JP7155855B2 - Optical filter and its use - Google Patents

Description

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

In recent years, information terminal devices such as smart phones and tablet terminals are rapidly becoming more sophisticated. In addition to the existing camera (imaging) function, the information terminal device will be newly equipped with an ambient light sensing function, a biometric authentication function such as iris recognition and face recognition, an AR/VR function, and a spatial recognition function such as air touch. flow.

Therefore, in addition to conventional camera modules, ambient light sensor modules, face recognition modules with sensing functions, AR/VR modules, and the like are being densely mounted in a narrow area of terminals.

On the other hand, light emitted from sensing light emitting elements such as LEDs with specific wavelengths used as light sources for sensing (dot projectors, floodlight illuminators, etc.) and light emitting elements for sensing such as laser light sources is reflected light that hits the sensing target. , and reflected light in the device enters the camera module and the ambient light sensor module, causing deterioration of the camera image quality and malfunction of the screen color tone adjustment by the ambient light sensor.

Furthermore, in order to increase the sensing distance, the output of the light source is increased, which increases the amount of reflected light. As a result, it is expected that the deterioration of the image quality of the camera and the poor adjustment of the screen color tone due to the ambient light sensor will increase.

In order to reduce the influence of the sensing light source, it is very effective to provide the optical filter for the ambient light sensor module and the camera module with the function of cutting the reflected light from the sensing light source. Light sources that emit light in the near-infrared wavelength region are generally used as light sources for sensing. has been proposed (see Patent Documents 1 and 2, for example).

However, in order to eliminate the influence of reflected light from the sensing light source, it is necessary to contain an absorbent at a very high concentration in the optical filter, which has the problem of reducing the visible light transmittance. In addition, 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 is conceivable. , a decrease in adhesion between the dielectric multilayer film and the substrate, and an increase in noise to the sensor due to reflection within the dielectric multilayer film.

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

The present invention effectively cuts the reflected light from the sensing light source, and has high visible light transmittance, low warpage, good adhesion of the dielectric multilayer film, and reflection on the dielectric multilayer film to the sensor. An object of the present invention is to provide an optical filter capable of achieving noiselessness. Another object of the present invention is to provide an optical filter that can cope with high output of light-emitting elements for sensing.

As a result of intensive studies to solve the above problems, the present inventors have found that by applying an absorbent that has an absorption maximum wavelength close to the emission wavelength of the sensing light source and has sharp absorption characteristics, reflected light from the sensing light source can be effectively cut, and the adverse effect of reflected light from the sensing light source on the ambient light sensor element or solid-state image sensor is reduced to a level that is not problematic, while the optical filter has high visible light transmittance, low warpage, and The inventors have found that it is possible to achieve good adhesion of a dielectric multilayer film, and have completed the present invention. Examples of aspects of the invention are provided below.

[1] An optical filter having a base material including a light absorption layer and transmitting visible light,
An optical filter characterized by having a maximum OD value (1) of 3.0 or more when measured from the vertical direction of the substrate in a wavelength range of 800 to 1000 nm.

[2] The optical system according to item [1], wherein the average value of the OD value (1) is 2.0 or less in the region of the wavelength ± 100 nm where the OD value (1) exhibits the maximum value. filter.

[3] Item [1] or [2], wherein the wavelength at which the OD value (1) exhibits the maximum value is in either a wavelength range of 820 to 880 nm or a wavelength range of 910 to 970 nm. optical filter.

[4] The optical filter of 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-based compounds, cyanine-based compounds, pyrrolopyrrole-based compounds, perylene-based compounds, croconium-based compounds, and metal dithiolate-based compounds. The optical filter according to item [4], characterized by:

[6] Any one of items [1] to [5], wherein the substrate includes a glass substrate, and the light absorption layer is provided on at least one surface of the glass substrate. optical filters.

[7] Any one of items [1] to [5], 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 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 side of the substrate.
[9] The optical device according to item [8], wherein the maximum value of the OD value (2) measured from 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 device according to item [8] or [9], wherein the average transmittance measured in the vertical direction of the optical filter is 60% or more in the wavelength region 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 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) comprising a sensing light-emitting element. are arranged on the same plane and within 4 cm from each other.

According to the present invention, while effectively cutting the reflected light from the sensing light source, the optical filter has high visible light transmittance, low warpage, good adhesion of the dielectric multilayer film, and reflection from the dielectric multilayer film. It is possible to provide an optical filter capable of achieving noiselessness to the sensor due to Moreover, such an optical filter of the present invention can be suitably used in an electronic device having a sensing light-emitting element 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. FIG. 4 is a schematic diagram showing a configuration example of a base material in the optical filter of the present 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. 4 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Example 1. FIG. 4 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 1. FIG. 4 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Example 2. FIG. 4 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 2. FIG. 4 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Example 3. FIG. 4 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 3. FIG. 10 is a graph showing the spectral transmittance of the substrate obtained in Example 4 measured in the vertical direction. 4 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 4. FIG. 10 is a graph showing the spectral transmittance of the substrate obtained in Example 5 measured in the vertical direction. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 5. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Example 6. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 6. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Example 7. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 7. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Example 8. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 8. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Example 9. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 9. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Example 10. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Example 10. FIG. 4 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Comparative Example 1. FIG. 4 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Comparative Example 1. FIG. 4 is a graph showing the spectral transmittance of the base material obtained in Comparative Example 2 measured in the vertical direction. 5 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Comparative Example 2. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Comparative Example 3. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Comparative Example 3. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Comparative Example 4. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Comparative Example 4. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Comparative Example 5. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Comparative Example 5. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the substrate obtained in Comparative Example 6. FIG. 10 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Comparative Example 6. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings etc. as necessary. However, the present invention can be implemented in many different aspects and should not be construed as being limited to the description of the embodiments exemplified below. In order to make the description clearer, the drawings may schematically show the width, thickness, shape, etc. of each part compared to the actual embodiment, but this is only an example and limits the interpretation of the present invention. not a thing In addition, in this specification and each figure, the same reference numerals or similar reference numerals (numbers followed by A, B, etc.) are given to the same elements as those described above with respect to the previous figures. and detailed description may be omitted as appropriate.

In this specification, the term "top" refers to a relative position with respect to the main surface of the support substrate (the light receiving surface of the sensor), and the direction away from the main surface of the support substrate is "up". In this drawing, "top" is the upper side toward the paper surface. "Above" includes the case of being in contact with the object (that is, the case of "on") and the case of being located above the object (that is, the case of "over"). Conversely, "lower" refers to a relative position with respect to the main surface of the supporting substrate, and the direction toward the main surface of the supporting substrate is "lower". In this drawing, the downward direction toward the paper surface is "bottom".

[Optical filter]
The optical filter according to the present invention is an optical filter that has a base material that includes a light absorption layer and 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 value of the OD value (1) of is 3.0 or more.

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

In the region of the wavelength ±100 nm where the OD value (1) exhibits the maximum value, the average value of the OD value (1) is preferably 2.0 or less, more preferably 0.1 to 1.8, and further It is preferably 0.2 to 1.5. When the average value of the OD value (1) is more than 2.0, the cut efficiency of the reflected light from the sensing light source by the light-absorbing compound is low, so, for example, it is necessary to use a high-concentration light-absorbing compound. may become. However, in such a case, the visible light transmittance of the optical filter is significantly degraded, so that the visible light incident on the solid-state imaging device or the ambient light sensor is insufficient, and the sensor sensitivity may be degraded.

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

Examples of light-absorbing compounds other than the compound (A) include a compound (B) having a maximum absorption in a wavelength range of 600 nm or more and less than 800 nm, and a compound (C) having an absorption maximum in a wavelength range of more than 1000 nm and 1200 nm or less. is mentioned.

A preferred embodiment of the light absorption layer includes 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. etc. Further, a light-absorbing compound other than the compound (A) may be contained in the light-absorbing layer, may be contained in a resin layer separate from the light-absorbing layer, or may be contained in a glass substrate or a transparent resin substrate. 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 transparency to visible light and a high shielding property to near-infrared rays. Phosphate glass also includes silicate phosphate glass in which a part of the glass skeleton is composed of SiO ₂ . Examples of 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%, with F 0.5-32%; A glass containing 0.5 to 7 parts by mass of CuO per 100 parts by mass of a base glass containing 26 to 54% 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' Glasses consisting of 3-18% ₂ O (R'=Li, Na, K), provided that up to 39% molar amount of O ^2- ions are replaced by F ^- ions.

(iii) P ₂ O ₅ 5-45%, ArF ₃ 1-35%, RF (R is Li, Na, K) 0-40%, R'F ₂ (R' is Mg, Ca, Sr, Ba, Pb, Zn) 10 to 75%, R"Fm (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 fluoride content can be replaced by oxides), and glasses containing 0.2-15% CuO.

(iv) P ^{5+ 11-43} %, Al ^{3+ 1-29} %, R cations (content of Mg, Ca, Ba, Pb, Zn ions) 14-50%, R′ cations (Li , Na, K ion content) 0-43%, R″ cations (La, Y, Cd, Si, B, Zr, Ta ion content) 0-8%, and Cu ²⁺ 0.5-13%. and further containing 17 to 80% F ^- in % anions.

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

(vi) 70-85% P ₂ O ₅ , 8-17% Al ₂ O ₃ , 1-10% B ₂ O ₃ , 0-3% Li ₂ O, 0-5% Na ₂ O, expressed in mass % , K ₂ O 0 to 5%, Li ₂ O + Na ₂ O + K ₂ O 0.1 to 5%, and SiO ₂ 0 to 3%. Glass containing 5 parts by mass.

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

Moreover, the CuO-containing glass may further contain a metal oxide. When one or more of Fe ₂ O ₃ , MoO ₃ , WO ₃ , CeO ₂ , Sb ₂ O ₃ , V ₂ O ₅ and the like are contained as metal oxides, the CuO-containing glass has ultraviolet absorption properties. . The content of the metal name oxide is at least _one selected from the group consisting of Fe ₂ O ₃ , MoO ₃ , WO ₃ and CeO ₂ with respect to 100 parts by mass of the CuO _- containing glass. 0.6 to 5 parts by mass, 0.5 to 5 parts by mass of MoO ₃ , 1 to 6 parts by mass of WO ₃ , 2.5 to 6 parts by mass of CeO ₂ , or two types of Fe ₂ O ₃ and Sb ₂ O ₃ 0.6 to 5 parts by mass of Fe ₂ O ₃ +0.1 to 5 parts by mass of Sb ₂ O ₃ , or two kinds of V ₂ O ₅ and CeO ₂ and 0.01 to 0.5 parts by mass of V ₂ O ₅ +CeO ₂ 1 to 6 parts by mass is preferable.

The thickness of the CuO-containing fluorophosphate glass or CuO-containing phosphate glass is preferably in the range of 0.03 to 5 mm. A range of 05 to 1 mm is more preferred.

Although the OD value in the wavelength region of 800 to 1000 nm can be improved by increasing the CuO content in the CuO glass, the strength of the glass decreases as the CuO content increases, resulting in poor handling properties when the glass substrate is thinned. There is a problem that the Therefore, it is preferable to improve the OD value by laminating a resin layer containing a light-absorbing compound on the glass.

In the present invention, a non-absorbing glass substrate can be used as the glass substrate. The glass substrate having no absorption is not particularly limited as long as it contains silicate as a main component, and examples thereof include a quartz glass substrate having a crystalline structure. In addition, borosilicate glass substrates, soda glass substrates, colored glass substrates, and the like can be used. In particular, glass substrates such as alkali-free glass substrates and low-α-ray glass substrates have little effect 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 cyclic polyolefin-based resins, aromatic polyether-based resins, fluorene polycarbonate-based resins, and polyester-based resins. , fluorene polyester resins, polycarbonate resins, polyimide resins, polyamide resins, polyamideimide resins, polyester resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyvinyl butyral resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curing resins, urethane acrylate resins, silsesquioxane curing resins, acrylic curing resins and Examples thereof include resins mainly composed of silica formed by a sol-gel method. The said transparent resin may be used individually by 1 type, or may use 2 or more types.

Examples of commercially available products of the cyclic (poly)olefin resin include Arton manufactured by JSR Corporation, Zeonor manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. can. Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. and the like can be cited as commercial products of the polyether sulfone-based resin. Commercially available products of the polyimide resin include Neoprim manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. Examples of the aromatic polyester resin film include Unitika's UNIFINER. Commercial products of the polycarbonate-based resin include Pure Ace manufactured by Teijin Chemicals Limited. Commercially available products of the fluorene polycarbonate resin include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc. and the like. As a commercial product of the fluorene polyester-based resin, OKP4HT manufactured by Osaka Gas Chemicals Co., Ltd. can be mentioned. Examples of commercially available acrylic resins include Acryvure manufactured by Nippon Shokubai Co., Ltd., and the like. Examples of commercially available products of the silsesquioxane-based UV-curable resin include Silplus manufactured by Nippon Steel Chemical Co., Ltd., and the like.

The transparent resin substrate may be used singly, or two or more transparent resin substrates may be bonded or laminated.
By using the base material as described above, the reflected light from the sensing light source can be effectively cut, while the optical filter has a 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 and noiselessness. Such an optical filter of the present invention can be used in an ambient light sensor module or a camera module in a device equipped with sensing light-emitting elements.

1A, 1B and 1C show configuration examples of the optical filter of the present invention. An optical filter 100a shown in FIG. 1A has a dielectric multilayer film 104 on at least one surface of a base material 103. As shown in FIG. The dielectric multilayer film 104 has a characteristic of reflecting near-infrared rays. FIG. 1B also shows an optical filter 100b in which a first dielectric multilayer film 104a is provided on one surface of a substrate 103 and a second dielectric multilayer film 104b is provided on the other surface. Thus, the dielectric multilayer film that reflects near-infrared rays may be provided on one side or both sides of the substrate. When provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when provided on both sides, it is possible to obtain an optical filter that 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 to provide the dielectric multilayer film on both sides of the base material because it is preferable that the optical filter is less warped or twisted.

The dielectric multilayer film 104 preferably transmits light of a wavelength corresponding to visible light and has a reflection characteristic over the entire wavelength range of 800 to 1150 nm with respect to light incident from the vertical direction, more preferably. It preferably has reflection properties over the entire wavelength range from 800 to 1200 nm, particularly preferably from 800 to 1250 nm. As a form having a dielectric multilayer film on both sides of the base material 103, when measured from an angle of 5 degrees with respect to the vertical direction of the optical filter (or base material), it has a reflection characteristic mainly in the vicinity of the wavelength of 800 to 1000 nm. 1 The dielectric multilayer film 104a is provided on one side of the substrate 102, and the optical filter (or substrate) on the other side of the substrate 103 is measured from an angle of 5 degrees with respect to the vertical direction of the optical filter (or substrate). (2) has a second dielectric multilayer film 104b mainly having reflective properties.

As another form, the optical filter 100c shown in FIG. 1C has a dielectric multilayer film 104 as a base material, which has reflection characteristics mainly in the vicinity of wavelengths of 800 to 1250 nm when measured from an angle of 5 degrees with respect to the vertical direction. 103, and the other surface of the substrate 103 has an antireflection film 106 having antireflection properties in the visible range. By combining the dielectric multilayer film and the anti-reflection film on the substrate, it is possible to reflect near-infrared rays while increasing the light transmittance in the visible region.

2A, 2B, 2C, 2D, and 2E show configuration examples of the substrate 103. FIG. The substrate 103 may be a single layer or a multilayer, and preferably has a layer containing one or more of the compound (A), and the layer containing the compound (A) is a transparent resin layer. is more preferred.

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 compound (B) and/or the compound (C) may be contained in the transparent resin substrate 105 . In FIG. 2B, the substrate is composed of two layers, and is composed of a laminated structure of a transparent glass substrate or transparent resin substrate 101 containing no light absorbing compound and a resin layer 110 containing the compound (A). The resin layer 110 may contain the compound (B) and/or the compound (C). In FIG. 2C, the substrate is composed of three layers, and is composed of a transparent glass substrate or transparent resin substrate 101 containing no light absorbing compound, and resin layers 110 and 111 laminated on both sides thereof. At least one of the resin layers may contain the compound (A), and the resin layers on both sides may contain the compound (B) and/or the compound (C) independently. In FIG. 2D, the substrate is composed of two layers, and is composed of a laminated structure of an absorption type 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 substrate is formed of three layers, consisting of an absorptive glass or transparent resin substrate 102 containing a light-absorbing compound, and resin layers 110 and 111 laminated on both sides thereof. At least one of the resin layers may contain the compound (A), and the resin layers on both sides may contain the compound (B) and/or the compound (C) independently. Moreover, 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, it is preferable that the glass substrate is a colorless and transparent glass substrate that does not contain an absorbent such as copper fluorophosphate in order to achieve both thinness and strength of the substrate. This tendency becomes remarkable when the thickness is 150 μm or less. A glass containing an absorber such as copper fluorophosphate has a problem that its strength is greatly reduced by thinning. When a transparent resin substrate is used, curable resin or thermoplastic resin is applied to both sides of the transparent resin substrate in order to facilitate adjustment of optical characteristics, achieve scratch-removing effects of the transparent resin substrate, and improve scratch resistance of the substrate. It is preferable that a resin layer such as an overcoat layer made of resin is laminated.

In order to obtain a base material containing a light-absorbing layer that satisfies the above characteristics, it is necessary to have an absorption maximum around the target wavelength (a wavelength close to the emission wavelength of the light source of the light-emitting element), and the absorption characteristics should be the shape of the emission spectrum of the light-emitting element. It is preferred 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 desired characteristics of the present invention. 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 to 880 nm, preferably 830 to 870 nm, more preferably 835 to 865 nm, or
(2) 910 to 970 nm, more preferably 920 to 960 nm, still more preferably 925 to 955 nm
It is desirable to be in the range of either Among these, the range of (2) is preferable.

Light-emitting elements with central emission wavelengths of 850 nm and 940 nm are commonly used as light sources for sensing, but light-emitting elements with a wavelength of 940 nm can be used in terms of visibility, linearity (less scattering), etc. This is because it is mainstream.

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

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

式（Ｉ）中、置換ユニットＡおよびＢは、それぞれ独立に下記式（I-i）、（I-ii）および（I-iii）で表される置換ユニットのいずれかを表す。

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

In formulas (Ii), (I-ii) and (I-iii), the portion represented by the wavy line represents the bonding site with the central four-membered ring, Xa is independently an oxygen atom, a sulfur atom, a selenium atom, tellurium represents an atom or —NR ¹² —, wherein R ¹ to R ¹¹ 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, a —NR ^g R ^h group; , —SR ⁱ group, —SO ₂ R ⁱ group, —OSO ₂ R ⁱ group, or any one of the following L ^a to L ^h , wherein R ^g and R ^h are each independently a hydrogen atom, —C(O) R ⁱ group or any one of L ^a to L ^e below, R ⁱ represents any one of L ^a to L ^e below,
(L ^a ) Aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) Halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) Alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) Carbon Aromatic hydrocarbon group having 6 to 14 carbon atoms (L ^e ) Heterocyclic group having 3 to 14 carbon atoms (L ^f ) Alkoxy group having 1 to 12 carbon atoms (L ^g ) Number of carbon atoms which may have substituent L 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L 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 group, hydroxyl group, amino group, dimethylamino group and nitro group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group and hydroxyl group.

R ² to R ¹¹ are preferably each independently hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and 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 amino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexynoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl 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, t-butanoylamino group, cyclohexynoylamino group, methylthio group and ethylthio group.

R ¹² is preferably a 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.

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

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 formula (I-i), formula (I-ii), or formula (I-iii). Although they may be present or different, it is preferred that they are the same, including the substituents in the units, for ease of synthesis.

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

式（Ｉ－ａ）～式（Ｉ－ｃ）においてＸa、Ｒ¹、Ｒ²～Ｒ⁷は上記と同様の原子または基を表す。

In formulas (Ia) to (Ic), Xa, R ¹ , R ² to R ⁷ represent the same atoms or groups as above.

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

前記化合物（Ａ）として用いることができるシアニン系化合物としては、特に限定されないが、下記式（ＩＩ）で表される化合物（ＩＩ）が好ましい。

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

式（ＩＩ）中、置換ユニットＣおよびＤは下記式（II-i） ～（II-v）のいずれかを表し、Ｘb^-は一価のアニオンを表す。

In formula (II), substitution units C and D represent any one of formulas (II-i) to (II-v) below, and Xb ^- represents a monovalent anion.

式（II-i） ～（II-v）中、波線で表わした部分が中央メチン鎖部との結合部位を表し、Ｘaは、独立に酸素原子、硫黄原子、セレン原子、テルル原子または－ＮＲ¹²－を表し、Ｒ¹～Ｒ⁷は、それぞれ独立に水素原子、ハロゲン原子、スルホン酸基、水酸基、シアノ基、ニトロ基、カルボキシル基、リン酸基、－ＮＲ^gＲ^h基、－ＳＲⁱ基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、－Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a～Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a～Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１～１２の脂肪族炭化水素基
（Ｌ^b）炭素数１～１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３～１４の脂環式炭化水素基
（Ｌ^d）炭素数６～１４の芳香族炭化水素基
（Ｌ^e）炭素数３～１４の複素環基
（Ｌ^f）炭素数１～１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１～１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１～１２のアルコキシカルボニル基
置換基Ｌは、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のハロゲン置換アルキル基、炭素数３～１４の脂環式炭化水素基、炭素数６～１４の芳香族炭化水素基および炭素数３～１４の複素環基からなる群より選ばれる少なくとも１種である。

In formulas (II-i) to (II-v), the portion represented by the wavy line represents the bonding site with the central methine chain portion, and Xa is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ¹² —, and 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, a —NR ^g R ^h group, and —SR ⁱ group, —SO ₂ R ⁱ group, —OSO ₂ R ⁱ group, or any one of L ^a to L ^h below, wherein R ^g and R ^h each independently represent a hydrogen atom, —C(O)R ⁱ group, or Represents any one of L ^a to L ^e below, R ⁱ represents any one of L ^a to L ^e below,
(L ^a ) Aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) Halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) Alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) Carbon Aromatic hydrocarbon group having 6 to 14 carbon atoms (L ^e ) Heterocyclic group having 3 to 14 carbon atoms (L ^f ) Alkoxy group having 1 to 12 carbon atoms (L ^g ) Number of carbon atoms which may have substituent L 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L 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 a 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 each independently represent 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 two adjacent Z's or two Y's selected from adjacent to each other, nitrogen atom, oxygen a 5- to 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 formed by bonding two adjacent Zs or two Ys selected from each other, or
represents a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms, formed by bonding two adjacent Zs or Ys selected from each other and containing at least one nitrogen atom, oxygen atom or sulfur atom;
These alicyclic hydrocarbon groups, aromatic hydrocarbon groups and heterocyclic aromatic hydrocarbon groups 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 represents a hydrogen atom or any of the above L ^a to L ^e ;
Q ³ represents a hydroxyl group or any one of L ^a to L ^e described above.

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

前記化合物（Ａ）として用いることができるピロロピロール系化合物としては、特に限定されないが、下記式（III）で表される化合物（III）が好ましい。

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

式（III）中、置換ユニットＥおよびＦは、下記式（III-i）～（III-ii）のいずれかを表し、Ｒ¹～Ｒ²⁰は、それぞれ独立に水素原子、ハロゲン原子、スルホン酸基、水酸基、シアノ基、ニトロ基、カルボキシル基、リン酸基、－ＮＲ^gＲ^h基、－ＳＲⁱ基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、－Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a～Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a～Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１～１２の脂肪族炭化水素基
（Ｌ^b）炭素数１～１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３～１４の脂環式炭化水素基
（Ｌ^d）炭素数６～１４の芳香族炭化水素基
（Ｌ^e）炭素数３～１４の複素環基
（Ｌ^f）炭素数１～１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１～１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１～１２のアルコキシカルボニル基
置換基Ｌは、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のハロゲン置換アルキル基、炭素数３～１４の脂環式炭化水素基、炭素数６～１４の芳香族炭化水素基および炭素数３～１４の複素環基からなる群より選ばれる少なくとも１種である。

In formula (III), substitution units E and F represent any one of the following formulas (III-i) to (III-ii), and R ¹ to R ²⁰ each independently represent a hydrogen atom, a halogen atom, a sulfonic acid a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -NR ^g R ^h group, a -SR ⁱ group, a -SO ₂ R ⁱ group, a -OSO ₂ R ⁱ group, or L ^a to L ^h below. R ^g and R ^h each independently represent a hydrogen atom, a —C(O)R ⁱ group, or any of L ^a to L ^e below, and R ⁱ is any one of L ^a to L ^e below represents
(L ^a ) Aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) Halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) Alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) Carbon Aromatic hydrocarbon group having 6 to 14 carbon atoms (L ^e ) Heterocyclic group having 3 to 14 carbon atoms (L ^f ) Alkoxy group having 1 to 12 carbon atoms (L ^g ) Number of carbon atoms which may have substituent L 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L 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, or 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 optionally having substituent L, optionally having substituent L is an alkoxycarbonyl group having 1 to 16 carbon atoms, 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, or an alicyclic group having 3 to 14 carbon atoms. It is at least one selected from the group consisting of hydrocarbon groups, aromatic hydrocarbon groups having 6 to 14 carbon atoms and heterocyclic groups having 3 to 14 carbon atoms.

Xc to Xf are each independently electrons such as cyano group, nitro group, carboxyl group, phosphate group, -SR ⁱ group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group, halogen atom, sulfonic acid group, hydroxyl group, etc. represents an attractive group.

式（III-i）～（III-ii）中、波線で表した部分がイミン構造部位との結合部位を表し、Ｘaは酸素原子、硫黄原子、セレン原子、テルル原子、または－ＮＲ¹²－を表し、 Ｒ²～Ｒ⁷は、それぞれ独立に水素原子、ハロゲン原子、スルホン酸基、水酸基、シアノ基、ニトロ基、カルボキシル基、リン酸基、－ＮＲ^gＲ^h基、－ＳＲⁱ基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、－Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a～Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a～Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１～１６の脂肪族炭化水素基
（Ｌ^b）炭素数１～１６のハロゲン置換アルキル基
（Ｌ^c）炭素数３～１８の脂環式炭化水素基
（Ｌ^d）炭素数６～１８の芳香族炭化水素基
（Ｌ^e）炭素数３～１８の複素環基
（Ｌ^f）炭素数１～１６のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１～１６のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１～１６のアルコキシカルボニル基
置換基Ｌは、炭素数１～１６の脂肪族炭化水素基、炭素数１～１６のハロゲン置換アルキル基、炭素数３～１８の脂環式炭化水素基、炭素数６～１８の芳香族炭化水素基および炭素数３～１８の複素環基からなる群より選ばれる少なくとも１種である。

In formulas (III-i) to (III-ii), the part represented by the wavy line represents the bonding site with the imine structural site, and Xa is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR ¹² -. R ² 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, a —NR ^g R ^h group, a —SR ⁱ group, and — SO ₂ R ⁱ group, —OSO ₂ R ⁱ group, or any one of L ^a to L ^h below, wherein R ^g and R ^h are each independently a hydrogen atom, —C(O)R ⁱ group, or L ^a below to L ^e , R ⁱ represents any one of L ^a to L ^e below,
(L ^a ) Aliphatic hydrocarbon group having 1 to 16 carbon atoms (L ^b ) Halogen-substituted alkyl group having 1 to 16 carbon atoms (L ^c ) Alicyclic hydrocarbon group having 3 to 18 carbon atoms (L ^d ) Carbon Aromatic hydrocarbon group having 6 to 18 carbon atoms (L ^e ) Heterocyclic group having 3 to 18 carbon atoms (L ^f ) Alkoxy group having 1 to 16 carbon atoms (L ^g ) Number of carbon atoms that may have substituent L 1 to 16 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 16 carbon atoms which may have a substituent L 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).

前記化合物（Ａ）として用いることができるクロコニウム系化合物としては、特に限定されないが、下記式（ＩＶ）で表される化合物（ＩＶ）が好ましい。

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

式（ＩＶ）中、Ｒ¹～Ｒ⁵は、それぞれ独立に水素原子、ハロゲン原子、スルホン酸基、水酸基、シアノ基、ニトロ基、カルボキシル基、リン酸基、－ＮＲ^gＲ^h基、－ＳＲⁱ基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、－Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a～Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a～Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１～１２の脂肪族炭化水素基
（Ｌ^b）炭素数１～１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３～１４の脂環式炭化水素基
（Ｌ^d）炭素数６～１４の芳香族炭化水素基
（Ｌ^e）炭素数３～１４の複素環基
（Ｌ^f）炭素数１～１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１～１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１～１２のアルコキシカルボニル基
置換基Ｌは、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のハロゲン置換アルキル基、炭素数３～１４の脂環式炭化水素基、炭素数６～１４の芳香族炭化水素基および炭素数３～１４の複素環基からなる群より選ばれる少なくとも１種である。

In formula (IV), R ¹ to R ⁵ 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, —OSO ₂ R ⁱ group, or any one of the following L ^a to L ^h , wherein R ^g and R ^h are each independently a hydrogen atom and —C(O)R ⁱ group; or represents any one of L ^a to L ^e below, and R ⁱ represents any one of L ^a to L ^e below,
(L ^a ) Aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) Halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) Alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) Carbon Aromatic hydrocarbon group having 6 to 14 carbon atoms (L ^e ) Heterocyclic group having 3 to 14 carbon atoms (L ^f ) Alkoxy group having 1 to 12 carbon atoms (L ^g ) Number of carbon atoms which may have substituent L 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L 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, 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- A decyl group and 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 and an n-decyl group.

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

前記化合物（Ａ）として用いることができるペリレン系化合物としては、特に限定されないが、クオタリレン、ペンタリレン、ヘキサリレン化合物を使用することができる。ペリレン系化合物の具体例としては、例えば特開2012-111863号公報に記載の化合物が挙げられる。

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

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

式（Ｖ）中、Ｒ²⁹～Ｒ³²は、それぞれ独立にメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル器、ｔｅｒｔ－ブチル基、シクロヘキシル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－へプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、フェニル基、メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、ｎ－ブチルチオ基、フェニルチオ基、ベンジルチオ基、隣り合うＲ²⁹とＲ³⁰、Ｒ³¹とＲ³²同士が環を形成する基である。隣り合うＲ²⁹とＲ³⁰、Ｒ³¹とＲ³²同士が環を形成する基である場合、環の中に少なくとも一つ以上の硫黄原子もしくは窒素原子が含まれる複素環であることが好ましい。Ｍaは金属原子であり、好ましくは遷移金属であり、より好ましくはＮｉ、Ｐｄ，Ｐｔである。ＱはＧ（Ｒⁱ）₄を表し、Ｇは窒素原子、リン原子またはビスマス原子を表し、Ｒⁱはメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル器、ｔｅｒｔ－ブチル基、シクロヘキシル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－へプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、フェニル基である。ｙは０もしくは１を表す。

In formula (V), R ²⁹ to R ³² each independently represent a 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-nonyl group, n-decyl group, phenyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, phenylthio group , a benzylthio group, adjacent R ²⁹ and R ³⁰ , R ³¹ and R ³² together forming a ring. When adjacent R ²⁹ and R ³⁰ or R ³¹ and R ³² are groups forming a ring, it is preferably a heterocyclic ring containing at least one sulfur atom or nitrogen atom in the ring. Ma is a metal atom, preferably a transition metal, more preferably Ni, Pd or Pt. Q represents G(R ⁱ ) ₄ , G represents a nitrogen atom, a phosphorus atom or a bismuth atom, R ⁱ represents a 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-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)>
Examples of the compound (B) include, but are not limited to, squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, and cyanine-based compounds. By using the compound (B), it is possible to obtain an optical filter whose optical properties are less dependent on the angle of incidence.

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

式（VI）中、Ｒ^a、Ｒ^bおよびＹは、下記（VI-i）または（VI-ii）の条件を満たす。

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

Condition (VI-i)
A plurality of R ^a 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 group. R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e .

A plurality of R ^b each independently represents 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 group (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 each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -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 L ^a to L ^h are
(L ^a ) an aliphatic hydrocarbon group having 1 to 9 carbon atoms which may have a substituent L,
(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 ) 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, or an aromatic hydrocarbon 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.

The 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

The total number of carbon atoms, including substituents, 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 exceeds this range, it may become difficult to synthesize the dye, and the absorption intensity per unit mass tends to decrease.

Condition (VI-ii)
at least one of two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a heterocyclic ring having 5 or 6 atoms and containing at least one nitrogen atom; The heterocyclic ring may have a substituent, and R ^b and R ^a that does not participate in the formation of the heterocyclic ring are each independently synonymous with R ^b and R ^a in (VI-i) above.

式（VII）中、Ｘhは、Ｏ、Ｓ、Ｓｅ、Ｎ－Ｒ^cまたはＣ－Ｒ^dＲ^dを表し；複数あるＲ^cは、それぞれ独立に水素原子、－Ｌ^a、－Ｌ^b、－Ｌ^c、－Ｌ^dまたは－Ｌ^eを表し；複数あるＲ^dは、それぞれ独立に水素原子、ハロゲン原子、スルホン酸基、水酸基、シアノ基、ニトロ基、カルボキシル基、リン酸基、－Ｌ¹または－ＮＲ^eＲ^f基を表し、隣り合うＲ^d同士は連結して置換基を有していてもよい環を形成してもよく；Ｌ^a～Ｌ^e、Ｌ¹、Ｒ^eおよびＲ^fは、前記式（VI）において定義したＬ^a～Ｌ^e、Ｌ¹、Ｒ^eおよびＲ^fと同義である。

In formula (VII), ^Xh represents O, S, ^Se , N—R ^c or ^C —R ^d R ^d ; L ^c , -L ^d or -L ^e ; multiple R ^d are each independently hydrogen atom, halogen atom, sulfonic acid group, hydroxyl group, cyano group, nitro group, carboxyl group, phosphoric acid group, -L ¹ or -NR ^e R ^f group, and adjacent R ^d may be linked to form a ring optionally having a substituent; L ^a to L ^e , L ¹ , R ^e and R ^f is synonymous with L ^a to L ^e , L ¹ , R ^e and R ^f defined in formula (VI) above.

Compound (VI) and compound (VII) are represented by the following formulas (VI-2) and (VII-2) in addition to the methods of describing formulas (VI-1) and (VII-1) below. The structure can also be represented by a description method such as taking a resonance structure. In other words, 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) is only the method of describing the structure, and as a compound both represent the same thing. In the present invention, unless otherwise specified, structures of squarylium-based compounds are represented by methods of description such as the following formulas (VI-1) and (VII-1) below.

化合物（VI）および化合物（VII）は、それぞれ上記式（VI）および上記式（VII）の要件を満たせば特に構造は限定されないが、例えば上記式（VI-1）および上記式（VII-1）のように構造を表した場合、中央の四員環に結合している左右の置換基は同一であっても異なっていてもよいが、同一であった方が合成上容易であるため好ましい。なお、例えば、下記式（VI-3）で表される化合物と下記式（VI-4）で表される化合物は、同一の化合物であると見なすことができる。

The structures of compound (VI) and compound (VII) are not particularly limited as long as they satisfy the requirements of formula (VI) and formula (VII) above, respectively. ), the left and right substituents bonded to the central four-membered ring may be the same or different, but the same one 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.

前記化合物（Ｂ）として用いることができるフタロシアニン系化合物としては、特に限定されないが、例えば、下記式（VIII）で表される化合物（VIII）が好ましい。

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

式（VIII）中、Ｍbは、２個の水素原子、２個の１価の金属原子、２価の金属原子、または３価もしくは４価の金属原子を含む置換金属原子を表し、複数あるＲ_a、Ｒ_b、Ｒ_cおよびＲ_dは、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシル基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴を表す。または、複数あるＲ_a、Ｒ_b、Ｒ_cおよびＲ_dは、Ｒ_aとＲ_b、Ｒ_bとＲ_cおよびＲ_cとＲ_dのうち少なくとも１つの組み合わせが結合した、下記式（VIII－Ａ）～（VIII－Ｈ）で表される基からなる群より選ばれる少なくとも１種の基を表す。ただし、同じ芳香環に結合したＲ_a、Ｒ_b、Ｒ_cおよびＲ_dのうち少なくとも１つが水素原子ではない。

In formula (VIII), M represents a substituted metal atom containing two hydrogen atoms, two monovalent metal atoms, divalent metal atoms, or trivalent or tetravalent metal atoms, and a plurality of R _a , R _b , R _c and R _d each independently represent 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 ; _{Alternatively} , _a plurality of R _a , R _b , R _c and R _d are _{represented by} the _following formula ₍ VIII-A ) to (VIII-H). 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, amido group, imido group and silyl group may have a substituent L as defined in formula (VI) above,
L ¹ is synonymous with L ¹ defined in the formula (VI),
L ² represents a hydrogen atom or any of L ^a to L ^e defined in the formula (VI);
L ³ represents a hydroxyl group or any one of L ^a to L ^e ;
L ⁴ represents any one of the above L ^a to L ^e .

式（VIII－Ａ）～（VIII－Ｈ）中、Ｒ_xとＲ_yの組み合わせは、Ｒ_aとＲ_b、Ｒ_bとＲ_cまたはＲ_cとＲ_dの組み合わせであり、
複数あるＲ_A～Ｒ_Lは、それぞれ独立に水素原子、ハロゲン原子、水酸基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴を表し、
前記アミノ基、アミド基、イミド基およびシリル基は、前記置換基Ｌを有してもよく、Ｌ¹～Ｌ⁴は前記式（VI）において定義したＬ¹～Ｌ⁴と同義である。

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 ;
A plurality of R _A to R _L are each independently 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 , -SL ² , -SS. -L ² , -SO ₂ -L ³ , -N=N-L ⁴ ,
The amino group, amido group, imide group and silyl group may have the substituent L, and L ¹ to L ⁴ have the same definitions as L ¹ to L ⁴ defined in formula (VI).

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

式（IX）中、Ｍcは、前記式（VIII）のＭbと同義であり、Ｒ_a、Ｒ_b、Ｒ_c、Ｒ_d、Ｒ_eおよびＲ_fは、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシル基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴を表す。

In formula (IX), Mc has the same definition 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, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=N- represents ^L4 .

The cyanine compound that can be used as the compound (B) is not particularly limited, but for example, compounds (X-1) to (X- 3) is preferred.

式（Ｘ－１）～（Ｘ－３）中、Ｘ_b ^-は１価のアニオンを表し、
複数あるXiは、独立に炭素原子、窒素原子、酸素原子または硫黄原子を表し、
複数あるＲ_a、Ｒ_b、Ｒ_c、Ｒ_d、Ｒ_e、Ｒ_f、Ｒ_g、Ｒ_hおよびＲ_iは、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシル基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴、または、Ｒ_bとＲ_c、Ｒ_dとＲ_e、Ｒ_eとＲ_f、Ｒ_fとＲ_g、Ｒ_gとＲ_hおよびＲ_hとＲ_iのうち少なくとも１つの組み合わせが結合した、下記式（Ｘ－Ａ）～（Ｘ－Ｈ）で表される基からなる群より選ばれる少なくとも１種の基を表し、
前記アミノ基、アミド基、イミド基およびシリル基は、前記式（VI）において定義した置換基Ｌを有してもよく、
Ｌ¹は、前記式（VI）において定義したＬ¹と同義であり、
Ｌ²は、水素原子または前記式（VI）において定義したＬ^a～Ｌ^eのいずれかを表し、
Ｌ³は、水素原子または前記Ｌ^a～Ｌ^eのいずれかを表し、
Ｌ⁴は、前記Ｌ^a～Ｌ^eのいずれかを表し、
Ｚ_a～Ｚ_dおよびＹ_a～Ｙ_dは、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシル基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴（Ｌ¹～Ｌ⁴は、前記Ｒ_a～Ｒ_iにおけるＬ¹～Ｌ⁴と同義である。）、あるいは、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成される、窒素原子、酸素原子もしくは硫黄原子を少なくとも１つ含んでもよい５乃至６員環の脂環式炭化水素基、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成される、炭素数６～１４の芳香族炭化水素基、または、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成され、窒素原子、酸素原子もしくは硫黄原子を少なくとも１つ含む、炭素数３～１４の複素芳香族炭化水素基を表し、
これらの脂環式炭化水素基、芳香族炭化水素基および複素芳香族炭化水素基は、炭素数１～９の脂肪族炭化水素基またはハロゲン原子を有してもよい。

In formulas (X-1) to (X-3), X _b ^- represents a monovalent anion,
multiple Xi's 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, amido group, imido group, cyano group, silyl group, -L ¹ , -SL 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 of 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 amino group, amido group, imido group and silyl group may have a substituent L as defined in formula (VI) above,
L ¹ has the same definition as L ¹ defined in the formula (VI),
L ² represents a hydrogen atom or any of L ^a to L ^e defined in the formula (VI);
L ³ represents a hydrogen atom or any one of L ^a to L ^e ;
L ⁴ represents any one of L ^a to L ^e ;
Z _a to Z _d and Y _a to Y _d each independently represent 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 , - SL ² , -SS-L ² , -SO ₂ -L ³ , -N=N-L ⁴ (L ¹ to L ⁴ have the same meanings as L ¹ to L ⁴ in R _a to R _i above. ),or,
a 5- to 6-membered alicyclic hydrocarbon group optionally containing at least one nitrogen atom, oxygen atom or sulfur atom, formed by bonding two adjacent Zs or Ys together,
an aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding two adjacent Zs or two Ys selected from each other, or
represents a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms, formed by bonding two adjacent Zs or Ys selected from each other and containing at least one nitrogen atom, oxygen atom or sulfur atom;
These alicyclic hydrocarbon groups, aromatic hydrocarbon groups and heteroaromatic hydrocarbon groups may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

式（Ｘ－Ａ）～（Ｘ－Ｈ）中、Ｒ_xとＲ_yの組み合わせは、Ｒ_bとＲ_c、Ｒ_dとＲ_e、Ｒ_eとＲ_f、Ｒ_fとＲ_g、Ｒ_gとＲ_hおよびＲ_hとＲ_iの組み合わせであり、
複数あるＲ_A～Ｒ_Lは、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシル基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³または－Ｎ＝Ｎ－Ｌ⁴（Ｌ¹～Ｌ⁴は、前記式（Ｘ－１）～（Ｘ－３）において定義したＬ¹～Ｌ⁴と同義である。）を表し、前記アミノ基、アミド基、イミド基およびシリル基は、前記置換基Ｌを有してもよい
＜化合物（Ｃ）＞
前記化合物（Ｃ）としては、近赤外線を吸収する色素として作用する金属錯体系化合物、染料または顔料を用いることができ、具体的には、ジイモニウム系化合物、金属ジチオラート錯体系化合物、およびリン酸銅錯体系化合物からなる群より選ばれる少なくとも１種の化合物を挙げることができる。このような化合物（Ｃ）を用いることにより、幅広い近赤外波長領域における吸収特性と優れた可視光透過率を達成することができる。化合物（Ｃ）は、１種単独で使用してもよく、２種以上を使用してもよい。

In formulas (XA) to (XH), 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 , R _g and R _h and combinations of R _h and R _i ;
A plurality of R _A to R _L each independently represent 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 and -SL ² . , -SS-L ² , -SO ₂ -L ³ or -N=N-L ⁴ (L ¹ to L ⁴ are L ¹ to L ⁴ defined in the above formulas (X-1) to (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 compound, dye or pigment that acts as a dye that absorbs near infrared rays can be used. Specifically, diimonium compounds, metal dithiolate complex compounds, and copper phosphate 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. Compound (C) may be used alone or in combination of two or more.

≪Diimmonium compound≫
Although the diimmonium-based compound is not particularly limited, for example, a compound represented by the following formula (XI) is preferable.

式（XI）中、Ｒ¹～Ｒ¹⁷は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、－ＮＲ^gＲ^h基、－ＳＲⁱ基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、－Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a～Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a～Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１～１２の脂肪族炭化水素基
（Ｌ^b）炭素数１～１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３～１４の脂環式炭化水素基
（Ｌ^d）炭素数６～１４の芳香族炭化水素基
（Ｌ^e）炭素数３～１４の複素環基
（Ｌ^f）炭素数１～１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１～１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１～１２のアルコキシカルボニル基
置換基Ｌは、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のハロゲン置換アルキル基、炭素数３～１４の脂環式炭化水素基、炭素数６～１４の芳香族炭化水素基および炭素数３～１４の複素環基からなる群より選ばれる少なくとも１種であり、ｎは０～４の整数、Ｘは電荷を中和させるのに必要なアニオンを表す。

In formula (XI), R ¹ to R ¹⁷ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a —NR ^g R ^h group, and —SR ⁱ group, —SO ₂ R ⁱ group, —OSO ₂ R ⁱ group, or any one of L ^a to L ^h below, wherein R ^g and R ^h each independently represent a hydrogen atom, —C(O)R ⁱ group, or Represents any one of L ^a to L ^e below, R ⁱ represents any one of L ^a to L ^e below,
(L ^a ) Aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) Halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) Alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) Carbon Aromatic hydrocarbon group having 6 to 14 carbon atoms (L ^e ) Heterocyclic group having 3 to 14 carbon atoms (L ^f ) Alkoxy group having 1 to 12 carbon atoms (L ^g ) Number of carbon atoms which may have substituent L 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L 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, and n is 0 to An integer of 4, X represents the anion required to neutralize the charge.

R ¹ is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, phenyl group or 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, trifluorometha noylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexynoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group and n-butylthio group, more preferably is chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoyl They are amino group, pentafluoroethanoylamino group, t-butanoylamino group and cyclohexynoylamino 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 0 or 1 is preferred.

The aforementioned Xc is an anion necessary for neutralizing electric charges, 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 are preferably the same from the viewpoint of synthesis. Xc is not particularly limited as long as it is such an anion, and examples thereof include those shown in Table 1 below.

Ｘcは、酸とした際の酸性度が高いものであればジイモニウム系化合物のアニオンとした際にジイモニウム系化合物の耐熱性を向上できる傾向にあり、上記表１中の（Ｘｃ－１０）、（Ｘｃ－１６）、（Ｘｃ－１７）、（Ｘｃ－２１）、（Ｘｃ－２２）、（Ｘｃ－２４）、（Ｘｃ－２８）が特に好ましい。

Xc tends to improve the heat resistance of the diimonium-based compound when used as an anion of the diimmonium-based compound as long as it has a high acidity when converted into an acid. Xc-16), (Xc-17), (Xc-21), (Xc-22), (Xc-24) and (Xc-28) are particularly preferred.

<<Metal dithiolate compound>>
Although the metal dithiolate-based compound is not particularly limited, a compound represented by the following formula (XII) is preferable.

式（XII）中、Ｒ²⁹～Ｒ³²は、それぞれ独立にメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル器、ｔｅｒｔ－ブチル基、シクロヘキシル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－へプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、フェニル基、メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、ｎ－ブチルチオ基、フェニルチオ基、ベンジルチオ基、隣り合うＲ²⁹とＲ³⁰、Ｒ³¹とＲ³²同士が環を形成する基である。隣り合うＲ²⁹とＲ³⁰、Ｒ³¹とＲ³²同士が環を形成する基である場合、環の中に少なくとも一つ以上の硫黄原子もしくは窒素原子が含まれる複素環であることが好ましい。Ｍａは金属原子であり、好ましくは遷移金属であり、より好ましくはＮｉ、Ｐｄ，Ｐｔである。ＱはＧ（Ｒⁱ）₄を表し、Ｇは窒素原子、リン原子またはビスマス原子を表し、Ｒⁱはメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル器、ｔｅｒｔ－ブチル基、シクロヘキシル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－へプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、フェニル基である。ｙは０もしくは１を表す。

In formula (XII), R ²⁹ to R ³² each independently represent a 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-nonyl group, n-decyl group, phenyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, phenylthio group , a benzylthio group, adjacent R ²⁹ and R ³⁰ , R ³¹ and R ³² together forming a ring. When adjacent R ²⁹ and R ³⁰ or R ³¹ and R ³² are groups forming a ring, it is preferably a heterocyclic ring containing at least one sulfur atom or nitrogen atom in the ring. Ma is a metal atom, preferably a transition metal, more preferably Ni, Pd or Pt. Q represents G(R ⁱ ) ₄ , G represents a nitrogen atom, a phosphorus atom or a bismuth atom, R ⁱ represents a 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-nonyl group, n-decyl group and phenyl group. y represents 0 or 1;

≪Commercial product≫
Commercially available products of the compound (C) include S2058 (manufactured by DKSH), CIR-108x, CIR-96x, CIR-RL, CIR-1080 (manufactured by Nippon Carlit), T090821, T091021, T89021, T090721, T090122 (manufactured by Tosco ), B4360, D4773, D5013 (manufactured by Tokyo Kasei Kogyo), S4253, S1426, S1445 (manufactured by Spectrum Info), and Excolor IR1, IR2, IR3 and IR4 (manufactured by Nippon Shokubai).

<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 within a range that does not impair the effects of the present invention. These other components may be used individually by 1 type, and may use 2 or more types together.

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

These other components may be mixed together with the resin when producing the transparent resin substrate and the resin layer, or may be added when synthesizing the resin. Further, the amount to be added is appropriately selected according to the desired properties, but it is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass, per 100 parts by mass of the resin. Department.

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

When the substrate comprises a transparent resin substrate (light-absorbing layer) containing a light-absorbing compound such as the compound (A), for example, a resin solution containing the light-absorbing compound is melt-molded or cast-molded. Thus, a substrate made of a transparent resin substrate (light absorbing layer) can be produced. Furthermore, if necessary, after the molding of the transparent resin substrate (light absorption layer), the base material on which the overcoat layer is laminated by coating a coating agent such as an antireflection agent, a hard coating agent and/or an antistatic agent. can be manufactured.

≪Melt molding≫
As the melt molding, specifically, a method of melt molding a pellet obtained by melt-kneading a resin, a light-absorbing compound, and optionally other components; A method of melt-molding a resin composition containing other components according to the method; Examples include a method of melt-molding pellets. Examples of melt molding methods 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 onto a suitable support to remove the solvent; A curable composition comprising a photocurable resin and/or a thermosetting resin and optionally other components is cast onto a suitable support, and the solvent is removed, followed by ultraviolet irradiation, heating, or the like. It can also be produced by a method of curing by an appropriate method of.

When the substrate comprises a transparent resin substrate containing a light-absorbing compound such as the compound (A), the substrate can be obtained by peeling off 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 not peeling off the coating film after cast molding. can be done.

The amount of residual solvent in the transparent resin layer (light absorbing layer) obtained by the above method should be as small as possible. Specifically, the residual solvent content is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, relative to the weight of the transparent resin layer. When the amount of residual solvent is within the above range, a transparent resin layer which is resistant to deformation and changes in properties and which can easily exhibit desired functions can be obtained.

≪Adhesion layer≫
Since the transparent resin layer and the glass substrate have different chemical compositions and coefficients of linear thermal expansion, it is possible to provide a cured layer 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 that can ensure adhesion between the transparent resin layer and the glass substrate. For example, (a) a structural unit derived from a (meth)acryloyl group-containing compound , (b) 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 increases, 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, monofunctional, bifunctional, or trifunctional (meth)acrylic acid esters are preferable from the viewpoint of good polymerizability. In the present invention, "(meth)acryl" means "acryl" or "methacryl".

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) Phthalate, (2-methacryloyloxyethyl)(2-hydroxypropyl) phthalate and ω-carboxypolycaprolactone monoacrylate may be mentioned.

These commercial products include trade names such as Aronix M-101, M-111, M-114 and M-5300 (manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S and TC. -120S (manufactured by Nippon Kayaku Co., Ltd.); Viscoat 158 and Viscoat 2311 (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.

These commercial products include trade names such as Aronix M-210, M-240, and M-6200 (manufactured by Toagosei Co., Ltd.); KAYARAD HDDA, HX-220, and R-604 ( Above, manufactured by Nippon Kayaku Co., Ltd.); Viscoat 260, 312, and 335HP (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 tri- 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 in the molecule A polyfunctional urethane acrylate compound obtained by reacting a compound having a hydroxyl group and having 3, 4 or 5 (meth)acryloyloxy groups can be mentioned.

Commercial products of trifunctional or higher (meth)acrylic acid esters include trade names such as Aronix M-309, Aronix M-315, Aronix M-400, Aronix M-405, Aronix M-450, and Aronix M-7100. , M-8030, M-8060, TO-1450 (manufactured by Toagosei Co., Ltd.); KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA- 120, DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.); Viscoat 295, 300, 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); Commercially available products containing polyfunctional urethane acrylate compounds include New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.).
These (meth)acryloyl group-containing compounds (a) can be used singly or in combination of two or more in the 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 carboxylic acid group-containing compounds include monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, and polymers having carboxylic acid groups.

Monocarboxylic acids include, for example, acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid and 2-methacryloyloxyethylhexahydrophthalate. 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.

In addition, the polymer having a carboxylic acid group is a compound containing a carboxylic acid group, such as one or more polymerizable compounds selected from acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and the like. A polymer or a copolymer of these compounds and the (meth)acryloyl group-containing compound can be preferably used.

Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid and maleic anhydride are preferred 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 epoxy group (oxiranyl group)-containing compounds include oxiranyl groups such as (meth)acrylic acid oxiranyl (cyclo)alkyl esters, α-alkylacrylic acid oxiranyl (cyclo)alkyl esters, and unsaturated bond-containing glycidyl ether compounds. unsaturated compounds having an oxetanyl group; unsaturated compounds having an oxetanyl group such as (meth)acrylic acid esters having an oxetanyl group.

(Meth)acrylic acid oxiranyl(cyclo)alkyl esters such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4 (meth)acrylic acid -epoxybutyl, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate, α-alkyl acrylic Acid oxiranyl(cyclo)alkyl esters such as glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate and α-ethyl acrylate Examples include 3,4-epoxycyclohexyl acrylate, and examples of glycidyl ether compounds having unsaturated bonds include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether. , (meth)acrylic acid esters having an oxetanyl group, such as 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxy Methyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyl Oxymethyloxetane and 3-ethyl-3-(meth)acryloyloxymethyloxetane may be mentioned.

Among these, in particular 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 preferred from the standpoint of polymerizability.

(d) Optional Components Optional components such as acid generators, adhesion aids, surfactants, and polymerization initiators can be added to the cured layer within limits that do not impair the effects of the present invention. The amount of these added is appropriately selected according to the desired properties, but usually 0.01 to 15.0 parts by mass, preferably 0.05 to 10.0 parts by mass.

The polymerization initiator is a component that generates active species capable of initiating polymerization of the monomer component in response to light rays such as ultraviolet rays and electron beams. Although such polymerization initiators are not particularly limited, O-acyloxime compounds, acetophenone compounds, biimidazole compounds, alkylphenone compounds, benzophenone compounds and the like can be mentioned. 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-hydroxycyclohexylbenzophenone, 1-hydroxycyclohexylphenylketone and the like. These polymerization initiators can be used alone or in combination 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. A method of melt-molding the composition (I) and a method of melt-molding pellets obtained by removing the solvent from the liquid composition containing the solvent, or a method of casting (cast molding) the above-mentioned liquid composition can be manufactured by

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

In addition, the amount of the optional component is appropriately selected according to the desired properties, preferably 0.01 to 15.0 parts by mass, more preferably 0.05 to 15.0 parts by mass, per 100 parts by mass of composition (I). 10.0 parts by mass.
The thickness of the cured layer is not particularly limited as long as it does not impair the effects of the present invention, 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 substrate. 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 range. cut properties can be achieved.

Dielectric multilayer films include those in which high refractive index material layers and low refractive index material layers are alternately laminated. A material having a refractive index of 1.7 or more can be used as a material constituting the high refractive index material layer, and a material having a refractive index of 1.7 to 2.5 is usually selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, etc., and titanium oxide, tin oxide and/or Alternatively, those containing a small amount (for example, 0 to 10% by mass relative to the main component) of cerium oxide or the like can be used.

A material having a refractive index of 1.6 or less can be used as a material constituting the low refractive index material layer, 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 stacking the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film is formed by stacking these material layers. 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 deposition method, an ion-assisted deposition method, an ion plating method, or the like. A film can be formed.

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, 700-1400 nm, preferably 750-1300 nm. When the thickness is within this range, the product (n × d) of the refractive index (n) and the film thickness (d) is calculated as λ / 4, and the optical film thickness, the high refractive index material layer and the low refractive index The thickness of each layer of the index material layer becomes almost the same value, and there is a tendency that the blocking and transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection and 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, more preferably 20 to 60 layers for the entire optical filter. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and warping of the optical filter and cracking of the dielectric multilayer film can be reduced. can do.

In the present invention, according to the absorption characteristics of the absorptive compound, the kind of material constituting the high refractive index material layer and the low refractive index material layer, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, the order of lamination, By appropriately selecting the number of layers, it has sufficient light blocking characteristics in the near-infrared wavelength range while ensuring sufficient transmittance in the visible range, and also reflects near-infrared light when incident from an oblique direction. rate can be reduced.

Here, in order to optimize the conditions, for example, optical thin film design software (for example, Essential Macleod, manufactured by Thin Film Center) is used, and both the antireflection effect in the visible range and the light cut effect in the near-infrared range can be achieved. You can set the parameters like this. In the case of the above software, for example, when 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. These parameters can be used to change the Target Tolerance value by dividing the wavelength range more finely according to various characteristics of the base material.

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 region of 800 to 1000 nm is preferably 5.0 or more. , more preferably 5.0 to 8.0, more preferably 5.0 to 7.0. In addition, in the wavelength range of 430 to 580 nm, the average value of the transmittance when measured from the vertical direction of the optical filter (hereinafter also referred to as "average transmittance") is preferably 60% or more, more preferably 65 to 65%. 99%, more preferably 70-90%. By having such optical characteristics, it is possible to reduce 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 is not problematic, while achieving high visible light transmittance (no decrease in sensor sensitivity). It is possible to achieve both, and it is possible to provide an ambient light sensor for electronic devices with a sensing function and a high-performance optical filter for solid-state imaging devices.

<Other functional films>
The optical filter of the present invention can be provided between the substrate and the dielectric multilayer film, the surface of the substrate opposite to the surface provided with the dielectric multilayer film, or the dielectric multilayer film, as long as the effects of the present invention are not impaired. An antireflection film and a hard coating are applied to the surface of the film opposite to the surface on which the base material is provided, for the purposes of improving the surface hardness of the base material and dielectric multilayer film, improving chemical resistance, antistatic and scratch removal. A functional film such as a coat film or an antistatic film can be appropriately provided.

The optical filter of the present invention may contain one layer of the functional film, or may contain two or more layers. When the optical filter of the present invention includes two or more layers of the functional film, it may include two or more similar layers or two or more different layers.

The method for 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 applied to the base material or the dielectric multilayer film, and melt molding or casting is performed in the same manner 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 and the like onto a base material or a dielectric multilayer film using a bar coater or the like, and then curing the film by ultraviolet irradiation or the like.

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethane, urethane acrylate, acrylate, 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.

Moreover, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

In the curable composition, the mixing 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% by mass. When the blending ratio of the polymerization initiator is within the above range, the curing properties and handling properties of the curable composition are excellent, and functional films such as antireflection films, hard coat films and antistatic films having desired hardness can be obtained. can.

Furthermore, an organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used. Specific examples of organic solvents 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 and 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- Amides such as methylpyrrolidone can be mentioned.

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

In addition, for the purpose of improving the adhesion between the base material and the functional film and/or the dielectric multilayer film and the adhesion between the functional film and the dielectric multilayer film, the surface of the substrate, the functional film or the dielectric multilayer film may be subjected to corona treatment. Alternatively, surface treatment such as plasma treatment may be applied.

[Applications of optical filters]
The optical filter of the present invention effectively cuts the reflected light from the sensing light source, while simultaneously achieving high visible light transmittance, warping, adhesion of the dielectric multilayer film, and noiselessness to the sensor due to reflection from the multilayer film. It has the property of being able to Therefore, it is particularly useful as an optical filter for ambient light sensor modules and camera modules in devices equipped with sensing functions such as smartphones, tablet terminals, wearable devices, automobile cameras, televisions, and game machines.

<Solid-state imaging device>
A solid-state imaging device of the present invention comprises the optical filter of the present invention. Here, the solid-state imaging device is an image sensor equipped with a solid-state imaging device such as a CCD or CMOS image sensor. Specifically, it includes digital still cameras, smartphone cameras, mobile phone cameras, wearable device cameras, digital It can be used for applications such as video cameras.

<Camera module>
A camera module of the present invention comprises the optical filter of the present invention. Here, the 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 cross-sectional view of the camera module. Although the optical filter 6 is arranged between the lens 5 and the image sensor 7 in FIG. 3, it can also be arranged above the lens.

<Ambient light sensor module>
The ambient light sensor module of the invention comprises the optical filter of the invention. That is, the optical filter, the photoelectric conversion element, the 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 sense the brightness and color tone of the surroundings (e.g. red is strong in the evening time). It is possible to control the illuminance and color of the

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

In addition, in the ambient light sensor 200a, another translucent layer may be interposed between the optical filter 100 and the photoelectric conversion element 202. FIG. For example, a translucent 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 . A passivation film 216 is provided on the light receiving surface side. The photoelectric conversion layer 208 is formed using 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 generates photovoltaic force due to 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 called a photoresistor, a light-dependent resistor, a photoconductor, or a photocell) or a phototransistor-type element. good too.

The photoelectric conversion layer 208 may use a germanium semiconductor or a silicon-germanium semiconductor other than a silicon semiconductor. Compound semiconductor materials such as GaP, GaAsP, CdS, CdTe, and CuInSe ₂ may be used as the photoelectric conversion layer 208 . The photoelectric conversion element 202 made of a semiconductor material is sensitive to light in the visible light band to the near-infrared band. For example, when the photoelectric conversion layer 208 is formed of a silicon semiconductor, since the silicon semiconductor has a bandgap energy of 1.12 eV, it can theoretically absorb near-infrared light having a wavelength of 700 to 1100 nm. However, since the optical filter 100 is provided, the ambient light sensor 200a is not sensitive to near-infrared light and is sensitive to light in the visible light range. Note that the photoelectric conversion element 202 is preferably surrounded by a light-shielding 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 near-infrared light.

FIG. 5 shows an example of an ambient light sensor 200b that senses color tone in addition to ambient brightness. The ambient light sensor 200b includes an optical filter 100, photoelectric conversion elements 202a-202c, and color filters 212a-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. With this configuration, the photoelectric conversion elements 202a to 202c can detect the illuminance independently. 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, in addition to the optical filter 100, by providing the color filters 212a to 212c corresponding to the photoelectric conversion elements 202a to 202c, the ambient light sensor 200b blocks near-infrared light to prevent malfunction of the sensor. , can detect light corresponding to each color. The ambient light sensor 200b is equipped with an optical filter 100 that blocks light in the near-infrared region and color filters 212a to 212c. It can be applied even in dark environments where conventional color sensors cannot detect accurately due to the influence of near-infrared rays.

<Electronic equipment>
An electronic device of the present invention includes the optical filter of the present invention, and in a more preferred embodiment, the ambient light sensor of the present invention described above. The electronic device of the present invention will be described below with reference to the drawings.

FIG. 6 shows an example of an electronic device 300 having an image sensor 7 and an ambient light sensor 200 according to one embodiment of the invention. Electronic device 300 includes housing 307 , display panel 306 , speaker unit 305 , RGB camera module 301 , ambient light sensor 200 , dot projector 302 , flood illuminator 303 and IR camera 304 . The display panel 306 employs a touch panel and has an input function as well as a display function.

Ambient light sensor 200 is provided on the rear surface of surface panel 306 provided on 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 surface panel. The surface panel blocks light in the near-infrared region by the optical filter 100 and allows light in the visible light region to enter the photoelectric conversion element 202 . The electronic device 300 can control the illuminance and color of the display panel 306 using the ambient light sensor 200 .

According to the present embodiment, the optical filter of the present invention detects reflected light (reflected light from the object and the inside of the housing) from the light emitting elements (luminescence center wavelength of 850 nm, 940 nm, etc.) of the dot projector 302 and the floodlight illuminator 303. Efficient cutting suppresses the incidence of noise light on the image sensor of the camera module and ambient light sensor, thereby preventing deterioration of camera image quality and malfunction of 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. With the miniaturization of modules, modules are being installed closer together. For example, when a light-emitting element for sensing and a photoelectric conversion element (environmental light sensor element, solid-state image sensor, etc.) are installed close to each other, the light from the light-emitting element is reflected inside the housing and enters the photoelectric conversion element. Although there is a problem that the adverse effect spreads, by applying the optical filter of the present invention, it becomes possible to reduce the adverse effect effectively. 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.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In addition, "parts" means "parts by mass" unless otherwise specified. In addition, the method for measuring each physical property value and the method for evaluating physical properties are as follows.

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

(a) Using a gel permeation chromatography (GPC) device (150C type, column: H type column manufactured by Tosoh Corporation, 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) Using a Tosoh GPC apparatus (HLC-8220, column: TSKgelα-M, developing solvent: THF), the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured.

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nanotechnologies Co., Ltd., the temperature was measured at a rate of temperature increase of 20°C per minute under a nitrogen stream.

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

<Warp evaluation>
An optical filter having a size of 200 mm long and 200 mm wide was placed on a flat glass plate, and the vertical height at which the corners of the optical filter were warped from the glass plate was measured using a ruler. The warpage of the four corners of the optical filter was measured, and the average value of the warpage of the four corners was taken as the amount of warpage. When the amount of warp was 10 mm or less, the warp characteristic was evaluated as "good", and when the amount of warp was 10 mm or more, the warp characteristic was evaluated as "x".

<Evaluation of Adhesion of Dielectric Multilayer Film>
A film with a dielectric multilayer film cut into 20 mm squares was boiled in pure water for 30 minutes. After that, the film taken out was cross-cut (11 vertical and horizontal lines) at intervals of 1 mm using a utility knife, and tape Nichiban No. 1 was applied to the cut surface. 405 was attached and peeled off, and the presence or absence of peeling was confirmed. A case where peeling was not observed was evaluated as "good", and a case where peeling was observed was evaluated as "poor".

<Ambient light sensor performance>
The near-infrared cut filter of the ambient light sensor module of Apple's “iPhone X” was taken out, and instead, the optical filters produced in Examples and Comparative Examples described later were incorporated into the ambient 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 Mightex was irradiated from a distance of about 1 m to the window section where the ambient light sensor module was installed. , and observed the operating status of the ambient light sensor. "◎" indicates that the ambient light sensor is working very well. The case where the operating condition was generally good, but the operating condition was sometimes recognized as "○", and the case where the operating condition was poor was judged as "x".

<Camera module image evaluation>
The near-infrared cut filter of the camera module of the front (sub) camera of Apple's “iPhone X” was taken out, and instead, the optical filters produced in Examples and Comparative Examples to be described later were incorporated into the camera module. Photograph taken with Mightex LED light LCS-0850-02 (emission peak wavelength: 850 nm) or LCS-0940-02 (emission peak wavelength: 940 nm) illuminated from a distance of about 1 m to the window of the front (sub) camera. were taken and the photographic image quality was evaluated. "◎" indicates that the photo quality is good, "○" indicates that the photo quality has poor color balance and looks reddish, and "X" indicates that the photo quality has poor color balance and looks reddish overall. and

The near-infrared absorbing dyes (light absorbing compounds) used in the following examples were synthesized by a generally known method. General synthesis methods include, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, JP-A-60-228448, JP-A-1-146846, Japanese Patent Application Laid-Open No. 1-228960, Japanese Patent No. 4081149, Japanese Patent Application Laid-Open No. 63-124054, “Phthalocyanine-Chemistry and Function-” (IPC, 1997), Japanese Patent Application Laid-Open No. 2007-169315, Japanese Patent Application Laid-Open No. 2009 -108267, JP-A-2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631 and the like.

<Resin Synthesis Example 1>
100 parts of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodeca-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 placed in a reaction vessel purged with nitrogen, and the solution was heated to 80°C. Next, 0.2 part of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.2 part of a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol/liter) were added as polymerization catalysts to the solution in the reaction vessel. 9 parts were added, and this solution was heated and stirred at 80° C. for 3 hours to carry out ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

An autoclave was charged with 1,000 parts of the ring-opened polymer solution thus obtained, 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 a hydrogen gas pressure of 100 kg/cm ² and a reaction temperature of 165° C., a hydrogenation reaction was carried out by heating and stirring for 3 hours. After cooling the resulting reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a solidified product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The obtained resin A 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, 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N,N-dimethylacetamide (hereinafter also referred to as "DMAc") and 111 g of toluene were added. Subsequently, the four-necked flask was equipped with a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube and a cooling tube. Then, after the inside of the flask was replaced with nitrogen, the obtained solution was reacted at 140° C. for 3 hours, and the generated water was removed from the Dean-Stark tube at any time. When the formation 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 poured into methanol to reprecipitate, and the filtrate (residue) was isolated by filtration. The obtained filter cake was vacuum-dried overnight at 60° C. to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B 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 Resin A obtained in Resin Synthesis Example 1, 0.25 parts by mass of a compound represented by the following formula (a-1) as compound (A) (absorption maximum wavelength: 940 nm), compound (B ) as 0.05 parts by mass of the compound represented by the following formula (b-1), 0.056 parts by mass of the compound represented by the following formula (b-2), and as the compound (C) light absorption manufactured by Nippon Carlit Co., Ltd. A resin solution (E1) having a resin concentration of 20% by mass by adding 0.09 parts by mass of the agent "CIR-RL" (absorption maximum wavelength 1095 nm) (hereinafter also referred to as "compound (c-1)") and dichloromethane. 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 off 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.

On one side of the obtained transparent resin substrate, the following resin composition (1) was applied 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 was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure the resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other surface of the transparent resin substrate. As a result, a substrate having resin layers containing no compound (A) on both sides of the transparent resin substrate containing compound (A) was obtained.

Resin composition (1): 60 parts by mass of tricyclodecanedimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexylphenyl ketone, methyl ethyl ketone (solvent, solid content concentration: 30%).

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

Subsequently, a dielectric multilayer film (α) is formed on one side of the obtained base material, and a dielectric multilayer film (β) is formed on the other side of the base material to form a dielectric film having a thickness of 0.110 mm. An optical filter was obtained by laminating a multilayer film.

The dielectric multilayer film (α) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a 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 both of the dielectric multilayer films (α) and (β), the silica layer and the titania layer are arranged in the order of titania layer, silica layer, titania layer, . . . silica layer, titania layer, silica layer from the substrate side. They are alternately laminated, and the outermost layer of the optical filter is a silica layer. The dielectric multilayer films (α) and (β) were designed as follows.

Regarding the thickness and number of each layer, the wavelength dependence characteristics of the substrate refractive index and the applied compound (A), (B ) and (C) were optimized using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When optimizing, in this embodiment, input parameters (target values) to the software are as shown in Table 2 below.

As a result of optimizing the film configuration, in Example 1, the dielectric multilayer film (α) was formed by alternately laminating silica layers with a thickness of about 32 to 158 μm and titania layers with a thickness of about 10 to 96 μm. The dielectric multilayer film (β) is a multilayer deposition film of 22 layers, and the dielectric multilayer film (β) is a multilayer of 18 layers, in which a silica layer with a thickness of about 38 to 192 μm and a titania layer with a thickness of about 10 to 112 μm are alternately laminated. Evaporated film. An example of optimized film configuration is shown in Table 3 below.

The obtained optical filter had a maximum OD value of 5.3 at a wavelength of 800 to 1000 nm and an average transmittance of 72.8% at a wavelength of 430 to 580 nm. FIG. 8 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0940-02 as an LED light source, 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 carried out. The ambient light sensor worked well, and the photographic image of the camera module was good.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[Example 2]
100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 4.3 parts by mass of the compound (a-1), and dichloromethane were added to a container to prepare a solution having a resin concentration of 20% by mass, and a pore diameter of 5 μm. Filtration was performed with a Millipore filter to obtain 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 are added to prepare a solution having a resin concentration of 20% by mass. Then, it was filtered through a Millipore filter with 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 applying the solution by spin coating, the solution was heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent, thereby forming a resin layer functioning as an adhesive layer with a transparent resin layer to be described later. Next, using a spin coater, the resin solution (E2-1) was applied onto the adhesive layer on one side so that the film thickness after drying was 10 μm, heated on a hot plate at 80° C. for 5 minutes, and was removed by volatilization to form a transparent resin layer. Furthermore, 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 form a transparent resin layer. formed. As a result, a substrate having a thickness of 220 μm was obtained by laminating a resin layer containing the compound (A) on one side of a colorless glass substrate and laminating a resin layer not containing the compound (A) on the other side.

Resin composition (2): isocyanuric acid ethylene oxide-modified triacrylate (shipment name: Aronic M-315, manufactured by Toagosei Chemical 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: IRGACURE 184, manufactured by Chiba Specialty Chemical Co., Ltd.) 5 parts by mass and San-Aid SI Mix 1 part by mass of -110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.), dissolve in propylene glycol monomethyl ether acetate so that the solid content concentration is 50% by mass, and then filter through a Millipore filter with a pore size of 0.2 μm. Then, a resin composition (2) was prepared.

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

Subsequently, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one side of the base material, and a dielectric multilayer film (β) is formed on the other side of the base material. An optical filter with a thickness of 224 μm was obtained.

The obtained optical filter had a maximum OD value of 6.3 (@940 nm) at a wavelength of 800-1000 nm, and an average transmittance of 71.1% at a wavelength of 430-580 nm. FIG. 10 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0940-02 as an LED light source, 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 carried out. The ambient light sensor worked well, and the photographic image of the camera module was good.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[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 the compound represented by the following formula (a-2) (absorption maximum wavelength: 940 nm), and the following formula (b-3) 0.06 parts by mass of the compound (b-3) represented by the following formula (b-4), 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 in vacuum at 140° C. for 8 hours, and then peeled off from the glass plate. The peeled film was further dried in vacuum at 100° C. for 8 hours to obtain a transparent resin substrate of 200 mm×200 mm with a thickness of 100 μm.

On one side of the obtained transparent resin substrate, the resin composition (1) was applied 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 was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other surface of the transparent resin substrate. As a result, a substrate having resin layers containing no compound (A) on both sides of the transparent resin substrate containing compound (A) was obtained.

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

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

The obtained optical filter had a maximum OD value of 6.5 (@940 nm) at a wavelength of 800 to 1000 nm, and an average transmittance of 73.2% at a wavelength of 430 to 580 nm. FIG. 12 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0940-02 as an LED light source, 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 carried out. The ambient light sensor worked well, and the photographic image of the camera module was good.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[Example 4]
In a container, 100 parts by mass of 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 adjust the resin concentration. was prepared and filtered through a Millipore filter with a pore size of 5 μm to obtain a resin solution (E4-1). Similarly, 0.6 parts by mass of compound (b-3), 0.7 parts by mass of compound (b-4), 1.2 parts by mass of compound (c-1), and dichloromethane were added to make the resin concentration 20. A mass % solution was prepared and filtered through a Millipore filter with a pore size of 5 μm to obtain a resin solution (E4-2).

The above 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., cut into a size of 200 mm×200 mm, and the film thickness after drying was about 1 μm. After applying the solution by spin coating, the solution was heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent, thereby forming a resin layer functioning as an adhesive layer with a transparent resin layer to be described later. Next, using a spin coater, the resin solution (E4-1) was applied to one side of the adhesive layer so that the film thickness after drying was 10 μm, and heated on a hot plate at 80° C. for 5 minutes to remove the solvent. A resin layer was formed by volatilization and removal. Furthermore, using a spin coater on the other surface, the resin solution (E4-2) is applied so that the film thickness after drying is 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes to volatilize and remove the solvent. Then, a transparent resin layer was formed. As a result, a substrate having a thickness of 222 μm was obtained by laminating a resin layer containing the compound (A) on one side of a colorless glass substrate and laminating a resin layer not containing the compound (A) on the other side.

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

Subsequently, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one side of the laminate, and a dielectric multilayer film (β) is formed on the other side of the laminate. An optical filter with a thickness of 226 μm was obtained.

The obtained optical filter had a maximum OD value of 5.8 (@874 nm) at a wavelength of 800-1000 nm, and an average transmittance of 75.2% at a wavelength of 430-580 nm. FIG. 14 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0850-02 as an LED light source, 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 carried out. The ambient light sensor worked well, and the photographic image of the camera module was good.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[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 are added to a container to obtain a resin solution (E5-1) having a resin concentration of 10% by mass. 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 In addition, a resin solution (E5-2) having a resin concentration of 10% by mass was obtained.

On one side of Zeonor Film ZF-16 (manufactured by Nippon Zeon, 100 μm thick), the resin solution (E5-1) is applied so that the thickness after drying is 10 μm, dried at 80 ° C. for 8 hours, and then further vacuumed. It was dried at 150° C. in medium for 8 hours. Furthermore, on the other surface, the resin solution (E5-2) was applied so that the thickness after drying was 10 μm, dried at 80 ° C. for 8 hours, and further dried in a vacuum at 150 ° C. for 8 hours. . As a result, a laminate (substrate) having a thickness of 120 μm and having a resin layer containing the compound (A) on one side of the transparent resin substrate and a resin layer not containing the compound (A) on the other side was obtained. .

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

Subsequently, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one side of the obtained laminate, and a dielectric multilayer film (β) is formed on the other side of the substrate. to obtain an optical filter with a thickness of 226 μm.

The obtained optical filter had a maximum OD value of 5.5 (@940 nm) at a wavelength of 800 to 1000 nm, and an average transmittance of 79.1% at a wavelength of 430 to 580 nm. FIG. 16 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0940-02 as an LED light source, 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 carried out. The ambient light sensor worked well, and the photographic image of the camera module was good.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[Example 6]
100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 2 parts of compound (a-1) and dichloromethane were added to a container to prepare a solution with a resin concentration of 20% by mass, and filtered through a Millipore filter with a pore size of 5 μm. was performed to obtain a resin solution (E6). The above resin composition (2) was applied to one side of an absorption glass substrate "BS-6" (thickness: 200 µm) manufactured by Matsunami Glass Co., Ltd., cut into a size of 200 mm x 200 mm, and the film thickness after drying was about 1 µm. After application by spin coating, the solution was heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent, thereby forming a resin layer functioning as an adhesive layer with a transparent resin layer to be described later.

Next, using a spin coater, the resin solution (E6) was applied to the adhesive layer 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, and a resin layer containing the compound (A) was laminated on the glass substrate. As a result, a substrate having a thickness of 211 μm was obtained by laminating a resin layer containing the compound (A) on one side of an absorption type glass substrate.

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

Subsequently, in the same manner as in Example 1, a dielectric multilayer film (α) is formed on one side of the laminate, and a dielectric multilayer film (β) is formed on the other side of the laminate. An optical filter with a thickness of 0.214 mm was obtained.

The obtained optical filter had a maximum OD value of 5.3 (@940 nm) at a wavelength of 800 to 1000 nm, and an average transmittance of 80.6% at a wavelength of 430 to 580 nm. FIG. 18 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0940-02 as an LED light source, 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 carried out. The ambient light sensor worked well, and the photographic image of the camera module was good.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[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) (maximum absorption wavelength: 850 nm), and 0.25 parts by mass of compound (b-1). 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 resulting solution 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 off from the glass plate. The peeled film was further dried in vacuum at 100° C. for 8 hours to obtain a transparent resin substrate of 200 mm×200 mm with a thickness of 100 μm.

On one side of the obtained transparent resin substrate, the resin composition (1) was applied 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 was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other surface of the transparent resin substrate. As a result, a substrate having resin layers containing no compound (A) on both sides of the transparent resin substrate containing compound (A) was obtained.

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

Subsequently, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one side of the base material, and a dielectric multilayer film (β) is formed on the other side of the base material. An optical filter with a thickness of 0.110 mm was obtained.

The obtained optical filter had a maximum OD value of 5.8 (@850 nm) at a wavelength of 800-1000 nm and an average transmittance of 72.7% at a wavelength of 430-580 nm. FIG. 20 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0850-02 as an LED light source, 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 carried out. The ambient light sensor worked well, and the photographic image of the camera module was good.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[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) (maximum absorption wavelength: 824 nm), and 0.1 part by mass of compound (b-1). 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 resulting solution 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 off from the glass plate. The peeled film was further dried in vacuum at 100° C. for 8 hours to obtain a transparent resin substrate of 200 mm×200 mm with a thickness of 100 μm.

On one side of the obtained transparent resin substrate, the resin composition (1) was applied 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 was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other surface of the transparent resin substrate. As a result, a substrate having resin layers containing no compound (A) on both sides of the transparent resin substrate containing compound (A) was obtained.

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

Subsequently, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one side of the base material, and a dielectric multilayer film (β) is formed on the other side of the base material. An optical filter with a thickness of 0.110 mm was obtained.

The obtained optical filter had a maximum OD value of 5.2 (@824 nm) at a wavelength of 800-1000 nm, and an average transmittance of 74.4% at a wavelength of 430-580 nm. FIG. 22 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0850-02 as an LED light source, 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 carried out. The operating condition of the ambient light sensor was generally good, but malfunction was occasionally observed, but the photographic images of the camera module were good.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[Example 9]
In a container, 100 parts by mass of the resin B obtained in Resin Synthesis Example 2, 0.30 parts of the compound (a-4), 0.10 parts of the compound represented by the following formula (b-5), the compound (c-1 ) 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 off 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 resin composition (1) was applied 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 was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other surface of the transparent resin substrate. As a result, a substrate having resin layers not containing compound (A) on both sides of the transparent resin substrate containing compound (A) was obtained.

The resulting substrate had a maximum OD value of 7.6 (@844 nm) at a wavelength of 800-1000 nm and an average OD value of 4.4 at a wavelength of 744-944 nm. Also, the average transmittance at wavelengths of 430 to 580 nm was 33.8%. FIG. 23 shows the spectral characteristics (transmittance by wavelength) of the substrate.

Subsequently, a dielectric multilayer film was formed on both sides of the obtained substrate by the same method as in Example 1 to obtain an optical filter with a thickness of 0.110 mm.
The obtained optical filter had a maximum OD value of 6.3 (@844 nm) at a wavelength of 800 to 1000 nm, and an average transmittance of 35.5% at a wavelength of 430 to 580 nm. FIG. 24 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0850-02 as an LED light source, 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 carried out. The ambient light sensor generally worked well, and the photographic images of the camera module were generally good, but the color tone balance of the photographic image quality was slightly poor, with a slightly reddish tone and slightly darker image quality.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[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, and the resin concentration was A 20% by mass solution was prepared and filtered through a Millipore filter with 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 filtered through a Millipore filter having a pore size of 5 μm. A resin solution (E10-2) was obtained.

The above 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., cut into a size of 200 mm×200 mm, and the film thickness after drying was about 1 μm. After applying the solution by spin coating, the solution was heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent, thereby forming a resin layer functioning as an adhesive layer with a transparent resin layer to be described later. Next, using a spin coater, the resin solution (E10-1) was applied to the adhesive layer on one side so that the film thickness after drying was 10 μm, heated on a hot plate at 80° C. for 5 minutes, and the solvent was removed. It was removed by volatilization to form a transparent resin layer. Furthermore, on the other surface, the glass substrate resin solution (E10-2) was applied 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 substrate having a thickness of 220 μm was obtained in which resin layers containing no compound (A) were laminated on both sides of a colorless glass substrate.

The resulting substrate has a maximum OD value of 5.1 (@982 nm) at a wavelength of 800-1000 nm, an average OD value of 4.3 at a wavelength of 882-1082 nm, and an average transmission of 430-580 nm. The rate was 53.4%. FIG. 25 shows the spectral characteristics (transmittance by wavelength) of the substrate.

Subsequently, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one side of the base material, and a dielectric multilayer film (β) is formed on the other side of the base material. An optical filter with a thickness of 224 μm was obtained.

The obtained optical filter had a maximum OD value of 6.0 (@982 nm) at a wavelength of 800-1000 nm, and an average transmittance of 55.9% at a wavelength of 430-580 nm. FIG. 26 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0940-02 as an LED light source, 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 carried out. The ambient light sensor works well, and the photographic images of the camera module are generally good, but the photographic image quality has a slightly poor color balance, and the color tone is a little reddish.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[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), and 0.056 part by mass of compound (b-2) Parts by mass, 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 resulting solution 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 off from the glass plate. The peeled film was further dried in vacuum at 100° C. for 8 hours to obtain a transparent resin substrate of 200 mm×200 mm with a thickness of 100 μm.

On one side of the obtained transparent resin substrate, the resin composition (1) was applied 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 was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other surface of the transparent resin substrate. As a result, a substrate having resin layers containing no compound (A) on both sides of the transparent resin substrate containing compound (A) was obtained.

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

In Comparative Example 1, an optical filter was manufactured in which the number of dielectric multilayer films was 52 in total and 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 and number of each layer, the wavelength dependence characteristics of the substrate refractive index and the applied compound (A), (B ) and (C) were optimized using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When optimizing, in this embodiment, input parameters (target values) to the software were as shown in Table 4 below.

As a result of optimizing the film structure, in Comparative Example 1, the dielectric multilayer film (γ) was formed by alternately laminating silica layers with a thickness of about 32 to 159 μm and titania layers with a thickness of about 9 to 94 μm. The dielectric multilayer film (δ) is a multilayer deposition film of 28 layers, and the dielectric multilayer film (δ) is a multilayer of 24 layers, in which a silica layer with a thickness of about 39 to 193 μm and a titania layer with a thickness of about 12 to 117 μm are alternately laminated. Evaporated film. An example of optimized film configuration is shown in Table 5 below.

The obtained optical filter had a maximum OD value of 5.5 (@940 nm) at a wavelength of 800-1000 nm, and an average transmittance of 74.3% at a wavelength of 430-580 nm. FIG. 28 shows the spectral characteristics (transmittance by wavelength) of the optical filter. The obtained optical filter had a large warpage, and peeling of the dielectric multilayer film was observed in the evaluation of the adhesion of the dielectric multilayer film. In addition, using LCS-0940-02 as an LED light source, the operating state 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 work well to change the color tone of the screen in response to changes in the outside light, and the operating conditions were poor. The photographic image of the camera module was strongly reddish, and the color tone balance of the photographic image quality was poor.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[Comparative Example 2]
A base material and an optical filter comprising a dielectric multilayer film laminated on the base material were prepared in the same manner as in Example 1, except that the compound (a-1) was not used.

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

The obtained optical filter had a maximum OD value of 2.0 (@982 nm) at a wavelength of 800 to 1000 nm, and an average transmittance of 83.0% at a wavelength of 430 to 580 nm. FIG. 30 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0940-02 as the LED light source, the operating conditions 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 work well to change the color tone of the screen in response to changes in the outside light, and the operating conditions were poor. The photographic image of the camera module was strongly reddish, and the color tone balance of the photographic image quality was poor.
Table 6 summarizes the evaluation results of the base material and the optical filter.

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

The obtained transparent resin substrate had a maximum OD value of 2.9 (@940 nm) at a wavelength of 800 to 1000 nm, an average OD value of 1.5 at a wavelength of 882 to 1082 nm, and a wavelength of 430 to 580 nm. had an average transmittance of 79.1%. FIG. 31 shows the optical properties (transmittance by wavelength) of the substrate.

The obtained optical filter had a maximum OD value of 4.9 (@940 nm) at a wavelength of 800 to 1000 nm, and an average transmittance of 82.9% at a wavelength of 430 to 580 nm. FIG. 32 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0940-02 as the LED light source, the operating conditions 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 work well to change the color tone of the screen in response to changes in the outside light, and the operating conditions were poor. The photographic image of the camera module was strongly reddish, and the color tone balance of the photographic image quality was poor.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[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 are added to a container to obtain a resin solution (CE4-1) having a resin concentration of 10% by mass. got 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), 0.9 parts by mass of compound (c-1), and dichlorobenzene was added to obtain a resin solution (CE4-2) having a resin concentration of 10% by mass.

On one side of Zeonor Film ZF-16 (manufactured by Nippon Zeon, 100 μm thick), the resin solution (CE4-1) is applied so that the thickness after drying is 10 μm, dried at 80 ° C. for 8 hours, and then vacuumed. It was dried at 150° C. in medium for 8 hours. On the other side, the resin solution (CE4-2) was applied to a thickness of 10 μm after drying, dried at 80° C. for 8 hours, and then dried in vacuum at 150° C. for 8 hours. As a result, a substrate having a thickness of 120 μm and having a resin layer containing the compound (A) on one side of the transparent resin substrate and a resin layer not containing the compound (A) on the other side was obtained.

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

Subsequently, by the same method as in Example 1, a dielectric multilayer film (α) is formed on one side of the obtained laminate, and a dielectric multilayer film (β) is formed on the other side of the substrate. to obtain an optical filter with a thickness of 226 μm.

The obtained optical filter had a maximum OD value of 4.8 (@940 nm) at a wavelength of 800 to 1,000 nm, and an average transmittance of 74.7% at a wavelength of 430 to 580 nm. FIG. 34 shows spectral characteristics (transmittance by wavelength) of an optical filter having dielectric multilayer films laminated. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-940-02 as an LED light source, the operating conditions 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 work well to change the color tone of the screen in response to changes in the outside light, and the operating conditions were poor. The photographic image of the camera module was strongly reddish, and the color tone balance of the photographic image quality was poor.
Table 6 summarizes the evaluation results of the base material and the optical filter having the dielectric multilayer film laminated thereon.

[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), 0 of compound (b-1) 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 resulting solution 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 off from the glass plate. The peeled film was further dried in vacuum at 100° C. for 8 hours to obtain a transparent resin substrate of 200 mm×200 mm and 100 μm thickness.

On one side of the obtained transparent resin substrate, the resin composition (1) was applied 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 was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other side of the transparent resin substrate. As a result, a substrate having resin layers containing no compound (A) on both sides of a transparent resin substrate containing no compound (A) was obtained.

In the resulting substrate, 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 wavelength of 430 to 580 nm is The average transmittance was 64.8%. FIG. 35 shows the spectral characteristics (transmittance by wavelength) of the substrate.

Subsequently, a dielectric multilayer film was formed on both sides of the obtained substrate by the same method as in Example 1 to obtain an optical filter with a thickness of 0.110 mm.
The obtained optical filter had a maximum OD value of 3.6 (@1000 nm) at a wavelength of 800 to 1000 nm, and an average transmittance of 67.9% at a wavelength of 430 to 580 nm. FIG. 36 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-940-02 as an LED light source, the operating conditions 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 work well to change the color tone of the screen in response to changes in the outside light, and the operating conditions were poor. The photographic image of the camera module was strongly reddish, and the color tone balance of the photographic image quality was poor.
Table 6 summarizes the evaluation results of the base material and the optical filter.

[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) (maximum absorption wavelength: 786 nm), and 0.15 parts by mass of compound (b-1). 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 resulting solution 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 off from the glass plate. The peeled film was further dried in vacuum at 100° C. for 8 hours to obtain a transparent resin substrate of 200 mm×200 mm with a thickness of 100 μm.

On one side of the obtained transparent resin substrate, the resin composition (1) was applied 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 was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other surface of the transparent resin substrate. Thus, a substrate having resin layers containing no compound (A) on both sides of a transparent resin substrate containing no compound (A) was obtained.

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

Subsequently, a dielectric multilayer film was formed on both sides of the obtained substrate by the same method as in Example 1 to obtain an optical filter with a thickness of 0.110 mm.
The obtained optical filter had a maximum OD value of 4.7 (@800 nm) at a wavelength of 800 to 1000 nm, and an average transmittance of 74.5% at a wavelength of 430 to 580 nm. FIG. 38 shows the spectral characteristics (transmittance by wavelength) of the optical filter. Moreover, the warpage of the obtained optical filter and the adhesion of the dielectric multilayer film were good. Furthermore, using LCS-0850-02 as an LED light source, the operating conditions 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 work well to change the color tone of the screen in response to changes in the outside light, and the operating conditions were poor. The photographic image of the camera module was strongly reddish, and the color tone balance of the photographic image quality was poor.
Table 6 summarizes the evaluation results of the base material and the optical filter.

The meanings of the symbols in "Form of base material" in Table 6 are as follows.
(1): A resin layer containing no compound (A) is provided on both sides of a transparent resin substrate containing compound (A).
(2): A glass substrate has a resin layer containing the compound (A) on one side and a resin layer not containing the compound (A) on the other side.
(3): A resin film containing no compound (A) has a resin layer containing compound (A) on one side and a resin layer containing no compound (A) on the other side.
(4): A resin layer containing the compound (A) is provided on one side of the near-infrared absorbing glass substrate.
(5): A resin layer containing no compound (A) is provided on both sides of the glass substrate.
(6): A resin layer containing no compound (A) is provided on both sides of a transparent resin substrate containing no compound (A).

1: Camera module 2: Lens barrel 3: Flexible substrate 4: Hollow package 5: Lens 6: (For solid-state imaging device) Optical filter 7: (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 306: Display panel 307: Housing

Claims (14)

An optical filter having a base material including a light absorption layer and transmitting visible light,
In the wavelength region of 800 to 1000 nm, the maximum value of the OD value (1) when measured from the vertical direction of the substrate is 3.0 or more , and
The average value of the OD value (1) is 2.0 or less in the region of the wavelength ± 100 nm where the OD value (1) exhibits the maximum value.
An optical filter characterized by: 2. The optical filter according to claim 1, wherein the wavelength at which the OD value (1) exhibits the maximum value is in either a wavelength range of 820 to 880 nm or a wavelength range of 910 to 970 nm. 3. The optical filter according to any one of claims 1 and 2 , wherein the light absorption layer contains a compound (A) having an absorption maximum in a wavelength range of 800 to 1000 nm. The compound (A) is at least one compound selected from the group consisting of squarylium-based compounds, cyanine-based compounds, pyrrolopyrrole-based compounds, perylene-based compounds, croconium-based compounds, and metal dithiolate-based compounds. 4. The optical filter according to claim 3 . 5. The optical filter according to any one of claims 1 to 4 , wherein the base material includes a glass substrate, and the light absorption layer is provided on at least one surface of the glass substrate. 5. The optical filter according to any one of claims 1 to 4 , 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. 7. The optical filter according to any one of claims 1 to 6 , comprising a dielectric multilayer film on at least one side of the substrate. 8. The optical filter according to claim 7 , wherein the maximum value of the OD value (2) measured from the vertical direction of the optical filter is 5.0 or more in the wavelength range of 800 to 1000 nm. 9. The optical filter according to claim 7 , wherein the average transmittance measured in the vertical direction of the optical filter is 60% or more in a wavelength range of 430 to 580 nm. A solid-state imaging device comprising the optical filter according to any one of claims 1 to 9 . A camera module comprising the optical filter according to any one of claims 1 to 9 . An ambient light sensor module comprising the optical filter according to any one of claims 1 to 9 . An electronic device comprising the optical filter according to any one of claims 1 to 9 . At least one module (A) selected from the group consisting of the camera module according to claim 11 and the ambient light sensor module according to claim 12 , and the module (B) provided with the sensing light emitting element are the same. An electronic device, characterized in that it is arranged on a plane and in a vicinity within 4 cm.

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