JP2008051985A - Near infrared ray absorbing filter - Google Patents

Near infrared ray absorbing filter Download PDF

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Publication number
JP2008051985A
JP2008051985A JP2006227251A JP2006227251A JP2008051985A JP 2008051985 A JP2008051985 A JP 2008051985A JP 2006227251 A JP2006227251 A JP 2006227251A JP 2006227251 A JP2006227251 A JP 2006227251A JP 2008051985 A JP2008051985 A JP 2008051985A
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near
film layer
infrared
transmittance
organic film
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Pending
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JP2006227251A
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Japanese (ja)
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Kazutoshi Mukai
和俊 迎
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Nidec Copal Corp
日本電産コパル株式会社
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Abstract

A near-infrared absorption filter that can be thinned and has high transmittance in the visible range is provided.
A near-infrared absorption filter includes a transparent substrate, an organic film layer that absorbs near-infrared rays, and inorganic film layers that block near-infrared rays. The organic film layer 2 has a transmittance in the visible region of 90% or more and a transmittance in the near infrared region of 20% to 60%. The organic film layer 2 is made of a polymer composition containing at least one near infrared absorbing dye. The inorganic film layers 3 and 4 are formed of multilayer films in which low refractive index dielectric films and high refractive index dielectric films are alternately stacked. By combining the organic film layer 2 containing a near-infrared absorbing dye and the inorganic film layers 3 and 4 made of an optical multilayer film, the thickness is reduced and the transmittance in the visible region is increased.
[Selection] Figure 1

Description

  The present invention relates to a near-infrared absorption filter that has a high light transmittance in the visible range and blocks light in the near-infrared range.

An imaging device (digital camera or video camera) including a color CCD image sensor has been developed to perform moving image shooting and still image shooting. The color CCD image sensor used in these imaging devices has a sensitivity that extends from the visible region to the near infrared region. For this reason, the image photographed by the color CCD image sensor is different from a real image seen by a human having sensitivity only in the visible range. Therefore, a conventional imaging device incorporates a near-infrared absorption filter, and by capturing near-infrared rays, the same imaging as an image seen by human eyes can be obtained. By incorporating a near-infrared absorption filter in this way, it is possible to prevent visualization different from the image seen by humans. The near-infrared absorption filters used for such applications are disclosed in the following Patent Documents 1 to 3.
JP-A-11-209144 JP 2000-007870 A JP 2002-303720 A

  Patent Document 1 discloses a near infrared absorption filter glass and a near infrared absorption filter using the same. This near-infrared absorption filter glass contains metal ions and utilizes the absorption action in the near-infrared region. Patent Document 2 discloses a resin composition for absorbing near infrared rays. In this resin composition, a substituted or unsubstituted amino group and a metal ion component containing copper ions are contained in an acrylic resin. This resin composition can also make a near-infrared absorption filter by utilizing the absorption action of metal ions for near-infrared rays. Patent document 3 is disclosing the near-infrared absorption filter. This filter is prepared by applying and drying a coating solution containing a composition in which a near infrared absorbing dye is dispersed in a binder resin on a substrate. For example, a near-infrared absorbing filter is prepared by dispersing a near-infrared absorbing pigment in a binder resin such as polyester and laminating the polyester on a polyester film substrate.

  Patent Document 1 discloses a glass infrared absorption filter, and Patent Document 2 discloses a resin infrared absorption filter. Both utilize the absorption effect of metal ions on near infrared rays. However, the absorption effect of metal ions on near infrared rays is not so strong, and in order to reduce the transmittance of near infrared rays to a practical level, some thickness is required. It is the thinnest filter at present and has a thickness t = 0.35 mm. Furthermore, if a near-infrared cut coat or an antireflection coat is added to this filter, the actual thickness will be further increased. Such a thick infrared absorption filter is an obstacle to thinning an imaging apparatus using a color CCD image sensor. In particular, when the imaging device is incorporated in a mobile phone or the like, the thickness of the infrared absorption filter hinders the reduction in thickness even though the reduction in thickness is essential. Further, a glass or resin filter may cause cracking or chipping of the resin or glass in the manufacturing process or the actual use stage, resulting in problems and being unable to be processed into a free shape.

  The near-infrared absorbing filter described in Patent Document 3 uses a near-infrared absorbing dye. However, since the near-infrared absorbing dye has some absorption not only in the near-infrared region but also in the visible region, increasing the absorption factor in the near-infrared region to a practical level increases the absorption factor in the visible region, and the transmittance is 80. It will be less than%. When the transmittance of the near-infrared absorbing filter in the visible region is less than 80%, there is a problem that the imaging performance of the imaging device including the color CCD image sensor is deteriorated.

  In view of the above-described problems of the conventional technology, an object of the present invention is to provide a near-infrared absorption filter that can be thinned and has high transmittance in the visible region. In order to achieve this purpose, the following measures were taken. That is, the present invention relates to a near-infrared absorption filter having a transparent substrate, an organic film layer that absorbs near-infrared rays, and an inorganic film layer that blocks near-infrared rays formed on one or both sides of the transparent substrate. The transmittance in the visible region is 90% or more, and the transmittance in the near infrared region is 20% to 60%.

  Preferably, the organic film layer is made of a polymer composition containing at least one near infrared absorbing dye. In this case, the polymer composition is preferably a plastic resin selected from a polyester resin, a polyacrylic resin, or a polyimide resin. The inorganic film layer is formed of a multilayer film in which a low refractive index dielectric film and a high refractive index dielectric film are alternately stacked.

  In the near-infrared absorbing filter according to the present invention, an organic film layer that absorbs near-infrared rays and an inorganic film layer that blocks near-infrared rays are formed on one or both sides of a transparent substrate. The organic film layer has a transmittance in the visible region set to 90% or more, while a transmittance in the near infrared region is set to 20% to 60%. Such an organic film layer is made of a polymer composition containing at least one kind of near-infrared absorbing dye. On the other hand, the inorganic film layer is composed of an optical multilayer film in which low-refractive index dielectric films and high-refractive index dielectric films are alternately stacked, and selectively blocks near-infrared rays using optical interference caused by multiple reflections. , Selectively transmits visible light. Thus, the present invention achieves a reduction in thickness and increases the transmittance in the visible region by combining an organic film layer containing a near-infrared absorbing dye and an inorganic film layer composed of an optical multilayer film. . The near-infrared absorption filter of the present invention can be formed on a polyester film substrate having a thickness t = 0.1 mm, for example, and can realize a thin imaging device including a color CCD image sensor. Moreover, there is no generation | occurrence | production of the crack of a filter, a chip, etc., and a shape can be selected freely. Furthermore, the near-infrared absorption filter of the present invention can reduce the near-infrared transmittance to 5% or less of the practical level. Even in this case, the transmittance in the visible range can be maintained at 90% or more, and a reduction in thickness can be realized without deteriorating the imaging performance of the imaging device including the color CCD image sensor.

  In addition, it is possible to obtain desired optical characteristics (high transmittance in the visible region and high absorption in the near infrared region) with only the inorganic film layer without combining the organic film layer and the inorganic film layer as in the present invention. It is. However, when the inorganic film layer alone is used, the number of laminated optical multilayer films increases, and the inorganic film layer becomes considerably thick. When the film thickness is increased, peeling or cracking (cracking) of the film occurs on a substrate of about 0.1 mm. This is due to the difference in the film stress of the inorganic film layer and the difference in thermal expansion coefficient between the inorganic film layer and the base film. In contrast, in the present invention, by using the organic film layer in combination, the transmittance in the near-infrared element region can be suppressed to some extent, and the optical characteristics required for the inorganic film layer (low transmission in the near-infrared element region) Therefore, the number of layers of the optical multilayer film constituting the inorganic film layer can be reduced, and as a result, the film thickness can be reduced.

  On the other hand, when an infrared absorption filter is formed with an organic film layer alone, not only the near-infrared element region but also the visible region transmittance is lowered. That is, the near-infrared absorbing dye contained in the organic film layer absorbs not only near-infrared rays but also visible light to some extent. In the present invention, by using an inorganic film layer in combination with the organic film layer, the organic film layer itself may have a near-infrared transmittance of about 20% to 60%, and the transmittance in the visible range can be increased accordingly. 90% or more can be secured. As described above, for example, even on a PET film substrate having a thickness of about 0.1 mm, there is no film peeling or cracking, low transmittance in the near infrared blocking region, and high near infrared absorption in the visible region. A film can be formed.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing a layer configuration of a near-infrared absorption filter according to the present invention. As illustrated, the near-infrared absorption filter according to the present invention includes a transparent substrate 1 and an organic film layer 2 and inorganic film layers 3 and 4 formed on one or both sides thereof. In the illustrated embodiment, the organic film layer 2 is formed on one surface of the transparent substrate 1, and the inorganic film layers 3 and 4 are formed on both surfaces of the transparent substrate 1. However, the present invention is not limited to this. For example, the organic film layer 2 may be formed on the upper surface of the transparent substrate 1 while the inorganic film layer may be formed on the lower surface of the transparent substrate 1. Alternatively, the organic film layer and the inorganic film layer may be formed on the upper surface of the transparent substrate 1, and the organic film layer and the inorganic film layer may be similarly formed on the lower surface of the transparent substrate. Regarding the order of film formation, the embodiment of FIG. 1 forms the organic film layer first and then forms the inorganic film layer, but it may be reversed.

  The organic film layer 2 has absorption in the near infrared. The inorganic film layers 3 and 4 each block near infrared rays. As a characteristic matter, the organic film layer 2 has a transmittance in the visible region of 90% or more and a transmittance in the near infrared region of 20% to 60%. In particular, the transmittance in the visible region is ensured to be as high as 90% or more so that the imaging performance is not impaired when a near-infrared absorption filter is applied to an imaging device or the like. The organic film layer 2 is made of a polymer composition containing at least one kind of near infrared absorbing dye. For this polymer composition, for example, a plastic resin such as a polyester resin, a polyacrylic resin, or a polyimide resin can be used.

FIG. 2 is a schematic cross-sectional view showing a specific configuration of the inorganic film layers 3 and 4 included in the near-infrared absorption filter shown in FIG. As shown in the drawing, each of the inorganic film layers 3 and 4 is formed of a multilayer film in which a low refractive index dielectric film and a high refractive index dielectric film are alternately stacked. In the illustrated embodiment, a SiO 2 film is used as the dielectric film having a low refractive index, and the refractive index n = 1.45. On the other hand, the high refractive index dielectric film is made of a TiO 2 film and has a refractive index n = 2.30. However, the present invention is not limited to this, and an inorganic film having various refractive indexes can be selectively used as a low refractive index dielectric film and a high refractive index dielectric film to form the illustrated multilayer film. The optical multilayer film constituting the inorganic film layers 3 and 4 can selectively transmit visible light using multiple interference by appropriately setting the number of film layers and the thickness of each dielectric film. It is possible to block infrared light.

  An embodiment of the method for manufacturing the near-infrared absorbing filter shown in FIG. 1 will be described in detail. First, the transparent substrate 1 is prepared. This transparent substrate consists of a polyester film base material, for example, and the thickness is t = 0.1 mm. However, the present invention is not limited to this, and the transparent substrate 1 can use other transparent resin film materials, and the thickness t is also set appropriately.

  Subsequently, an organic film layer 2 is formed on one side of the transparent substrate 1. In this example, an appropriate coating agent was prepared and coated on one side of the transparent substrate 1. The coating agent (coating solution) is prepared by mixing an acrylic resin binder and a near-infrared absorbing pigment in an appropriate ratio and uniformly dissolving in a soluble solvent. Specifically, 10 g of acrylic binder (Halus Hybrid IR-G205 manufactured by Nippon Shokubai Co., Ltd.), 74.2 mg of near infrared absorbing dye SDA6104 (HW SANDS CORP.) Having absorption at wavelengths of 826 nm to 850 nm, wavelength A near-infrared absorbing dye SDA6825 (HW SANDS CORP.) 23.2 mg having absorption at 726 nm to 750 nm was dissolved in 40 ml of cyclohexane to prepare a desired coating solution.

  This coating solution was coated to a thickness of 1.0 μm to form an organic film layer 2 on the transparent substrate 1.

  As the coating means, a coating machine, a thin film coating apparatus such as a spin coater, or a technique such as spraying or dipping can be used. The spin coater rotates the substrate 1 to drop the coating solution at the center, and performs coating to a uniform film thickness by centrifugal force. The coating machine applies a uniform film thickness with the head while dropping the coating solution onto the substrate 1. Alternatively, there is a method of coating the lower side of the substrate while pulling up the coating solution by utilizing capillary action. In dipping, the substrate is immersed in a coating solution and then pulled up to perform a uniform film thickness. In all these coating methods, the organic film layer 2 is basically formed by evaporating the solvent and solidifying the resin binder.

  FIG. 3A is a graph showing the spectral optical characteristics of the organic film layer 2 produced as described above. In this graph, the horizontal axis represents wavelength (nm) and the vertical axis represents transmittance (%). As is apparent from the graph, the organic film layer 2 has an average transmittance of 90% or more in the visible region (wavelength region of 400 to 700 nm). On the other hand, the transmittance is adjusted to about 40% in the wavelength region of the near infrared region (700 to 900 nm). In order to obtain such spectral characteristics, the film thickness of the organic film layer 2 and the composition of the coating solution are determined. The composition of the coating solution is mainly determined by the amount of the near infrared absorbing dye added to the resin binder. The organic film layer 2 is characterized by having a high transmittance of 90% or more in the visible region. Accordingly, the transmittance in the near infrared region may be within a range of ± 20% centering on 40%. FIG. 3B is a graph showing optical characteristic curves when the transmittance of the organic film layer 2 is adjusted to the upper limit of 60% and the lower limit of 20% in the near infrared region.

Next, the formation of the inorganic film layer 3 will be described in detail. In the present embodiment, the inorganic film layer 3 is formed by vacuum deposition on the organic film layer 2 previously formed. The present invention is not limited to this, and PVD techniques such as an ion plating method, an ion assist method, and a sputtering method can be used instead of the vacuum deposition method. First, a SiO 2 film having a refractive index n = 1.45 is formed to a predetermined thickness by vacuum deposition. Subsequently, a TiO 2 film having a refractive index n = 2.30 is formed to a predetermined thickness by the same vacuum deposition method. Such a low refractive index optical film and a high refractive index optical film are alternately laminated up to 11 layers to form a desired inorganic film layer 3. With 11 layers, the total thickness is 1088 nm.

The inorganic film layer 4 is also formed on the opposite surface of the transparent substrate 1 in the same manner as the inorganic film layer 3. This inorganic film layer 4 is formed by alternately stacking 13 layers of SiO 2 and TiO 2 with a predetermined thickness, and the total thickness of 13 layers is 1591 nm.

  FIG. 4 is a graph showing the spectral characteristics of the inorganic film layer 3 and the inorganic film layer 4 thus prepared. Similar to the graph of FIG. 3, the horizontal axis represents wavelength (nm) and the vertical axis represents transmittance (%). The inorganic film layer 3 is an optical multilayer film in which a low-refractive index dielectric film and a high-refractive index dielectric film are stacked. . The inorganic film layer 3 has a transmittance of about 90% in the visible region, and a transmittance of about 10% in the wavelength region of 700 to 850 nm. On the other hand, the inorganic film layer 4 shows a relatively high transmittance in the wavelength region of 800 nm or less, while the transmittance is 10% or less in the wavelength region of 850 nm or more. These inorganic film layers 3 and 4 have a transmittance of about 10% in the near infrared region. In order to reduce the transmittance to about 5%, the number of stacked layers must be increased. However, when the number of laminated dielectric films constituting the inorganic film layer is increased, problems such as cracks occur. In the present invention, the number of laminated dielectric films constituting the inorganic film layer is about 10, and the transmittance is correspondingly about 10%.

  FIG. 5 is a graph showing the spectral characteristics of the near-infrared absorption filter finally obtained. In other words, the spectral characteristics of a laminate in which the organic film layer 2 and the inorganic film layers 3 and 4 are stacked. As is apparent from the graph, the near-infrared absorption filter of the present invention has a high transmittance exceeding 90% in the visible region, while the transmittance in the near-infrared region is 5% or less and the near-infrared filter is sufficiently practical. It is cut. Such practically excellent spectral characteristics are realized by combining an organic film layer and an inorganic film layer according to the present invention. The organic film layer is prepared so as to have a high transmittance in the visible range, whereby high transparency is obtained in the visible range. On the other hand, in the near infrared region, the slightly higher transmittance of 10% exhibited by the inorganic film layer is reduced to a practical 5% by overlapping the organic film layer thereon.

It is typical sectional drawing which shows the basic composition of the near-infrared absorption filter concerning this invention. It is sectional drawing which similarly shows embodiment of the near-infrared absorption filter concerning this invention. It is a graph which shows the spectral characteristic of an organic film layer. It is a graph which similarly shows the spectral characteristic of an organic film layer. It is a graph which shows the spectral characteristic of an inorganic film layer. It is a graph which shows the spectral characteristic of the near-infrared absorption filter concerning this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent substrate, 2 ... Organic film layer, 3 ... Inorganic film layer, 4 ... Inorganic film layer

Claims (4)

  1. In a near-infrared absorbing filter having a transparent substrate, an organic film layer that absorbs near-infrared rays, and an inorganic film layer that blocks near-infrared rays, formed on one or both sides thereof,
    The near-infrared absorbing filter, wherein the organic film layer has a transmittance in the visible region of 90% or more and a transmittance in the near-infrared region of 20% to 60%.
  2.   The near-infrared absorption filter according to claim 1, wherein the organic film layer is made of a polymer composition containing at least one kind of near-infrared absorbing dye.
  3.   The near-infrared absorbing filter according to claim 2, wherein the polymer composition is a plastic resin selected from a polyester resin, a polyacrylic resin, or a polyimide resin.
  4. The near-infrared absorption filter according to claim 1, wherein the inorganic film layer is formed of a multilayer film in which a low refractive index dielectric film and a high refractive index dielectric film are alternately stacked.
JP2006227251A 2006-08-24 2006-08-24 Near infrared ray absorbing filter Pending JP2008051985A (en)

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JP2010061119A (en) * 2008-08-04 2010-03-18 Fujifilm Corp Infrared region selective reflection coat and infrared region selective reflection film
CN101750654A (en) * 2008-11-28 2010-06-23 Jsr株式会社 Near infra red cut filter, and device comprising the same
JP2012137650A (en) * 2010-12-27 2012-07-19 Canon Electronics Inc Optical filter
JP2012137651A (en) * 2010-12-27 2012-07-19 Canon Electronics Inc Optical filter
JP2012137647A (en) * 2010-12-27 2012-07-19 Canon Electronics Inc Optical filter
JP2012137645A (en) * 2010-12-27 2012-07-19 Canon Electronics Inc Optical filter
JP2012137648A (en) * 2010-12-27 2012-07-19 Canon Electronics Inc Imaging optical unit
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JP2012185468A (en) * 2010-12-17 2012-09-27 Nippon Shokubai Co Ltd Light selective transmission filter, resin sheet and solid state image sensor
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JP2013210585A (en) * 2012-03-30 2013-10-10 Nippon Shokubai Co Ltd Substrate for light selective transmission filter, resin sheet, light selective transmission filter, and solid state imaging element
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JPWO2013161492A1 (en) * 2012-04-25 2015-12-24 株式会社Adeka Wavelength cut filter
US9445017B2 (en) 2012-08-23 2016-09-13 Asahi Glass Company, Limited Near-infrared cut filter and solid-state imaging device
US10082611B2 (en) 2012-12-06 2018-09-25 AGC Inc. Near-infrared cut filter
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US10228500B2 (en) 2015-04-23 2019-03-12 AGC Inc. Optical filter and imaging device
US10310150B2 (en) 2015-01-14 2019-06-04 AGC Inc. Near-infrared cut filter and solid-state imaging device
US10324240B2 (en) 2014-09-19 2019-06-18 AGC Inc. Optical filter
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JP2010061119A (en) * 2008-08-04 2010-03-18 Fujifilm Corp Infrared region selective reflection coat and infrared region selective reflection film
JP2014044431A (en) * 2008-11-28 2014-03-13 Jsr Corp Near-infrared cut filter, and device provided with the same
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JP2013228759A (en) * 2010-12-17 2013-11-07 Nippon Shokubai Co Ltd Light selective transmission filter, resin sheet and solid state image sensor
JP2012185468A (en) * 2010-12-17 2012-09-27 Nippon Shokubai Co Ltd Light selective transmission filter, resin sheet and solid state image sensor
JP2012137646A (en) * 2010-12-27 2012-07-19 Canon Electronics Inc Optical filter
JP2012137648A (en) * 2010-12-27 2012-07-19 Canon Electronics Inc Imaging optical unit
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JP2012137647A (en) * 2010-12-27 2012-07-19 Canon Electronics Inc Optical filter
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US9445017B2 (en) 2012-08-23 2016-09-13 Asahi Glass Company, Limited Near-infrared cut filter and solid-state imaging device
US10082611B2 (en) 2012-12-06 2018-09-25 AGC Inc. Near-infrared cut filter
US10495796B2 (en) 2012-12-06 2019-12-03 AGC Inc. Near-infrared cut filter
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CN103923438A (en) * 2013-01-11 2014-07-16 株式会社日本触媒 Resin Composition For Laminating And Use Thereof
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US10324240B2 (en) 2014-09-19 2019-06-18 AGC Inc. Optical filter
US10310150B2 (en) 2015-01-14 2019-06-04 AGC Inc. Near-infrared cut filter and solid-state imaging device
US10365417B2 (en) 2015-01-14 2019-07-30 AGC Inc. Near-infrared cut filter and imaging device
KR101913482B1 (en) 2015-01-14 2018-10-30 에이지씨 가부시키가이샤 Near-infrared cut filter and imaging device
US10351718B2 (en) 2015-02-18 2019-07-16 AGC Inc. Optical filter and imaging device
US10228500B2 (en) 2015-04-23 2019-03-12 AGC Inc. Optical filter and imaging device

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