JP2020064201A - Optical filter and use thereof - Google Patents

Abstract

To provide an optical filter that can achieve high visible light transmittance, low warpage, excellent adhesion of a dielectric multilayer film, and noiseless to a sensor due to reflection on the dielectric multilayer film while effectively cutting reflected light from a sensing light source.SOLUTION: An optical filter has a substrate including a light absorption layer and transmits visible light. In a wavelength range of 800 to 1000 nm, a maximum value of an OD value (1) when measured from a vertical direction of the substrate is equal to or larger than 3.0.SELECTED DRAWING: None

Description

  The present invention relates to an optical filter and its use. More specifically, the present invention relates to an optical filter including a light absorbing compound having an absorption maximum in a specific wavelength range, and a solid-state imaging device, a camera module, an ambient light sensor module and an electronic device including the optical filter.

  In recent years, information terminal devices such as smartphones and tablet terminals are rapidly becoming more sophisticated. In addition to the existing camera (imaging) functions, ambient light sensing functions, biometric authentication functions such as iris authentication and face authentication, AR / VR functions, spatial recognition functions such as air touch, etc. are newly incorporated in the information terminal device. It is flowing.

  Therefore, in addition to the conventional camera module, an ambient light sensor module, a face authentication module having a sensing function, an AR / VR module, and the like have been densely mounted in a narrow area of the terminal.

  On the other hand, light emitted from a light emitting element for sensing such as an LED of a specific wavelength used as a light source for these sensing (dot projector, floodlight illuminator, etc.) or a laser light source, is reflected light that hits a sensing target. It has been pointed out that the reflected light in the device and the device enters the camera module and the ambient light sensor module, which causes the deterioration of the image quality of the camera and the malfunction of the screen color adjustment by the ambient light sensor.

  Furthermore, in order to increase the distance that can be sensed, the reflected light is increased due to the improvement of the output of the light source, so that the influence such as the deterioration of the image quality of the camera and the poor adjustment of the screen color tone by the ambient light sensor is expected to increase.

  In order to reduce the influence of the sensing light source, it is very effective to provide an optical filter for the ambient light sensor module and the camera module with a function of cutting the reflected light from the sensing light source. As a light source for sensing, a light source having a light emitting property in the near infrared wavelength region is generally used, but as an optical filter for cutting light in the near infrared region, for example, an absorbent having a wide absorption property in the near infrared region. An optical filter using is proposed (for example, see Patent Documents 1 and 2).

  However, in order to eliminate the influence of the reflected light from the sensing light source, it is necessary to make the optical filter contain a very high concentration of the absorbent, which causes a problem of reducing the visible light transmittance. As a method of cutting the reflected light from the sensing light source, a method of cutting by increasing the number of layers of the dielectric multilayer film can be considered, but the warp of the optical filter due to the increase of the number of layers of the dielectric multilayer film. However, there are problems such as a decrease in adhesion between the dielectric multilayer film and the substrate and an increase in noise to the sensor due to reflection in the dielectric multilayer film.

International Publication No. 2018/043564 JP, 2008-10296, A

  INDUSTRIAL APPLICABILITY The present invention effectively cuts reflected light from a sensing light source, and has high visible light transmittance, low warpage, good adhesion of a dielectric multilayer film, and a sensor due to reflection at the dielectric multilayer film. It is an object to provide an optical filter that can achieve noiselessness. Furthermore, it aims at providing the optical filter which can respond | correspond to high output of the light emitting element for sensing.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have an absorption maximum wavelength close to the emission wavelength of the sensing light source, and by applying an absorbent having sharp absorption characteristics, reflected light from the sensing light source Can be effectively cut, while reducing the adverse effect of the reflected light from the sensing light source to the ambient light sensor element or the solid-state image sensor to a level where there is no problem, high visible light transmittance of the optical filter, low warp, and The inventors have found that it is possible to achieve good adhesion of the dielectric multilayer film, and have reached the present invention. Examples of aspects of the invention are shown below.

[1] An optical filter which has a base material including a light absorbing layer and transmits visible light,
An optical filter having a maximum OD value (1) of 3.0 or more when measured from a direction perpendicular to the substrate in a wavelength range of 800 to 1000 nm.

  [2] The optics according to item [1], wherein the average value of the OD value (1) is 2.0 or less in a region of wavelength ± 100 nm at which the OD value (1) shows a maximum value. filter.

  [3] The wavelength at which the OD value (1) shows the maximum value is in one of the wavelengths 820 to 880 nm or the wavelengths 910 to 970 nm, according to item [1] or [2]. Optical filter.

  [4] The optical filter according to any one of items [1] to [3], wherein the light absorption layer contains a compound (A) having an absorption maximum in a wavelength range of 800 to 1000 nm.

  [5] The compound (A) is at least one compound selected from the group consisting of squarylium compounds, cyanine compounds, pyrrolopyrrole compounds, perylene compounds, croconium compounds, and metal dithiolate compounds. The optical filter according to item [4].

  [6] The item includes any one of items [1] to [5], wherein the base material includes a glass substrate, and the light absorption layer is provided on at least one surface of the glass substrate. Optical filter.

  [7] The base material includes a transparent resin substrate, and the light absorbing layer is provided on at least one surface of the transparent resin substrate. [1] to [5] The optical filter described in.

[8] The optical filter according to any one of items [1] to [7], which has a dielectric multilayer film on at least one surface of the base material.
[9] The optics as described in the item [8], wherein the maximum OD value (2) when measured in the vertical direction of the optical filter is 5.0 or more in the wavelength range of 800 to 1000 nm. filter.

  [10] The optical element according to item [8] or [9], which has an average transmittance of 60% or more when measured in the vertical direction of the optical filter in the wavelength range of 430 to 580 nm. filter.

[11] A solid-state imaging device comprising the optical filter according to any one of items [1] to [10].
[12] A camera module comprising the optical filter according to any one of items [1] to [10].

[13] An ambient light sensor module comprising the optical filter according to any one of items [1] to [10].
[14] An electronic device comprising the optical filter according to any one of items [1] to [10].

  [15] At least one type of module (A) selected from the group consisting of the camera module according to item [12] and the ambient light sensor module according to claim 13, and a module (B) including a light emitting element for sensing. Are arranged on the same plane and within 4 cm of each other.

  According to the present invention, while effectively cutting the reflected light from the sensing light source, high visible light transmittance of the optical filter, low warpage, good adhesion of the dielectric multilayer film, and reflection on the dielectric multilayer film. It is possible to provide an optical filter capable of achieving noiselessness to the sensor due to. Further, such an optical filter of the present invention can be suitably used for an electronic device including a light emitting element for sensing and a photoelectric conversion element such as an ambient light sensor module or a camera module in the same device.

It is a schematic diagram which shows the structural example of the optical filter of this invention. It is a schematic diagram which shows the structural example of the base material in the optical filter of this invention. It is a cross-sectional schematic diagram which shows an example of the camera module of this invention. It is a schematic diagram which shows the structural example of the ambient light sensor of this invention. It is a schematic diagram which shows the structural example of the ambient light sensor of this invention. It is a schematic diagram which shows an example of the electronic device of this invention. 3 is a graph showing the spectral transmittance of the substrate obtained in Example 1 measured in the vertical direction. 5 is a graph showing the spectral transmittance of the optical filter obtained in Example 1 measured in the vertical direction. 5 is a graph showing the spectral transmittance of the substrate obtained in Example 2 measured from the vertical direction. 5 is a graph showing the spectral transmittance of the optical filter obtained in Example 2 measured in the vertical direction. 7 is a graph showing the spectral transmittance measured in the vertical direction of the substrate obtained in Example 3. 7 is a graph showing the spectral transmittance of the optical filter obtained in Example 3 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the substrate obtained in Example 4 measured in the vertical direction. 7 is a graph showing the spectral transmittance of the optical filter obtained in Example 4 measured in the vertical direction. 7 is a graph showing the spectral transmittance of the substrate obtained in Example 5 measured from the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Example 5 measured in the vertical direction. 7 is a graph showing the spectral transmittance of the substrate obtained in Example 6 measured from the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Example 6 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the substrate obtained in Example 7 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Example 7 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the substrate obtained in Example 8 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Example 8 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the substrate obtained in Example 9 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Example 9 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the base material obtained in Example 10 measured in the vertical direction. 13 is a graph showing the spectral transmittance of the optical filter obtained in Example 10 measured in the vertical direction. 7 is a graph showing the spectral transmittance of the base material obtained in Comparative Example 1 measured in the vertical direction. 5 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 1 measured in the vertical direction. 7 is a graph showing the spectral transmittance of the base material obtained in Comparative Example 2 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 2 measured in the vertical direction. 7 is a graph showing the spectral transmittance of the base material obtained in Comparative Example 3 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 3 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the base material obtained in Comparative Example 4 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 4 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the base material obtained in Comparative Example 5 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 5 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the base material obtained in Comparative Example 6 measured in the vertical direction. 9 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 6 measured in the vertical direction.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings and the like as necessary. However, the present invention can be implemented in many different modes, and should not be construed as being limited to the description of the embodiments illustrated below. In order to make the description clearer, the drawings may schematically show the width, thickness, shape, etc. of each part as compared with the actual mode, but this is merely an example and limits the interpretation of the present invention. Not a thing. In the specification and the drawings, the same elements as those described above with reference to the already-existing drawings are designated by the same reference numerals or similar reference numerals (reference numerals having only A and B after the numeral). The detailed description may be omitted as appropriate.

  In the present specification, "upper" refers to a relative position with respect to the main surface of the supporting substrate (light receiving surface of the sensor), and the direction away from the main surface of the supporting substrate is "upper". In this drawing, the upper side toward the paper surface is “upper”. Further, "upper" includes a case where the object is in contact with the object (that is, "on") and a case where the object is located above the object (that is, "over"). On the contrary, “down” refers to a relative position with respect to the main surface of the support substrate, and “down” is the direction toward the main surface of the support substrate. In this drawing, the lower side toward the paper surface is "lower".

[Optical filter]
The optical filter according to the present invention has a base material including a light absorption layer, and is an optical filter that transmits visible light, and is measured from a direction perpendicular to the base material in a wavelength range of 800 to 1000 nm. The maximum OD value (1) is 3.0 or more.

  In the optical filter of the present invention, the maximum OD value (1) of the substrate is 3.0 or more. When the maximum value of the OD value (1) is less than 3.0, the reflected light from the sensing light source is not sufficiently cut, which deteriorates the camera image quality of the camera module and the screen color tone by the ambient light sensor of the ambient light sensor module. It may cause malfunction of adjustment. Moreover, the upper limit of the maximum value of the OD value (1) is not particularly limited, but in order to achieve a high OD value, for example, it may be necessary to include a large amount of a light absorbing compound described later. However, in such a case, there is a problem that the visible light transmittance is lowered, and therefore it is preferable to set the amount of the light absorbing compound used in consideration of the visible light transmittance. The upper limit of the maximum value of the OD value (1) is preferably 6 or less, and more preferably 5 or less.

  In the region of wavelength ± 100 nm where the OD value (1) shows the maximum value, the average value of the OD value (1) is preferably 2.0 or less, more preferably 0.1 to 1.8, It is preferably 0.2 to 1.5. If the average value of the OD value (1) is more than 2.0, the efficiency of cutting the reflected light from the sensing light source by the light absorbing compound is low, and thus it is necessary to use a high concentration of the light absorbing compound. May be. However, in such a case, the visible light transmittance of the optical filter is significantly deteriorated, so that the visible light incident light to the solid-state imaging device or the ambient light sensor is insufficient, which may cause deterioration of the sensor sensitivity.

The wavelength at which the OD value (1) exhibits the maximum value is preferably in the region of either wavelength 820 to 880 nm or wavelength 910 to 970 nm.
The light absorption layer preferably contains a light absorption compound, for example, the compound (A) having an absorption maximum in the wavelength region of 800 to 1000 nm.

  As the light absorbing compound other than the compound (A), for example, a compound (B) having a maximum absorption in a wavelength region of 600 nm or more and less than 800 nm, and a compound (C) having an absorption maximum in a wavelength region of more than 1000 nm and 1200 nm or less. Is mentioned.

  As a preferred embodiment of the light absorbing layer, a transparent resin substrate containing the compound (A), or a resin layer containing the compound (A), which is laminated on at least one surface of a glass substrate or a transparent resin substrate. And so on. Further, a light absorbing compound other than the compound (A) may be contained in the light absorbing layer, or may be contained in a resin layer different from the light absorbing layer. May be included.

As the glass substrate, CuO-containing fluorophosphate glass or CuO-containing phosphate glass (hereinafter collectively referred to as "CuO-containing glass") can be used. By using the CuO-containing glass, it has a high transmittance for visible light and a high shielding property for near infrared rays. It should be noted that the phosphate glass also includes silicophosphate glass in which a part of the glass skeleton is made of SiO ₂ . Examples of the CuO-containing glass include those having the following compositions.

_{(I) P 2 O 5 46~70} %, AlF 3 0.2~20%, LiF + NaF + KF 0~25%, MgF 2 + CaF + SrF 2 + BaF 2 + PbF 2 1~50%, however, F 0.5~32%, A glass containing 0.5 to 7 parts by mass of CuO based on 100% by mass of the basic glass containing 26 to 54% of O.

_{(Ii) P 2 O 5 25~60} %, Al 2 OF 3 1~13%, MgO 1~10%, CaO 1~16%, BaO 1~26%, SrO 0~16%, ZnO 0~16% _{, Li 2 O 0~13%, Na} 2 O 0~10%, K 2 O 0~11%, CuO 1~7%, ΣRO (R = Mg, Ca, Sr, Ba) 15~40%, ΣR ' ₂ O (R ′ = Li, Na, K) 3-18% (provided that up to 39% molar amount of O ²⁻ ion is replaced with F ⁻ ion).

(Iii) P ₂ O ₅ 5 to 45%, ArF _{3 1 to} 35%, RF (R is Li, Na, K) 0 to 40%, R′F ₂ (R ′ is Mg, Ca, Sr, Ba, Pb, Zn) 10 to 75%, R "F _m (R" is La, Y, Cd, Si, B, Zr, Ta, and m is a number corresponding to the valence of R ") 0 to 15% ( However, up to 70% of the total amount of fluoride can be replaced with oxide), and glass containing 0.2 to 15% CuO.

(Iv) In terms of cation%, P ⁵⁺ 11 to 43%, Al ³⁺ 1 to 29%, R cation (content of Mg, Ca, Ba, Pb, Zn ions) 14 to 50%, R ′ cation (Li , Na, K ion content) 0-43%, R "cation (La, Y, Cd, Si, B, Zr, Ta ion content) 0-8%, and Cu ²⁺ 0.5-13%. A glass containing and further containing F ^- 17 to 80% in anion%.

(V) In terms of cation%, P ⁵⁺ 23 to 41%, Al ³⁺ 4 to 16%, Li ⁺ 11 to 40%, Na ⁺ 3 to 13%, R ²⁺ (Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ content) 12 to 53%, and Cu ²⁺ 2.6 to 4.7%, and further, in terms of anion%, F ⁻ 25 to 48% and O ^{2 −} 52 to. Glass containing 75%.

(Vi) represented by _{mass%, P 2 O 5 70~85%,} Al 2 O 3 8~17%, B 2 O 3 1~10%, Li 2 O 0~3%, Na 2 O 0~5% , K ₂ O 0 to 5%, but Li ₂ O + Na ₂ O + K ₂ O 0.1 to 5% and SiO ₂ 0 to 3% to 100 parts by mass of the basic glass, CuO is 0.1 to 0.1% by external proportion. Glass containing 5 parts by mass.

  Examples of commercially available products include (i) NF50-E, NF50-EX (manufactured by Asahi Glass Co., Ltd.), (ii) BG-60, BG-61 (manufactured by SHOTT), and (v) CD5000 (manufactured by HOYA). Is mentioned.

The CuO-containing glass may further contain a metal oxide. As the metal oxide, for example, _{Fe 2 O 3, MoO 3,} WO 3, CeO 2, Sb 2 O 3, V 2 O 1 type of such ₅ or containing two or more, CuO-containing glass has an ultraviolet absorbing properties . The content of the metal name oxides, relative to the CuO-containing glass 100 parts by weight, the _{Fe 2 O 3, MoO 3,} WO 3 and at least one selected from the group consisting of CeO _2, Fe ₂ O ₃ 0.6-5 parts by mass, MoO ₃ 0.5-5 parts by mass, WO ₃ 1-6 parts by mass, CeO ₂ 2.5-6 parts by mass, or two kinds of Fe ₂ O ₃ and Sb ₂ O ₃ . the Fe ₂ O ₃ 0.6 to 5 parts by + Sb ₂ O ₃ 0.1 to 5 parts by weight, or, V ₂ O ₅ and 2 kinds of V ₂ O ₅ 0.01 to 0.5 parts by weight of CeO ₂ The amount of + CeO ₂ is preferably 1 to 6 parts by mass.

  The thickness of the fluorophosphate-based glass containing CuO or the phosphate-based glass containing CuO is preferably in the range of 0.03 to 5 mm, and in terms of strength, weight reduction, and height reduction, The range of 05 to 1 mm is more preferable.

  The CuO content in the CuO glass can be increased to improve the OD value in the wavelength range of 800 to 1000 nm, but the strength of the glass decreases as the CuO content increases, and the handleability when the glass substrate is thinned. Is not preferable because there is a problem that it significantly deteriorates. Therefore, it is preferable to improve the OD value by laminating a resin layer containing a light absorbing compound on glass.

  In the present invention, a glass substrate that does not absorb can be used as the glass substrate. The non-absorption glass substrate is not particularly limited as long as it is a substrate containing silicate as a main component, and a quartz glass substrate having a crystal structure or the like can be used. In addition, a borosilicate glass substrate, a soda glass substrate, a colored glass substrate, or the like can be used. In particular, a glass substrate such as a non-alkali glass substrate or a low α-ray glass substrate has little influence on the sensor element, preferable.

  Examples of the transparent resin used for the transparent resin substrate or the resin layer laminated on the transparent resin substrate or the glass substrate include a cyclic polyolefin resin, an aromatic polyether resin, a fluorene polycarbonate resin, and a polyester resin. , Fluorene polyester resin, polycarbonate resin, polyimide resin, polyamide resin, polyamideimide resin, polyester resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyvinyl Butyral resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester curable resin, urethane acrylate resin, silsesquioxane curable resin, acrylic curable resin and A resin mainly composed of silica formed by Rugeru method. The transparent resin may be used alone or in combination of two or more.

  Examples of commercial products of the cyclic (poly) olefin resin include JSR Co., Ltd. Arton, Nippon Zeon Co., Ltd. Zeonoa, Mitsui Chemicals, Inc. APEL, Polyplastics Co., Ltd., TOPAS, and the like. it can. Examples of commercially available products of the polyether sulfone resin include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available products of the polyimide resin include Neoprim manufactured by Mitsubishi Gas Chemical Co., Inc. Examples of the aromatic polyester resin film include Unitika's Unifiner. Examples of commercially available products of the polycarbonate resin include Pure Ace manufactured by Teijin Chemicals Ltd. and the like. Examples of commercially available products of the fluorene polycarbonate resin include Upizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Inc. Examples of commercially available products of the fluorene polyester resin include OKP4HT manufactured by Osaka Gas Chemicals Co., Ltd. Examples of commercially available products of the acrylic resin include ACRYBUA manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available products of the silsesquioxane-based UV curable resin include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

The transparent resin substrate may be used alone, or two or more types of transparent resin substrates may be bonded or laminated and used.
By using the above-mentioned substrate, while effectively cutting the reflected light from the sensing light source, the optical filter has high visible light transmittance, low warpage, adhesion of the dielectric multilayer film, and a sensor based on reflected light. It is possible to obtain a high-performance optical filter that can achieve both noiselessness. Such an optical filter of the present invention can be used for an ambient light sensor module or a camera module in an apparatus including a light emitting element for sensing.

  1A, 1B, and 1C show a configuration example of the optical filter of the present invention. The optical filter 100a shown in FIG. 1A has a dielectric multilayer film 104 on at least one surface of a base material 103. The dielectric multilayer film 104 has a property of reflecting near infrared rays. Further, FIG. 1B shows an optical filter 100b in which the first dielectric multilayer film 104a is provided on one surface of the base material 103 and the second dielectric multilayer film 104b is provided on the other surface. As described above, the dielectric multilayer film that reflects near-infrared rays may be provided on one side or both sides of the base material. When it is provided on one side, it is possible to obtain an optical filter which is excellent in manufacturing cost and easiness of production, and when it is provided on both sides, it has high strength and is less likely to warp or twist. When the optical filter is applied to a camera module or an ambient light sensor, it is preferable that the optical filter has less warp or twist, and therefore it is preferable to provide the dielectric multilayer film on both surfaces of the substrate.

  It is preferable that the dielectric multilayer film 104 transmits light having a wavelength corresponding to visible light and then has reflection characteristics over the entire wavelength range of 800 to 1150 nm with respect to light incident from the vertical direction, and more preferably. It is preferable to have reflective properties over the entire wavelength range of 800 to 1200 nm, particularly preferably 800 to 1250 nm. As a form having a dielectric multilayer film on both surfaces of the base material 103, a dielectric layer mainly having a reflection characteristic around a wavelength of 800 to 1000 nm when measured from an angle of 5 degrees with respect to the vertical direction of the optical filter (or the base material). 1 dielectric multilayer film 104a is provided on one surface of the base material 102, and 1000 nm to 1250 nm is measured on the other surface of the base material 103 from an angle of 5 degrees with respect to the vertical direction of the optical filter (or the base material). Another example is a mode in which the second dielectric multilayer film 104b having mainly reflection characteristics is included.

  As another form, the optical filter 100c shown in FIG. 1C has a dielectric multilayer film 104 having a reflection characteristic mainly in the wavelength range of 800 to 1250 nm as a base material when measured from an angle of 5 degrees with respect to the vertical direction. One example is a mode in which an antireflection film 106 having an antireflection property in the visible range is provided on one surface of the base material 103 on the other surface. By combining the dielectric multilayer film and the antireflection film with respect to the base material, near infrared rays can be reflected while increasing the light transmittance in the visible region.

  2A, FIG. 2B, FIG. 2C, FIG. 2D, and FIG. 2E show a configuration example of the base material 103. The base material 103 may be a single layer or a multilayer, and preferably has a layer containing at least one type of the compound (A), and the layer containing the compound (A) is a transparent resin layer. Is more preferable.

  In FIG. 2A, the base material is composed of a single layer, and the compound (A) is contained in the transparent resin substrate 105. The transparent resin substrate 105 may contain the compound (B) and / or the compound (C). In FIG. 2B, the base material is composed of two layers, and is composed of a laminated structure of a transparent glass substrate or a transparent resin substrate 101 containing no light absorbing compound and a resin layer 110 containing the compound (A). The resin layer 110 may include the compound (B) and / or the compound (C). In FIG. 2C, the base material is composed of three layers, and is composed of a transparent glass substrate or a transparent resin substrate 101 containing no light absorbing compound and resin layers 110 and 111 laminated on both surfaces thereof, and formed on both surfaces. At least one of the resin layers may contain the compound (A), and the resin layers on both sides may independently contain the compound (B) and / or the compound (C). In FIG. 2D, the base material is composed of two layers, and is composed of a laminated structure of an absorptive glass or transparent resin substrate 102 containing a light absorbing compound and a resin layer 110 containing the compound (A). The compound (B) and / or the compound (C) may be contained in the transparent resin substrate 102 and / or the resin layer 110. In FIG. 2E, the base material is formed of three layers, and is composed of an absorptive glass or transparent resin substrate 102 containing a light absorbing compound and resin layers 110 and 111 laminated on both surfaces thereof, and formed on both surfaces. At least one of the resin layers may contain the compound (A), and the resin layers on both sides may independently contain the compound (B) and / or the compound (C). Further, an overcoat layer made of a curable resin, a thermoplastic resin or the like may be laminated on one side or both sides of these base materials.

  When using a glass substrate, the glass substrate is preferably a colorless and transparent glass substrate that does not contain an absorber such as copper fluorophosphate in order to achieve both thinness and strength of the substrate, and particularly the thickness of the substrate is This tendency becomes remarkable when the thickness is 150 μm or less. Glass containing an absorber such as copper fluorophosphate has a problem that its strength is significantly reduced due to thinning. When a transparent resin substrate is used, both sides of the transparent resin substrate are made of a curable resin or a thermoplastic resin from the viewpoints of easy adjustment of optical properties, achieving the effect of eliminating scratches on the transparent resin substrate, and improving scratch resistance of the substrate. It is preferable that a resin layer such as an overcoat layer made of a resin is laminated.

  In order to obtain a substrate containing a light absorption layer satisfying the above characteristics, the absorption maximum has a maximum absorption around the target wavelength (a wavelength close to the emission wavelength of the light emitting element light source), and the absorption characteristic is the shape of the emission spectrum of the light emitting element. It is preferable to use a light absorbing compound close to When a light-absorbing compound having a wide range of absorption characteristics is used, it is necessary to add a large amount of the light-absorbing compound in order to obtain the characteristics aimed at by the present invention, and decrease in uniform solubility in the transparent resin layer or This is not preferable because it causes a decrease in visible light transmittance.

<Compound (A)>
The maximum absorption wavelength of the compound (A) is
(1) 820-880 nm, preferably 830-870 nm, more preferably 835-865 nm, or
(2) 910 to 970 nm, more preferably 920 to 960 nm, further preferably 925 to 955 nm
It is desirable to be in either range. Of these, the range (2) is preferable.

  As the light emitting element used as the sensing light source, those having emission center wavelengths of 850 nm and 940 nm are usually used, but it is preferable to use the light emitting element of 940 nm in view of visibility, linearity (small scattering) and the like. This is because it is the mainstream.

  The compound (A) is not particularly limited, but at least one compound selected from squarylium compounds, cyanine compounds, pyrrolopyrrole compounds, perylene compounds, croconium compounds, and metal dithiolate compounds is used. Is preferred.

Among the above compounds, it is more preferable to use a squarylium compound, a cyanine compound, or a pyrrolopyrrole compound. These compounds have a good balance between the absorption coefficient at the maximum absorption wavelength and the visible light transmittance, and an optical filter having both a high OD maximum value and a high visible light transmittance can be obtained.
The squarylium compound that can be used as the compound (A) is not particularly limited, but a compound (I) represented by the following formula (I) is preferable.

In the formula (I), the substitution units A and B each independently represent one of the substitution units represented by the following formulas (Ii), (I-ii) and (I-iii).

In the formulas (Ii), (I-ii) and (I-iii), the wavy line represents the bonding site with the central four-membered ring, and Xa is independently an oxygen atom, a sulfur atom, a selenium atom or tellurium. Represents an atom or —NR ¹² —, R ^{1 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a —NR ^g R ^h group. represents -SR ⁱ group, -SO ₂ R ⁱ groups, one of -OSO ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h are each independently a hydrogen atom, -C (O) represents any R ⁱ groups or the following L ^a ~L ^e, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) C 1-12 aliphatic hydrocarbon group (L ^b ) ^C 1-12 halogen-substituted alkyl group (L ^c ) ^C 3-14 alicyclic hydrocarbon group (L ^d ) carbon Number of carbon atoms which may have an aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms (L ^f ) and an alkoxy group having 1 to 12 carbon atoms (L ^g ) substituent L 1 to 12 acyl groups,
(L ^h ) C1-C12 alkoxycarbonyl group which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1-12 carbon atoms, a halogen-substituted alkyl group having 1-12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.

R ¹ is preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, phenyl. A group, a hydroxyl group, an amino group, a dimethylamino group and a nitro group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and a hydroxyl group.

R ^{2 to} R ¹¹ are preferably each independently a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group. Group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetyl group Amino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group Group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, and an ether group. Group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, a t-butanoylamino group, a cyclohexinoylamino group, a methylthio group, and an ethylthio group.

R ¹² is preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, more preferably hydrogen atom, methyl group, ethyl group, n-propyl group. , Isopropyl group, n-butyl group, tert-butyl group, and n-decyl group.

Examples of the Xa, preferably an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NR ¹² -, and particularly preferably an oxygen atom, a sulfur atom in the substituted units of formula (Ii), wherein (I- The substitution unit of ii) is —NR ¹² —, and the substitution unit of formula (I-iii) is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom.

  In the compound (I), the left and right units bonded to the central four-membered ring are the same as long as they are represented by the formula (Ii), the formula (I-ii) or the formula (I-iii). It may be present or different, but it is preferable that the units including the substituents in the unit are the same because it is easy to synthesize.

  Examples of preferable structures of the compound (I) include the following formulas (Ia), (Ib) and (Ic).

In formulas (Ia) to (Ic), Xa, R ¹ and R ^{2 to} R ⁷ represent the same atom or group as described above.

  Specific examples of the compound (I) include compound (I-1) and compound (I-2) represented by the following formula.

The cyanine compound that can be used as the compound (A) is not particularly limited, but a compound (II) represented by the following formula (II) is preferable.

In Formula (II), substituted units C and D represents either of the following formulas (II-i) ~ (II -v), Xb - represents a monovalent anion.

In the formulas (II-i) to (II-v), the wavy line represents a binding site with the central methine chain, and Xa is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR. ¹² - represents, R ¹ to R ⁷ each independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R ⁱ group, or an -OSO ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or represents one of the following L ^a ~L ^e, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) C 1-12 aliphatic hydrocarbon group (L ^b ) ^C 1-12 halogen-substituted alkyl group (L ^c ) ^C 3-14 alicyclic hydrocarbon group (L ^d ) carbon Number of carbon atoms which may have an aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms (L ^f ) and an alkoxy group having 1 to 12 carbon atoms (L ^g ) substituent L 1 to 12 acyl groups,
(L ^h ) C1-C12 alkoxycarbonyl group which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1-12 carbon atoms, a halogen-substituted alkyl group having 1-12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.

R ¹² is preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, more preferably hydrogen atom, methyl group, ethyl group, n-propyl group. , Isopropyl group, n-butyl group, tert-butyl group, and n-decyl group.

Z _{a to} Z _c and Y _{a to} Y _b are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -Q ¹ ,-. ^{N = N-Q 1, -S} -Q 2, -SSQ 2, -SO 2 Q 3, or Z together or Y together are selected from the two adjacent is formed adjacent to each other, a nitrogen atom, an oxygen 5- or 6-membered alicyclic hydrocarbon group which may contain at least one atom or sulfur atom,
An aromatic hydrocarbon group having 6 to 14 carbon atoms, which is formed by mutually bonding Zs or Ys selected from two adjacent groups, or
Zs or Ys selected from two adjacent groups are formed by being bonded to each other, and contain at least one nitrogen atom, oxygen atom or sulfur atom, and represent a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms,
These alicyclic hydrocarbon group, aromatic hydrocarbon group and heterocyclic aromatic hydrocarbon group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom,
Q ¹ represents any ^one of the above L ^{a to} L ^e ,
Q ² is, represents either a hydrogen atom or the L ^a ~L ^e,
Q ³ are representative of either a hydroxyl group or the L ^a ~L ^e.

  Specific examples of the compound (II) include compounds represented by the following formulas (II-1) to (II-3).

The pyrrolopyrrole compound that can be used as the compound (A) is not particularly limited, but a compound (III) represented by the following formula (III) is preferable.

In the formula (III), the substitution units E and F represent any of the following formulas (III-i) to (III-ii), and R ^{1 to} R ²⁰ are each independently a hydrogen atom, a halogen atom or a sulfonic acid. group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R ⁱ groups, of -OSO ₂ R ⁱ group or a group represented by L ^a ~L ^h It represents either, R ^g and R ^h are each independently a hydrogen atom, represents one of -C (O) R ⁱ groups or the following L ^a ~L ^e, either R ⁱ is below L ^a ~L ^e Or
(L ^a ) C 1-12 aliphatic hydrocarbon group (L ^b ) ^C 1-12 halogen-substituted alkyl group (L ^c ) ^C 3-14 alicyclic hydrocarbon group (L ^d ) carbon Number of carbon atoms which may have an aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms (L ^f ) and an alkoxy group having 1 to 12 carbon atoms (L ^g ) substituent L 1 to 12 acyl groups,
(L ^h ) C1-C12 alkoxycarbonyl group which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1-12 carbon atoms, a halogen-substituted alkyl group having 1-12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.

R ^{21 to} R ²⁸ are an aliphatic hydrocarbon group having 1 to 16 carbon atoms, a halogen-substituted alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Group hydrocarbon group, heterocyclic group having 3 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, acyl group having 1 to 16 carbon atoms which may have a substituent L, and substituent L A good C1-16 alkoxycarbonyl group is shown, and the substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, and an alicyclic group having 3 to 14 carbon atoms. It is at least one selected from the group consisting of a hydrocarbon group, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms.

Each Xc~Xf independently a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -SR ⁱ group, -SO ₂ R ⁱ groups, -OSO ₂ R ⁱ groups, halogen atoms, electrons such as a sulfonic acid group, a hydroxyl group Represents a suction group.

In the formulas (III-i) to (III-ii), the wavy line represents a binding site with the imine structure site, and Xa represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or —NR ¹² —. R ^{2 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a —NR ^g R ^h group, a —SR ⁱ group, SO ₂ R ⁱ group, or an -OSO ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ group or a group represented by L ^a To L ^e , R ⁱ represents any of the following L ^{a to} L ^e ,
(L ^a ) C 1-16 aliphatic hydrocarbon group (L ^b ) ^C 1-16 halogen-substituted alkyl group (L ^c ) ^C 3-18 alicyclic hydrocarbon group (L ^d ) carbon Number of carbon atoms which may have an aromatic hydrocarbon group (L ^e ) having 6 to 18 carbon atoms, a heterocyclic group having 3 to 18 carbon atoms (L ^f ) and an alkoxy group having 1 to 16 carbon atoms (L ^g ) substituent L 1 to 16 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 16 carbon atoms which may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, a halogen-substituted alkyl group having 1 to 16 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a heterocyclic group having 3 to 18 carbon atoms.

  Specific examples of the compound (III) include compounds represented by the following formulas (III-1) to (III-2).

The croconium compound that can be used as the compound (A) is not particularly limited, but a compound (IV) represented by the following formula (IV) is preferable.

In formula (IV), R ^{1 to} R ⁵ are each independently a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a —NR ^g R ^h group, or —SR. ⁱ group, -SO ₂ R ⁱ group, or an -OSO ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or represents one of the following L ^a ~L ^e, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) C 1-12 aliphatic hydrocarbon group (L ^b ) ^C 1-12 halogen-substituted alkyl group (L ^c ) ^C 3-14 alicyclic hydrocarbon group (L ^d ) carbon Number of carbon atoms which may have an aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms (L ^f ) and an alkoxy group having 1 to 12 carbon atoms (L ^g ) substituent L 1 to 12 acyl groups,
(L ^h ) C1-C12 alkoxycarbonyl group which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1-12 carbon atoms, a halogen-substituted alkyl group having 1-12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.

Xg independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or —NR ¹² —, and R ¹² is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n. -Butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-octyl group, n-nonyl group, n- It is a decyl group or a phenyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group or an n-decyl group.

  Specific examples of the compound (IV) include compounds represented by the following formulas (IV-1) to (IV-2).

The perylene-based compound that can be used as the compound (A) is not particularly limited, but quaterrylene, pentarylene, and hexarylene compounds can be used. Specific examples of the perylene-based compound include compounds described in JP 2012-111863 A.

  The metal dithiolate compound that can be used as the compound (A) is not particularly limited, but a compound (V) represented by the following formula (V) is preferable.

In formula (V), R ^{29 to} R ³² are each independently a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl device, tert-butyl group, cyclohexyl group, n- Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, phenylthio group , A benzylthio group, and adjacent R ²⁹ and R ³⁰ , and R ³¹ and R ³² are groups forming a ring. When adjacent R ²⁹ and R ³⁰ , and R ³¹ and R ³² are groups forming a ring, it is preferably a heterocycle having at least one sulfur atom or nitrogen atom in the ring. Ma is a metal atom, preferably a transition metal, and more preferably Ni, Pd or Pt. Q represents G (R ⁱ ) ₄ , G represents a nitrogen atom, a phosphorus atom or a bismuth atom, and R ⁱ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl container. , Tert-butyl group, cyclohexyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and phenyl group. y represents 0 or 1.

  Specific examples of the compound (V) include compounds represented by the following formula (V-1).

<Compound (B)>
The compound (B) is not particularly limited, but examples thereof include squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, and cyanine compounds. By using the compound (B), it is possible to obtain an optical filter having a small incident angle dependence of optical characteristics.

  The squarylium compound that can be used as the compound (B) is not particularly limited, but compounds (VI) and (VII) represented by the following formula (VI) and formula (VII) are preferable.

In the formula (VI), R ^a , R ^b and Y satisfy the following condition (VI-i) or (VI-ii).

Condition (VI-i)
Plural R ^a represents each independently a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -L ¹ or -NR ^e R ^f group. R ^e and R ^f represent each independently a hydrogen ^{atom, -L a, -L b, -L} c, a -L ^d or -L ^e.

Plural R ^b's each independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -L ¹ or -NR ^g R ^h group. R ^g and R ^h are each independently a hydrogen ^{atom, -L a, -L b, -L} c, -L d, -L e or -C (O) R ⁱ groups (R ⁱ is -L ^a, Represents -L ^b , -L ^c , -L ^d or -L ^e ).

Plural Y's each independently represent a —NR ^j R ^k group. R ^j and R ^k represent each independently a hydrogen ^{atom, -L a, -L b, -L} c, a -L ^d or -L ^e.
L ¹ is L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h .

The above L ^{a to} L ^h are
(L ^a) substituted with a group L 1 to 9 carbon atoms which may aliphatic hydrocarbon group,
(L ^b ) a halogen-substituted alkyl group having 1 to 9 carbon atoms which may have a substituent L,
(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L,
(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L,
(L ^e ) a heterocyclic group having 3 to 14 carbon atoms which may have a substituent L,
(L ^f ) an alkoxy group having 1 to 9 carbon atoms which may have a substituent L,
(L ^g ) represents an acyl group having 1 to 9 carbon atoms which may have a substituent L, or (L ^h ) an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L.

  The substituent L is an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and an aromatic carbon group having 6 to 14 carbon atoms. It is at least one selected from the group consisting of a hydrogen group and a heterocyclic group having 3 to 14 carbon atoms.

L ^{a to} L ^h further have at least one atom or group selected from the group consisting of a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group and an amino group. May be.

The total number of carbon atoms including the substituents in each of L ^{a to} L ^h is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. If the number of carbon atoms is larger than this range, it may be difficult to synthesize the dye, and the absorption intensity per unit mass tends to be small.

Condition (VI-ii)
At least one of two R ^a on one benzene ring is mutually bonded to Y on the same benzene ring to form a heterocycle having 5 or 6 constituent atoms containing at least one nitrogen atom, the heterocyclic ring may have a substituent, R ^b and R ^a which is not involved in the formation of the heterocycle have the same meanings as R ^b and R ^a of the independently (VI-i).

Wherein (VII), Xh is, O, S, Se, N -R represents ^c or C-R ^d R ^d; plural R ^c each independently represents a hydrogen atom, -L ^a, -L ^b, - L ^c represents -L ^d or -L ^e ; a plurality of R ^d's each independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -L ¹ or -NR ^e R ^f represents a group, R ^d adjacent may form a ring which may have a substituent ^{linked; L a ~L e, L 1} , R e and R ^f is, L ^a ~L ^e as defined in formula (VI), the same meaning as L ^1, R ^e and R ^f.

  Compound (VI) and compound (VII) are represented by the following formula (VI-1) and formula (VII-1), as well as the following formula (VI-2) and formula (VII-2). The structure can be represented by a description method such as taking a resonance structure. That is, the difference between the following formula (VI-1) and the following formula (VI-2), and the difference between the following formula (VII-1) and the following formula (VII-2) are only the method of describing the structure, and Both represent the same thing. Unless otherwise specified, in the present invention, the structure of a squarylium compound is represented by the method described in the following formulas (VI-1) and (VII-1).

The compounds (VI) and (VII) are not particularly limited in structure as long as they satisfy the requirements of the above formula (VI) and the above formula (VII). For example, the above formula (VI-1) and the above formula (VII-1) ), The left and right substituents bonded to the central four-membered ring may be the same or different, but the same is preferable because it is easier to synthesize. . In addition, for example, the compound represented by the following formula (VI-3) and the compound represented by the following formula (VI-4) can be regarded as the same compound.

The phthalocyanine compound that can be used as the compound (B) is not particularly limited, but for example, the compound (VIII) represented by the following formula (VIII) is preferable.

In formula (VIII), Mb represents two hydrogen atoms, two monovalent metal atoms, two divalent metal atoms, or a substituted metal atom containing a trivalent or tetravalent metal atom, and a plurality of R's are present. _a , R _b , R _c and R _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ or -S. ^{-L 2, -SS-L 2,} -SO 2 -L 3, represents the -N = N-L ^4. Alternatively, a plurality of R _a , R _b , R _c, and R _d have the following formula (VIII-A ₎ in which at least one combination of R _a and R _b , R _b and R _c, and R _c and R _d is bound. ) To (VIII-H) represents at least one group selected from the group consisting of groups represented by: However, at least one of R _a , R _b , R _c and R _d bonded to the same aromatic ring is not a hydrogen atom.

The amino group, amide group, imide group and silyl group may have the substituent L defined in the above formula (VI),
L ¹ has the same meaning as L ¹ defined in the above formula (VI),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (VI),
L ³ represents either a hydroxyl group or the L ^a ~L ^e,
L ⁴ represents any one of the above L ^{a to} L ^e .

In formulas (VIII-A) to (VIII-H), the combination of R _x and R _{y is} a combination of R _a and R _b , R _b and R _c or R _c and R _d ,
The plurality of R _A to R _L, each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl ^{group, -L 1, -S-L 2} , -SS -L _^2, -SO ² -L ^3, represents the -N = N-L ^4,
The amino group, amide group, imide group and silyl group may have the substituent L, L ¹ ~L ⁴ has the same meaning as L ¹ ~L ⁴ as defined in formula (VI).

  The naphthalocyanine compound that can be used as the compound (B) is not particularly limited, but for example, the compound (IX) represented by the following formula (IX) is preferable.

In formula (IX), Mc has the same meaning as Mb in formula (VIII), and R _a , R _b , R _c , R _d , R _e, and R _f are each independently a hydrogen atom, a halogen atom, or a hydroxyl group. , carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl ^{group, -L 1, -S-L 2} , -SS-L 2, -SO 2 -L 3, -N = N- Represents L ⁴ .

  The cyanine compound that can be used as the compound (B) is not particularly limited, but examples thereof include compounds (X-1) to (X-) represented by the following formulas (X-1) to (X-3). 3) is preferable.

In formulas (X-1) to (X-3), X _b ⁻ represents a monovalent anion,
Multiple Xi independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom,
A plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl ^{group, -L 1, -S-L 2} , -SS-L 2, -SO 2 -L 3, -N = N-L 4 or,, R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h, and R _h and R _i in combination with at least one of the following formulas (XA) to (X -H) represents at least one group selected from the group consisting of groups represented by the following:
The amino group, amide group, imide group and silyl group may have the substituent L defined in the above formula (VI),
L ¹ has the same meaning as L ¹ defined in the above formula (VI),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (VI),
L ³ represents a hydrogen atom or any of the above L ^{a to} L ^e ,
L ⁴ represents any one of the above L ^{a to} L ^e ,
Z _{a to} Z _d and Y _{a to} Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ ,-. ^{S-L 2, -SS-L} 2, -SO 2 -L 3, -N = N-L 4 (L 1 ~L 4 has the same meaning as L ¹ ~L ⁴ in the R _a to R _i. ), Or
A 5- to 6-membered alicyclic hydrocarbon group which may contain at least one of a nitrogen atom, an oxygen atom or a sulfur atom, which is formed by mutually bonding Z or Y selected from two adjacent groups,
An aromatic hydrocarbon group having 6 to 14 carbon atoms, which is formed by mutually bonding Zs or Ys selected from two adjacent groups, or
Zs or Ys selected from two adjacent groups are formed by being bonded to each other, and contain at least one nitrogen atom, oxygen atom or sulfur atom, and represent a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms,
These alicyclic hydrocarbon group, aromatic hydrocarbon group and heteroaromatic hydrocarbon group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

In formulas (X-A) to (X-H), combinations of R _x and R _y are R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , and R _g . R _h and a combination of R _h and R _i ,
A plurality of _{RA to RL} are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -S-L ^{2 _{, -SS-L 2, -SO 2}} -L 3 or ^{-N = N-L 4 (L} 1 ~L 4 , the formula (X-1) ~ (L 1 ~L 4 as defined in X-3) And the amino group, amide group, imide group and silyl group may have the substituent L. <Compound (C)>
As the compound (C), a metal complex-based compound, a dye or a pigment that acts as a dye that absorbs near infrared rays can be used, and specifically, a diimonium-based compound, a metal dithiolate complex-based compound, and copper phosphate can be used. At least one compound selected from the group consisting of complex compounds can be mentioned. By using such a compound (C), it is possible to achieve absorption characteristics in a wide near infrared wavelength region and excellent visible light transmittance. As the compound (C), one type may be used alone, or two or more types may be used.

<< Diimonium compounds >>
The diimonium compound is not particularly limited, but for example, a compound represented by the following formula (XI) is preferable.

In formula (XI), R ^{1 to} R ¹⁷ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a —NR ^g R ^h group, or —SR ^i. group, -SO ₂ R ⁱ group, or an -OSO ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or represents one of the following L ^a ~L ^e, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) C 1-12 aliphatic hydrocarbon group (L ^b ) ^C 1-12 halogen-substituted alkyl group (L ^c ) ^C 3-14 alicyclic hydrocarbon group (L ^d ) carbon Number of carbon atoms which may have an aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms (L ^f ) and an alkoxy group having 1 to 12 carbon atoms (L ^g ) substituent L 1 to 12 acyl groups,
(L ^h ) C1-C12 alkoxycarbonyl group which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1-12 carbon atoms, a halogen-substituted alkyl group having 1-12 carbon atoms, At least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms, and n is 0 to 0. An integer of 4 and X represents an anion necessary for neutralizing the charge.

R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group or a benzyl group. , And more preferably isopropyl group, sec-butyl group, tert-butyl group, and benzyl group.

R ^{2 to} R ¹⁷ are preferably chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group and phenyl group. , Hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluorometa group Noylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, and more preferably Is chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group Group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexino Ilamino group, and particularly preferably methyl group, ethyl group, n-propyl group, and isopropyl group. The number of R ² (value of n) bonded to the same aromatic ring is not particularly limited as long as it is 0 to 4, but it is preferably 0 or 1.

  Xc is an anion necessary for neutralizing the electric charge, and one molecule is required when the anion is divalent, and two molecules are required when the anion is monovalent. In the latter case, the two anions may be the same or different, but the same is preferable from the viewpoint of synthesis. Xc is not particularly limited as long as it is such an anion, and examples thereof include those described in Table 1 below.

Xc tends to be able to improve the heat resistance of the diimonium-based compound when it is used as the anion of the diimonium-based compound if it has a high acidity when converted to an acid, and (Xc-10) in Table 1 above, ( Xc-16), (Xc-17), (Xc-21), (Xc-22), (Xc-24) and (Xc-28) are particularly preferable.

<< Metal dithiolate compounds >>
The metal dithiolate compound is not particularly limited, but a compound represented by the following formula (XII) is preferable.

In formula (XII), R ^{29 to} R ³² are each independently a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl device, a tert-butyl group, a cyclohexyl group, an n- Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, phenylthio group , A benzylthio group, and adjacent R ²⁹ and R ³⁰ , and R ³¹ and R ³² are groups forming a ring. When adjacent R ²⁹ and R ³⁰ , and R ³¹ and R ³² are groups forming a ring, it is preferably a heterocycle having at least one sulfur atom or nitrogen atom in the ring. Ma is a metal atom, preferably a transition metal, and more preferably Ni, Pd, or Pt. Q represents G (R ⁱ ) ₄ , G represents a nitrogen atom, a phosphorus atom or a bismuth atom, and R ⁱ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl container. , Tert-butyl group, cyclohexyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and phenyl group. y represents 0 or 1.

≪Commercial product≫
As commercial products of the compound (C), S2058 (manufactured by DKSH), CIR-108x, CIR-96x, CIR-RL, CIR-1080 (manufactured by Nippon Carlit), T090821, T0901021, T89021, T090721, T090122 (manufactured by Tosco). ), B4360, D4773, D5013 (manufactured by Tokyo Kasei Kogyo), S4253, S1426, S1445 (manufactured by Spectrum Info), Excolor IR1, IR2, IR3, IR4 (manufactured by Nippon Shokubai) and the like.

<Other ingredients>
The transparent resin substrate and the resin layer may further contain an antioxidant, a near-ultraviolet absorber, a fluorescence quencher, and the like as other components as long as the effects of the present invention are not impaired. These other components may be used alone or in combination of two or more.

Examples of the near-ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, and triazine compounds.
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane and tetrakis. [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (2,4-di-t-butylphenyl) phosphite, and the like.

  Note that these other components may be mixed with the resin or the like when manufacturing the transparent resin substrate and the resin layer, or may be added when the resin is synthesized. The addition amount is appropriately selected according to the desired characteristics, but is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the resin. It is a department.

<Production method of base material>
When a transparent resin layer (light absorbing layer) containing a light absorbing compound such as the compound (A) is laminated on a glass substrate or a transparent resin substrate as the base material, for example, on the glass substrate or the transparent resin substrate. By melt-molding or cast-molding a resin solution containing a light-absorbing compound, the solvent is preferably dried and removed after coating by a method such as spin coating, slit coating, or inkjet, and further irradiation with light or as necessary. By heating, it is possible to manufacture a base material having a light absorption layer formed on the glass substrate or the transparent resin substrate.

  When the base material is composed of a transparent resin substrate (light absorbing layer) containing a light absorbing compound such as the compound (A), for example, melt molding or cast molding of a resin solution containing the light absorbing compound. Thus, a base material made of a transparent resin substrate (light absorbing layer) can be manufactured. Further, if necessary, after coating the transparent resin substrate (light absorbing layer), a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is coated to form a base material on which an overcoat layer is laminated. Can be manufactured.

<< Melting >>
As the melt-molding, specifically, a method of melt-molding a pellet obtained by melt-kneading a resin, a light-absorbing compound and, if necessary, other components; a resin and a light-absorbing compound are required. A method of melt-molding a resin composition containing other components as required; or obtained by removing the solvent from the resin composition containing a light-absorbing compound, a resin, a solvent and, if necessary, other components. Examples include a method of melt-forming pellets. Examples of the melt molding method include injection molding, melt extrusion molding and blow molding.

≪Cast molding≫
As the cast molding, a method of casting a resin composition containing a light absorbing compound, a resin, a solvent and, if necessary, other components on a suitable support to remove the solvent; or a light absorbing compound and , A photocurable resin and / or a thermosetting resin, and optionally a curable composition containing other components are cast on a suitable support to remove the solvent, and then irradiated with ultraviolet rays or heated. It can also be produced by a method of curing by an appropriate method described above.

  When the base material is a transparent resin substrate containing a light absorbing compound such as the compound (A), the substrate can be obtained by peeling the coating film from the support after cast molding. In addition, when the base material is a glass substrate or a transparent resin substrate on which a light absorbing layer is laminated, the base material can be obtained by cast molding without peeling the coating film. You can

  The amount of residual solvent in the transparent resin layer (light absorbing layer) obtained by the above method is preferably as small as possible. Specifically, the residual solvent amount is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less, based on the weight of the transparent resin layer. When the amount of the residual solvent is within the above range, a transparent resin layer which does not easily change its shape or characteristics and can easily exhibit a desired function can be obtained.

<< Adhesion layer >>
Since the transparent resin layer and the glass substrate are different from each other in chemical composition and coefficient of linear thermal expansion, a cured layer may be provided between the transparent resin layer and the glass substrate to ensure sufficient adhesion therebetween. preferable. The cured layer used in the present invention is not particularly limited as long as it is made of a material capable of ensuring the adhesiveness between the transparent resin layer and the glass substrate. For example, (a) a structural unit derived from a (meth) acryloyl group-containing compound. , (B) having a structural unit derived from a carboxylic acid group-containing compound and (c) a structural unit derived from an epoxy group-containing compound, the adhesiveness between the resin layer and the glass substrate becomes high, which is preferable.

(A) Structural unit derived from (meth) acryloyl group-containing compound The structural unit (a) is not particularly limited as long as it is a structural unit derived from a (meth) acryloyl group-containing compound. As the (meth) acryloyl group-containing compound, for example, a monofunctional, difunctional, or trifunctional or higher functional (meth) acrylic acid ester is preferable from the viewpoint of good polymerizability. In the present invention, “(meth) acrylic” means “acrylic” or “methacrylic”.

  Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl). Mention may be made of phthalates, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalates and ω-carboxypolycaprolactone monoacrylates.

  Commercially available products thereof include, for example, Aronix M-101, M-111, M-114, and M-5300 (all manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S and TC. -120S (all manufactured by Nippon Kayaku Co., Ltd.); VISCOAT 158 and 2311 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate and 1,9-nonanediol Mention may be made of dimethacrylate.

  Examples of commercially available products thereof include trade names of Aronix M-210, M-240, and M-6200 (all manufactured by Toagosei Co., Ltd.); KAYARAD HDDA, HX-220, and R-604 ( As mentioned above, Nippon Kayaku Co., Ltd .; Viscoat 260, 312, 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light acrylate 1,9-NDA (manufactured by Kyoeisha Chemical Co., Ltd.); be able to.

  Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol. Pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2-acryloyl) Oxyethyl) Phosphate, tri (2-methacryloyloxyethyl) phosphate, a compound having a linear alkylene group and an alicyclic structure, and having two or more isocyanate groups, and one or more hydroxyl groups in the molecule. Further, a polyfunctional urethane acrylate compound obtained by reacting with a compound having 3, 4 or 5 (meth) acryloyloxy groups can be mentioned.

Commercially available tri- or higher functional (meth) acrylic acid esters are trade names such as Aronix M-309, M-315, M-400, M-405, M-450 and M-7100. , M-8030, M-8060, TO-1450 (all manufactured by Toagosei Co., Ltd.); KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-. 120, the same DPEA-12 (above, manufactured by Nippon Kayaku Co., Ltd.); Viscoat 295, the same 300, 360, the same GPT, 3PA, the same 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); As a commercial product containing a polyfunctional urethane acrylate compound, New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); KAYARAD DPHA-40H (Nippon Kayaku) Co., Ltd.)) can be mentioned.
These (meth) acryloyl group-containing compounds (a) can be used alone or in admixture of two or more in the above-mentioned cured layer.

(B) Structural unit derived from carboxylic acid group-containing compound The structural unit (b) is not particularly limited as long as it is a structural unit derived from a compound containing a carboxylic acid group. Examples of the carboxylic acid group-containing compound include monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, and polymers having carboxylic acid groups.

  Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid. Mention may be made of acids.

Examples of the dicarboxylic acid include maleic acid, fumaric acid and citraconic acid.
Examples of the anhydride of the dicarboxylic acid include the anhydride of the dicarboxylic acid.

  Further, the polymer having a carboxylic acid group is a compound having a carboxylic acid group, for example, one or more kinds of compounds having a polymerizability selected from acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like. Polymers or copolymers of these compounds and the (meth) acryloyl group-containing compound can be preferably used.

  Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride is preferable from the viewpoint of copolymerization reactivity.

(C) Structural Unit Derived from Epoxy Group-Containing Compound The structural unit (c) is not particularly limited as long as it is a structural unit derived from an epoxy group-containing compound. Examples of the epoxy group (oxiranyl group) -containing compound include oxiranyl groups such as (meth) acrylic acid oxiranyl (cyclo) alkyl ester, α-alkylacrylic acid oxiranyl (cyclo) alkyl ester and glycidyl ether compound having an unsaturated bond. An unsaturated compound having: an unsaturated compound having an oxetanyl group such as a (meth) acrylic acid ester having an oxetanyl group.

  Examples of the (meth) acrylic acid oxiranyl (cyclo) alkyl ester include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylic acid 3,4. -Epoxybutyl, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate may be mentioned, α-alkyl acryl Examples of acid oxiranyl (cyclo) alkyl esters include α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl and α-ethyl acrylate. Acrylic acid 3,4 Examples thereof include epoxycyclohexyl, and examples of the glycidyl ether compound having an unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether, which have an oxetanyl group ( Examples of the (meth) acrylic acid ester include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, and 3-((meth) acryloyloxymethyl) -2-methyl. Oxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyloxymethyloxetane Beauty 3-ethyl-3- (meth) acryloyloxy methyl oxetane and the like.

  Among these, especially glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl- 3-methacryloyloxymethyloxetane or 3-ethyl-3-methyloxetane is preferable from the viewpoint of polymerizability.

(D) Optional components To the cured layer, optional components such as an acid generator, an adhesion aid, a surfactant, and a polymerization initiator can be added as long as the effects of the present invention are not impaired. The addition amount of these is appropriately selected according to the desired characteristics, but is usually each with respect to a total of 100 parts by mass of the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound and the epoxy group-containing compound. It is desirable that the amount is 0.01 to 15.0 parts by mass, preferably 0.05 to 10.0 parts by mass.

  The polymerization initiator is a component that produces active species capable of initiating the polymerization of the monomer component in response to light rays such as ultraviolet rays and electron beams. Such a polymerization initiator is not particularly limited, but examples thereof include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds, alkylphenone compounds, and benzophenone compounds. Specific examples thereof include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl- 6-benzoyl-9. H. -Carbazol-3-yl] -octan-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9- Ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4 -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1 -Phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl benzophenone, 1-hydroxy cyclohexyl phenyl ketone, etc. can be mentioned. These polymerization initiators may be used alone or in admixture of two or more.

  The cured layer is, for example, a pellet obtained by melt-kneading the composition (I) containing the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound, the epoxy group-containing compound, and optionally the optional component. Melt-molding, a method of melt-molding pellets obtained by removing the solvent from a liquid composition containing the composition (I) and a solvent, or a method of casting (cast molding) the above-mentioned liquid composition. Can be manufactured by.

Examples of the melt molding method and the cast molding method include the same methods as described above.
The compounding amount of the (meth) acryloyl group-containing compound is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, relative to 100 parts by mass of the composition (I), and the compounding amount of the carboxylic acid group-containing compound. The amount is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and the compounding amount of the epoxy group-containing compound is 100 parts by mass of the composition (I) per 100 parts by mass of the composition (I). Therefore, it is preferably 15 to 50 parts by mass, more preferably 20 to 40 parts by mass.

Further, the blending amount of the optional component is appropriately selected according to the desired characteristics, but is preferably 0.01 to 15.0 parts by mass, more preferably 0.05 to 100 parts by mass per 100 parts by mass of the composition (I). It is 10.0 parts by mass.
The thickness of the cured layer is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm.

<Dielectric multilayer film>
The optical filter of the present invention preferably has a dielectric multilayer film on at least one surface of the base material. The dielectric multilayer film in the present invention is a film having the ability to reflect near-infrared rays or a film having an antireflection effect in the visible region, and by having a dielectric multilayer film, the visible light transmittance and near-infrared rays are more excellent. Cut characteristics can be achieved.

  Examples of the dielectric multilayer film include layers in which high refractive index material layers and low refractive index material layers are alternately laminated. As the material forming the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of 1.7 to 2.5 is usually selected. Examples of such a material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, and the like, and titanium oxide, tin oxide, and / or Alternatively, a material containing a small amount of cerium oxide or the like (for example, 0 to 10 mass% with respect to the main component) can be used.

  As the material forming the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index of 1.2 to 1.6 is usually selected. Such materials include, for example, silica, alumina, lanthanum fluoride, magnesium fluoride and sodium aluminum hexafluoride.

  The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a dielectric multilayer in which a high refractive index material layer and a low refractive index material layer are alternately laminated directly on a substrate by a CVD method, a sputtering method, a vacuum vapor deposition method, an ion assisted vapor deposition method or an ion plating method. A film can be formed.

  Generally, the thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ, where λ (nm) is the near infrared wavelength to be blocked. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is within this range, the product of the refractive index (n) and the film thickness (d) (n × d) is calculated by λ / 4, the high refractive index material layer and the low refractive index material layer. The thickness of each layer of the index material layer has almost the same value, and the blocking / transmitting of a specific wavelength tends to be easily controlled from the relationship of the optical characteristics of reflection / refraction.

  The total number of laminated layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is preferably 16 to 70 layers, and more preferably 20 to 60 layers as a whole of the optical filter. When the thickness of each layer, the thickness of the dielectric multilayer film as the entire optical filter, and the total number of layers are within the above ranges, it is possible to secure a sufficient manufacturing margin and reduce the warp of the optical filter and the crack of the dielectric multilayer film. can do.

  In the present invention, the material type constituting the high refractive index material layer and the low refractive index material layer in accordance with the absorption characteristics of the absorptive compound, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, the order of lamination, Proper selection of the number of layers ensures sufficient transmittance in the visible range and sufficient light-cutting characteristics in the near-infrared wavelength range, and reflection when near-infrared rays are incident from an oblique direction. The rate can be reduced.

  Here, in order to optimize the conditions, for example, an optical thin film design software (for example, Essential Macleod, manufactured by Thin Film Center) can be used to achieve both the antireflection effect in the visible range and the light cutting effect in the near infrared range. You can set the parameters as follows. In the case of the above-mentioned software, for example, in designing the first optical layer, the target transmittance at a wavelength of 400 to 700 nm is 100%, the target tolerance value is 1, and the target transmittance at a wavelength of 705 to 950 nm is 0%. A parameter setting method such as setting the value of Target Tolerance to 0.5 can be mentioned. With respect to these parameters, the value of Target Tolerance can be changed by further dividing the wavelength range according to various characteristics of the substrate.

  When the optical filter of the present invention has the dielectric multilayer film, the maximum value of the OD value (2) when measured from the vertical direction of the optical filter in the wavelength range of 800 to 1000 nm is preferably 5.0 or more. , More preferably 5.0 to 8.0, and further preferably 5.0 to 7.0. Further, in the wavelength range of 430 to 580 nm, the average value of the transmittances (hereinafter, also referred to as “average transmittances”) when measured in the vertical direction of the optical filter is preferably 60% or more, more preferably 65 to It is 99%, more preferably 70 to 90%. By having such optical characteristics, while reducing the influence of reflected light from the sensing light source on the ambient light sensor element and the solid-state image sensor to a level that does not cause a problem, a high visible light transmittance (there is no decrease in sensor sensitivity). It becomes possible to satisfy both requirements, and it becomes possible to provide an environment light sensor for electronic devices having a sensing function and a high-performance optical filter for a solid-state imaging device.

<Other functional films>
The optical filter of the present invention is, as far as the effect of the present invention is not impaired, between the base material and the dielectric multilayer film, the surface of the base material opposite to the surface on which the dielectric multilayer film is provided, or the dielectric multilayer film. On the surface of the film opposite to the surface on which the base material is provided, an antireflection film, a hard film is used for the purpose of improving the surface hardness of the base material and the dielectric multilayer film, improving chemical resistance, and preventing static electricity and scratches. A functional film such as a coat film or an antistatic film can be provided as appropriate.

  The optical filter of the present invention may include one layer including the functional film, or may include two or more layers. When the optical filter of the present invention includes two or more layers composed of the functional film, it may include two or more layers similar to each other or two or more layers different from each other.

  The method of laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded or cast on the base material or the dielectric multilayer film as described above. A molding method and the like can be mentioned.

  It can also be produced by applying a curable composition containing the coating agent or the like on a substrate or a dielectric multilayer film with a bar coater or the like and then curing the composition by irradiating with ultraviolet rays.

  Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, epoxy And epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl-based, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxy acrylate-based curable compositions.

  Further, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can be used, and the photopolymerization initiator and the thermal polymerization initiator may be used in combination. The polymerization initiators may be used alone or in combination of two or more.

  In the curable composition, the compounding ratio of the polymerization initiator is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, when the total amount of the curable composition is 100% by mass. More preferably, it is 1 to 5 mass%. When the mixing ratio of the polymerization initiator is within the above range, the curable composition has excellent curing characteristics and handleability, and a functional film such as an antireflection film, a hard coat film or an antistatic film having a desired hardness can be obtained. it can.

  Furthermore, an organic solvent may be added to the curable composition as a solvent, and known organic solvents can be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene. Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, N- Examples thereof include amides such as methylpyrrolidone.

These solvents may be used alone or in combination of two or more.
The thickness of the functional film is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 0.7 to 5 μm.

  Further, in order to improve the adhesion between the base material and the functional film and / or the dielectric multilayer film, or the adhesion between the functional film and the dielectric multilayer film, corona treatment is performed on the surface of the substrate, the functional film or the dielectric multilayer film. Surface treatment such as or plasma treatment may be performed.

[Uses of optical filter]
The optical filter of the present invention effectively cuts the reflected light from the sensing light source, while achieving high visible light transmittance, warpage, adhesion of the dielectric multilayer film, and noiselessness to the sensor due to reflection in the multilayer film. It has the property that it is possible. Therefore, it is particularly useful as an ambient light sensor module or an optical filter for a camera module in a device having a sensing function such as a smartphone, a tablet terminal, a wearable device, an automobile camera, a television, and a game machine.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device is an image sensor including a solid-state imaging device such as a CCD or a CMOS image sensor, and specifically, a digital still camera, a smartphone camera, a mobile phone camera, a wearable device camera, a digital camera. It can be used for applications such as video cameras.

<Camera module>
The camera module of the present invention comprises the optical filter of the present invention. Here, a case where the optical filter of the present invention is used in a camera module will be specifically described. FIG. 3 shows an example of a schematic sectional view of the camera module. In FIG. 3, the optical filter 6 is arranged between the lens 5 and the image sensor 7, but it may be arranged above the lens.

<Ambient light sensor module>
The ambient light sensor module of the present invention comprises the optical filter of the present invention. That is, the optical filter, photoelectric conversion element, light diffusion film, and the like of the present invention can be combined and used as an ambient light sensor module. Here, the ambient light sensor is a sensor that can detect ambient brightness and color tone (red is strong in the evening time zone), and for example, a display installed in the device based on the information detected by the ambient light sensor. It is possible to control the illuminance and shade of the.

  FIG. 4 shows an example of the ambient light sensor 200a that detects the ambient brightness. The ambient light sensor 200a includes an optical filter 100 and a photoelectric conversion element 202. The photoelectric conversion element 202 generates a current or a voltage by the photovoltaic effect when light enters the light receiving portion. The optical filter 100 is provided on the light receiving surface side of the photoelectric conversion element 202. By the optical filter 100, the light incident on the light receiving surface of the photoelectric conversion element 202 becomes the light in the visible light band, and the light in the near infrared band (800 nm to 2500 nm) is blocked. The ambient light sensor 200a outputs a signal in response to visible light.

  In the ambient light sensor 200a, another translucent layer may be interposed between the optical filter 100 and the photoelectric conversion element 202. For example, a light-transmitting resin layer may be provided as a sealing material between the optical filter 100 and the photoelectric conversion element 202.

  The photoelectric conversion element 202 has a first electrode 206, a photoelectric conversion layer 208, and a second electrode 210. Further, a passivation film 216 is provided on the light receiving surface side. The photoelectric conversion layer 208 is formed of a semiconductor that exhibits a photoelectric effect. For example, the photoelectric conversion layer 208 is formed using a silicon semiconductor. The photoelectric conversion layer 208 is a diode-type element and expresses a photoelectromotive force by a built-in electric field. Note that the photoelectric conversion element 202 is not limited to a diode-type element and may be a photoconductive-type element (also referred to as a photoresistor, a light-dependent resistor, a photoconductor, or a photocell) or a phototransistor-type element. Good.

For the photoelectric conversion layer 208, a germanium semiconductor or a silicon-germanium semiconductor may be used instead of the silicon semiconductor. Further, as the photoelectric conversion layer 208, a compound semiconductor material such as GaP, GaAsP, CdS, CdTe, CuInSe ₂ may be used. The photoelectric conversion element 202 formed of a semiconductor material has sensitivity to light in the visible light band to the near infrared light band. For example, when the photoelectric conversion layer 208 is formed of a silicon semiconductor, the band gap energy of the silicon semiconductor is 1.12 eV, so that light having a wavelength of 700 to 1100 nm, which is near infrared light in principle, can be absorbed. However, by including the optical filter 100, the ambient light sensor 200a is insensitive to near infrared light and has sensitivity to light in the visible light range. Note that the photoelectric conversion element 202 is preferably surrounded by a light-blocking housing 204 so that the light transmitted through the optical filter 100 is selectively irradiated. By including the optical filter 100, the ambient light sensor 200a can block near-infrared light and detect ambient light. As a result, it is possible to solve the problem that the ambient light sensor 200a malfunctions in response to the near infrared light.

  FIG. 5 illustrates an example of an ambient light sensor 200b that detects color tone in addition to ambient brightness. The ambient light sensor 200b is configured to include the optical filter 100, photoelectric conversion elements 202a to 202c, and color filters 212a to 212c. A color filter 212a that transmits light in the red light band is provided on the light receiving surface of the photoelectric conversion element 202a, and a color filter 212b that transmits light in the green light band is provided on the light receiving surface of the photoelectric conversion element 202b. A color filter 212c that transmits light in the blue light band is provided on the light receiving surface of the photoelectric conversion element 202c. The photoelectric conversion elements 202a to 202c have the same configuration as that shown in FIG. 4 except that they are insulated by the element isolation insulating layer 214. With this configuration, the photoelectric conversion elements 202a to 202c can independently detect the illuminance. Note that a passivation film 216 may be provided between the color filters 212a to 212c and the photoelectric conversion elements 202a to 202c.

  The photoelectric conversion elements 202a to 202c have sensitivity over a wide range from the visible light wavelength region to the near infrared wavelength region. Therefore, by providing the color filters 212a to 212c corresponding to the photoelectric conversion elements 202a to 202c in addition to the optical filter 100, the ambient light sensor 200b blocks near-infrared light and prevents malfunction of the sensor. , The light corresponding to each color can be detected. The ambient light sensor 200b includes the optical filter 100 that blocks light in the near-infrared region and the color filters 212a to 212c, so that not only can ambient light be spectrally detected into light in a plurality of wavelength bands, but also It can be applied even in a dark environment where conventional color sensors cannot detect accurately due to the influence of near infrared rays.

<Electronic equipment>
The electronic device of the present invention includes the optical filter of the present invention, and in a more preferable aspect, includes the above-described ambient light sensor of the present invention. Hereinafter, an electronic device of the present invention will be described with reference to the drawings.

  FIG. 6 shows an example of an electronic device 300 including the image sensor 7 and the ambient light sensor 200 according to the embodiment of the present invention. The electronic device 300 includes a housing 307, a display panel 306, a speaker unit 305, an RGB camera module 301, an ambient light sensor 200, a dot projector 302, a floodlight illuminator 303, and an IR camera 304. A touch panel is adopted as the display panel 306, and it has an input function in addition to a display function.

  The ambient light sensor 200 is provided on the back surface of the front panel 306 provided on the housing 307. That is, the ambient light sensor 200 does not appear in the external appearance of the electronic device 300, and light enters through the translucent front panel. The surface panel blocks light in the near infrared region by the optical filter 100, and light in the visible light region enters the photoelectric conversion element 202. The electronic device 300 can control the illuminance and color tone of the display panel 306 by the ambient light sensor 200.

  According to the present embodiment, the optical filter of the present invention allows reflected light (reflected light from the object and inside the housing) from the light emitting elements (emission center wavelengths of 850 nm, 940 nm, etc.) of the dot projector 302 and the projection illuminator 303 to be reflected. By cutting efficiently, it is possible to prevent noise light from entering the image sensor of the camera module and the ambient light sensor, and prevent deterioration of the camera image quality and malfunction of the screen color adjustment by the ambient light sensor. .

  In recent years, as electronic devices have become more sophisticated, a wide variety of sensors have come to be installed in electronic devices, and it is necessary to mount many sensors in a limited space in the device. With the miniaturization of modules, each module is being installed closer to each other. For example, when the light-emitting element for sensing and the photoelectric conversion element (ambient light sensor element, solid-state image sensor, etc.) are installed close to each other, the light from the light-emitting element is reflected in the housing and enters the photoelectric conversion element. Although there is a problem that the adverse effect expands, it is possible to effectively reduce the adverse effect by applying the optical filter of the present invention. The optical filter of the present invention can be effectively used when the distance between the light emitting element module, the ambient light sensor module, and the camera module in the same device is within 4 cm, and more effectively when the distance is within 3 cm. Can be used.

  Hereinafter, the present invention will be described more specifically based on Examples, but the present invention is not limited to these Examples. In addition, "part" means "part by mass" unless otherwise specified. Moreover, the measuring method of each physical property value and the evaluation method of physical property are as follows.

<Molecular weight>
The molecular weight of the resin was measured by the method (a) or (b) below in consideration of the solubility of each resin in a solvent.

  (A) Using a gel permeation chromatography (GPC) device (150C type, column: Tosoh H-type column, developing solvent: o-dichlorobenzene) manufactured by WATERS, weight average molecular weight in terms of standard polystyrene (Mw) and number average molecular weight (Mn) were measured.

  (B) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a GPC device manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgel α-M, developing solvent: THF).

<Glass transition temperature (Tg)>
A differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc. was used to measure the temperature rising rate: 20 ° C./min under a nitrogen stream.

<Spectral transmittance and optical density (OD value)>
The reflectance and the transmittance in each wavelength range of the optical filter were measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.
Moreover, the optical density (OD value) of the optical filter was calculated from the transmittance value measured by using JASCO Corporation UV-visible infrared spectrophotometer V-7300.

<Warp evaluation>
An optical filter having a length of 200 mm and a width of 200 mm was allowed to stand still on a flat glass plate, and the vertical height at which the corner of the optical filter was warped from the glass plate was used as the warp, and measurement was performed using a ruler. The warp was measured at the four corners of the optical filter, and the average value of the warp at the four corners was taken as the warp amount. When the warp amount was 10 mm or less, the warp characteristic was evaluated as “◯”, and when the warp amount was 10 mm or more, the warp characteristic was evaluated as “x”.

<Adhesion evaluation of dielectric multilayer film>
The film with the dielectric multilayer film cut into 20 mm square was boiled in pure water for 30 minutes. After that, a cross-cut (11 lengths and 11 widths) at 1 mm intervals was attached to the taken-out film using a cutter knife, and the tape Nichiban No. 405 was attached and peeled off, and the presence or absence of peeling was confirmed. The case where peeling was not recognized was evaluated as “◯”, and the case where peeling was recognized was evaluated as “x”.

<Ambient light sensor performance>
The near-infrared cut filter of the environmental light sensor module of "iphone X" manufactured by Apple Inc. was taken out, and instead, the optical filters produced in Examples and Comparative Examples described later were incorporated in the environmental light sensor module. The LED light LCS-0850-02 (emission peak wavelength: 850 nm) or LCS-0940-02 (emission peak wavelength: 940 nm) manufactured by Migtex Co. is irradiated to the window part where the ambient light sensor module is incorporated from a distance of about 1 m. , The operation status of the ambient light sensor was observed. "◎" when the operating condition of the ambient light sensor is very good. Generally, the operation status was good, but sometimes the operation failure was sometimes observed, and the case where the operation status was poor was evaluated as "x".

<Camera module image evaluation>
The near-infrared cut filter of the camera module of the front (sub) camera of "iphone X" manufactured by Apple Inc. was taken out, and instead, the optical filters produced in Examples and Comparative Examples described later were incorporated in the camera module. Photograph with the LED light LCS-0850-02 (emission peak wavelength: 850 nm) or LCS-0940-02 (emission peak wavelength: 940 nm) manufactured by Migtex Co., illuminating the window of the front (sub) camera from a distance of about 1 m. Was photographed, and the photographic image quality was evaluated. "◎" when the photo quality is good, "○" when the color balance of the photo quality is slightly poor and looks reddish, and "x" when the color balance of the photo quality is poor and looks reddish overall. And

  The near infrared absorbing dye (light absorbing compound) used in the following examples was synthesized by a generally known method. As a general synthesis method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open No. 1-146846, JP-A-1-228960, JP-A-4081149, JP-A-63-124054, "Phthalocyanine-Chemistry and Function-" (IPC, 1997), JP-A 2007-169315, JP-A 2009 The methods described in JP-A-108267, JP-A-2010-241873, JP-A-3699464, JP-A-4740631 and the like can be mentioned.

<Resin synthesis example 1>
100 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] dodec-3-ene (hereinafter also referred to as "DNM") represented by the following formula (XIII) , 1-hexene (molecular weight modifier) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were charged in a reaction vessel purged with nitrogen, and the solution was heated to 80 ° C. Then, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol / liter) were added to the solution in the reaction vessel as a polymerization catalyst. And 9 parts were added, and the solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opened polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution. Then, under the conditions of hydrogen gas pressure of 100 kg / cm ² and reaction temperature of 165 ° C., the mixture was heated and stirred for 3 hours to carry out the hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and collect a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The resin A thus obtained had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000 and a glass transition temperature (Tg) of 165 ° C.

<Resin synthesis example 2>
35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, and 41.46 g of potassium carbonate were added to a 3 L four-necked flask. 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as "DMAc") and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask. Then, after replacing the inside of the flask with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and the produced water was removed from the Dean-Stark tube at any time. When the generation of water was no longer observed, the temperature was gradually raised to 160 ° C. and the reaction was carried out at that temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was thrown into methanol for reprecipitation, and the filter cake (residue) was isolated by filtration. The obtained filter cake was vacuum dried at 60 ° C. overnight to obtain a white powder (hereinafter, also referred to as “resin B”) (yield 95%). The resin B thus obtained had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000 and a glass transition temperature (Tg) of 285 ° C.

[Example 1]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.25 parts by mass of a compound (absorption maximum wavelength: 940 nm) represented by the following formula (a-1) as the compound (A), the compound (B ) As a compound represented by the following formula (b-1): 0.05 part by mass, a compound represented by the following formula (b-2): 0.056 part by mass, and as a compound (C), light absorption by Nippon Carlit Co., Ltd. 0.09 parts by mass of an agent “CIR-RL” (absorption maximum wavelength 1095 nm) (hereinafter also referred to as “compound (c-1)”) and dichloromethane, and a resin solution having a resin concentration of 20% by mass (E1). Got The obtained solution (E1) was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, further dried in vacuum at 140 ° C. for 8 hours, and then peeled from the glass plate. The peeled film was further dried in vacuum at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 100 μm and a size of 210 mm × 210 mm.

The following resin composition (1) was coated on one surface of the obtained transparent resin substrate with a bar coater so that the thickness of the coating layer after drying was 3 μm, and heated in an oven at 70 ° C. for 2 minutes to volatilize the solvent. Removed. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate. This obtained the base material which has the resin layer which does not contain the compound (A) on both surfaces of the transparent resin substrate which contains the compound (A).

  Resin composition (1): tricyclodecane dimethanol acrylate 60 parts by mass, dipentaerythritol hexaacrylate 40 parts by mass, 1-hydroxycyclohexyl phenyl ketone 5 parts by mass, methyl ethyl ketone (solvent, solid content concentration: 30%).

  In the obtained base material, the maximum OD value at a wavelength of 800 to 1000 nm is 3.3 (@ 940 nm), the average OD value at a wavelength of 840 to 1040 nm is 1.1, and the OD value at a wavelength of 430 to 580 nm. The average transmittance was 69.6%. FIG. 7 shows the optical characteristics (transmittance by wavelength) of the base material.

  Subsequently, a dielectric multilayer film (α) is formed on one surface of the obtained base material, and a dielectric multilayer film (β) is further formed on the other surface of the base material, and a dielectric material having a thickness of 0.110 mm is formed. An optical filter in which multilayer films were laminated was obtained.

The dielectric multilayer film (α) is formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a vapor deposition temperature of 100 ° C. The dielectric multilayer film (β) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers. In each of the dielectric multilayer films (α) and (β), the silica layer and the titania layer are, from the base material side, a titania layer, a silica layer, a titania layer, ... A silica layer, a titania layer, and a silica layer in this order. The layers were alternately laminated, and the outermost layer of the optical filter was a silica layer. The dielectric multilayer films (α) and (β) were designed as follows.

  Regarding the thickness of each layer and the number of layers, the wavelength dependence of the refractive index of the base material and the applied compounds (A) and (B) are used so that the antireflection effect in the visible region and the selective transmission and reflection performance in the near infrared region can be achieved. ) And (C), etc., and optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When performing the optimization, in this embodiment, the input parameters (Target value) to the software are as shown in Table 2 below.

  As a result of the optimization of the film structure, in Example 1, the dielectric multilayer film (α) was formed by alternately stacking a silica layer having a thickness of about 32 to 158 μm and a titania layer having a thickness of about 10 to 96 μm. The multilayered vapor deposition film has 22 layers, and the dielectric multilayer film (β) is a multilayered film having 18 layers, in which a silica layer having a thickness of about 38 to 192 μm and a titania layer having a thickness of about 10 to 112 μm are alternately laminated. It was a vapor deposition film. Table 3 below shows an example of the optimized film structure.

In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 5.3, and the average transmittance at a wavelength of 430 to 580 nm was 72.8%. FIG. 8 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0940-02 was used as an LED light source, and the operation status of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The operating condition of the ambient light sensor was good, and the photographic image of the camera module was good.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 2]
To a container, 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 4.3 parts by mass of compound (a-1), and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass, and a solution having a pore diameter of 5 μm. Filtration with a Millipore filter gave a resin solution (E2-1). Similarly, 100 parts by mass of resin A, 0.5 parts by mass of compound (b-1), 0.56 parts by mass of compound (b-2), and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass. Then, filtration was performed with a Millipore filter having a pore size of 5 μm to obtain a resin solution (E2-2).

  The following resin composition (2) was applied to both sides of a transparent glass substrate “OA-10G” (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd., which was cut into a size of 200 mm × 200 mm, and the film thickness after drying was about 1 μm. After being applied by spin coating so as to be, a solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes to form a resin layer that functions as an adhesive layer with a transparent resin layer described later. Next, the resin solution (E2-1) was applied onto the adhesive layer on one side using a spin coater so that the film thickness after drying would be 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes to remove the solvent. Was removed by evaporation to form a transparent resin layer. Further, the resin solution (E2-2) was applied to the other surface so that the film thickness after drying was 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes to volatilize and remove the solvent to obtain a transparent resin layer. Was formed. Thus, a resin layer containing the compound (A) was laminated on one surface of the colorless glass substrate, and a resin layer not containing the compound (A) was laminated on the other surface to obtain a base material having a thickness of 220 μm.

  Resin composition (2): isocyanuric acid ethylene oxide-modified triacrylate (delivery name / Aronic M-315, manufactured by Toa Gosei Kagaku Co., Ltd.) 30 parts by mass, 1,9-nonanediol diacrylate 20 parts by mass, methacrylic acid 20 Parts by mass, glycidyl methacrylate 30 parts by mass, 3-glycidoxypropyltrimethoxysilane 5 parts by mass, 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and San-Aid SI. 1 part by mass of -110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) was mixed, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration became 50% by mass, and then filtered through a Millipore filter having a pore size of 0.2 μm. Then, a resin composition (2) was prepared.

  In the obtained base material, the maximum OD value of wavelengths 800 to 1000 nm is 4.5 (@ 940 nm), the average OD value of wavelengths 840 to 1040 nm is 0.6, and the wavelength 430 to 580 nm is 430 nm. The average transmittance was 67.9%. FIG. 9 shows the spectral characteristics (transmittance by wavelength) of the base material.

  Then, a dielectric multilayer film (α) was formed on one surface of the base material and a dielectric multilayer film (β) was formed on the other surface of the base material by the same method as in Example 1, and the thickness was increased. An optical filter having a size of 224 μm was obtained.

In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 6.3 (@ 940 nm), and the average transmittance at a wavelength of 430 to 580 nm was 71.1%. FIG. 10 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0940-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The operating condition of the ambient light sensor was good, and the photographic image of the camera module was good.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 3]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.18 parts by mass of a compound represented by the following formula (a-2) (absorption maximum wavelength: 940 nm), and the following formula (b-3) were used. 0.06 parts by mass of the compound (b-3) represented, 0.07 parts by mass of the compound (b-4) represented by the following formula (b-4), 0.12 parts by mass of the compound (c-1), And dichloromethane were added to obtain a resin solution (E3) having a resin concentration of 20% by mass. The obtained solution (E3) was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, further dried at 140 ° C. for 8 hours in vacuum, and then peeled from the glass plate. The peeled film was further dried in vacuum at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 100 μm and 200 mm × 200 mm.

On one side of the obtained transparent resin substrate, the above resin composition (1) was applied by a bar coater so that the thickness of the coating layer after drying was 3 μm, and heated in an oven at 70 ° C. for 2 minutes to volatilize the solvent. Removed. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate. This obtained the base material which has the resin layer which does not contain the compound (A) on both surfaces of the transparent resin substrate which contains the compound (A).

  In the obtained base material, the maximum OD value at wavelengths 800 to 1000 nm is 4.7 (@ 940 nm), the average OD value at wavelengths 840 to 1040 nm is 1.6, and the wavelength 430 to 580 nm. The average transmittance was 69.9%. FIG. 11 shows the spectral characteristics (transmittance by wavelength) of the base material.

  Then, in the same manner as in Example 1, a dielectric multilayer film (α) was formed on one surface of the obtained base material, and a dielectric multilayer film (β) was formed on the other surface of the base material. An optical filter having a thickness of 0.110 mm was obtained.

In the obtained optical filter, the maximum OD value at wavelengths of 800 to 1000 nm was 6.5 (@ 940 nm), and the average transmittance at wavelengths of 430 to 580 nm was 73.2%. FIG. 12 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0940-02 was used as an LED light source, and the operation status of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The operating condition of the ambient light sensor was good, and the photographic image of the camera module was good.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 4]
To the container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 2.5 parts by mass of the compound represented by the following formula (a-3) (absorption maximum wavelength: 874 nm), and dichloromethane were added to obtain a resin concentration. Of 20% by mass was prepared and filtered with a Millipore filter having a pore size of 5 μm to obtain a resin solution (E4-1). In the same manner, 0.6 parts by mass of the compound (b-3), 0.7 parts by mass of the compound (b-4), 1.2 parts by mass of the compound (c-1), and dichloromethane were added to give a resin concentration of 20. A mass% solution was prepared and filtered with a Millipore filter having a pore size of 5 μm to obtain a resin solution (E4-2).

  The resin composition (2) was dried on both sides of a transparent glass substrate “OA-10G” (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd., which was cut into a size of 200 mm × 200 mm, and the film thickness after drying was about 1 μm. After being applied by spin coating so as to be, a solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes to form a resin layer that functions as an adhesive layer with a transparent resin layer described later. Next, a resin solution (E4-1) was applied to one surface of the adhesive layer using a spin coater so that the film thickness after drying would be 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes to remove the solvent. It was removed by volatilization and a resin layer was formed. Further, the resin solution (E4-2) was applied to the other surface using a spin coater so that the film thickness after drying would be 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes to volatilize and remove the solvent. To form a transparent resin layer. As a result, a substrate having a thickness of 222 μm was obtained in which the resin layer containing the compound (A) was laminated on one surface of the colorless glass substrate and the resin layer containing no compound (A) was laminated on the other surface.

  In the obtained base material, the maximum OD value at 800 to 1000 nm is 3.9 (@ 874 nm), the average OD value at wavelengths 774 to 974 nm is 1.1, and the average at wavelengths 430 to 580 nm. The transmittance was 71.8%. FIG. 13 shows the spectral characteristics (transmittance by wavelength) of the base material.

  Then, by the same method as in Example 1, a dielectric multilayer film (α) was formed on one surface of the laminate, and a dielectric multilayer film (β) was formed on the other surface of the laminate, and the thickness was increased. An optical filter having a size of 226 μm was obtained.

In the obtained optical filter, the maximum OD value at wavelengths of 800 to 1000 nm was 5.8 (@ 874 nm), and the average transmittance at wavelengths of 430 to 580 nm was 75.2%. FIG. 14 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0850-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The operating condition of the ambient light sensor was good, and the photographic image of the camera module was good.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 5]
100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 1.5 parts by mass of compound (a-2), and dichlorobenzene were added to a container, and a resin solution having a resin concentration of 10% by mass (E5-1). Got Similarly, 100 parts by mass of resin A, 0.6 parts by mass of compound (b-3), 0.7 parts by mass of compound (b-4), 0.5 parts by mass of compound (c-1), and dichlorobenzene were added. In addition, a resin solution (E5-2) having a resin concentration of 10% by mass was obtained.

  The resin solution (E5-1) was applied to one surface of ZEONOR film ZF-16 (manufactured by Zeon Corporation, 100 μm thick) so that the thickness after drying was 10 μm, and dried at 80 ° C. for 8 hours, and further vacuumed. Medium was dried at 150 ° C. for 8 hours. Further, the resin solution (E5-2) was applied to the other surface so that the thickness after drying was 10 μm, dried at 80 ° C. for 8 hours, and further dried in vacuum at 150 ° C. for 8 hours. . Thus, a 120 μm-thick laminate (base material) having a resin layer containing the compound (A) on one surface of the transparent resin substrate and a resin layer not containing the compound (A) on the other surface was obtained. .

  In the obtained base material, the maximum OD value at a wavelength of 800 to 1000 nm is 3.5 (@ 940 nm), the average OD value at a wavelength of 840 to 1040 nm is 1.0, and the average transmission at a wavelength of 430 to 580 nm. The rate was 75.6%. FIG. 15 shows the spectral characteristics (transmittance by wavelength) of the base material.

  Then, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one surface of the obtained laminate, and a dielectric multilayer film (β) is further formed on the other surface of the base material. Then, an optical filter having a thickness of 226 μm was obtained.

In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 5.5 (@ 940 nm), and the average transmittance at a wavelength of 430 to 580 nm was 79.1%. FIG. 16 shows the spectral characteristic (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0940-02 was used as an LED light source, and the operation status of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The operating condition of the ambient light sensor was good, and the photographic image of the camera module was good.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 6]
To a container, 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 2 parts of compound (a-1) and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass, and filtered with a Millipore filter having a pore size of 5 μm. The resin solution (E6) was obtained. The resin composition (2) is dried on one surface of an absorption glass substrate "BS-6" (thickness: 200 µm) manufactured by Matsunami Glass Co., Ltd., which is cut into a size of 200 mm × 200 mm, and the film thickness after drying is about 1 µm After coating by spin coating as described above, the solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes to form a resin layer functioning as an adhesive layer with a transparent resin layer described later.

  Next, a resin solution (E6) was applied to the adhesive layer using a spin coater so that the film thickness after drying would be 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes to volatilize and remove the solvent. A transparent resin layer was formed, and a resin layer containing the compound (A) was laminated on a glass substrate. As a result, a substrate having a thickness of 211 μm, in which a resin layer containing the compound (A) was laminated on one surface of the absorption type glass substrate, was obtained.

  In the obtained substrate, the maximum OD value at wavelengths 800 to 1000 nm is 3.4 (@ 940 nm), the average OD value at wavelengths 840 to 1040 nm is 1.5, and the wavelength 430 to 580 nm. The average transmittance was 77.0%. FIG. 17 shows the spectral characteristics (transmittance by wavelength) of the base material.

  Then, in the same manner as in Example 1, a dielectric multilayer film (α) was formed on one surface of the above laminated body, and a dielectric multilayer film (β) was formed on the other surface of the laminated body. An optical filter having a size of 0.214 mm was obtained.

In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 5.3 (@ 940 nm), and the average transmittance at a wavelength of 430 to 580 nm was 80.6%. FIG. 18 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0940-02 was used as an LED light source, and the operation status of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The operating condition of the ambient light sensor was good, and the photographic image of the camera module was good.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 7]
In a container, 100 parts by mass of Resin B obtained in Resin Synthesis Example 2, 0.25 parts by mass of a compound represented by the following formula (a-4) (absorption maximum wavelength: 850 nm), compound (b-1) 0. 05 parts by mass, compound (b-2) 0.056 parts by mass, compound (c-1) 0.09 parts by mass, and dichloromethane were added to obtain a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, further dried at 140 ° C. in vacuum for 8 hours, and then peeled from the glass plate. The peeled film was further dried in vacuum at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 100 μm and 200 mm × 200 mm.

On one side of the obtained transparent resin substrate, the above resin composition (1) was applied by a bar coater so that the thickness of the coating layer after drying was 3 μm, and heated in an oven at 70 ° C. for 2 minutes to volatilize the solvent. Removed. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate. This obtained the base material which has the resin layer which does not contain the compound (A) on both surfaces of the transparent resin substrate which contains the compound (A).

  In the obtained base material, the maximum OD value at wavelengths 800 to 1000 nm is 4.0 (@ 844 nm), the average OD value at wavelengths 744 to 944 nm is 1.3, and the wavelength 430 to 580 nm. The average transmittance was 69.4%. FIG. 19 shows the spectral characteristics (transmittance by wavelength) of the base material.

  Then, a dielectric multilayer film (α) was formed on one surface of the base material and a dielectric multilayer film (β) was formed on the other surface of the base material by the same method as in Example 1, and the thickness was increased. An optical filter having a size of 0.110 mm was obtained.

In the obtained optical filter, the maximum OD value at wavelengths of 800 to 1000 nm was 5.8 (@ 850 nm), and the average transmittance at wavelengths of 430 to 580 nm was 72.7%. FIG. 20 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0850-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The operating condition of the ambient light sensor was good, and the photographic image of the camera module was good.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 8]
In a container, 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 0.14 parts by mass of a compound represented by the following formula (a-5) (absorption maximum wavelength: 824 nm), compound (b-1) 0. 05 parts by mass, compound (b-2) 0.056 parts by mass, compound (c-1) 0.09 parts by mass and dichloromethane were added to obtain a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, further dried at 140 ° C. in vacuum for 8 hours, and then peeled from the glass plate. The peeled film was further dried in vacuum at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 100 μm and 200 mm × 200 mm.

On one side of the obtained transparent resin substrate, the above resin composition (1) was applied by a bar coater so that the thickness of the coating layer after drying was 3 μm, and heated in an oven at 70 ° C. for 2 minutes to volatilize the solvent. Removed. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate. This obtained the base material which has the resin layer which does not contain the compound (A) on both surfaces of the transparent resin substrate which contains the compound (A).

  In the obtained base material, the maximum OD value at wavelengths 800 to 1000 nm is 3.2 (@ 824 nm), the average OD value at wavelengths 724 to 924 nm is 1.1, and the wavelength 430 to 580 nm. The average transmittance was 70.9%. FIG. 21 shows the spectral characteristics (transmittance by wavelength) of the base material. The OD value of this base material at a wavelength of 850 nm was 1.3.

  Then, a dielectric multilayer film (α) was formed on one surface of the base material and a dielectric multilayer film (β) was formed on the other surface of the base material by the same method as in Example 1, and the thickness was increased. An optical filter having a size of 0.110 mm was obtained.

In the obtained optical filter, the maximum OD value at wavelengths of 800 to 1000 nm was 5.2 (@ 824 nm), and the average transmittance at wavelengths of 430 to 580 nm was 74.4%. FIG. 22 shows the spectral characteristic (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0850-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The operating condition of the ambient light sensor was generally good, but some malfunctions were occasionally observed, but the photographic image of the camera module was good.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 9]
In a container, 100 parts by mass of Resin B obtained in Resin Synthesis Example 2, 0.30 part of compound (a-4), 0.10 part of compound represented by the following formula (b-5), compound (c-1) ) 1.00 parts and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, dried at 60 ° C. for 8 hours, further dried at 140 ° C. under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm.

On one side of the obtained transparent resin substrate, the above resin composition (1) was applied by a bar coater so that the thickness of the coating layer after drying was 3 μm, and heated in an oven at 70 ° C. for 2 minutes to volatilize the solvent. Removed. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate. This obtained the base material which has the resin layer which does not contain a compound (A) on both surfaces of the transparent resin substrate which contains a compound (A).

  In the obtained base material, the maximum OD value at a wavelength of 800 to 1000 nm was 7.6 (@ 844 nm), and the average OD value at a wavelength of 744 to 944 nm was 4.4. Moreover, the average transmittance at a wavelength of 430 to 580 nm was 33.8%. FIG. 23 shows the spectral characteristics (transmittance by wavelength) of the base material.

Subsequently, a dielectric multilayer film was formed on both surfaces of the obtained base material by the same method as in Example 1 to obtain an optical filter having a thickness of 0.110 mm.
In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 6.3 (@ 844 nm), and the average transmittance at a wavelength of 430 to 580 nm was 35.5%. The spectral characteristics (transmittance by wavelength) of the optical filter are shown in FIG. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Further, LCS-0850-02 was used as the LED light source, and the operating conditions of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The ambient light sensor was in good working condition, and the photographic image of the camera module was generally good, but the color balance of photographic image quality was slightly unbalanced, and the image quality was slightly reddish and slightly dark.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Example 10]
100 parts by mass of resin A obtained in Resin Synthesis Example 1, 0.5 parts by mass of compound (b-1), 0.56 parts by mass of compound (b-2), and dichloromethane were added to a container so that the resin concentration was A 20% by mass solution was prepared and filtered with a Millipore filter having a pore size of 5 μm to obtain a resin solution (E10-1). Similarly, 100 parts by mass of resin A, 6.0 parts by mass of compound (c-1), and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass, and filtration was performed with a Millipore filter having a pore size of 5 μm. A resin solution (E10-2) was obtained.

  The resin composition (2) was dried on both sides of a transparent glass substrate “OA-10G” (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd., which was cut into a size of 200 mm × 200 mm, and the film thickness after drying was about 1 μm. After being applied by spin coating so as to be, a solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes to form a resin layer that functions as an adhesive layer with a transparent resin layer described later. Next, a resin solution (E10-1) was applied to the adhesive layer on one side using a spin coater so that the film thickness after drying would be 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes to remove the solvent. It was volatilized and removed to form a transparent resin layer. Furthermore, the resin solution (E10-2) on the glass substrate was applied to the other surface so that the film thickness after drying was 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes to volatilize and remove the solvent. A transparent resin layer was formed. As a result, a base material having a thickness of 220 μm was obtained by laminating resin layers not containing the compound (A) on both surfaces of the colorless glass substrate.

  In the obtained base material, the maximum OD value at a wavelength of 800 to 1000 nm is 5.1 (@ 982 nm), the average OD value at a wavelength of 882 to 1082 nm is 4.3, and the average transmission at a wavelength of 430 to 580 nm. The rate was 53.4%. FIG. 25 shows the spectral characteristics (transmittance by wavelength) of the base material.

  Then, a dielectric multilayer film (α) was formed on one surface of the base material and a dielectric multilayer film (β) was formed on the other surface of the base material by the same method as in Example 1, and the thickness was increased. An optical filter having a size of 224 μm was obtained.

In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 6.0 (@ 982 nm), and the average transmittance at a wavelength of 430 to 580 nm was 55.9%. FIG. 26 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0940-02 was used as an LED light source, and the operation status of the ambient light sensor incorporating the optical filter of this example and the photographic image evaluation of the camera module were performed. The ambient light sensor was in good working condition and the photographic image of the camera module was generally good, but the color balance of photographic image quality was slightly unbalanced and the color tone was a little reddish.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Comparative Example 1]
In a container, 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 0.18 parts by mass of compound (a-1), 0.05 parts by mass of compound (b-1), 0.056 of compound (b-2). Parts by mass, 0.09 parts by mass of the compound (c-1), and dichloromethane were added to obtain a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, further dried at 140 ° C. in vacuum for 8 hours, and then peeled from the glass plate. The peeled film was further dried in vacuum at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 100 μm and 200 mm × 200 mm.

On one side of the obtained transparent resin substrate, the above resin composition (1) was applied by a bar coater so that the thickness of the coating layer after drying was 3 μm, and heated in an oven at 70 ° C. for 2 minutes to volatilize the solvent. Removed. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate. This obtained the base material which has the resin layer which does not contain the compound (A) on both surfaces of the transparent resin substrate which contains the compound (A).

  In the obtained base material, the maximum OD value at wavelengths 800 to 1000 nm is 2.6 (@ 940 nm), the average OD value at wavelengths 840 to 1040 nm is 1.0, and the wavelength 430 to 580 nm. The average transmittance was 72.1%. FIG. 27 shows the spectral characteristics (transmittance by wavelength) of the base material.

  In Comparative Example 1, the number of layers of the dielectric multilayer film was 52 in total, and an optical filter was manufactured in which the transmittance in the 800 to 1000 nm region was reduced by reflection of the dielectric multilayer film. The dielectric multilayer films (γ) and (δ) were designed as follows.

  Regarding the thickness of each layer and the number of layers, the wavelength dependence of the refractive index of the base material and the applied compounds (A) and (B) are used so that the antireflection effect in the visible region and the selective transmission and reflection performance in the near infrared region can be achieved. ) And (C), etc., and optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When performing the optimization, in this embodiment, the input parameters (Target value) to the software are as shown in Table 4 below.

  As a result of the optimization of the film structure, in Comparative Example 1, the dielectric multilayer film (γ) was formed by alternately stacking a silica layer having a film thickness of about 32 to 159 μm and a titania layer having a film thickness of about 9 to 94 μm. A multilayer vapor-deposited film of 28 layers, wherein the dielectric multilayer film (δ) is a multilayer of 24 layers in which a silica layer having a thickness of approximately 39 to 193 μm and a titania layer having a thickness of approximately 12 to 117 μm are alternately laminated. It was a vapor deposition film. Table 5 below shows an example of the optimized film structure.

In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 5.5 (@ 940 nm), and the average transmittance at a wavelength of 430 to 580 nm was 74.3%. FIG. 28 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The obtained optical filter had a large warp, and peeling of the dielectric multilayer film was observed in the evaluation of the adhesion of the dielectric multilayer film. Moreover, LCS-0940-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this comparative example and the photographic image evaluation of the camera module were carried out. The ambient light sensor did not function well in changing the color tone of the screen in response to changes in outside light, and the operating condition was poor. The photographic image of the camera module was strongly reddish and the color balance of photographic quality was poor.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Comparative Example 2]
An optical filter was produced in the same manner as in Example 1 except that the compound (a-1) was not used, and a substrate and an optical filter in which a dielectric multilayer film was laminated on the substrate.

  In the obtained base material, the maximum OD value at a wavelength of 800 to 1000 nm is 0.8 (@ 982 nm), the average OD value at a wavelength of 882 to 1082 nm is 0.8, and the OD value at a wavelength of 430 to 580 nm. The average transmittance was 79.3%. FIG. 29 shows the optical characteristics (transmittance by wavelength) of the base material.

In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 2.0 (@ 982 nm), and the average transmittance at a wavelength of 430 to 580 nm was 83.0%. FIG. 30 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0940-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this comparative example and the photographic image evaluation of the camera module were performed. The ambient light sensor did not function well in changing the color tone of the screen in response to changes in outside light, and the operating condition was poor. The photographic image of the camera module was strongly reddish and the color balance of photographic quality was poor.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Comparative Example 3]
An optical filter in which a transparent resin substrate and a dielectric multilayer film were laminated was produced in the same manner as in Example 6 except that the amount of the compound (a-1) used was changed to 1.5 parts by weight.

  In the obtained transparent resin substrate, the maximum OD value at wavelengths 800 to 1000 nm is 2.9 (@ 940 nm), the average OD value at wavelengths 882 to 1082 nm is 1.5, and the wavelength 430 to 580 nm. The average transmittance was 79.1%. FIG. 31 shows the optical characteristics (transmittance by wavelength) of the base material.

In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 4.9 (@ 940 nm), and the average transmittance at a wavelength of 430 to 580 nm was 82.9%. FIG. 32 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0940-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this comparative example and the photographic image evaluation of the camera module were performed. The ambient light sensor did not function well in changing the color tone of the screen in response to changes in outside light, and the operating condition was poor. The photographic image of the camera module was strongly reddish and the color balance of photographic quality was poor.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Comparative Example 4]
100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 2.0 parts by mass of compound (a-1), and dichlorobenzene were added to a container, and a resin solution having a resin concentration of 10% by mass (CE4-1). Got Similarly, resin A 100 mass part, compound (b-1) 0.5 mass part, compound (b-2) 0.56 mass part, and compound (c-1) 0.9 mass part, and dichlorobenzene. Was added to obtain a resin solution (CE4-2) having a resin concentration of 10% by mass.

  The resin solution (CE4-1) was applied to one side of ZEONOR film ZF-16 (manufactured by Zeon Corporation, 100 μm thick) so that the thickness after drying would be 10 μm, dried at 80 ° C. for 8 hours, and then vacuumed. Medium was dried at 150 ° C. for 8 hours. Further, the resin solution (CE4-2) was applied to the other surface so that the thickness after drying was 10 μm, dried at 80 ° C. for 8 hours, and further dried in vacuum at 150 ° C. for 8 hours. Thus, a substrate having a thickness of 120 μm was obtained, which had a resin layer containing the compound (A) on one surface of the transparent resin substrate and a resin layer containing no compound (A) on the other surface.

  In the obtained base material, the maximum OD value at wavelengths 800 to 1000 nm is 2.8 (@ 940 nm), the average OD value at wavelengths 840 to 1040 nm is 1.0, and the wavelength 430 to 580 nm. The average transmittance was 71.4%. FIG. 33 shows the spectral characteristics (transmittance by wavelength) of the base material.

  Then, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one surface of the obtained laminate, and a dielectric multilayer film (β) is further formed on the other surface of the base material. Then, an optical filter having a thickness of 226 μm was obtained.

In the obtained optical filter, the maximum OD value at wavelengths of 800 to 1,000 nm was 4.8 (@ 940 nm), and the average transmittance at wavelengths of 430 to 580 nm was 74.7%. FIG. 34 shows the spectral characteristics (transmittance by wavelength) of the optical filter in which the dielectric multilayer films are laminated. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-940-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this comparative example and the photographic image evaluation of the camera module were performed. The ambient light sensor did not function well in changing the color tone of the screen in response to changes in outside light, and the operating condition was poor. The photographic image of the camera module was strongly reddish and the color balance of photographic quality was poor.
Table 6 summarizes the evaluation results of the optical filter in which the base material and the dielectric multilayer film are laminated.

[Comparative Example 5]
In a container, 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 0.18 parts by mass of a compound represented by the following formula (a′-1) (absorption maximum wavelength: 1037 nm), compound (b-1) 0 0.05 parts by mass, 0.056 parts by mass of compound (b-2), 0.09 parts by mass of compound (c-1), and dichloromethane were added to obtain a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, further dried at 140 ° C. in vacuum for 8 hours, and then peeled from the glass plate. The peeled film was further dried in vacuum at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 100 μm and 200 mm × 200 mm.

On one side of the obtained transparent resin substrate, the above resin composition (1) was applied by a bar coater so that the thickness of the coating layer after drying was 3 μm, and heated in an oven at 70 ° C. for 2 minutes to volatilize the solvent. Removed. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate. This obtained the base material which has the resin layer which does not contain the compound (A) on both surfaces of the transparent resin substrate which does not contain the compound (A).

  In the obtained base material, the maximum OD value at a wavelength of 800 to 1000 nm is 2.3 (@ 1000 nm), the average OD value at a wavelength of 900 to 1100 nm is 1.7, and the OD value at a wavelength of 430 to 580 nm. The average transmittance was 64.8%. FIG. 35 shows the spectral characteristics (transmittance by wavelength) of the base material.

Subsequently, a dielectric multilayer film was formed on both surfaces of the obtained base material by the same method as in Example 1 to obtain an optical filter having a thickness of 0.110 mm.
In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 3.6 (@ 1000 nm), and the average transmittance at a wavelength of 430 to 580 nm was 67.9%. FIG. 36 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-940-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this comparative example and the photographic image evaluation of the camera module were performed. The ambient light sensor did not function well in changing the color tone of the screen in response to changes in outside light, and the operating condition was poor. The photographic image of the camera module was strongly reddish and the color balance of photographic quality was poor.
The evaluation results of the base material and the optical filter are summarized in Table 6.

[Comparative Example 6]
In a container, 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 0.15 parts by mass of a compound represented by the following formula (b-6) (absorption maximum wavelength: 786 nm), compound (b-1) 0. 05 parts by mass, compound (b-2) 0.056 parts by mass, compound (c-1) 0.09 parts by mass and dichloromethane were added to obtain a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, further dried at 140 ° C. in vacuum for 8 hours, and then peeled from the glass plate. The peeled film was further dried in vacuum at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 100 μm and 200 mm × 200 mm.

On one side of the obtained transparent resin substrate, the above resin composition (1) was applied by a bar coater so that the thickness of the coating layer after drying was 3 μm, and heated in an oven at 70 ° C. for 2 minutes to volatilize the solvent. Removed. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate. By the step r, a base material having a resin layer containing no compound (A) on both surfaces of a transparent resin substrate containing no compound (A) was obtained.

  In the obtained base material, the maximum OD value at wavelengths 800 to 1000 nm is 2.8 (@ 800 nm), the average OD value at wavelengths 700 to 900 nm is 0.9, and the wavelength 430 to 580 nm. The average transmittance was 71.1%. FIG. 37 shows the spectral characteristics (transmittance by wavelength) of the base material.

Subsequently, a dielectric multilayer film was formed on both surfaces of the obtained base material by the same method as in Example 1 to obtain an optical filter having a thickness of 0.110 mm.
In the obtained optical filter, the maximum OD value at a wavelength of 800 to 1000 nm was 4.7 (@ 800 nm), and the average transmittance at a wavelength of 430 to 580 nm was 74.5%. FIG. 38 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The warp of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, LCS-0850-02 was used as an LED light source, and the operating condition of the ambient light sensor incorporating the optical filter of this comparative example and the photographic image evaluation of the camera module were carried out. The ambient light sensor did not function well in changing the color tone of the screen in response to changes in outside light, and the operating condition was poor. The photographic image of the camera module was strongly reddish and the color balance of photographic quality was poor.
The evaluation results of the base material and the optical filter are summarized in Table 6.

Meanings of symbols in "form of base material" in Table 6 are as follows.
(1): A resin layer containing no compound (A) is provided on both surfaces of a transparent resin substrate containing the compound (A).
(2): The glass substrate has a resin layer containing the compound (A) on one surface and a resin layer containing no compound (A) on the other surface.
(3): The resin film containing no compound (A) has a resin layer containing the compound (A) on one surface and the resin layer containing no compound (A) on the other surface.
(4): A resin layer containing the compound (A) is provided on one surface of the near-infrared absorption type glass substrate.
(5): The resin layer not containing the compound (A) is provided on both surfaces of the glass substrate.
(6): A transparent resin substrate containing no compound (A) has resin layers containing no compound (A) on both surfaces.

1: camera module 2: lens barrel 3: flexible substrate 4: hollow package 5: lens 6: optical filter 7 (for solid-state image sensor): (CCD or CMOS) image sensor 100: optical filter 101: transparent glass substrate or transparent Resin substrate 102: Transparent glass substrate or transparent resin substrate 103: Base material 104: Dielectric multilayer film 105: Transparent resin substrate 106: Antireflection film 110: Resin layer 111: Resin layer 200: Ambient light sensor 202: Photoelectric conversion element 204 : Housing 206: first electrode 208: photoelectric conversion layer 210: second electrode 212: color filter 214: element isolation insulating layer 216: passivation film 300: electronic device 301: RGB camera 302: dot projector 303: light projection Illuminator 304: IR camera 305: Speaker 30 : Display panel 307: housing

Claims (15)

An optical filter having a base material including a light absorption layer, and transmitting visible light,
An optical filter having a maximum OD value (1) of 3.0 or more when measured from a direction perpendicular to the substrate in a wavelength range of 800 to 1000 nm.   The optical filter according to claim 1, wherein an average value of the OD value (1) is 2.0 or less in a region of wavelength ± 100 nm where the OD value (1) shows a maximum value.   The optical filter according to claim 1 or 2, wherein the wavelength at which the OD value (1) shows the maximum value is in one of the wavelengths 820 to 880 nm or the wavelengths 910 to 970 nm.   The optical filter according to any one of claims 1 to 3, wherein the light absorption layer contains a compound (A) having an absorption maximum in a wavelength region of 800 to 1000 nm.   The compound (A) is at least one compound selected from the group consisting of squarylium compounds, cyanine compounds, pyrrolopyrrole compounds, perylene compounds, croconium compounds, and metal dithiolate compounds. The optical filter according to claim 4.   The optical filter according to any one of claims 1 to 5, wherein the base material includes a glass substrate, and the light absorption layer is provided on at least one surface of the glass substrate.   The optical filter according to claim 1, wherein the base material includes a transparent resin substrate, and the light absorption layer is provided on at least one surface of the transparent resin substrate.   The optical filter according to any one of claims 1 to 7, wherein a dielectric multilayer film is provided on at least one surface of the base material.   The optical filter according to claim 8, wherein the maximum value of the OD value (2) measured in the vertical direction of the optical filter is 5.0 or more in the wavelength range of 800 to 1000 nm.   The optical filter according to claim 8 or 9, wherein the average value of the transmittance measured in the vertical direction of the optical filter is 60% or more in the wavelength range of 430 to 580 nm.   A solid-state imaging device comprising the optical filter according to claim 1.   A camera module comprising the optical filter according to claim 1.   An ambient light sensor module comprising the optical filter according to claim 1.   An electronic device comprising the optical filter according to claim 1.   At least one type of module (A) selected from the group consisting of the camera module according to claim 12 and the ambient light sensor module according to claim 13, and the module (B) including a light emitting element for sensing are the same. An electronic device characterized in that the electronic device is arranged in a plane and within 4 cm.