxide = 97.5
70 mol%: 2 to 29.5 mol%: 0.5 to 28 mol% is preferable. Particularly preferably, silicon oxide:
Fluoride of alkaline earth metal: Cooxide of silicon dioxide and magnesium oxide = 95 to 90 mol%: 4.5 to 9.
5 mol%: It is in the range of 0.5 to 5.5 mol%.

As an example of silicon oxide used as a raw material
Is a mixture of silicon and silicon dioxide, silicon monoxide alone
Body and mixture of silicon, silicon dioxide and silicon monoxide
And Si ₂O₃, Si₃O_FourAnd a mixture thereof. Silicon
The oxides are silicon (Si) and silicon dioxide (SiO).₂)of
When used as a mixture, the composition ratio at that time is basically
Equimolar is preferred, but Si: SiO₂= 40-60 mol
%: It may be in the range of 60 to 40 mol%. Also as a raw material
Silicon oxide used is Si, SiO, SiO₂A mixture of
If it is a product, Si: SiO₂Are almost equimolar
Well, (Si + SiO₂): The ratio of SiO is not particularly limited
I can't.

The vacuum thin film forming technique for forming the thin film layer (C) on the plastic film (A) may be either a continuous winding method or a single-wafer method, and a vacuum vapor deposition method or the like may be used. You can Further, the heating method for vacuum vapor deposition is not particularly limited as long as it does not cause vapor deposition droplets called splash during vapor deposition and is small enough to be removed without trouble, and conventional methods such as high frequency induction heating, resistance heating, and electron beam heating are used. A known heating method can be used. When a large amount of this vapor deposition droplet is generated, the vapor droplet remains as a foreign substance on the vapor deposition film, and many problems occur in the emulsion coating step, the exposure step, the developing step, etc., which are the subsequent steps. A general crucible system may be used as an evaporation source for vacuum evaporation, but the evaporation shown in JP-A-1-252768 and JP-A-2-277774 is capable of always uniformly vacuum-depositing substances having different sublimation points and melting points. A method of continuously supplying and discharging raw materials is desirable.

This silicon oxide and alkaline earth metal flux
Fluoride mixture, Silicon oxide, Alkaline earth gold
Fluorides and genus of silicon dioxide and magnesium oxide
The degree of vacuum when vacuum-depositing a mixture of oxides as a raw material is
1 x 10^-Four5 × 10 from torr ^-3I hope it is within the range of torr
Yes. When the degree of vacuum is high, the composition of the raw material is the same as that of the thin film layer.
It can be reflected in the composition of (C), but on the contrary, low
In the case of voidiness, the composition of the thin film layer (C) is higher than that of the raw material.
Becomes oxygen excess (high degree of oxidation). This is the steam during vapor deposition
It is considered to be a reaction between the deposited particles and oxygen atoms. Also, the membrane structure
In the case of high vacuum, a high density thin film layer can be obtained,
It is estimated that when the degree of vacuum is low, the film has a low density.
Use a vacuum degree within the above range and use the raw material of the above composition
To obtain a desired composition ratio for the thin film layer (C).
it can.

As a method of laminating a thin film layer (C) other than the above, a method of vacuum vapor deposition while oxidizing or fluorinating a metal or a compound containing a metal such as an organometallic compound,
Further, there is a method in which a fluoride of an alkaline earth metal is formed as a vapor deposition layer on a plastic film and the vapor deposition layer is subjected to an oxidation treatment in a subsequent step. The method of oxidation treatment is not particularly limited as long as it is a method of performing treatment within the usable temperature range of the plastic film, and examples thereof include an oxygen gas introduction method during vapor deposition, a discharge treatment method, an oxygen plasma method, and a thermal oxidation method.
The thin film layer (C) may be laminated on one side of the plastic film, but it is particularly preferable to be laminated on both sides.

The thin film layer (C) obtained by the present invention is
It is considered to consist of a siloxane unit and a fluoride of an alkaline earth metal combined with the siloxane unit, or a fluoride of an alkaline earth metal combined with the siloxane unit and a magnesium oxide. The siloxane unit forming the thin film layer (C) refers to a unit in which a thin film layer is continuously bonded with a silicon atom and an oxygen atom such as —O—Si—O—, and an alkaline earth compound combined with the siloxane unit. What is a metal fluoride? -O-Si-O-alkaline earth metal-
It is considered that an alkaline earth metal fluoride is bonded to a unit in which silicon atoms and oxygen atoms are continuously bonded like F. Further, the alkaline earth metal fluoride and magnesium oxide combined with the siloxane unit are such that a silicon atom and an oxygen atom are continuously bonded to each other like -O-Si-O-alkaline earth metal-F. Alkaline earth metal fluoride is bound to the unit
A state in which a magnesium oxide is bonded to a unit in which a silicon atom and an oxygen atom are continuously bonded, such as -Si-O-Mg-O-, is mixed in a bonded state with a siloxane unit interposed. Is considered to indicate.

The thickness of the thin film layer (C) is selected according to the plastic film (A) used, but in the present invention, it is preferably 50 to 1800 angstroms per side. Particularly, 300 to 800 angstrom is desirable. Further, the thin film layers (C) to be laminated may be double-layered or multi-layered as long as the required function of the finally obtained layer is obtained. That is, the lamination may be performed twice or more, and at that time, fluorides of different types of alkaline earth metals may be laminated. It is considered that most of the factors of dimensional stability obtained from the thin film layer (C) and the SiO ₂ layer (B) are the effects as a moisture-proof layer using the vapor barrier property.

The photosensitive photographic material of the present invention comprises the above-mentioned base film of the present invention as a support and a photosensitive layer (D) laminated on one side or both sides thereof. The photosensitive layer (D) is not particularly limited, but a photosensitive layer mainly composed of gelatin-containing silver halide emulsion is usually used.
Examples of silver halides include silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like. Various additives used in photographic emulsions, such as chemical sensitizers, antifoggants,
There are no particular restrictions on the surfactant, protective colloid, hardener, polymer latex, color coupler, matting agent, sensitizing dye, etc. For example, Research Closure Magazine 17
Volume 6, pages 22-28 (December 1978) can be used. Particularly, those containing the silane compound described in claim 6 of JP-A-5-289236 are preferable.

The method for producing a photographic emulsion and the method for coating a dry plating layer on a plastic film are not particularly limited, and those described in Research Closure Magazine can be used. Photosensitive layer (D) to thin film layer (C)
A conventionally known method can be applied to the above method. At this time, an undercoat layer for improving the adhesiveness may be provided between the thin film layer (C) and the photosensitive layer (D). In the photosensitive photographic material of the present invention, in addition to the photosensitive layer (D) provided on one side or both sides of the base film, a conductive layer (E) may be further provided on one side. When the photosensitive layer (D) is provided on one side of the substrate film, the conductive layer (E) is usually provided on the opposite surface of the substrate film (A) to the side where the photosensitive layer (D) is provided.

Examples of the conductive layer (E) include an inorganic compound such as a conductive metal oxide alone, a mixture of a conductive metal oxide and an insulating metal oxide, or a metal alone, a surfactant system and a polymer electrolyte system. Organic compounds such as can be used, but there is no particular limitation. However, when the metal alone is used as the conductive layer (E), since the conductive layer itself has a low transmittance of visible light to near-infrared light, a metal is applied as thinly as possible to a support within a range where a predetermined conductivity is obtained, Transparency from visible light to near-ultraviolet rays used for exposing the photosensitive layer must be improved. As a method for laminating the conductive metal oxide alone, the mixture of the conductive metal oxide and the insulating metal oxide, or the conductive metal alone on the plastic film (A), the thin film layer (C) is replaced with the plastic film (A). ) Can be applied.

As the conductive metal oxide, ITO (In
(Tin / tin / oxide), indium oxide, tin oxide, etc.
The insulating metal oxide is silicon oxide,
Aluminum oxide, etc., can be cited as a conductive metal.
Are common metals such as aluminum and nickel.
Be done. Also, the surfactant and the polyelectrolyte are not particularly limited.
However, a conventionally known one can be used. Support for each
As a method of stacking on the body, a conventionally known method can be applied. Plastic
SiO laminated on the stick film (A) ₂layer
(B), the thin film layer (C) and the conductive layer (E) are applied separately.
You can do this, but in the case of the continuous
It is also possible to provide each layer. In the present invention,
Plastic film (A), SiO2 layer (B), thin film
The layer (C), the photosensitive layer (D), and the conductive layer (E) are D / C / B /
By stacking A / B / C / E in this order, temperature, humidity, etc.
Dimensionally stable against static electricity, etc.
Light transmittance in the near-ultraviolet region that is required without adverse effects
To provide a base film and a photosensitive photographic material having good
However, this stacking order is D / B / C / A / C / B /
E, D / B / C / B / A / B / C / B / E, D / C / B
/ A / B / C / E / C, D / C / B / A / B / C / D /
It may be changed to E, D / C / B / A / B / C, or the like.
If necessary, a backing layer may be provided outside the photosensitive layer (D).
A surface protective layer on the outside of the photosensitive layer (D),
(D), thin film layer (C), plastic film (A),
Between the conductive layers (E) or on the outside, an undercoating adhesive layer or
An antihalation layer is provided on the outside of the laminated photosensitive photographic material.
A surface protective layer on the surface is used singly or in combination of two or more kinds.
A functional layer may be provided by a method.

[0026]

EXAMPLES The present invention will now be described in more detail based on the examples of the present invention, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The test method in the examples is as follows. Composition analysis of thin film layers:
Using ESCA PHI-5400 manufactured by Perkin Elmer, the surface was evacuated and then argon sputter etching was performed, followed by measurement. The composition ratio was calculated from the peak area of each element, and the x value of SiOx was calculated from the result. Also, the carbon peak due to the adhesion of a trace amount of organic matter was excluded from the calculation of the composition ratio. The composition ratio obtained by ESCA is represented by atom%, which corresponds to mol%.

Light transmittance: Light transmittance in the near ultraviolet region is
The transmittance was measured at 350 nm using a spectrophotometer (U-best30, manufactured by JASCO Corporation) with air as a reference. The wavelength of 350 nm is a wavelength often used when exposing a general original film for a printed wiring board to the printed wiring board. Dimensional stability: The change in length when the temperature and humidity change
Length measuring device (Dainippon Screen, DR-8011-C
A transparent constant temperature and constant humidity chamber in which the humidity can be adjusted was provided on the measurement plate of U), and the dimensional change was measured when the sample was put in the constant temperature and humidity chamber and the humidity was changed. The smaller the dimensional change, the better. Particularly, in a field of a printed wiring board, a general original film for a printed wiring board is required to have dimensional stability against humidity.

Plastic film / SiO₂Layer / Thin film
Adhesion test between layers: Adhesion of each layer constituting the base film
In the sexuality test, the obtained base film was tested at 40 ° C. and 90% RH.
SiO 2 after being exposed to the conditions for 24 hours₂Layer / thin film layer
Make a checkerboard-like scratch with a cutter, and then use tape to cut the tape.
A peel peel test was conducted. After tape peeling, SiO
₂Pass if all layers or thin film layers remain. Example 1 Biaxially oriented polyethylene terephthalate film with a thickness of 100μ
Sputtering method on both sides of the film (PET film)
Using SiO₂Layers were provided. This SiO₂The layer thickness is 50
It was Angstrom. Both sides of this PET film
On the SiO ₂On the outer side of the layer, JP-A-1-25
2768 and the evaporation described in JP-A-2-277774.
Continuous winding type resistance adding method of continuously supplying and discharging raw materials
Use a thermal-type vacuum deposition device, and use silicon and dioxide on both sides of
Mixture of silicon and magnesium fluoride (mixing ratio 45 mol
%: 45 mol%: 10 mol%) is vacuum-deposited on both sides by heating.
(Thickness is about 600 angstroms on both sides). Example 2 Vapor deposition apparatus used in Example 1, polyethylene terephthalate
Of the polyester film and the same procedure as in Example 1.
Using the sputtering method on both sides of ren terephthalate
SiO₂The layers were laminated in the same manner as in Example 1. That's it
Further outside of the SiO2 layer, silicon and silicon dioxide
Mixture of elemental and calcium fluoride (mixing ratio 48 mol%: 4
(7 mol%: 5 mol%) as a raw material by heating vacuum deposition on both sides
(Thickness is about 300 angstroms on both sides). Example 3 Vapor deposition apparatus used in Example 1, polyethylene terephthalate
Of the polyester film and the same procedure as in Example 1.
Using the sputtering method on both sides of ren terephthalate
SiO₂The layers were laminated in the same manner as in Example 1. That's it
This SiO₂Further outside the layer, silicon monoxide and fluorine
Barium bromide mixture (mixing ratio 85 mol%: 15 mol%)
Was vacuum-deposited on both sides using
About 200 Å). Example 4 Vapor deposition apparatus used in Example 1, polyethylene terephthalate
Of the polyester film and the same procedure as in Example 1.
Using the sputtering method on both sides of ren terephthalate
SiO₂The layers were laminated in the same manner as in Example 1. That's it
This SiO₂Further outside the layer, silicon monoxide and fluorine
Magnesium oxide, silicon oxide and magnesium oxide
Co-oxide (forsterite: SiO₂・ 2MgO)
(Mixing ratio 93 mol%: 5 mol%: 2 mol%)
As a raw material, vacuum deposition was performed on both sides by heating.
800 Angstrom). Example 5 Heating method of the evaporation source of the thin film layer evaporation apparatus used in Example 1
Was changed from the resistance heating method to the electron beam heating method,
The polyethylene terephthalate film used is
Len film and spatter on both sides of the polystyrene.
SiO using the tarring method₂Layer as in Example 1
It was laminated with. Further outside of each SiO2 layer,
Silicon, silicon dioxide, magnesium fluoride and false
Mixture of terite (mixing ratio 36.5 mol%: 36.5 m
(Le%: 10 mol%: 17 mol%) as a raw material and heated under vacuum
Evaporated (thickness is about 600 angstroms on both sides
Mu). Example 6 Use the vapor deposition device and polystyrene film used in Example 5.
Further, as in Example 5, the polystyrene was spread on both sides.
SiO using the putting method₂Layer as in Example 5
Laminated by the method. Each SiO₂Further out of the layer
A mixture of silicon monoxide and strontium fluoride.
80% by mole: 20% by mole) as a raw material and heated under vacuum.
I wore it (thickness is about 600 angstroms on both sides). Comparative Example 1 Vapor deposition apparatus used in Example 1, polyethylene terephthalate
Film and the sputtering method on both sides
SiO₂The layers were laminated in the same manner as in Example 1. Comparative example 2 Vapor deposition apparatus used in Example 1, polyethylene terephthalate
Film on both sides₂Layer spatter
Directly, without performing
And continuous evaporation materials described in JP-A-2-277774.
Of continuous winding resistance heating method of supplying and discharging efficiently
Use a vapor deposition device to remove silicon, silicon dioxide, and fluorine on both sides.
Mixture of magnesium fluoride (mixing ratio 45 mol%: 45 mol%
(% By mole: 10 mol%) was vacuum-deposited on both sides by heating (thickness:
Both sides are about 600 Å). Comparative Example 3 Vapor deposition apparatus used in Example 1, polyethylene terephthalate
Of the high frequency induction heating method on both sides
SiO was vapor-deposited using an empty vapor deposition machine (this SiO layer was
The film thickness was 50 Å. ). PET file
On both sides of the SiO layer provided on both sides of the rum, there is
252768 and JP-A-2-277774.
A continuous winding-type resistor that continuously supplies and discharges evaporation raw materials.
Use an anti-heating type vacuum evaporation system,
Mixture of silicon oxide and magnesium fluoride (mixing ratio 45
(% Mol: 45 mol%: 10 mol%) is heated on both sides by vacuum vaporization.
I wore it (thickness is about 600 angstroms on both sides).

With respect to the vapor-deposited films obtained in Examples and Comparative Examples, the composition of the vapor-deposited film on both sides, the light transmittance of the vapor-deposited film, the dimensional stability and the adhesion were measured. The results are shown in Table 1.

[0030]

[Table 1]

Examples 7 to 12 With respect to the vapor deposition films obtained in Examples 1 to 6, ITO (indium tin oxide S) was formed on one vapor deposition surface.
Vacuum vapor deposition was carried out (thickness of about 500 angstroms) while introducing oxygen gas using the same device as described above. The oxygen gas partial pressure at that time is 3
It was × 10 ^-4 torr. Further, an ordinary photosensitive silver halide gelatin layer containing 6% by weight of an epoxysilane compound was coated on the opposite surface provided with ITO using a bar coater (4.5 g / m ² dry weight). The dimensional stability of the obtained photosensitive photographic film was measured by the method described above. The results are shown in Table 2. Comparative Examples 4 to 6 ITO (indium tin oxide S) was formed on one of the vapor deposition films obtained in Comparative Examples 1 to 3.
Vacuum vapor deposition was carried out (thickness of about 500 angstroms) while introducing oxygen gas using the same device as described above. The oxygen gas partial pressure at that time is 3
It was × 10 ^-4 torr. Further, an ordinary photosensitive silver halide gelatin layer containing 6% by weight of an epoxysilane compound was coated on the opposite surface provided with ITO using a bar coater (4.5 g / m ² dry weight). The dimensional stability of the obtained photosensitive photographic film was measured by the method described above. The results are shown in Table 2.

[0032]

[Table 2]

[0033]

Industrial Applicability The base film and the photosensitive photographic material of the present invention are excellent in dimensional stability against temperature and humidity, particularly humidity, adhesiveness of each layer, and light transmittance in the near-ultraviolet region. It is possible to obtain a photosensitive photographic material in which generation of static electricity is suppressed by application, and as a result, problems caused by foreign matter are prevented even during coating of the photosensitive layer and exposure of the photosensitive layer.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 G03C 1/76-1/95

Claims (9)

(57) [Claims] 1. A SiO ₂ layer (B) is provided on one or both sides of a plastic film (A) by a vacuum thin film forming technique, and SiO x (x is larger than 1.8 ) on one or both sides thereof by a vacuum thin film forming technique. , Less than 2.0) 9
8 to 80 mol%, and alkaline earth metal fluoride 2 to
A substrate film formed by forming a thin film layer (C) comprising 20 mol% . 2. An SiO ₂ layer (B) is provided on one or both sides of a plastic film (A) by a vacuum thin film forming technique, and SiO x (x is larger than 1.8 ) on one or both sides thereof by a vacuum thin film forming technique. , Less than 2.0) 9
7.5 to 80 mol%, fluoride of alkaline earth metal 2 to
19.5 mol% and magnesium oxide 0.5 to 18
A base film formed by forming a thin film layer (C) composed of mol% . 3. The substrate film according to claim 1, wherein the fluoride of the alkaline earth metal in the thin film layer (C) is one or more selected from magnesium fluoride and calcium fluoride. 4. The substrate film according to claim 1, wherein the vacuum thin film forming technique for providing the SiO ₂ layer (B) is sputtering or ion plating. 5. A vacuum thin film is formed by using silicon, silicon dioxide, silicon monoxide, a fluoride of an alkaline earth metal and / or a mixture of silicon dioxide and a co-oxide of magnesium oxide as a raw material. Item 5. The base film according to any one of items 1 to 4. 6. A vacuum thin film formation comprising a SiO ₂ layer (B) on one side or both sides of a plastic film (A), and comprising a siloxane unit and a fluoride of an alkaline earth metal combined with the siloxane unit on one side or both sides. 5. A thin film layer (C) formed by using a technique .
The base film according to item 1 . 7. A plastic film (A) is provided with a SiO ₂ layer (B) on one or both sides, and a siloxane unit and a fluoride or magnesium oxide of an alkaline earth metal combined with the siloxane unit are provided on one or both sides thereof. The substrate film according to claim 2, wherein the thin film layer (C) is formed by using the vacuum thin film forming technique. 8. A photosensitive photographic material obtained by laminating a photosensitive layer (D) on one side or both sides of the base film according to any one of claims 1 to 7. 9. A photosensitive layer (D) is laminated on one side or both sides of the base film according to claim 1.
A photosensitive photographic material further comprising a conductive layer (E) laminated on one side.