JP4811294B2 - Method for manufacturing absorption multilayer ND filter - Google Patents

Description

  The present invention relates to an absorptive multilayer ND filter in which an absorptive multilayer film is provided on a resin film, and more particularly to an improvement in environmental resistance of an absorptive multilayer ND filter that attenuates transmitted light of 400 to 700 nm.

  As an ND (Neutral Density Filter) filter that attenuates transmitted light in the visible light region, a reflective ND filter that reflects and attenuates incident light and an absorption ND filter that absorbs and attenuates incident light are known. . In particular, when an ND filter is incorporated in a lens optical system in which reflected light is a problem, an absorption ND filter is generally used.

  The absorption type ND filter includes a type in which an absorbing substance is mixed with the substrate itself (color glass ND filter), a type in which an absorbing substance is applied to the substrate, and a thin film formed on the substrate surface without absorption in the substrate itself. There are certain types. In the case of a type in which the thin film has absorption, the thin film can be composed of a multilayer film in order to prevent reflection on the surface of the thin film, and can have an antireflection effect as well as a function of attenuating transmitted light.

  In particular, in an absorption type multilayer ND filter used for a small and thin digital camera or the like, a resin film is regarded as an optimal substrate because the mounting space is narrow and the substrate itself needs to be thinned. For example, JP 2006-178395 A discloses an absorptive multilayer ND filter in which an oxide dielectric film layer and a metal absorptive film layer are alternately laminated on a resin film to form an absorptive multilayer film. Yes.

  Japanese Patent Application Laid-Open No. 2003-322709 discloses a plasma electrode for cleaning a substrate surface on a traveling path of a film, and a vapor deposition source for forming a light absorption film and a transparent dielectric film on the surface. A method is described in which a substrate surface is first cleaned by plasma discharge generated at a plasma electrode, then a light absorbing film is formed by sputtering of a vapor deposition source, and then a transparent dielectric film is formed by sputtering. Here, it is disclosed that plasma treatment is performed on a resin film before film formation in order to improve the adhesion of the absorption multilayer film.

JP 2006-178395 A JP 2003-322709 A

  The absorption multilayer film ND filter in which an absorption multilayer film is formed on the resin film described above has a valley shape in which the average transmittance at a wavelength of 400 to 700 nm is usually about 25% and the transmittance around a wavelength of 400 to 550 nm is high. Spectral transmission characteristics.

  Since the absorption multilayer ND filter is incorporated in a digital camera, a security camera or the like, environmental resistance is also required. In particular, an absorptive multilayer film ND filter formed on a substrate made of a resin film may crack in the absorptive multilayer film like a mesh when left in a high-temperature and high-humidity environment. .

  The present invention has been made paying attention to such conventional problems, and relates to an absorptive multilayer ND filter in which a resin film as a substrate is provided with an absorptive multilayer film that attenuates transmitted light in the visible light region. It is an object of the present invention to provide an absorptive multilayer ND filter that has excellent optical characteristics without changing the film structure of the absorptive multilayer film, and at the same time, does not generate cracks even in a high-temperature and high-humidity environment.

  As a result of earnest research to achieve the above object, the present inventor changed the film structure of the absorption film based on the knowledge that the transparent resin multilayer film is slightly colored by the treatment with plasma or ion beam irradiation. Without irradiating the resin film with plasma or ion beam and causing thermal shrinkage, the environmental resistance of the absorption multilayer film formed on the resin film under high temperature and high humidity environment is improved. This is the headline and the present invention.

  That is, the method for manufacturing an absorption multilayer ND filter according to the present invention is a method for manufacturing an absorption multilayer ND filter in which a resin film is provided with an absorption multilayer that attenuates transmitted light in the visible light region. The resin film is thermally contracted by 0.2% or more by plasma treatment or ion beam treatment, and then oxide dielectric film layers and metal absorption film layers are alternately laminated on at least one surface of the resin film. Forming an absorption-type multilayer film.

  According to the present invention, the absorption multilayer film is maintained without changing the film structure of the absorption multilayer film ND filter, while maintaining excellent optical characteristics without increasing the manufacturing cost or complicating the film formation process. In addition, it is possible to prevent cracking of the absorption multilayer film in a high temperature and high humidity environment.

  In the absorptive multilayer ND filter of the present invention, the resin film as the substrate is irradiated with plasma or ion beams before the absorptive multilayer film is formed. The resin film is heat-shrinked by 0.2% or more by plasma treatment or ion beam treatment of the resin film, thereby improving the adhesion between the resin film and the absorbent multilayer film and absorbing the multilayer film in a high-temperature and high-humidity environment. Cracking can be prevented.

  Conventionally, in order to improve the adhesion between the resin film and the multilayer film, plasma treatment or ion beam treatment is performed on the resin film before the multilayer film is formed. In that case, the adhesion strength of the multilayer film is improved in accordance with the plasma processing voltage (power) or the ion beam voltage (power), but when the voltage (power) exceeds a certain level, the adhesion strength of the multilayer film is no longer improved. When the voltage (power) is increased, the adhesion strength of the multilayer film is lowered. This is considered because the surface of the resin film is deteriorated by plasma treatment or ion beam treatment.

  As described above, since the conventional plasma treatment or ion beam treatment for the resin film was intended only to improve the adhesion strength, the conditions were studied within the range in which the adhesion strength of the multilayer film was improved, and the plasma treatment or ion beam treatment was performed. In the past, it has not been possible to raise the processing voltage (electric power) to a level at which there is no change in the adhesion strength.

  In the present invention, the plasma treatment voltage (electric power) or ion beam voltage (electric power) is raised to a level where there is no change in the adhesion strength, and the resin film is thermally shrunk by 0.2% or more, so that it is in a high temperature and high humidity environment. It prevents the occurrence of cracks in the absorption multilayer film of the installed absorption multilayer film ND filter. Moreover, the plasma treatment or ion beam treatment is performed under the condition that the surface temperature of the resin film is close to the glass transition temperature of the resin film, that is, the condition range before the adhesive strength of the absorption multilayer film is lowered due to deterioration of the resin film surface. I also found it desirable to use it.

  It is difficult to express a specific condition range of the plasma processing voltage (power) or ion beam voltage (power) as described above. This is because the above processing effect depends on the processing time, gas introduction amount, gas pressure, and the like on the resin film. Therefore, in the present invention, plasma treatment or ion beam treatment is used as a condition for obtaining the effect of preventing the occurrence of cracking in the absorption multilayer film of the absorption multilayer film ND filter installed in a high temperature and high humidity environment. The heat shrinkage rate of the resin film is adopted.

  Although the material of the resin film used as a board | substrate is not specifically limited, A transparent thing is preferable and the flexible thing which can be dry-type roll-coated is preferable when mass productivity is considered. A flexible substrate is less expensive than a conventional glass substrate, and is excellent in that it is light and rich in deformability.

  Specific examples of the resin film include a film made of a resin selected from polyethylene terephthalate (PET), polyether sulfone (PES), polyarylate (PAR), polycarbonate (PC), polyolefin (PO) and norbornene, or The composite film which coat | covered the one or both surfaces of the resin film with the acrylic type organic film is mentioned. In particular, norbornene resin is preferable because it has characteristics such as transparency and heat resistance in the visible wavelength range, and representative examples thereof include ZEONOR (trade name) manufactured by Nippon Zeon Co., Ltd., which has a low absorption rate, and film adhesion. A high JSR Arton (trade name) can be mentioned.

The absorption multilayer film provided on one side or both sides of the resin film is composed of a multilayer film in which oxide dielectric film layers and metal absorption film layers are alternately laminated. As the oxide dielectric film layer, SiO ₂ , Al ₂ O ₃ , a mixture of these oxides, or a composite oxide can be used. In addition, as the metal absorption film layer, at least one metal selected from Ni, Ti, Cr, W, Ta, and Nb can be used.

  The oxide dielectric film layer and the metal absorption film layer constituting the absorption multilayer film are subjected to the plasma treatment or the ion beam treatment as described above, and then the vacuum deposition method, the ion beam sputtering method, the magnetron sputtering method, the ion plate method. Each film can be formed by a film forming method such as a coating method.

  Next, the manufacturing method of the absorption multilayer ND filter according to the present invention will be described in more detail. In the absorptive multilayer ND filter, an absorptive multilayer film that attenuates transmitted light is provided on at least one surface of a resin film serving as a substrate. In the present invention, before the absorption multilayer film is formed, at least the resin film surface on which the absorption multilayer film is formed is subjected to plasma treatment or ion beam treatment, and the resin film is thermally contracted by 0.2% or more. In addition, there is no restriction | limiting in particular about plasma processing and ion beam processing, The gas which mixed oxygen or nitrogen with argon gas single-piece | unit or argon gas can be used for introduction gas.

  In the case of a resin film such as a PET film, since the film is stretched in the longitudinal and lateral biaxial directions, there is stress in the stretching direction, and a shrinkage phenomenon occurs due to heating and humidity. At that time, it is known that the amount of stretching differs in the longitudinal direction (length direction) and the lateral direction (width direction), and therefore the thermal shrinkage rate differs, and the thermal shrinkage rate in the longitudinal direction is larger than that in the lateral direction. In general, the absorption multilayer film is formed by using a roll coater and winding it while applying tension in the vertical direction. Therefore, the heat shrinkage rate of 0.2% or more in the present invention may be measured in the longitudinal direction of the resin film. The heat shrinkage rate is obtained from the dimensional change by measuring the film length marked on the resin film before the treatment before and after the treatment.

  In the plasma treatment or ion beam treatment, it is necessary to thermally shrink the resin film by 0.2% or more. This is because if the heat shrinkage of the resin film is less than 0.2%, it is difficult to obtain the effect of preventing cracking of the absorption multilayer film in a high temperature and high humidity environment. However, if the thermal shrinkage of the resin film is 0.5% or more, it is possible to prevent cracking of the absorbent multilayer film in a high-temperature and high-humidity environment, but the resin film surface deteriorates, so that the adhesion of the absorbent multilayer film is reduced. The strength tends to decrease. Therefore, it is preferable to adjust the conditions for plasma treatment or ion beam treatment so that the thermal shrinkage of the resin film is 0.2% or more and less than 0.5%.

  On the resin film subjected to the plasma treatment or the ion beam treatment, an oxide dielectric film layer and a metal film layer constituting an absorption multilayer film are alternately formed. For example, when forming an absorption multilayer film on both surfaces of a PET film with an easy-adhesion layer, first, plasma processing is performed on the A surface with a desired plasma processing voltage, and then the absorption multilayer film is formed on the A surface. Next, plasma treatment is performed on the B surface in the same manner as the A surface, and an absorption multilayer film is subsequently formed on the B surface.

  The oxide dielectric film layer and the metal film layer constituting the absorption multilayer film can be formed by a film forming method such as a vacuum deposition method, an ion beam sputtering method, a magnetron sputtering method, or an ion plating method, respectively. it can. In particular, the characteristics of the metal absorption film layer, such as the refractive index and absorption coefficient, may vary greatly depending on the additive and impurities of the film material, the residual gas during film formation, the gas released from the substrate, and the film formation speed. These conditions may be appropriately selected and set so as to obtain the desired absorption multilayer ND filter characteristics.

By using a PET film with an easy-adhesion layer (Toyobo Co., Ltd.) having a thickness of 100 μm as the substrate, the oxide dielectric film layer constituting the absorption multilayer film is formed of SiO ₂ and the metal absorption film layer is formed of Ni. An absorptive multilayer ND filter having the film structure shown in 1 was produced. The absorption multilayer ND filter having the film structure shown in Table 1 has a valley-shaped spectral transmission characteristic shown in FIG. 1, and has an average transmittance of 25% at a wavelength of 400 to 700 nm.

First, the A-side of the PET film with an easy-adhesion layer is subjected to plasma treatment at a plasma treatment voltage of 1.6 kV, leaving an undeposited portion at the end of the PET film, and an oxide dielectric film layer made of SiO ₂ Absorption-type multilayer films were formed by alternately laminating metal absorption film layers made of Ni. After that, plasma treatment is performed on the B surface at the same position on the A surface with the same plasma processing voltage, and an absorptive multilayer film is formed at the end of the PET film leaving an undeposited portion in the same manner as the A surface. A multilayer ND filter was obtained. In addition, in order to measure temperature, the thermo-label which changes in color when it reaches to 85 degreeC was affixed previously to the non-film-forming part of the said PET film.

  More specifically, a sputtering roll coater equipped with a DC plasma processing mechanism was used as the absorption multilayer film forming apparatus. The plasma treatment of the PET film was performed by introducing Ar gas into the DC plasma treatment apparatus at 100 sccm and lowering the rotation speed of the turbo pump so that the Ar gas pressure was 3 Pa and the film conveyance speed was 1 m / min. .

For the formation of the absorption multilayer film, a Ni alloy target (manufactured by Sumitomo Metal Mining Co., Ltd.) is used for forming a metal absorption film layer, and a Si target (Sumitomo Metal Mining Co., Ltd.) is used for forming an oxide dielectric film layer. Product). That is, the Ni alloy target is formed by a DC magnetron sputtering method in which Ar gas is introduced, the Si target is subjected to dual magnetron sputtering in which Ar gas is introduced, and an oxygen introduction amount is measured by an impedance monitor in order to form SiO ₂ from Si. Controlled.

  Also, an absorption multilayer ND filter was manufactured in the same manner as described above except that the plasma treatment voltage of the PET film was changed. That is, when plasma-treating the A side and the B side of the PET film, the plasma treatment voltage is set to 1.8 kV, 2.1 kV, 2.3 kV, 2.5 kV, and 2.8 kV, respectively. After this, an absorption type multilayer film ND filter was manufactured by forming an absorption type multilayer film.

  About the obtained absorption type multilayer ND filter, the thermal contraction rate of the PET film in which the plasma treatment was performed on both sides with each plasma treatment voltage was measured, and the result is shown in Table 2 below. In addition, the measurement of the thermal contraction rate was obtained by measuring the dimension of the portion marked in advance in the longitudinal direction (length direction) at 1000 mm intervals on the non-deposited portion of the PET film after the plasma treatment.

  Each of the obtained absorption multilayer ND filters was cut into 50 mm squares and left in an environmental tester at a temperature of 80 ° C. and a humidity of 90% for 24 hours. Then, each absorption type ND filter was observed with a 100 × Nomarski differential interference microscope, and the state of cracking of the absorption type multilayer film was examined. The obtained observation results are shown in Table 2 below.

  From the above results, it can be seen that cracking of the absorption multilayer film in a high temperature and high humidity environment can be prevented by thermally shrinking the PET film by 0.2% or more by plasma treatment before film formation. In addition, when the plasma treatment voltage is 1.8 kV or higher, the color of the thermolabel that changes color when it reaches 85 ° C attached to the non-deposited portion of the PET film changes. It can be determined that the temperature has approached (105 ° C.).

  Aside from the environmental test, a test was conducted for 24 hours in an oven at 80 ° C. where humidity control was not performed. However, the absorption multilayer ND filter subjected to any of the above plasma treatments also has a crack in the absorption multilayer film. No cracking occurred.

  Further, in the absorption type multilayer ND filter that has been subjected to the plasma processing at a plasma processing voltage of 1.6 to 2.5 kV, the adhesion strength of the absorption type multilayer film was sufficient, but the absorption at a plasma processing voltage of 2.8 kV. In the type multilayer ND filter, a tendency that the adhesion strength slightly decreases within a practically acceptable range was observed. This is presumably because the adhesion strength of the absorption multilayer film was lowered due to the deterioration of the resin film surface.

  In addition, although the said Example demonstrated only the case where a plasma process was performed to PET film, the result similar to the above was obtained also in the ion beam process.

It is a graph which shows the spectral transmission characteristic of an absorption type multilayer ND filter with an average transmittance of 25%.

Claims (2)

A manufacturing method of an absorption type multi-layer film ND filter provided with absorption type multi-layer film for attenuating the transmitted light in the visible light range to the resin film produced by stretching horizontally and vertically biaxial directions, a plasma treatment to the resin film And the resin film is thermally shrunk by 0.2% or more in the longitudinal direction , and then an oxide dielectric film layer and a metal absorption film layer are alternately laminated on at least one surface of the resin film to form an absorptive multilayer film The manufacturing method of the absorption type multilayer ND filter characterized by forming.
  The oxide dielectric film layer and the metal absorption film layer are formed by any one of a vacuum vapor deposition method, an ion beam sputtering method, a magnetron sputtering method, and an ion plating method, respectively. Manufacturing method of absorption type multilayer ND filter.

Images