JPH0728189A - Photosensitive film - Google Patents

Abstract

PURPOSE:To provide a photosensitive photographic film effective when used as a substrate film for film lithography, an original picture film, etc., to fabricate a printed circuit board by laminating a specific metal oxide thin film layer on one or both surfaces of a plastic film, and thereover laminating a photosensitive layer. CONSTITUTION:On one or both surfaces of a plastic film, a metal oxide layer is laminated, which presents a water vapor barrier property and has a smaller thermal expansion than the plastic film, and thereover a photo-sensitive layer is laminated, and further if necessary, an electroconductive layer is laminated on the plastic film surface opposite its surface where the photosensitive layer is laminated. The plastic film should preferably be of polyethylene terephthalate which presents a high dimensional stability. Examples of the metal oxide are silicon oxide, aluminum oxide, magnesium oxide, and titanium oxide, or may be a mixture of two or more of these. The conductive layer is with no restriction particularly, but will favorably be ITO or the like.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base film for making a photographic film, an original film for a printed wiring board, and the like.

[0001]

2. Description of the Related Art Base films such as base films for photographic film plate making and original films for printed wiring boards have relatively good dimensional stability against changes in relative humidity (hereinafter abbreviated as humidity) and temperature. A polyethylene terephthalate film having is used. This is because, in the case of a base film for photographic film plate making, a deviation in exposure occurs in the superposed films due to changes in humidity and temperature. 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 is a film that has a relatively small dimensional change with respect to humidity and temperature, but also a certain dimensional change is unavoidable. Therefore, photographic film plate making film,
Original films for printed wiring boards, etc. are used in a room where the humidity is controlled at about 55-60% RH and the temperature is controlled at 20-27 ° C, and the film is exposed to the environment for a long time before use. It is necessary to control the humidity and temperature of the film itself. The cost of the temperature and humidity of the working room and the time required for the humidity control and temperature control of the film are currently serious problems. Humidity change is especially important in this field, and when the humidity changes, it directly affects the dimensional change amount, but generally when the temperature changes, the relative humidity also changes at the same time (for example, if the temperature rises, , The humidity decreases), and the total effect on the dimensional change is considered to be small. Solutions for reducing this dimensional change include thickening the base film and providing a moisture-proof layer such as PVDC (polyvinylidene chloride). However, the thickness of the base film is important in terms of manufacturing and workability. There is a limit in terms of. In addition, at present, the dimensional stability of PVDC or the like is not sufficient when a moisture-proof layer is applied.

[0002]

The present inventors have previously invented a base film having dimensional stability. Further, a photosensitive film which is particularly effective as a base film for photographic film plate making, an original film for printed wiring boards and the like. He found a sex photo film.

[0003]

According to the present invention, a metal oxide thin film layer (B) having a water vapor barrier property on one or both sides of a plastic film (A) and having less expansion with temperature than the plastic film (A). And a photosensitive layer (C) is laminated on the metal oxide thin film layer, and if necessary, a conductive layer (D) is laminated on the opposite surface of the plastic on which the photosensitive layer (C) is laminated. The present invention provides a photosensitive photographic film which is dimensionally stable against changes in temperature and humidity (particularly changes in humidity) and which is not adversely affected by the generation of static electricity or the like. The polyethylene terephthalate film used as a base film for photographic film plate making and an original image film for printed wiring boards has appropriate mechanical strength and has a relatively small dimensional change with respect to humidity as compared with other films. However, compared to inorganic metal oxides, dimensional changes easily occur due to changes in humidity and temperature. Many of the causes are swelling and drying due to moisture absorption of polyethylene terephthalate itself due to changes in humidity, and it is considered that expansion and contraction of molecular bonds of polyethylene terephthalate due to changes in temperature are part of the cause. That is, in order to reduce the dimensional change, it is necessary to add a metal oxide having a water vapor barrier property to the film in order to prevent the film from swelling due to moisture absorption with respect to humidity change, and that the metal oxide does not easily expand or contract with respect to temperature change. Is important, and the present invention provides a photosensitive photographic film having dimensional stability by the combined effect of these two.

In the present invention, a polyethylene terephthalate film having high dimensional stability is desirable as the plastic film (A), but the dimensional stability of the film can be improved by the present invention, and thus the film is slightly inferior in dimensional stability. However, since it can be used, other films such as polyethylene-2,6-naphthalate, cellulose acetate, and polycarbonate can be applied. Among them, a heat-fixed film is preferable, and a biaxially stretched film is preferable. The plastic film (A) may be previously coated with an organic conductive agent such as a surfactant system or a polymer electrolyte system, or an inorganic conductive agent such as a conductive metal oxide, and an adhesive agent. . The thickness of the plastic film (A) varies depending on the application, but is 5 to 500 μ, preferably 50 to 250.
is μ.

The metal oxide thin film layer (B) has good permeability from visible light to near-ultraviolet rays used when exposing the photosensitive layer, and has a high water vapor barrier property (that is, low water vapor transmission rate) with respect to the plastic film. In addition, the temperature expansion is small, and the metal oxide thin film layer (B) and the plastic film (A) must be firmly adhered.
Generally, metal oxides have a better water vapor barrier property and less expansion with temperature than plastic films (eg polyethylene terephthalate). Specifically, there are silicon oxide, aluminum oxide, magnesium oxide, titanium oxide and the like, and a mixture of two or more thereof may be used. For example, in the case of silicon oxide, the vapor barrier property of the vapor deposition film is 1 to ² g / m ² . 24 hrs
It is about 40 ° C. and 90% RH, and the temperature expansion (coefficient of thermal expansion) of a silicon oxide vacuum-deposited film is difficult to measure, but it is 5.5 × 10 ⁻⁷ / K when compared to quartz glass. Yes, polyethylene terephthalate is 1 × 10 ⁻⁵ / K
Is. The metal oxide thin film layer (B) formed on the plastic film may eventually be in an oxide state,
The raw material may be any of metal oxides, metals, organometallic compounds and the like. That is, even when the metal oxide thin film layer (B) is directly formed on the plastic film by using a metal oxide as a raw material by a method such as vacuum deposition, or while oxidizing a compound containing a metal or a metal such as an organic metal oxide. The metal oxide thin film layer (B) may be formed by vacuum vapor deposition, or a metal may be formed as a vapor deposition layer on a plastic film, and the vapor deposition layer may be oxidized in a subsequent step to form the metal oxide thin film layer (B). . 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.

These metal oxides have a water vapor barrier property for preventing the plastic film from swelling and a small dimensional change (low linear expansion coefficient) with respect to temperature, as well as the plastic film (A) and the photosensitive layer (C). It also provides the easy adhesion property of. The metal oxide thin film layer (B) may be in a completely oxidized state or in an oxygen-deficient state. The oxygen-deficient state is, for example, a completely oxidized state of SiO _{2 in} the case of silicon oxide, but the oxygen-deficient state is that SiO _x is less than X = 2. When the metal oxide thin film layer (B) is completely oxidized, the transparency is improved, but the flexibility is deteriorated, and the metal oxide thin film layer of the photosensitive photographic film finally has dimensional stability. Cracks occur in (B), which causes problems with the water vapor barrier property and dimensional stability of itself. Also Si
If O _x and X are about 1.4 or less, the visible light used for exposing the photosensitive layer loses the transparency in the near-ultraviolet light.
SiO _x , X = about 1.5 to 1.9 is suitable.

The metal oxide thin film layer (B) may be formed on the plastic film (A) by either a continuous winding method or a single-wafer method. The forming method is not particularly limited and may be vacuum vapor deposition, Ion plating, sputtering, plasma CVD, microwave CVD, etc. can be used. Further, as a heating method for vacuum vapor deposition, if vapor deposition droplets called splash are not generated during the vapor deposition, and there is no particular limitation as long as it is small, there are no conventional heating methods such as high frequency induction heating, resistance heating, and electron beam heating. Any 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. Metal oxide thin film layer (B)
The thickness is selected according to the plastic film (A) used, but is preferably 50 to 2000 angstroms in the present invention. Further, this lamination may be performed twice or more, and different kinds of metal oxides may be laminated at that time.

The photosensitive layer (C) is not particularly limited, but a gelatin-containing silver halide emulsion is preferable. Examples of silver halides include silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Various additives used in photographic emulsions,
For example, chemical sensitizers, antifoggants, surfactants, protective colloids, hardeners, polymer latices, color couplers, matting agents, sensitizing dyes, etc. are not particularly limited. For example, Research Closure, Vol. 176, 22. ~ 2
The description on page 8 (December 1978) can be referred to. The emulsion may be either a solvent type or an aqueous type. 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 the description in Research Closure Magazine can be referred to. As a method of applying the photosensitive layer (C) to the metal oxide thin film layer (B), a conventionally known method can be applied.

The conductive layer (D) laminated on the opposite surface of the plastic on which the photosensitive layer (C) is laminated is a conductive metal oxide alone, a mixture of a conductive metal oxide and an insulating metal oxide, or a conductive metal. There are inorganic compounds such as alone, and organic compounds such as surfactant-based and polyelectrolyte-based,
There is no particular limitation and either may be used. When a conductive metal alone is used as the conductive layer (D), it becomes opaque, so it must be applied as thin as possible to the plastic film (A) to improve the transparency from visible light to near-ultraviolet light used when exposing the photosensitive layer. I have to. As the method and 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 metal oxide (B) is a plastic A method of laminating on the film (A) can be applied.

As the conductive layer (D), the conductive metal oxide alone which is laminated on the plastic film (A) is IT.
Examples thereof include one or more metal oxides having conductivity such as O (indium / tin / oxide), indium oxide, and tin oxide. Further, the conductive layer (D) formed on the plastic film (A) may be in an oxide state as a result, and the same method as in the case of laminating the metal oxide can be applied. As the conductive layer (D), as a mixture of a conductive metal oxide and an insulating metal oxide to be laminated on the plastic film (A), one or more having conductivity such as ITO, indium oxide, tin oxide, etc. There is no particular limitation as long as it is a mixture of the conductive metal oxide of (1) and one or more insulating metal oxides having an insulating property such as aluminum oxide and silicon oxide. Further, the mixing ratio is finally determined by the required conductivity. Naturally, when the ratio of the conductive metal oxide in the mixture is high, the resistance value of the conductive layer decreases, and when the ratio of the insulating metal oxide is high, the opposite is true. Further, the conductive layer (D) formed on the plastic film (A) may be in an oxide state as a result, and the same method as in the case of laminating the metal oxide can be applied. Examples of the conductive metal to be laminated on the plastic film (A) for the conductive layer (D) include general metals such as aluminum, and organic conductive compounds such as surfactant-based and polyelectrolyte-based compounds. Also, conventionally known ones can be mentioned.
Further, as a method for laminating each of the plastic films (A), a conventionally known method can be applied.

The metal oxide thin film layer (B) and the conductive layer (D), which are laminated on the plastic film (A), can be applied separately, but in the case of the continuous winding method, each of them is formed on both sides at once. It is also possible to provide a layer of. In the present invention, the plastic film (A), the metal oxide thin film layer (B), the photosensitive layer (C) and the conductive layer (D) are laminated in the order of C / B / A / D or C / B / A / B / D. By doing so, it is possible to provide a photosensitive photographic film which is dimensionally stable against temperature and humidity and which is not adversely affected by the generation of static electricity and the like, but this stacking order is C / B / A / B / D /
B, C / B / A / D / B, C / A / B / D, or C /
It may be changed to A / B / D / B. If necessary, a surface protective layer may be provided outside the photosensitive layer (C), the photosensitive layer (C), the metal oxide thin film layer (B), the plastic film (A),
An undercoating easy-adhesion or antihalation layer is provided between or outside each of the conductive layers (D), and a surface protective layer is provided on the outer surface of the laminated photosensitive photographic film, either alone or in combination of two or more by a conventional method. A functional layer may be provided.

[0012]

The laminate obtained according to the present invention is provided with a metal oxide thin film layer (B) having a water vapor barrier property and a small expansion against temperature on one or both sides of a plastic film (A), and is provided thereon. By providing the photosensitive layer (C) and the conductive layer (D) on the opposite surface, the dimensional stability is excellent against temperature and humidity, especially humidity, and the addition of the conductive layer suppresses the generation of static electricity. Thus, it is possible to obtain a photosensitive photographic film which can prevent problems due to foreign matter even when the photosensitive layer is coated or the photosensitive layer is exposed. Specifically, when a dry plating layer of a metal oxide (B) such as a silicon oxide is provided on both sides of the polyethylene terephthalate film (A), the dimension with respect to humidity is larger than when a metal oxide thin film layer is not provided. Since the change is about 1/3 to 1/20, it is possible to eliminate the need to use it in a room where the humidity and temperature are controlled, and to further expose the film to its use environment for a long time before use. The need for humidity control can be reduced. Further, the metal oxide thin film layer (B) and the conductive layer (D) can be applied to the plastic film (A) at the same time, in which case the production cost can be greatly reduced.

[0013]

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. Dimensional stability: The change in length when the temperature and humidity are changed is measured by a length measuring device (DR-8011-manufactured by Dainippon Screen Co., Ltd.).
CU) is provided with a transparent constant temperature and humidity chamber in which the humidity and temperature can be adjusted, and the sample is put in the chamber to measure the dimensional change when the humidity is changed. The smaller the dimensional change, the better. Water vapor transmission rate: Measured using Permatran-W-TWIN manufactured by Modern Controls in accordance with ASTM-F1249. The smaller the value of this water vapor transmission rate, the better the water vapor barrier property. Composition analysis of metal oxide thin film layer and conductive layer: Measured using ESCA PHI-5400 manufactured by Perkin Elmer and argon sputter etching.

Example 1 A continuous winding type resistance heating type vapor deposition apparatus was used, and a thickness of 10 was used.
Silicon monoxide was vacuum-deposited by heating on both sides of a 0 μ biaxially oriented polyethylene terephthalate film (thickness: about 500).
Angstrom). Vacuum vapor deposition was performed (thickness: about 500 angstroms) while introducing oxygen gas (indium tin oxide Sn: 5 wt% added) on one of the vapor deposition surfaces using the same device as the above-mentioned device while introducing oxygen gas.
The oxygen gas partial pressure at that time was 2 × 10 ⁻⁴ torr. The composition of the vapor deposition film on both surfaces of the obtained vapor deposition film and the water vapor permeability of the vapor deposition film were measured.
The results are shown in the table. Further, a gelatin silver halide graphic arts emulsion was coated on the opposite surface provided with ITO using a bar coater, cooled at 30 ° C. for 30 minutes and dried.
Further, it was aged at room temperature for 16 hours. The dimensional stability of the obtained photosensitive photographic film was measured by the method described above. The results are shown in Table 1.

Example 2 Using the biaxially stretched polyethylene terephthalate film used in Example 1 and the vapor deposition method, aluminum was vacuum-deposited on both surfaces in an oxygen atmosphere (oxygen partial pressure of 7 × 10 ⁻⁴ torr) to about 500. A thin film of Angstrom aluminum oxide was formed on both sides of a polyethylene terephthalate film. After that, ITO was vapor-deposited in the same manner as in Example 1, and then the composition of the vapor-deposited film and the water vapor permeability were measured in the same manner as in Example 1. Thereafter, the photosensitive layer was coated by the same method as in Example 1, and the dimensional stability of the obtained photosensitive photographic film was measured by the above method. The results are shown in Table 1.

Example 3 Using the biaxially stretched polyethylene terephthalate film used in Example 2, the vapor deposition method was changed to an electron beam heating method, and the vapor deposition raw material was changed from aluminum to aluminum oxide. Pressure 2 × 10 ^-4 torr
In step r), aluminum oxide was vacuum-deposited to form a thin film of aluminum oxide having a thickness of about 500 Å. After that, after performing ITO vapor deposition in the same manner as in Example 1,
The composition of the deposited film and the water vapor transmission rate were measured. Thereafter, the photosensitive layer was coated by the same method as in Example 1, and the dimensional stability of the obtained photosensitive photographic film was measured by the above method. The results are shown in Table 1.

Example 4 Using the biaxially stretched polyethylene terephthalate film and vapor deposition method used in Example 1, magnesium oxide was vacuum-deposited on both surfaces in an oxygen atmosphere (oxygen partial pressure of 2 × 10 ⁻⁴ torr) to obtain about 500. A thin film of angstrom magnesium oxide was formed, and tin oxide was deposited instead of ITO on one deposition surface, and then surface oxidation was performed while heating in an oxygen atmosphere. Next, the composition of the deposited film and the water vapor transmission rate were measured. Thereafter, the photosensitive layer was coated by the same method as in Example 1, and the dimensional stability of the obtained photosensitive photographic film was measured by the above method. The results are shown in Table 1.

Example 5 Using the biaxially stretched polyethylene terephthalate film and vapor deposition method used in Example 1, a mixture of silicon monoxide and magnesium oxide was vapor-deposited on both sides instead of silicon oxide alone (mixing ratio 1 Silicon oxide: 95% by weight, magnesium oxide: 5% by weight), and a film of a silicon-magnesium oxide domain of about 500 angstrom was formed. Then I
After vapor deposition of a mixture of TO and silicon monoxide (mixing ratio ITO: 50% by weight, silicon monoxide: 50% by weight) using the vapor deposition method used in Example 1, the composition of the deposited film and water vapor transmission The rate was measured as in Example 1. Thereafter, the photosensitive layer was coated by the same method as in Example 1, and the dimensional stability of the obtained photosensitive photographic film was measured by the above method. The results are shown in Table 1.

Example 6 Using the biaxially stretched polyethylene terephthalate film and vapor deposition method used in Example 1, a mixture of silicon monoxide and titanium oxide was vapor-deposited on both sides instead of silicon oxide alone (mixing ratio). Silicon monoxide: 95% by weight Titanium oxide: 5
% By weight), about 500 Å of silicon-titanium oxide thin film was formed. In addition, IT on one vapor deposition surface
Aluminum was vapor-deposited in place of O (approximately 50 Å). Then, the composition of the vapor-deposited film and the water vapor transmission rate were measured as in Example 1. Thereafter, the photosensitive layer was coated by the same method as in Example 1, and the dimensional stability of the obtained photosensitive photographic film was measured by the above method. The results are shown in Table 1.

Example 7 Using the biaxially stretched polyethylene terephthalate film used in Example 1 and the vapor deposition method, silicon monoxide and silicon dioxide-aluminum oxide compounds are used on both sides instead of silicon oxide alone. A mixture of mullite was evaporated (mixing ratio / silicon monoxide: 90% by weight mullite: 10% by weight) to form a silicon-aluminum oxide thin film of about 500 Å. After that, ITO was vapor-deposited in the same manner as in Example 1, and then the composition of the vapor-deposited film and the water vapor permeability were measured in the same manner as in Example 1. Thereafter, the photosensitive layer was coated by the same method as in Example 1, and the dimensional stability of the obtained photosensitive photographic film was measured by the above method. The results are shown in Table 1.

Comparative Example 1 The biaxially stretched polyethylene terephthalate film used in Example 1 was subjected to vapor deposition of ITO and coating of the photosensitive layer in the same manner as in Example 1 without vapor deposition of silicon oxide on both sides. I worked. The dimensional stability of the obtained vapor-deposited film was measured by the method described above. The results are shown in Table 1.

[0022]

[Table 1]

Claims (4)

[Claims] 1. A metal oxide thin film layer (B), which has a water vapor barrier property and has less expansion against temperature than the plastic film (A), is laminated on one or both sides of the plastic film (A), and the metal oxide is formed. A photosensitive photographic film obtained by laminating a photosensitive layer (C) on a thin film layer. 2. The photosensitive material according to claim 1, wherein the metal oxide thin film layer (B) is one kind or a mixture of two or more kinds selected from silicon oxide, aluminum oxide, magnesium oxide and titanium oxide. Sex photographic film. 3. A conductive layer (D) is laminated on the opposite surface of the plastic, and the conductive layer (D) is made of ITO (indium.
(Tin / oxide), indium oxide, a conductive metal oxide selected from tin oxide alone, or a conductive metal oxide selected from ITO, indium oxide and tin oxide, and a silicon oxide and an aluminum oxide. The photosensitive photographic film according to claim 1, which is a mixture of insulating metal oxides selected from among the above. 4. The photosensitive photographic film according to claim 1, wherein the plastic film (A) is a polyethylene terephthalate film. [0001]