Optical members, optical filters, solid-state imaging devices, and optical sensor devices

Abstract

To provide an optical member including a resin layer which reduces a shoulder peak in a red to near infrared region based on a near infrared absorbing agent, and has high transmittance of visible light including the red region and a wide absorption band in the near infrared region.SOLUTION: A resin layer contains a compound (A) and a compound (B), and the resin layer satisfies the following requirements (a) to (d) when an absorption maximum wavelength of the compound (A) is represented by λA, and an absorption maximum wavelength of the compound (B) is represented by λB. (a)λA<λB. (b) 680 nm≤λA≤870 nm. (c) 760 nm≤λB≤900 nm. (d) When transmittance when light at an arbitrary wavelength of X nm in wavelengths of 600-(λA-1) nm is incident from a perpendicular direction to a surface direction of the resin layer is represented by Ta, when transmittance when light at a wavelength of (X+1) nm is incident from the perpendicular direction to the surface direction of the resin layer is represented by Tb, and when the maximum value of Tb-Ta is represented by Tx, Tx<0 is satisfied.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an optical member, an optical filter, a solid-state imaging device, and an optical sensor device. [Background technology]

[0002] Solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions use CCD and CMOS image sensors, which are solid-state imaging elements for color images. These solid-state imaging elements use silicon photodiodes in their light receiving sections, which are sensitive to near-infrared light that the human eye cannot detect. Silicon photodiodes are also used in optical sensor devices. For example, solid-state imaging devices require visibility correction to make colors appear natural to the human eye, and optical components that selectively transmit or block light in specific wavelength ranges, particularly optical filters (e.g., near-infrared cut filters), are often used.

[0003] As such near-infrared cut filters, filters manufactured by various methods have been used, and for example, optical filters containing near-infrared absorbents are known. Furthermore, for example, Patent Document 1 discloses a light selective transmission filter having a resin layer containing a resin and two or more types of near-infrared absorbing agents. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-67019 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the light selective transmission filter (near-infrared cut filter) described in Patent Document 1 has low visible light transmittance and insufficient near-infrared absorption properties.

[0006] Conventionally, compounds such as squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, and diimonium-based compounds have been used as the near-infrared absorbent. However, these conventionally used compounds often have a shoulder peak on the short wavelength side of the absorption peak in the red to near-infrared region, a small ratio of absorbance in the infrared region to absorbance in the visible light region, an insufficient absorption bandwidth in the near-infrared region, or a low transmittance in the red region of visible light (R transmittance). Conventional optical filters using these compounds have had room for improvement in these problems.

[0007] Furthermore, conventional optical filters can adversely affect images such as camera images due to the reflected light from the filter appearing as flare or ghosts. In particular, when the reflection band of the near-infrared cut filter overlaps with the wavelength band capable of photoelectric conversion by a sensor, the adverse effects can become more pronounced.

[0008] The present invention has been made in view of the above, and aims to provide an optical component including a resin layer that reduces the shoulder peak in the red to near-infrared region due to a near-infrared absorbent, and has high transmittance for visible light including the red region, and a wide absorption band in the near-infrared region. [Means for solving the problem]

[0009] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration examples, and have thus completed the present invention. An example of the configuration of the present invention is as follows. In the present invention, the expression "A to B" or the like that expresses a numerical range is synonymous with "A or more, B or less," and A and B are included in the numerical range. In addition, in the present invention, a wavelength of A to B nm represents characteristics at a wavelength resolution of 1 nm in a wavelength region of wavelengths of Am or more and wavelengths of B nm or less.

[0010] [1] A resin layer containing compound (A) and compound (B), The resin layer is an optical member, wherein when the absorption maximum wavelength of the compound (A) is λA and the absorption maximum wavelength of the compound (B) is λB, the resin layer satisfies the following requirements (a) to (d): (a) λA<λB (b) 680 nm ≦ λ A ≦ 870 nm (c) 760 nm ≦ λ B ≦ 900 nm (d) When light of any wavelength X nm in the wavelength range of 600 to (λA-1) nm is incident from a direction perpendicular to the surface of the resin layer, Ta is the transmittance, and when light of wavelength (X+1) nm is incident from a direction perpendicular to the surface of the resin layer, Tb is the transmittance. When the maximum value of Tb-Ta is Tx, Tx<0 is satisfied.

[0011] [2] The optical member according to [1], wherein the compound (A) satisfies the following requirement (i): (i) When the transmittance of compound (A) to light of an arbitrary wavelength X nm in the wavelength range of 600 to (λA-1) nm is TaA and the transmittance of compound (A) to light of a wavelength (X+1) nm is TbA, the wavelength X nm that satisfies TbA-TaA>0 is included in a part of the wavelength range of 600 to (λA-1) nm.

[0012] [3] The optical member according to [1] or [2], wherein the minimum transmittance of light having a wavelength of λA to λB nm incident from a direction perpendicular to the surface direction of the resin layer is 3% or less.

[0013] [4] The optical member according to any one of [1] to [3], wherein Wmin is in the range of 650 to 750 nm, when Wmin is the shortest wavelength at which the transmittance is 50% for light having a wavelength of 600 to 900 nm incident from a direction perpendicular to the surface direction of the resin layer.

[0014] [5] An optical member according to any one of [1] to [4], wherein, for light having a wavelength of 600 to 900 nm incident from a direction perpendicular to the surface direction of the resin layer, the shortest wavelength Wmin at which the transmittance is 50% and the longest wavelength Wmax at which the transmittance is 50% satisfy the relationship Wmax-Wmin≧130 nm.

[0015] [6] The optical member according to any one of [1] to [5], wherein the compounds (A) and (B) are compounds selected from the group consisting of phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, croconium compounds, cyanine compounds, polymethine compounds (provided that the polymethine compounds are compounds other than squarylium compounds, croconium compounds and cyanine compounds), diimonium compounds, dithiol metal complex compounds and pyrrolopyrrole compounds.

[0016] [7] The optical member according to any one of [1] to [6], wherein the average transmittance of light having a wavelength of 450 to 570 nm incident from a direction perpendicular to the surface direction of the resin layer is 80% or more.

[0017] [8] The optical member according to any one of [1] to [7], wherein the resin layer contains at least one resin selected from the group consisting of cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, polyester resins, polycarbonate resins, polyamide resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins.

[0018] [9] An optical filter comprising the optical member according to any one of [1] to [8] and a dielectric multilayer film.

[10] The optical filter according to [9], which is a near-infrared cut filter, a dual bandpass filter, or a single bandpass filter.

[0019]

[11] A solid-state imaging device comprising the optical member according to any one of [1] to [8] or the optical filter according to any one of [9] to

[10] .

[12] An optical sensor device comprising the optical member according to any one of [1] to [8] or the optical filter according to any one of [9] to

[10] . [Effects of the Invention]

[0020] According to the present invention, it is possible to provide an optical member and an optical filter including a resin layer that can reduce the shoulder peak in the red to near-infrared region due to a near-infrared absorbent and has high transmittance for visible light including the red region and a wide absorption band in the near-infrared region.

[0021] Furthermore, the present invention can provide optical components and optical filters that have these properties, particularly those that can sufficiently block a wide range of light in the near-infrared region while transmitting a high proportion of light in the visible region. Therefore, the present invention can easily produce optical filters such as not only near-infrared cut filters (NIR-CFs) but also dual bandpass filters (DBPFs, e.g., visible-near-infrared selective transmission filters) and single bandpass filters (e.g., near-infrared transmission filters (IRPFs)). These NIR-CFs, DBPFs, and single bandpass filters have excellent light selective transmittance, being able to sharply block the wavelength range that you want to block (e.g., the infrared region) while showing high transmittance in the wavelength range that you want to transmit (e.g., the visible light region).

[0022] As described above, the present invention can provide an optical element and an optical filter having the above-mentioned characteristics, and in particular, can provide an optical element and an optical filter having high transmittance even for light in the red region. Therefore, by using the optical element or optical filter, it is possible to obtain a good image with excellent RGB balance, and it is possible to easily obtain an optical element and an optical filter that can suppress reflected light by a wide absorption band in the near-infrared region and provide a good image with little flare or ghosting. Furthermore, when the optical filter is a filter having a dielectric multilayer film, the dielectric multilayer film can reduce the incidence angle dependency, thereby enabling the acquisition of a good captured image. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 1 shows the spectral transmittance curve of the resin layer obtained in Example 4. [Figure 2] FIG. 2 shows the spectral transmittance curves of the resin layers obtained in Comparative Examples 1 to 3. [Figure 3] FIG. 3 shows the spectral transmittance curve of the optical filter obtained in Example 4. [Figure 4] FIG. 4 shows the spectral transmittance curves of the optical filters obtained in Comparative Examples 1 to 3. [Figure 5] FIG. 5 is an explanatory diagram of the captured images in the RGB balance evaluation and color shading evaluation of the embodiment. [Figure 6] FIG. 6 is an explanatory diagram of a photographed image (one example) in the ghost evaluation of the embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0024] <Optical components and optical filters> The optical member according to the present invention (hereinafter also referred to as "the present optical member") has a resin layer (hereinafter also referred to as "the present resin layer") containing compound (A) and compound (B), The resin layer satisfies the following requirements (a) to (d), where λA is the maximum absorption wavelength of the compound (A) and λB is the maximum absorption wavelength of the compound (B). (a) λA<λB (b) 680 nm ≦ λ A ≦ 870 nm (c) 760 nm ≦ λ B ≦ 900 nm (d) When light of any wavelength X nm in the wavelength range of 600 to (λA-1) nm is incident from a direction perpendicular to the surface of the resin layer, Ta is the transmittance, and when light of wavelength (X+1) nm is incident from a direction perpendicular to the surface of the resin layer, Tb is the transmittance. When the maximum value of Tb-Ta is Tx, Tx<0 is satisfied.

[0025] The optical element may consist of one or more layers of the resin layer (only), may include the resin layer and a glass support (functional film), or may include the resin layer and another resin layer (functional film) other than the resin layer. Specific examples of the present optical member include an optical member consisting of only the present resin layer, an optical member in which the present resin layer is laminated on a support (functional film) such as a glass support or a base resin support, and an optical member in which a resin layer (functional film) such as an overcoat layer made of a curable resin or the like is laminated on the present resin layer. Among these, optical members in which a resin layer (functional film) such as an overcoat layer made of a curable resin or the like is laminated on the present resin layer are particularly preferred in terms of production costs, ease of adjusting optical properties, and further, the ability to achieve the scratch-repelling effect of the present resin layer and improve the scratch resistance of the present resin layer.

[0026] The optical filter according to the present invention (hereinafter also referred to as "the filter") may have any conventionally known configuration other than the inclusion of the optical member, and the optical member alone may serve as the filter, but it is preferable for the filter to have the optical member and a dielectric multilayer film, and it is particularly preferable for the optical member to have a dielectric multilayer film on at least one surface. Note that "at least one surface of the optical member" refers to one of the surfaces (main surfaces) of the optical member that has the largest area. The present filter may have two or more dielectric multilayer films. In this case, two or more dielectric multilayer films may be provided on one side of the present optical component, but it is preferable that the present optical component have one or more dielectric multilayer films on each side. In this case, each dielectric multilayer film is counted as one. When two or more dielectric multilayer films are provided, they may include two or more similar multilayer films, or two or more different multilayer films.

[0027] As the present filter having such a dielectric multilayer film, a filter having a dielectric multilayer film on one of the main surfaces of the present optical element, or a filter having a dielectric multilayer film on both of the main surfaces of the present optical element is preferred. When the dielectric multilayer film is provided on one surface, it is possible to easily obtain an optical filter that is low in manufacturing cost and easy to manufacture, and when provided on both surfaces, it is possible to easily obtain an optical filter that has high strength and is resistant to warping and twisting. When the present filter is used in a solid-state imaging device or the like, it is preferable that the filter has little warping or twisting, so it is preferred that the dielectric multilayer film is provided on both surfaces of the present optical element.

[0028] Within the scope of the present invention, the present filter may be provided with a functional film such as a support, an anti-reflection film, a hard coat film or an anti-static film between the present optical element and the dielectric multilayer film, on the surface of the present optical element opposite to the surface on which the dielectric multilayer film is provided, or on the surface of the dielectric multilayer film opposite to the surface on which the present optical element is provided, for the purpose of improving the surface hardness of the present optical element or the dielectric multilayer film, improving chemical resistance, preventing static electricity and eliminating scratches, etc. The present filter may contain one or more of the functional membranes. When the present filter contains two or more layers of the functional membranes, the functional membranes may contain two or more of the same membranes, or two or more of different membranes.

[0029] Specific examples of the present filter, which can be used to enhance the effects of the present invention, include a near-infrared cut filter (NIR-CF), a dual bandpass filter (DBPF) such as a visible-near-infrared selective transmission filter, and a single bandpass filter such as a near-infrared transmission filter (IRPF). The present filter can also be used as a filter for alternative light sources (ALS) used in forensic science and the like, or as a filter for environmental light sensors.

[0030] When the present filter is an NIR-CF or DBPF, it is preferable that the filter satisfies the following requirement (F1) or (F2), and it is more preferable that the filter satisfies the following requirements (F1) and (F2).

[0031] (F1): The average transmittance (Tf_ave) of light having a wavelength of 450 to 570 nm incident from a direction perpendicular to the surface of the filter is preferably 85% or more, more preferably 87% or more, and even more preferably 90% or more. Since a higher average transmittance is preferable, the upper limit is not particularly limited and may be 100%. If the filter satisfies this requirement (F1), it can be said to have high visible light transmittance, and since it can adequately cut light in the near-infrared wavelength range that is desired to be cut while further suppressing the decrease in visible light transmittance, it can be more suitably used as an NIR-CF or DBPF.

[0032] In the present invention, the average transmittance for wavelengths A to B nm is a value calculated by measuring the transmittance at each wavelength from A nm to B nm in 1 nm increments, and dividing the sum of the transmittances by the number of measured transmittances (wavelength range, B-A+1). The direction perpendicular to the surface direction of the present filter means the direction perpendicular to the surface (main surface) of the present filter that has the largest area.

[0033] (F2): The minimum transmittance (Tf_min) of light having wavelengths λA to λB nm incident from a direction perpendicular to the surface of the filter is preferably 1% or less, more preferably 0.5% or less. Since a smaller minimum transmittance is preferable, the lower limit is not particularly limited and may be 0%. If the present filter satisfies this requirement (F2), it is possible to easily obtain an optical filter that can transmit a high proportion of light in the visible light range while sufficiently blocking light in the near-infrared range.

[0034] When the present filter is intended to transmit light in the red region (wavelengths of 580 to 650 nm) such as NIR-CF, it is preferable that the filter satisfies the following requirement (F3). (F3): The average transmittance (R transmittance) of light having a wavelength of 580 to 650 nm incident from a direction perpendicular to the surface of the filter is preferably 80 to 96%, more preferably 82 to 94%. If the present filter satisfies this requirement (F3), it can be said that the transmittance of light in the red region is sufficiently high, and by using this optical filter, a good image with excellent RGB balance can be easily obtained.

[0035] Furthermore, the present filter preferably satisfies the following requirement (F4). (F4): When Wf_min is the shortest wavelength at which transmittance is 50% for light with a wavelength of 600 to 900 nm that is incident perpendicularly to the surface of this filter, Wf_min is preferably in the range of 650 to 750 nm, more preferably 660 to 740 nm. When the present filter satisfies this requirement (F4), the transmittance in the red region of visible light is improved, and by using this optical filter, a good image with excellent RGB balance can be easily obtained.

[0036] Furthermore, the present filter preferably satisfies the following requirement (F5). (F5): In the wavelength range of 600 to 900 nm, the difference (ΔT20(0°-30°)) between the shortest wavelength at which the transmittance of light incident perpendicularly to the surface of the filter is 20% and the shortest wavelength at which the transmittance of light incident at an angle of 30° to the surface of the filter is 20% is preferably 1 to 10 nm, and more preferably 1 to 8 nm. If the present filter satisfies this requirement (F5), an optical filter with small incidence angle dependency and excellent luminous efficiency correction can be easily obtained.

[0037] Furthermore, the present filter preferably satisfies the following requirement (F6). (F6): The average transmittance (750-850 nm Tave) of light with a wavelength of 750-850 nm incident from a direction perpendicular to the surface of the filter is preferably 0.0-6.0%, more preferably 0.0-4.0%. If this filter satisfies this requirement (F6), light in the near-infrared region will be reduced, resulting in good images with less flare and ghosting.

[0038] The thickness of the present filter may be appropriately selected depending on the desired application, but in accordance with the recent trend toward thinner and lighter solid-state imaging devices, it is preferable that the thickness of the present filter is also thin. The present filter can be made thinner because it contains the present resin layer.

[0039] The thickness of the present filter is preferably 300 μm or less, more preferably 280 μm or less, even more preferably 250 μm or less, and particularly preferably 240 μm or less. There is no particular lower limit, but it is desirable that the thickness is, for example, 20 μm.

[0040] NIR-CF The NIR-CF is preferably an optical filter that has excellent cutoff performance in the wavelength range of 850 to 1200 nm and excellent transmittance in the visible light wavelength range. The dielectric multilayer film used in this NIR-CF is preferably a near-infrared reflective film.

[0041] When NIR-CF is used in solid-state imaging devices, etc., low transmittance in the near-infrared wavelength range is preferable. In particular, it is known that solid-state imaging devices have relatively high light sensitivity in the 800 to 1200 nm wavelength range. By reducing the transmittance in this wavelength range, it is possible to effectively correct the visibility between the camera image and the human eye, thereby achieving excellent color reproducibility. Furthermore, by reducing the transmittance in the 850 to 1200 nm wavelength range, it is possible to effectively prevent near-infrared light used for security authentication functions from reaching the image sensor, etc.

[0042] The average transmittance of the NIR-CF, measured in the wavelength range of 850 to 1200 nm from the perpendicular direction of the filter, is preferably 5% or less, more preferably 4% or less, even more preferably 3% or less, and particularly preferably 2% or less. If the average value of the transmittance in the wavelength range of 850 to 1200 nm is in this range, near-infrared rays can be sufficiently blocked, and excellent color reproducibility can be achieved, which is preferable.

[0043] DBPF The DBPF is not particularly limited as long as it is an optical filter that transmits visible light and near-infrared light of a wavelength that is desired to be transmitted and cuts near-infrared light of a wavelength that is desired to be cut. The dielectric multilayer film used in this DBPF is preferably a film that transmits visible light and near-infrared light of wavelengths that are desired to be transmitted, and cuts near-infrared light of wavelengths that are desired to be cut.

[0044] IRPF The IRPF is not particularly limited as long as it is an optical filter that cuts visible light and transmits near-infrared light of a wavelength that is desired to be transmitted. The dielectric multilayer film used in this IRPF is preferably a film that cuts off light of a wavelength that is desired to be cut off (a part of visible light and / or near-infrared light). The IRPF may also use a visible light absorber to cut visible light.

[0045] IRPF can be suitably used in optical systems such as infrared surveillance cameras, in-vehicle infrared cameras, infrared communications, various sensing systems, infrared warning devices, and night vision devices. When used in these applications, it is preferable that the transmittance of light at wavelengths other than the near-infrared light that is desired to be transmitted is low. In particular, in the wavelength region of 380 to 700 nm, the average transmittance when measured from the perpendicular direction of the present filter is preferably 10% or less, more preferably 5% or less.

[0046] In addition, it is preferable that the transmittance of the near-infrared light to be transmitted is high. Specifically, the IRPF has a light transmission band Ya in the wavelength region of 750 nm or more, and the maximum transmittance (T IR ) is preferably 45% or more, more preferably 50% or more.

[0047] This filter, for example, has excellent ability to cut light in the wavelength range you want to cut and transmit light in the wavelength range you want to transmit. Therefore, it is useful for correcting the visibility of solid-state imaging elements such as CCD and CMOS image sensors in camera modules. It is particularly useful in digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, cameras for wearable devices, PC cameras, surveillance cameras, automotive cameras, infrared cameras, televisions, car navigation systems, personal digital assistants, video game consoles, portable game consoles, fingerprint authentication systems, digital music players, optical sensors (e.g., ambient light sensors), various sensing systems, infrared communications, and the like. It is also useful as a heat-blocking filter attached to glass panels in automobiles and buildings.

[0048] <Main resin layer> The resin layer contains a resin, a compound (A), and a compound (B), and satisfies the following requirements (a) to (d), where λA is the absorption maximum wavelength of the compound (A) and λB is the absorption maximum wavelength of the compound (B): When the compound (A) or (B) has a plurality of absorption maxima, the wavelength of the absorption maximum with the highest absorbance (lowest transmittance) is designated as λA or λB.

[0049] (a): λA<λB (=λB-λA>0) λB-λA is preferably 1 to 100 nm, more preferably 5 to 80 nm, and even more preferably 10 to 70 nm. By using compounds (A) and (B) having a relationship between λA and λB within the above ranges, the shoulder peak in the red to near-infrared region due to the near-infrared absorbent is reduced, and an optical component and an optical filter that can sharply block the wavelength region that is desired to be blocked (for example, the infrared region) can be easily obtained.

[0050] (b): 680 nm ≦ λ A ≦ 870 nm The lower limit of λA is preferably 700 nm, more preferably 720 nm, and the upper limit of λA is preferably 850 nm, more preferably 840 nm. When λA is within the above range, it is possible to easily obtain an optical element and an optical filter that can transmit light in the visible light region with high transmittance while sufficiently blocking light in the near-infrared region.

[0051] (c): 760 nm ≦ λ B ≦ 900 nm The lower limit of λB is preferably 765 nm, more preferably 770 nm, and the upper limit of λB is preferably 880 nm, more preferably 870 nm. When λ is within the above range, an optical member and an optical filter including a resin layer having a wide absorption band in the infrared region can be easily obtained, and an optical member and an optical filter that can provide a good image with little flare or ghost can be easily obtained. Furthermore, by satisfying the requirements (b) and (c), it is possible to easily obtain an optical member and an optical filter including a resin layer in which the shoulder peak in the red to near-infrared region due to the near-infrared absorbent is further reduced.

[0052] (d): When light of any wavelength X nm in the wavelength range of 600 to (λA-1) nm is incident from a direction perpendicular to the surface of the resin layer, Ta is the transmittance, and light of a wavelength (X+1) nm is incident from a direction perpendicular to the surface of the resin layer, Tb is the transmittance, and Tx is the maximum value of Tb-Ta, Tx<0 is satisfied. The upper limit of Tx is preferably −0.0005, more preferably −0.001, and the lower limit of Tx is usually −1. Satisfying requirement (d) means that the spectral transmittance curve of the resin layer in its absorption region is always downward sloping to the right, with no shoulder peak in the absorption region from red onward. Therefore, satisfying requirement (d) makes it easy to obtain optical components and optical filters with excellent light selective transmittance, which can sharply block the wavelength range you want to block (e.g., the infrared region) while showing high transmittance in the wavelength range you want to transmit (e.g., the visible light region). Furthermore, excellent light selective transmittance allows you to capture images with good color shading.

[0053] It is preferable that the resin layer further satisfies the following requirement (e). (e): When the maximum value of Tb-Ta at a wavelength of 600 to (λA-1) nm and a transmittance of 5 to 70% is Ty, Ty<-0.05 is satisfied. The upper limit of Ty is preferably −0.06, more preferably −0.08, and the lower limit of Ty is not particularly limited, but is preferably −10. Satisfying requirement (e) means that in the absorption region of the resin layer, the spectral transmittance curve slopes downward to the right and is gentle, without any sudden changes in slope. Therefore, satisfying requirement (e) makes it easy to obtain optical components and optical filters with excellent light selective transmittance. Furthermore, excellent light selective transmittance allows for the capture of images with good color shading.

[0054] The present resin layer preferably further satisfies at least one of the following requirements (R1) to (R3), and more preferably satisfies all of the following requirements (R1) to (R3).

[0055] (R1): The average transmittance (Ts_ave) of light having a wavelength of 450 to 570 nm incident from a direction perpendicular to the surface of the resin layer is preferably 80% or more, more preferably 85% or more, and even more preferably 87% or more. Since a higher average transmittance is preferable, the upper limit is not particularly limited and may be 100%. When the resin layer satisfies this requirement (R1), it is possible to easily obtain an optical component and an optical filter that can sufficiently cut light of wavelengths in the near-infrared region that are desired to be cut, while further suppressing a decrease in visible light transmittance.

[0056] The direction perpendicular to the surface direction of the resin layer refers to the direction perpendicular to the surface (principal surface) of the resin layer having the largest area.

[0057] (R2): The minimum transmittance (Ts_min) of light having wavelengths λA to λB nm incident from a direction perpendicular to the surface of the resin layer is preferably 3% or less, more preferably 1% or less, and even more preferably 0.5% or less. Since a smaller minimum transmittance is preferable, the lower limit is not particularly limited and may be 0%. When the resin layer satisfies this requirement (R2), it is possible to easily obtain an optical element and an optical filter that can transmit light in the visible light region with high transmittance while sufficiently blocking light in the near-infrared region.

[0058] (R3): When Wmin is the shortest wavelength at which the transmittance is 50% for light having a wavelength of 600 to 900 nm incident from a direction perpendicular to the surface of the resin layer, and Wmax is the longest wavelength at which the transmittance is 50%, Wmax - Wmin is preferably 130 nm or more, more preferably 140 nm or more, and even more preferably 150 nm or more. The upper limit of Wmax - Wmin is not particularly limited, but is, for example, 280 nm. When the resin layer satisfies this requirement (R3), it is possible to suppress reflected light through a wide absorption band in the near-infrared region, and it is possible to easily obtain optical components and optical filters that can provide good images with little flare or ghosting. The fact that the present resin layer satisfies this requirement (R3) is also advantageous when the optical filter using the present resin layer is used as, for example, an infrared transmission filter.

[0059] Furthermore, the resin layer preferably satisfies the following requirement (R4). (R4): The Wmin is preferably in the range of 650 to 750 nm, more preferably 660 to 740 nm. When the present resin layer satisfies this requirement (R4), the transmittance in the red region of visible light is improved, and by using an optical element and optical filter containing the present resin layer, a good image with excellent RGB balance can be easily obtained.

[0060] When the present resin layer is used in an optical filter that is intended to transmit light in the red region (wavelength 580 to 650 nm) such as NIR-CF, the present resin layer preferably satisfies the following requirement (R5). (R5): The average transmittance (R transmittance) of light with a wavelength of 580 to 650 nm incident from a direction perpendicular to the surface of the resin layer is preferably 72 to 96%, more preferably 74 to 94%. When the present resin layer satisfies this requirement (R5), it can be said that the transmittance of light in the red region is sufficiently high, and by using an optical component and an optical filter containing the present resin layer, it is possible to easily obtain a good image with excellent RGB balance.

[0061] The resin layer preferably satisfies the following requirement (R6). (R6): The maximum transmittance (Ts_max) of light having wavelengths λA to λB nm incident from a direction perpendicular to the surface of the resin layer is preferably 11% or less, more preferably 10% or less, and even more preferably 8% or less. Since a smaller maximum transmittance is preferable, the lower limit is not particularly limited and may be 0%. When the present resin layer satisfies this requirement (R6), the transmittance in the near-infrared region is reduced, and by using an optical element and optical filter containing the present resin layer, good images with little ghosting can be easily obtained.

[0062] The present resin layer may be a single layer or multiple layers, in which case the two or more present resin layers may be the same or different.

[0063] The thickness of the resin layer can be appropriately selected depending on the desired application and is not particularly limited, but is usually 0.5 to 300 μm, preferably 1 to 250 μm, more preferably 2 to 230 μm, and particularly preferably 3 to 150 μm. When the thickness of the present resin layer is within the above range, the optical member and the present filter using the present resin layer can be made thinner and lighter, and can be suitably used in various applications such as solid-state imaging devices, etc. In particular, when the present resin layer as a single layer is used in a lens unit such as a camera module, it is preferable because the lens unit can be made thinner and lighter.

[0064] [Compound (A) and Compound (B)] Compound (A) and compound (B) are not particularly limited as long as they are compounds whose absorption maximum wavelengths satisfy the above requirements (a) to (c), and conventionally known near-infrared absorbents can be used.

[0065] The resin layer may contain two or more compounds having a maximum absorption wavelength in the range of 680 to 870 nm. When the resin layer contains two or more compounds having a maximum absorption wavelength in the range of 680 to 870 nm, the compound having the longest maximum absorption wavelength among these compounds is referred to as compound (A). The resin layer may contain two or more compounds having a maximum absorption wavelength in the range of 760 to 900 nm. When the resin layer contains two or more compounds having a maximum absorption wavelength in the range of 760 to 900 nm, the compound having the shortest maximum absorption wavelength (provided that the compound satisfies the above requirement (a)) is referred to as compound (B). When the resin layer contains two or more compounds whose absorption maximum wavelengths are in the range of 680 to 870 nm or two or more compounds whose absorption maximum wavelengths are in the range of 760 to 900 nm, the absorption maximum wavelength that is the second longest or longer among the absorption maximum wavelengths of the compounds contained in the resin layer and that is in the range of 680 to 870 nm is designated as λA, and the absorption maximum wavelength that is the shortest among the absorption maximum wavelengths of the compounds contained in the resin layer that is longer than the absorption maximum wavelength λA and that is in the range of 760 to 900 nm is designated as λB. That is, for example, when the resin layer contains compound 1 having a maximum absorption wavelength of 700 nm, compound 2 having a maximum absorption wavelength of 800 nm, and compound 3 having a maximum absorption wavelength of 850 nm, λB is 850 nm, λA is 800 nm, compound 2 is compound (A), and compound 3 is compound (B). Also, when the resin layer contains compound 1 having a maximum absorption wavelength of 700 nm, compound 2 having a maximum absorption wavelength of 800 nm, compound 3 having a maximum absorption wavelength of 880 nm, and compound 4 having a maximum absorption wavelength of 900 nm, λB is 880 nm, λA is 800 nm, compound 2 is compound (A), and compound 3 is compound (B).

[0066] The compounds (A) and (B) are preferably compounds selected from the group consisting of phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, croconium compounds, cyanine compounds, polymethine compounds (provided that the polymethine compounds are compounds other than squarylium compounds, croconium compounds and cyanine compounds), diimonium compounds, dithiol metal complex compounds and pyrrolopyrrole compounds. Among these, polymethine compounds are preferred because they have excellent light selective transparency, i.e., they can easily reduce the shoulder peak in the red to near-infrared region due to the near-infrared absorbent, can sharply block the wavelength region that is desired to be blocked (for example, the infrared region), and show high transmittance in the wavelength region that is desired to be transmitted (for example, the visible light region), and they can easily provide optical members and optical filters that include a resin layer that has high visible light transmittance and a wide absorption band in the near-infrared region.

[0067] Polymethine pigments The polymethine dye is a compound other than a squarylium compound, a croconium compound, or a cyanine compound, and is not particularly limited as long as it does not impair the effects of the present invention. However, compounds described in JP 2021-134350 A, WO 2021 / 085372 A, JP 2019-164269 A, JP 2022-025669 A, etc. are preferred, as they make it easy to obtain optical components and optical filters that better demonstrate the effects. The polymethine dyes may be synthesized by commonly known methods.

[0068] Phthalocyanine compounds The phthalocyanine compound is not particularly limited as long as it does not impair the effects of the present invention. Examples of the phthalocyanine compound include compounds described in JP-A-2005-220060, JP-A-2007-169343, JP-A-2013-195480, WO 2015 / 025779, and WO 2017 / 164024, and these compounds may be synthesized by a commonly known method. When a phthalocyanine compound is used, it is preferable to use it in combination with at least one other near-infrared absorbing agent.

[0069] Naphthalocyanine compounds The naphthalocyanine compound is not particularly limited as long as it does not impair the effects of the present invention. For example, the naphthalocyanine compound may be the compounds described in JP-A-2015-225290, JP-A-2017-142332, and WO 2018 / 186490, and may be synthesized by a commonly known method.

[0070] Squarylium compounds The squarylium compound is not particularly limited as long as it does not impair the effects of the present invention. Examples of the squarylium compound include squarylium-based compounds represented by the following formula (4) and compounds described in JP 2014-074002 A, JP 2014-052431 A, and WO 2017 / 164024 A, and may be synthesized by a commonly known method.

[0071] [ka]

[0072] Specific examples of Rsq1 to Rsq6 in the formula (4) include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group; groups in which an alkyl group is partially substituted with a substituent, such as a 2-hydroxyethyl group, a 2-cyanoethyl group, a 3-hydroxypropyl group, a 3-cyanopropyl group, a methoxyethyl group, an ethoxyethyl group, and a butoxyethyl group; aryl groups or groups in which an aryl group is partially substituted with a substituent, such as a phenyl group, a fluorophenyl group, a chlorophenyl group, a tolyl group, a diethylaminophenyl group, and a naphthyl group; alkenyl groups such as a vinyl group, a propenyl group, a butenyl group, and a pentenyl group; and aralkyl groups or groups in which an aralkyl group is partially substituted with a substituent, such as a benzyl group, a p-fluorobenzyl group, a phenylpropyl group, and a naphthylethyl group.

[0073] Any number of hydrogen atoms contained in these Rsq1 to Rsq6 may be substituted with a substituent L. Examples of the substituent L include a fluorine atom, a chlorine atom, a bromine atom, an amino group (which may be alkylated), a cyano group, a nitro group, an alkyl group, a hydroxyl group, a thiol group, an alkyl ether group, an alkylthioether group, or a group containing an ester group.

[0074] In terms of solubility in resins, Rsq1 to Rsq6 in formula (4) are preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, or a group in which any number of hydrogen atoms of these groups have been substituted with the substituent L, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, or a group in which any number of hydrogen atoms of these groups have been substituted with the substituent L.

[0075] Croconium compounds The croconium-based compound is not particularly limited as long as it does not impair the effects of the present invention. For example, the croconium-based compound may be the compound described in JP-A-2007-31644, JP-A-2007-169315, or WO 2019 / 021767, and may be synthesized by a commonly known method.

[0076] Cyanine compounds The cyanine compound is not particularly limited as long as it does not impair the effects of the present invention. For example, the cyanine compound may be the compounds described in JP-A-2009-108267, JP-A-2010-072575, and JP-A-2016-060774, and may be synthesized by a commonly known method.

[0077] Diimonium compounds The diimonium compound is not particularly limited as long as it does not impair the effects of the present invention. For example, the diimonium compound represented by the following formula (5) and the compounds described in JP-A-2005-234558, WO-A-2004 / 048480, and WO-A-2017 / 164024 may be mentioned, and may be synthesized by a generally known method.

[0078] [ka]

[0079] Rdi1 to Rdi12 each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, or -NR g R h Group, -SR i Group, -SO2R i Group, -OSO2R i group or the following L a ~L h R g and R h are each unique In the upright position, hydrogen atoms, -C(O)R i group or the following L a ~L e R i is the following L a ~L e represents one of the following: (L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L b ) Halogen-substituted alkyl group having 1 to 12 carbon atoms (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K (L d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K; (L e ) a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K (L f ) an alkoxy group having 1 to 12 carbon atoms (L g) an acyl group having 1 to 12 carbon atoms which may have a substituent L; (L h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L; the substituent K is at least one selected from an aliphatic hydrocarbon group having 1 to 12 carbon atoms and a halogen-substituted alkyl group having 1 to 12 carbon atoms, and the substituent L is at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, 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; X represents the anion required to neutralize the charge.

[0080] The Rdi1 to Rdi8 are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, or a benzyl group, and more preferably an isopropyl group, a sec-butyl group, a tert-butyl group, or a benzyl group.

[0081] The Rdi9 to Rdi12 are preferably a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a cyano group, a nitro group, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an acetylamino group, a propionylamino group, an N-methylacetylamino group, a trifluoromethanoylamino group, a pentafluoroethanoylamino group, a tert-butanoylamino group, a cyclohexynoylamino group, Rdi9 to Rdi12 are preferably 0 to 4, and more preferably 1 to 4. Rdi9 to Rdi12 are preferably 0 to 4. The number of Rdi9 to Rdi12 bonded to the same aromatic ring is not particularly limited as long as it is 0 to 4, but is preferably 0 or 1.

[0082] X is an anion required to neutralize the charge; if the anion is divalent, one molecule is required, and if the anion is monovalent, two molecules are required. In the latter case, the two anions may be the same or different, but from the viewpoint of synthesis, they are preferably the same. X is not particularly limited as long as it is an anion, and examples thereof include the anions listed in Table 1 below.

[0083] [Table 1]

[0084] As X, if the acid has a high acidity when converted into an acid, the heat resistance of the diimonium compound when converted into an anion of the diimonium compound tends to be improved, and therefore (X-10), (X-16), (X-17), (X-21), (X-22), (X-24), and (X-28) in Table 1 are particularly preferred.

[0085] Dithiol metal complex compounds The dithiol metal complex compound is not particularly limited as long as it does not impair the effects of the present invention. For example, the compounds described in JP 2004-010822 A, JP 2005-232158 A, JP 2006-215395 A, WO 2008 / 086931 A, JP 2012-007038 A, WO 2012 / 152584 A, and JP 2015-40895 A can be mentioned, and they may be synthesized by a generally known method. Chlorides may also be used, for example as described in WO 1998 / 034988.

[0086] Pyrrolopyrrole compounds The pyrrolopyrrole compound is not particularly limited as long as it does not impair the effects of the present invention. For example, the pyrrolopyrrole compound may be a compound described in JP 2018-119077 A and WO 2018 / 020861 A, which may be synthesized by a commonly known method.

[0087] The compounds (A) and (B) are preferably compounds soluble in organic solvents, and particularly preferably compounds soluble in dichloromethane. Here, "soluble in organic solvent" means that 0.1 g or more of compound (A) or (B) dissolves in 100 g of organic solvent at 25°C.

[0088] The compounds (A) and (B) are preferably compounds that satisfy the following requirement (C1). Requirement (C1): In a transmission spectrum measured using a solution of compound (A) or (B) dissolved in dichloromethane (wherein the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%), the average transmittance at wavelengths of 430 to 580 nm is preferably 93% or more, more preferably 95% or more. Since a higher average transmittance is preferable, the upper limit is not particularly limited and may be 100%. When the compounds (A) and (B) satisfy this requirement (C1), it is possible to further suppress a decrease in visible light transmittance while sufficiently cutting light of wavelengths in the near-infrared region that are desired to be cut.

[0089] It is more preferable that the compounds (A) and (B) satisfy the following requirement (C2). Requirement (C2): In a spectroscopic absorption spectrum measured using a solution of compound (A) or (B) dissolved in dichloromethane, when the absorbance at the longest wavelength among the maximum absorption wavelengths is εa and the maximum absorbance at wavelengths of 430 to 580 nm is εbmax, εa / εbmax is preferably 20 or more, more preferably 25 or more, and even more preferably 27 or more. Since a larger εa / εbmax is preferable, the upper limit is not particularly limited, but is, for example, 10,000 or less. When the compounds (A) and (B) satisfy this requirement (C2), it is possible to further suppress a decrease in visible light transmittance while sufficiently cutting light of wavelengths in the near-infrared region that are desired to be cut.

[0090] In order to enhance the effects of the present invention, the compound (A) preferably satisfies the following requirement (i): (i): When the transmittance of compound (A) for light of an arbitrary wavelength X nm in the wavelength range of 600 to (λA-1) nm is TaA and the transmittance of compound (A) for light of a wavelength (X+1) nm is TbA, the wavelength X nm that satisfies TbA-TaA>0 is included in a part of the wavelength range of 600 to (λA-1) nm. The compound (A) satisfying the requirement (i) can be said to be a compound having a shoulder peak in the red to near-infrared region. According to the present invention, even when such a compound (A) is used, an optical element and an optical filter including a resin layer in which the shoulder peak in the red to near-infrared region based on the near-infrared absorbent is reduced can be easily obtained. Specifically, the requirement (i) can be measured by the method described in the examples below.

[0091] The content of the compound (A) in the resin layer is preferably 0.02 to 5.0 parts by mass, more preferably 0.02 to 3.0 parts by mass, based on 100 parts by mass of the resin. When the content of compound (A) is within the above range, it is possible to easily obtain an optical component and an optical filter that can transmit a high proportion of light in the visible light range while sufficiently blocking light in the infrared range.

[0092] The content of the compound (B) in the resin layer is preferably 0.02 to 5.0 parts by mass, more preferably 0.02 to 3.0 parts by mass, based on 100 parts by mass of the resin. When the content of compound (B) is within the above range, an optical element and an optical filter including a resin layer having a wide absorption band in the infrared region can be easily obtained, and an optical element and an optical filter that can provide a good image with little flare or ghost can be easily obtained.

[0093] 〔resin〕 The resin used in the resin layer is not particularly limited, and any conventionally known resin can be used. The resin used in the present resin layer may be one type alone or two or more types.

[0094] The resin is not particularly limited as long as it does not impair the effects of the present invention, but examples thereof include resins having a glass transition temperature (Tg) of preferably 110 to 380°C, more preferably 110 to 370°C, and particularly preferably 120 to 360°C, from the viewpoints of excellent thermal stability and moldability into film (plate) shapes, and of easily obtaining a film that can be used to form a dielectric multilayer film by high-temperature deposition at a deposition temperature of about 100°C or higher. Furthermore, resins having a Tg of 140°C or higher are particularly preferred, because they can obtain a film that can be used to form a dielectric multilayer film by deposition at higher temperatures.

[0095] The resin is a resin plate made of the resin with a thickness of 0.1 mm, and the total light transmittance (JIS K 7375:2008) is preferably 75 to 95%, more preferably 78 to 95%, and particularly preferably 80 to 95%. By using a resin having a total light transmittance within the above range, optical members and optical filters having excellent transparency can be easily obtained.

[0096] The weight average molecular weight (Mw) of the resin, measured by gel permeation chromatography (GPC) in terms of polystyrene, is usually 15,000 to 350,000, preferably 30,000 to 250,000, and the number average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.

[0097] Examples of the resin include cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins. Specific examples of these resins include the resins described in WO 2019 / 168090.

[0098] [Other ingredients] The resin layer may further contain other components such as an absorber other than the compounds (A), (B) and the ultraviolet absorber (hereinafter also referred to as "compound (X)"), an ultraviolet absorber, an antioxidant, a fluorescence quencher, a metal complex compound, an antistatic agent, a light diffusing material, etc., within the scope of not impairing the effects of the present invention. These other components may be used singly or in combination of two or more.

[0099] These other components may be mixed with the resin when forming the resin layer, or may be added when synthesizing the resin. The amount added may be selected appropriately depending on the desired properties, etc., but is usually 0.01 to 5.0 parts by mass, and preferably 0.05 to 2.0 parts by mass, per 100 parts by mass of the resin.

[0100] [Compound (X)] The resin layer may contain one or more compounds (X). Examples of the compound (X) include phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, croconium compounds, polymethine compounds (provided that the polymethine compounds are compounds other than squarylium compounds and croconium compounds), octaphylline compounds, diimonium compounds, perylene compounds, dithiol metal complex compounds, and metal oxide fine particles.

[0101] Examples of the phthalocyanine-based compounds, naphthalocyanine-based compounds, squarylium-based compounds, croconium-based compounds, polymethine-based compounds, diimonium-based compounds, perylene-based compounds, and dithiol metal complex-based compounds include the same compounds as those listed in the columns for Compound (A) and Compound (B), except that the absorption maximum wavelength falls outside the ranges of the requirements (b) and (c). The octaphylline-based compound is not particularly limited as long as it does not impair the effects of the present invention. For example, the octaphylline-based compound may be the compounds described in JP-A-2013-53120 and JP-A-2016-102074, and may be synthesized by a commonly known method. The metal oxide fine particles are not particularly limited as long as they do not impair the effects of the present invention. For example, the metal oxide fine particles described in WO 2017 / 018419 can be used, and they can be synthesized by a commonly known method.

[0102] The compound (X) preferably includes a squarylium-based compound, and more preferably includes one or more squarylium-based compounds and one or more other compounds (X'). The other compounds (X') are particularly preferably phthalocyanine-based compounds and polymethine-based compounds.

[0103] The squarylium-based compound has a sharp absorption peak, excellent visible light transmittance, and a high molar absorption coefficient, but may generate fluorescence that causes scattered light when absorbing light. In this case, the squarylium-based compound may be used in combination with the compound (X'). By suppressing scattered light in this way, when the resulting optical member and optical filter are used in an imaging device or the like, the resulting camera image quality is improved.

[0104] [UV absorber] Examples of the ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, triazine compounds, anthracene compounds, cyanoacrylate compounds, and compounds described in JP-A-2019-014707, etc. Among these, azomethine compounds, indole compounds, benzotriazole compounds, and cyanoacrylate compounds are particularly preferred from the viewpoint of absorption wavelength and compound stability. By including an ultraviolet absorber, it is possible to easily obtain an optical element and an optical filter that have little incidence angle dependency even in the near-ultraviolet wavelength region, and when the optical element and the optical filter are used in an imaging device or the like, the obtained camera image quality is better.

[0105] [Antioxidants] Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane.

[0106] [Method for producing the present resin layer] The resin layer can be formed, for example, by melt molding or cast molding, and may further be coated with a coating agent such as an anti-reflection agent, a hard coating agent and / or an anti-static agent after molding, if necessary.

[0107] A laminate in which the present resin layer is laminated on the support (functional film) can be produced, for example, by melt-molding or cast-molding the present resin layer-forming material onto the support, preferably by a method such as spin coating, slit coating, or inkjet, and then, if necessary, by drying and removing the solvent or by irradiating with light or heating.

[0108] Examples of the support include glass plates (including absorbing glass such as near-infrared absorbing glass), steel belts, steel drums, and supports made of resin (for example, polyester films, cyclic olefin resin films).

[0109] Furthermore, the resin layer can also be formed on an optical component by coating a liquid resin layer-forming material on an optical component such as a glass plate, quartz, or plastic and then drying the solvent, or by coating a curable resin layer-forming material on the optical component and then curing and drying it.

[0110] The amount of residual solvent in the present resin layer or in the resin layer should be as small as possible. Specifically, the amount of residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on 100% by mass of the resin layer. Furthermore, the solvent content in the present resin layer or in the resin layer is preferably kept to 100 ppm by mass or less. When the amount of residual solvent is within the above range, a resin layer that is resistant to deformation and changes in properties and can easily exhibit the desired functions can be obtained.

[0111] <Dielectric multilayer film> The dielectric multilayer film may be a laminate in which high refractive index material layers and low refractive index material layers are alternately stacked.

[0112] The material constituting the high refractive index material layer includes a material having a refractive index of 1.7 or more, and a material having a refractive index of 1.7 to 2.5 is usually selected. Examples of such materials include those containing titanium oxide (titania), zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, or the like as a main component, and containing small amounts (e.g., 0 to 10% by mass of the main component) of titanium oxide, tin oxide, and / or cerium oxide, or the like.

[0113] The low refractive index material layer can be made of a material having a refractive index of 1.6 or less, and typically has a refractive index of 1.2 to 1.6, such as silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

[0114] The method for laminating the high-refractive index material layers and the low-refractive index material layers is not particularly limited as long as a dielectric multilayer film is formed by laminating these material layers. For example, a dielectric multilayer film in which high-refractive index material layers and low-refractive index material layers are alternately laminated can be formed directly on the optical element by a CVD method, a sputtering method, a vacuum deposition method, an ion-assisted deposition method, an ion plating method, or the like.

[0115] The thickness of each of the high-refractive-index material layers and the low-refractive-index material layers is preferably 0.1λ to 0.5λ, where λ (nm) is the near-infrared wavelength to be blocked. The high-refractive-index material layers and the low-refractive-index material layers may have thicknesses outside the range of 0.1λ to 0.5λ depending on the purpose, such as reducing reflection in the visible light region or improving blocking performance in a specific wavelength region. The value of λ (nm) for NIR-CF is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness of each of the high-refractive-index material layers and the low-refractive-index material layers is within this range, the optical film thickness, which is the product (n × d) of the refractive index (n) and the film thickness (d), is approximately equal to λ / 4. This tends to facilitate control of blocking and transmitting specific wavelengths based on the relationship between the optical properties of reflection and refraction.

[0116] In the case of NIR-CF, for example, the total number of layers of high refractive index material and low refractive index material in the dielectric multilayer film is preferably 16 to 70 layers for the entire optical filter, and more preferably 20 to 60. When the thickness of each layer, the thickness of the dielectric multilayer film as the entire optical filter, and the total number of layers are within the above ranges, sufficient manufacturing margins can be ensured, and warping of the optical filter and cracks in the dielectric multilayer film can be reduced.

[0117] In this filter, by appropriately selecting the type of material constituting the high refractive index material layer and the low refractive index material layer, the thickness of each of the high refractive index material layer and the low refractive index material layer, the order of lamination, and the number of laminations in accordance with the absorption characteristics, etc. of compounds (A) and (B), it is possible to ensure sufficient transmittance in the wavelength range that is to be transmitted (e.g., the visible light range), while having sufficient light-blocking properties in the near-infrared wavelength range that is to be blocked, and to reduce the reflectance when near-infrared light is incident from an oblique direction.

[0118] Here, to optimize the conditions of the dielectric multilayer film, for example, optical thin film design software (e.g., Essential Macleod, manufactured by Thin Film Center) can be used to set parameters so that both the anti-reflection effect in the wavelength range to be transmitted (e.g., the visible light range) and the light blocking effect in the near-infrared range to be blocked are achieved. In the case of the software, for example, when forming an NIR-CF dielectric multilayer film, a parameter setting method can be used in which the target transmittance for wavelengths of 400 to 700 nm is set to 100% and the Target Tolerance value is set to 1, and the target transmittance for wavelengths of 705 to 950 nm is set to 0% and the Target Tolerance value is set to 0.5. These parameters can be used to further divide the wavelength range into smaller sections to change the Target Tolerance value in accordance with the various characteristics of the resin layer.

[0119] <Functional membrane> The method for laminating the functional film is not particularly limited, but examples include a method in which a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded or cast-molded onto the optical element or the dielectric multilayer film in the same manner as described above.

[0120] Alternatively, the optical member or the dielectric multilayer film can be coated with a curable composition containing the coating agent using a bar coater or the like, and then cured by irradiation with ultraviolet light or the like to produce the optical member or the dielectric multilayer film.

[0121] Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins, and specific examples include vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based, and epoxy acrylate-based resins. The coating agent may be used alone or in combination of two or more. Examples of the curable compositions containing these coating agents include vinyl-based, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxy acrylate-based curable compositions.

[0122] The curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator may be used, or a photopolymerization initiator and a thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more.

[0123] The blending ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%, when the total amount of the curable composition is taken as 100 mass%. When the blending ratio of the polymerization initiator is within the above range, a curable composition excellent in curing properties and handleability can be easily obtained, and a functional film such as an antireflection film, a hard coat film, or an antistatic film having a desired hardness can be easily obtained.

[0124] Furthermore, an organic solvent may be added to the curable composition as a solvent, and known solvents can be used as the organic solvent. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene 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; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0125] The thickness of the functional film is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 0.7 to 5 μm.

[0126] In addition, in order to improve the adhesion between the optical component and the functional film and / or the dielectric multilayer film, or between the functional film and the dielectric multilayer film, the surface of the optical component, the functional film, or the dielectric multilayer film may be subjected to a surface treatment such as corona treatment or plasma treatment.

[0127] <Solid-state imaging device> A solid-state imaging device according to the present invention includes the optical member or the filter. Here, the solid-state imaging device is a device equipped with a solid-state imaging element such as a CCD or CMOS image sensor, and specific examples include digital still cameras, cameras for smartphones, cameras for mobile phones, cameras for wearable devices, and digital video cameras.

[0128] <Optical sensor device> The optical sensor device according to the present invention is not particularly limited as long as it includes the present optical member or the present filter, and may have a conventionally known configuration. The optical sensor device is preferably an ambient light sensor device. For example, it may include a device having the present filter, a photoelectric conversion element, and a light diffusion film. Here, the optical sensor is a sensor capable of sensing the ambient brightness and color tone (e.g., strong red in the evening), and it is possible, for example, to control the illuminance and color tone of a display installed in a device based on information sensed by the optical sensor. [Example]

[0129] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0130] [Resin synthesis example] 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1] represented by the following formula (a) 2,5 .1 7,10 ] 100 parts by mass of dodeca-3-ene (hereinafter also referred to as "DNM"), 1 18 parts by weight of hexene (molecular weight modifier) ​​and 300 parts by weight of toluene (solvent for ring-opening polymerization reaction) were placed in a nitrogen-purged reaction vessel, and the solution was heated to 80°C. Next, 0.2 parts by weight of a toluene solution of triethylaluminum (0.6 mol / L) and 0.9 parts by weight of a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol / L) were added as polymerization catalysts to the solution in the reaction vessel, and the solution was heated and stirred at 80°C for 3 hours to carry out a ring-opening polymerization reaction, yielding a ring-opened polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

[0131] [ka]

[0132] 1,000 parts by mass of the ring-opened polymer solution obtained above was charged into an autoclave, and 0.12 parts by mass of RuHCl(CO)[P(C6H5)3]3 was added to this ring-opened polymer solution, and the mixture was heated under a hydrogen gas pressure of 100 kg / cm 2 The mixture was heated and stirred at a reaction temperature of 165°C for 3 hours to carry out the hydrogenation reaction. The reaction was carried out. The resulting reaction solution (hydrogenated polymer solution) was cooled, and then the hydrogen gas pressure was released. The resulting reaction solution was poured into a large amount of methanol, and a coagulated product was separated and recovered. This was dried to obtain a hydrogenated polymer (hereinafter also referred to as "Resin A").

[0133] <Molecular weight> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin A, calculated in terms of standard polystyrene, were measured using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgel α-M, developing solvent: THF). The Mn was 32,000 and the Mw was 137,000.

[0134] <Glass transition temperature> The glass transition temperature (Tg) of the obtained resin A was measured using a differential scanning calorimeter (DSC6200) manufactured by Hitachi High-Tech Science Corporation at a temperature rise rate of 20°C per minute in a nitrogen stream. The Tg was 165°C.

[0135] [Compound synthesis example] The compounds (A) and (B) used in the following examples were synthesized based on commonly known synthesis methods. Compounds (A) and (B) can be prepared by the methods described in, for example, JP 2009-108267 A, JP 5-59291 A, JP 2014-95007 A, JP 2011-52218 A, WO 2007 / 114398 A, JP 2003-246940 A, Chemistry of Heterocyclic Compounds: The Cyanine Dyes and Related Compounds, Volume 1 18 (Wiley, 1964), Near-Infrared Dyes for High Technology Applications(Springer, It can be synthesized by referring to the method described in (1997).

[0136] [Intermediate Synthesis Example 1] [ka]

[0137] In a 200 mL eggplant-shaped flask containing a stirrer, 4 g of compound a-9 and 21.8 g of ethyl pivalate were added and stirred. After 5 minutes, 3.2 g of sodium hydride (60%, dispersion in paraffin liquid) was added, and the mixture was stirred at 80°C for 3 hours. After that, the mixture was cooled to room temperature. After neutralizing the mixture with 30 mL of 1N hydrochloric acid, the organic phase was extracted with 150 mL of ethyl acetate. Next, 15 g of magnesium sulfate was added to the organic phase and stirred for 15 minutes. The magnesium sulfate was then removed by filtration, and the filtrate was placed in a 300 mL eggplant-shaped flask. The solvent was removed using an evaporator to obtain compound a-10.

[0138] A stir bar was placed in the eggplant-shaped flask containing compound a-10, and 20 mL of concentrated hydrochloric acid was added and stirred at 40°C. After stirring for 1 hour, the reaction solution was ice-cooled and neutralized by adding 240 mL of 1N aqueous sodium hydroxide solution. The solution was then transferred to a separatory funnel, and 200 mL of ethyl acetate was added to extract the organic phase, after which 15 g of magnesium sulfate was added and stirred for 15 minutes. The magnesium sulfate was then removed by filtration, and the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was removed using an evaporator. The compound remaining in the flask was then isolated and purified by silica gel chromatography to obtain 2.0 g of the target compound a-11. The compound was identified using LC-MS and 1 This was determined by H-NMR analysis.

[0139] [Intermediate synthesis example 2] [ka]

[0140] In a 200 mL eggplant-shaped flask containing a stirrer, 2.7 g of compound a-11 and 50 mL of diethyl ether were added and cooled on ice. After 5 minutes of ice cooling, 24.7 mL of a 1 mol / L methylmagnesium iodide diethyl ether solution was added over 10 minutes, and the mixture was then heated to 35°C and stirred for 2 hours. Next, the reaction solution was ice-cooled, and 50 mL of a 20% aqueous perchloric acid solution was added. The precipitated solid was filtered, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 0.7 g of compound a-12. The compound was identified as follows: 1 This was determined by H-NMR analysis.

[0141] [Synthesis example of compound (z1)] [ka]

[0142] In a 100 mL eggplant-shaped flask containing a stirrer, 0.5 g of compound a-12, 0.22 g of malonaldehyde dianilide hydrochloride, 7.5 mL of acetonitrile, 2.5 mL of acetic anhydride, and 0.2 mL of pyridine were added and heated under reflux for 2 hours. After cooling to room temperature, the precipitated solid was collected by vacuum filtration, washed with 10 mL of acetic acid and 10 mL of acetonitrile, and dried at 50 °C under reduced pressure to obtain 0.35 g of compound a-13.

[0143] A 100 mL eggplant-shaped flask containing a stir bar was charged with 0.3 g of compound a-13, 0.8 g of lithium tetrakispentafluorophenylborate, 50 mL of dichloromethane, and 20 mL of water, and the mixture was stirred at room temperature for 3 hours. The mixture was then transferred to a separatory funnel, and the aqueous phase was removed. The organic phase was washed twice with 20 mL of water, and the solvent was removed from the organic phase using an evaporator. The residue was then dissolved in 20 mL of acetone, 100 mL of water was added, and 13 g of the solvent was removed using an evaporator. The mixture was then ice-cooled. The precipitated solid was then collected by suction filtration, washed with 50 mL of methanol, and dried under reduced pressure at 50°C to obtain 0.5 g of compound (z1). Compound (z1) was identified using LC-MS and 1 HN This was done by MR analysis.

[0144] The compound (z1) was dissolved in dichloromethane to prepare a 7.5 mg / L solution. The prepared solution was filled into a 1 cm thick transparent quartz cell, and the wavelength-specific transmittance was measured using an ultraviolet-visible spectrophotometer (Shimadzu Corporation, UV-3100). The absorption maximum wavelength of compound (z1) was 770 nm. In addition, when the transmittance of compound (z1) to light of an arbitrary wavelength X nm in the wavelength range of 600 to (maximum absorption wavelength - 1) nm is defined as Ta(z1), and the transmittance of compound (z1) to light of a wavelength (X + 1) nm is defined as Tb(z1), the wavelength X nm at which Tb(z1) - Ta(z1) > 0 is found to be in the wavelength range of 700 to 720 nm. Table 2 shows the measured values ​​of Ta(z1) and Tb(z1) at wavelengths of 695 to 730 nm and the calculated values ​​of Tb(z1)-Ta(z1).

[0145] [Table 2]

[0146] [Synthesis example of compound (z2)] The following compound (z2) was obtained in the same manner as for compound (z1), except that the starting compound used was changed. [ka]

[0147] Using the same method as for compound (z1), the absorption maximum wavelength of compound (z2) and the wavelength Xnm at which Tb-Ta>0 were satisfied were determined. As a result, the absorption maximum wavelength of compound (z2) was 790 nm, and Xnm was within the wavelength range of 717 to 736 nm.

[0148] [Synthesis example of compound (z3)] The following compound (z3) was obtained in the same manner as for compound (z1), except that the starting compound used was changed. [ka]

[0149] Using the same method as for compound (z1), the absorption maximum wavelength of compound (z3) and the wavelength Xnm at which Tb-Ta>0 were satisfied were determined. As a result, the absorption maximum wavelength of compound (z3) was 802 nm, and Xnm was within the wavelength range of 727 to 746 nm.

[0150] [Synthesis example of compound (z4)] The following compound (z4) was obtained in the same manner as for compound (z1), except that the starting compound used was changed. [ka]

[0151] Using the same method as for compound (z1), the absorption maximum wavelength of compound (z4) and the wavelength Xnm where Tb-Ta>0 were determined. As a result, the absorption maximum wavelength of compound (z4) was 808 nm, and Xnm was within the wavelength range of 732 to 752 nm.

[0152] [Intermediate Synthesis Example 3] [ka]

[0153] In a 300 mL eggplant-shaped flask containing a stirrer, 5 g of flavone (compound a-6) and 50 mL of THF were added and cooled on ice. After 5 minutes of cooling on ice, 24.7 mL of a 1 mol / L solution of methylmagnesium iodide in diethyl ether was added over 10 minutes, and the mixture was then heated to 35°C and stirred for 2 hours. The reaction solution was then cooled on ice, and 50 mL of a 20% aqueous solution of perchloric acid was added. The precipitated solid was filtered, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 4.5 g of compound a-7. The compound was identified as follows: 1 This was determined by H-NMR analysis.

[0154] [Synthesis example of compound (z5)] [ka]

[0155] In a 100 mL eggplant-shaped flask containing a stirrer, 0.7 g of compound a-7, 0.26 g of malonaldehyde dianilide hydrochloride, 10 mL of acetonitrile, 5 mL of acetic anhydride, and 0.2 mL of pyridine were added and heated under reflux for 2 hours. After cooling to room temperature, the precipitated solid was collected by filtration under reduced pressure and washed with 10 mL of diethyl ether to obtain 0.6 g of compound a-8.

[0156] In a 100 mL eggplant-shaped flask equipped with a stir bar, 0.1 g of compound a-8, 0.2 g of lithium tetrakispentafluorophenylborate, 20 mL of dichloromethane, and 10 mL of water were added and stirred at room temperature for 3 hours. The mixture was then transferred to a separatory funnel, and after removing the aqueous phase, the organic phase was washed twice with 20 mL of water. The solvent was then removed from the organic phase using an evaporator. The residue was then dissolved in 0.5 mL of acetone, and 10 mL of methanol was added and cooled on ice. The precipitated solid was collected by suction filtration and dried under reduced pressure at 50 °C to obtain compound (z). 0.07 g of compound (z5) was obtained. Compound (z5) was identified by LC-MS and 1 H-NMR min This was done by analysis.

[0157] Using the same method as for compound (z1), the absorption maximum wavelength of compound (z5) and the wavelength Xnm where Tb-Ta>0 were determined. As a result, the absorption maximum wavelength of compound (z5) was 825 nm, and Xnm was within the wavelength range of 745 to 769 nm.

[0158] [Synthesis example of compound (z6)] The following compound (z6) was obtained in the same manner as for compound (z1), except that the starting compound used was changed. [ka]

[0159] The absorption maximum wavelength of compound (z6) and the wavelength Xnm where Tb-Ta>0 were determined using a method similar to that for compound (z1). As a result, the absorption maximum wavelength of compound (z6) was 835 nm, and Xnm was within the wavelength range of 749 to 773 nm.

[0160] [Synthesis example of compound (z7)] The following compound (z7) was obtained in the same manner as for compound (z1), except that the starting compound used was changed. [ka]

[0161] Using the same method as for compound (z1), the absorption maximum wavelength of compound (z7) and the wavelength Xnm where Tb-Ta>0 were determined. As a result, the absorption maximum wavelength of compound (z7) was 842 nm, and Xnm was within the wavelength range of 764 to 779 nm.

[0162] [Synthesis example of compound (z8)] The following compound (z8) was obtained by a known method. [ka]

[0163] Using the same method as for compound (z1), the absorption maximum wavelength of compound (z8) and the wavelength Xnm at which Tb-Ta>0 are satisfied were determined. As a result, the absorption maximum wavelength of compound (z8) was 712 nm, and Xnm did not exist.

[0164] [Synthesis example of compound (z9)] The following compound (z9) was obtained by the method described in JP 2014-67019 A. [ka]

[0165] Using the same method as for compound (z1), the absorption maximum wavelength of compound (z9) and the wavelength Xnm where Tb-Ta>0 were determined. As a result, the absorption maximum wavelength of compound (z9) was 696 nm, and Xnm was within the wavelength range of 626 to 648 nm.

[0166] [Synthesis example of compound (z10)] The following compound (z10) was obtained by a known method. [ka]

[0167] The absorption maximum wavelength of compound (z10) and the wavelength Xnm where Tb-Ta>0 were determined using the same method as for compound (z1). As a result, the absorption maximum wavelength of compound (z10) was 738 nm, and Xnm was in the wavelength range of 662 to 682 nm.

[0168] [Synthesis example of compound (z11)] The following compound (z11) was obtained by a known method. [ka]

[0169] The absorption maximum wavelength of compound (z11) and the wavelength Xnm where Tb-Ta>0 were determined using the same method as for compound (z1). As a result, the absorption maximum wavelength of compound (z11) was 882 nm, and Xnm was within the wavelength range of 786 to 813 nm.

[0170] [Synthesis example of compound (z12)] The following compound (z12) was obtained by the method described in JP 2022-025669 A. [ka]

[0171] The absorption maximum wavelength of compound (z12) and the wavelength Xnm where Tb-Ta>0 were determined using a method similar to that for compound (z1). As a result, the absorption maximum wavelength of compound (z12) was 735 nm, and Xnm was within the wavelength range of 664 to 687 nm.

[0172] [Synthesis example of compound (z13)] The following compound (z13) was obtained by the method described in JP 2019-164269 A. [ka]

[0173] The absorption maximum wavelength of compound (z13) and the wavelength Xnm where Tb-Ta>0 were determined using a method similar to that for compound (z1). As a result, the absorption maximum wavelength of compound (z13) was 827 nm, and Xnm was within the wavelength range of 751 to 777 nm.

[0174] [Example 1] In Example 1, an optical filter was produced using a resin layer containing the compound (A) and the compound (B).

[0175] [Production of optical member (resin layer)] A solution with a resin concentration of 20% by mass was prepared by adding 100 parts by mass of resin A obtained in Resin Synthesis Example, 0.07 parts by mass of compound (z1) as compound (A), 0.07 parts by mass of compound (z2) as compound (B), and dichloromethane to a container. The resulting solution was cast onto a smooth glass plate, dried at 20°C for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100°C for 8 hours to obtain a resin layer (1) with a thickness of 0.1 mm, length of 210 mm, and width of 210 mm.

[0176] The spectral transmittance of the obtained resin layer (1) was measured for light incident from a direction perpendicular to the surface of the resin layer (1) using a spectrophotometer (V-7200) manufactured by JASCO Corporation. Specifically, the following spectral transmittances were measured, and the results are shown in Table 7. Ts_ave: Average transmittance of light with wavelengths between 450 and 570 nm Ts_min: Minimum transmittance of light with wavelengths λA to λB nm Ts_max: Maximum transmittance of light with wavelengths λA to λB nm Tx: The maximum value of Tb-Ta, where Ta is the transmittance when light of any wavelength X nm in the wavelength range of 600 to (λA-1) nm is incident perpendicular to the surface of the resin layer, and Tb is the transmittance when light of wavelength (X+1) nm is incident perpendicular to the surface of the resin layer. Wmin: The shortest wavelength at which transmittance is 50% for light with wavelengths between 600 and 900 nm R transmittance: Average transmittance of light with wavelengths of 580 to 650 nm Wmax-Wmin: The difference between the shortest wavelength at which transmittance is 50% (Wmin) and the longest wavelength at which transmittance is 50% (Wmax) for light with wavelengths between 600 and 900 nm.

[0177] [Preparation of Optical Filter] The resin layer (1) obtained by the preparation of the resin layer was used as an optical element, and a dielectric multilayer film (I) was formed on one side of the resin layer (1), and a dielectric multilayer film (II) was further formed on the other side of the resin layer (1), to obtain an optical filter having a thickness of approximately 0.110 mm.

[0178] The dielectric multilayer film (I) was formed by depositing a silica (SiO2) layer and a titania (Ti The dielectric multilayer film (II) is a laminated film consisting of alternating layers of SiO2 and SiO2 (26 layers in total). The deposition temperature was 100°C and the laminate consisted of alternating silica (SiO2) layers and titania (TiO2) layers (22 layers in total). In both the dielectric multilayer films (I) and (II), silica layers and titania layers were alternately laminated in the order of titania layer, silica layer, titania layer, silica layer, titania layer, silica layer from the resin layer (1) side, with the silica layer being the outermost layer of the optical filter.

[0179] The thickness and number of each layer were optimized using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) in accordance with the wavelength dependency of the refractive index of the resin layer (1) and the absorption characteristics of the compounds (A) and (B) used, so as to achieve good transmittance in the visible light region and reflectivity in the near-infrared region. When performing optimization, the input parameters (target values) to the software in this example were as shown in Table 3 below.

[0180] [Table 3]

[0181] As a result of optimizing the film configuration, the dielectric multilayer film (I) was a multilayer vapor deposition film with 26 layers, in which silica layers with a physical thickness of about 37 to 168 nm and titania layers with a physical thickness of about 11 to 104 nm were alternately stacked, and the dielectric multilayer film (II) was a multilayer vapor deposition film with 22 layers, in which silica layers with a physical thickness of about 40 to 191 nm and titania layers with a physical thickness of about 10 to 110 nm were alternately stacked. An example of the optimized film configuration is shown in Table 4 below.

[0182] [Table 4]

[0183] For the obtained optical filter, the spectral transmittance of light incident from a direction perpendicular to the surface direction of the optical filter was measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation, except when measuring T20 (30°) described below. Specifically, the following spectral transmittances were measured, and the results are shown in Table 7. Tf_ave: Average transmittance of light with wavelengths between 450 and 570 nm Tf_min: Minimum transmittance of light with wavelengths λA to λB nm ΔT20 (0°-30°): For light with wavelengths between 600 and 900 nm, the difference between the shortest wavelength (T20 (0°)) at which the transmittance of light incident perpendicular to the surface of the optical filter is 20% and the shortest wavelength (T20 (30°)) at which the transmittance of light incident at an angle of 30° to the surface of the optical filter is 20%. 750~850nmTave: Average transmittance of light with wavelengths of 750~850nm Wf_min: The shortest wavelength at which the transmittance is 50% in the wavelength range of 600 to 900 nm R transmittance: Average transmittance of light with wavelengths of 580 to 650 nm

[0184] <Evaluating the RGB balance of a captured image> The RGB balance evaluation when the optical filter was incorporated into a camera module was carried out using the following method. The results are shown in Table 7. A camera module was fabricated using the same method as in JP 2016-110067 A, and a 300 mm x 400 mm white plate was photographed using the fabricated camera module under a D65 light source (X-Rite's standard light source device "Macbeth Judge II"). As shown in FIG. 5, when taking the photograph, the positional relationship between the white board 112 and the camera module was adjusted so that the white board 112 occupies 90% or more of the area of ​​the photographed image 111. The color tone of the central portion 113 (shown in FIG. 5) of the white board in the photographed image was visually evaluated according to the following criteria.

[0185] An acceptable level of no blue tinge in the captured image was rated as A, and an unacceptable level of blue tinge in the captured image for camera module use was rated as C. Specifically, the result of the RGB balance evaluation for Example 1 was rated as "A," and a case where the captured image was bluish compared to Example 1 was rated as "C." When the optical filter has low red transmittance, the RGB balance of the captured image is disrupted, which is thought to result in the captured image appearing bluish.

[0186] <Color shading evaluation of captured images> The color shading evaluation when the optical filter was incorporated into a camera module was carried out using the following method. The results are shown in Table 7. A camera module was fabricated using the same method as in JP 2016-110067 A, and a 300 mm x 400 mm white plate was photographed using the fabricated camera module under a D65 light source (X-Rite's standard light source device "Macbeth Judge II"). As shown in FIG. 5, when taking the photograph, the positional relationship between the white board 112 and the camera module was adjusted so that the white board 112 occupies 90% or more of the area of ​​the photographed image 111. The difference in color tone between the center 113 (shown in FIG. 5) and the edge 114 (shown in FIG. 5) of the white board in the photographed image was visually evaluated according to the following criteria.

[0187] A level where there was no difference in color and it was acceptable was rated as A, a level where there was a slight difference in color but it was not a problem in practical use as a camera module and it was acceptable was rated as B, and a level where there was a clear difference in color and it was unacceptable for use as a camera module was rated as C. Specifically, the color shading evaluation result of Example 5 was rated as "B", and when there was absolutely no difference in color between the edge and center of the captured image compared to Example 5 it was rated as "A", when there was the same difference in color as in Example 5 it was rated as "B", and when there was a large difference in color compared to Example 5 it was rated as "C". It is thought that the large Ty and inability to block light in the infrared region sharply resulted in worsening color shading.

[0188] <Ghost evaluation of captured images> The ghosting when the optical filter was incorporated into a camera module was evaluated by the following method. A camera module was fabricated using the same method as in JP 2016-110067 A, and photographs were taken using the fabricated camera module in a darkroom under a halogen lamp light source ("Luminar Ace LA-150TX" manufactured by Hayashi Watch Co., Ltd.). As shown in FIG. 6, when taking the photograph, the light source 122 was adjusted to be at the upper right corner of the photographed image 121. The extent of ghost occurrence around a light source 122 in a photographed image 121 (shown in FIG. 6) was visually evaluated according to the following criteria.

[0189] An acceptable level with no ghosting was rated A, a level where some ghosting was observed but not problematic for practical use as a camera module and acceptable was rated B, and a level where the ghosting was severe (large color change in the light source peripheral area 123 due to the ghosting) and unacceptable for use as a camera module was rated C. Specifically, the ghost evaluation result of Example 14 was rated "B", and a case where the color change in the light source peripheral area 123 due to the ghosting was small compared to Example 14 was rated "A", a case where a ghosting equivalent to that of Example 14 occurred was rated "B", and a case where the color change in the light source peripheral area 123 due to the ghosting was large compared to Example 14 was rated "C". It is believed that when the maximum value (Ts_max) of the transmittance of light with wavelengths λA to λB nm is large, the amount of near-infrared light incident on the sensor increases, which increases the color change in the light source peripheral area 123 due to ghosts.

[0190] [Examples 2 to 6, 12 to 14 and Comparative Examples 1 to 3] A resin layer (optical member) was prepared in the same manner as in Example 1, except that the compounds shown in Table 7 were used instead of compound (z1) and compound (z2) in Example 1. An optical filter was also prepared, and the spectral properties of these were evaluated. The spectral transmittance curve of the resin layer obtained in Example 4 is shown in Figure 1, and the spectral transmittance curve of the optical filter obtained in Example 4 is shown in Figure 3. The spectral transmittance curves of the resin layers obtained in Comparative Examples 1 to 3 are shown in Figure 2, and the spectral transmittance curves of the optical filters obtained in Comparative Examples 1 to 3 are shown in Figure 4. Furthermore, the Tb-Ta values ​​for the resin layer obtained in Example 4 when the wavelength was 600 to (λA-1) nm and the transmittance was 5 to 70% are shown in Table 5 below. Table 5 shows that the Ty of the resin layer obtained in Example 4 was -0.143. Ty was determined in the same manner for other examples and comparative examples.

[0191] [Table 5]

[0192] [Example 7] A solution with a resin concentration of 20% by mass was prepared by adding 100 parts by mass of the resin A obtained in Resin Synthesis Example, 0.07 parts by mass of the compound (z1) as compound (A), 0.07 parts by mass of the compound (z2) as compound (B), 0.17 parts by mass of a UV absorber (compound (x1) below), and dichloromethane to a container. The resulting solution was cast onto a smooth glass plate, dried at 20°C for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100°C for 8 hours to obtain a resin layer (7) with a thickness of 0.1 mm, length of 210 mm, and width of 210 mm. An optical filter was produced in the same manner as in Example 1 except that the resin layer (7) was used as an optical member, and the spectral characteristics of the resin layer (7) and the obtained optical filter were evaluated.

[0193] Compound (x1): Maximum absorption wavelength in dichloromethane: 394 nm [ka]

[0194] [Example 8] In Example 8, an optical member was produced using a transparent glass support having a resin layer containing compound (A) and compound (B) on one side thereof, and an optical filter was also produced.

[0195] A resin layer-forming composition (1) having the following composition was applied by a spin coater onto a transparent glass support "OA-10G" (manufactured by Nippon Electric Glass Co., Ltd., thickness 200 μm) cut to a size of 60 mm length and 60 mm width, and the composition was heated on a hot plate at 80°C for 2 minutes to volatilize and remove the solvent. At this time, the application conditions of the spin coater were adjusted so that the thickness after drying would be 4 μm. Next, the applied composition was exposed to light (exposure amount: 500 mJ / cm2) using a conveyor-type exposure machine. 2 , illuminance :200mW / cm 2 ) was carried out to cure the composition (1), thereby producing an optical member having a resin layer (8) containing the compound (A) and the compound (B).

[0196] Resin layer-forming composition (1): 20 parts by mass of tricyclodecane dimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone, 1.75 parts by mass of compound (z1), 1.75 parts by mass of compound (z2), methyl ethyl ketone (solvent, TSC: 35%)

[0197] An optical filter was prepared in the same manner as in Example 1, except that an optical element having the prepared resin layer (8) was used instead of the resin layer (1), and the spectral characteristics of the resin layer (8) and the obtained optical filter were evaluated in the same manner as in Example 1. When evaluating the spectral characteristics of the resin layer (8), the resin layer (8) was peeled off from the transparent glass support.

[0198] [Example 9] In Example 8, an optical element having a resin layer (9) was prepared in the same manner as in Example 8, except that the following resin layer-forming composition (2) was used instead of the resin layer-forming composition (1). In addition, an optical filter was prepared using the optical element having the resin layer (9), and the spectral characteristics of the resin layer (9) and the optical filter were evaluated. When evaluating the spectral characteristics of the resin layer (9), the resin layer (9) was peeled off from the transparent glass support.

[0199] Resin layer-forming composition (2): 20 parts by mass of tricyclodecane dimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone, 2.0 parts by mass of compound (z1), 2.0 parts by mass of compound (z3), methyl ethyl ketone (solvent, TSC: 35%)

[0200] [Example 10] In Example 10, an optical member was produced using a near-infrared absorbing glass support having a resin layer containing compound (A) and compound (B) on one side thereof, and an optical filter was also produced.

[0201] An optical element having a resin layer (10) was prepared in the same manner as in Example 8, except that a near-infrared absorbing glass support "BS-6" (manufactured by Matsunami Glass Industry Co., Ltd., thickness 210 μm) cut to a size of 60 mm in length and 60 mm in width was used instead of the transparent glass support (OA-10G). An optical element having a resin layer (10) was also prepared as an optical filter, and the spectral characteristics of these were evaluated. When evaluating the spectral characteristics of the resin layer (10), the resin layer (10) was peeled off from the near-infrared absorbing glass support.

[0202] [Example 11] In Example 10, an optical element having a resin layer (11) was prepared in the same manner as in Example 10, except that the resin layer-forming composition (2) was used instead of the resin layer-forming composition (1) in Example 10. In addition, an optical filter was prepared using the optical element having the resin layer (11), and the spectral characteristics of these filters were evaluated. When evaluating the spectral characteristics of the resin layer (11), the resin layer (11) was peeled off from the near-infrared absorbing glass support.

[0203] [Comparative Examples 4 to 5] A dielectric multilayer film (III) was formed on one side of each of the resin layers obtained in Comparative Examples 2 and 3, and a dielectric multilayer film (IV) was further formed on the other side of each of the resin layers to obtain an optical filter having a thickness of approximately 0.110 mm. The spectral characteristics of the obtained resin layer and optical filter were evaluated in the same manner as in Example 1.

[0204] The dielectric multilayer film (III) is a laminate of alternating silica (SiO2) and titania (TiO2) layers deposited at a deposition temperature of 100°C (26 layers in total). The dielectric multilayer film (IV) is The film is a laminate of alternating silica (SiO2) and titania (TiO2) layers (20 layers in total) deposited at a deposition temperature of 100°C. In both dielectric multilayer films (III) and (IV), silica layers and titania layers were alternately laminated in the order of titania layer, silica layer, titania layer, silica layer, titania layer, silica layer from the resin layer side, with the silica layer being the outermost layer of the optical filter.

[0205] As a result of optimizing the film configuration, the dielectric multilayer film (III) was a multilayer vapor deposition film with 26 layers, in which silica layers with a physical thickness of about 28 to 139 nm and titania layers with a physical thickness of about 9 to 83 nm were alternately stacked, and the dielectric multilayer film (IV) was a multilayer vapor deposition film with 20 layers, in which silica layers with a physical thickness of about 35 to 177 nm and titania layers with a physical thickness of about 10 to 103 nm were alternately stacked. An example of the optimized film configuration is shown in Table 6 below.

[0206] [Table 6]

[0207] [Table 7]

[0208] Comparative Example 1 did not contain compound (B), and therefore did not satisfy requirements (d) and (F5). As a result, the optical filter obtained had a high incidence angle dependency, and therefore an optical filter with excellent visibility correction performance could not be obtained. Comparative Example 2 did not satisfy requirements (c), (R4), (R5), (F3), (F4), and (F6), and the optical component (resin layer) and the optical filter had low transmittance in the red region of visible light, so an optical filter capable of producing an image with excellent RGB balance could not be obtained. In Comparative Example 4, in which a dielectric multilayer film with different properties was formed using the same resin layer as in Comparative Example 2, the optical filter had low transmittance in the red region of visible light and did not satisfy requirement (F5), so an optical filter that could produce good images was not obtained. Comparative Example 3 did not satisfy requirements (c), (d), (R4), (R5), (F3), (F4), and (F6), and the optical component (resin layer) and the optical filter had low transmittance in the red region of visible light, so an optical filter capable of producing an image with excellent RGB balance could not be obtained. In Comparative Example 5, in which a dielectric multilayer film with different properties was formed using the same resin layer as in Comparative Example 3, the optical filter had low transmittance in the red region of visible light and did not satisfy requirement (F5), so an optical filter that could produce good images was not obtained.

Claims

1. a resin layer containing the compound (A) and the compound (B), The resin layer of the optical member satisfies the following requirements (a) to (d), where λA is the absorption maximum wavelength of the compound (A) and λB is the absorption maximum wavelength of the compound (B): (a) λA<λB (b) 770nm≦λA≦870nm (c) 770nm≦λB≦900nm (d) When the transmittance when light of an arbitrary wavelength X nm in the wavelength range of 600 to (λA-1) nm is incident from a direction perpendicular to the surface direction of the resin layer is defined as Ta, the transmittance when light of a wavelength (X+1) nm is incident from a direction perpendicular to the surface direction of the resin layer is defined as Tb, and the maximum value of Tb-Ta is defined as Tx, Tx<0 is satisfied.

2. The optical element according to claim 1 , wherein the compound (A) satisfies the following requirement (i): (i) When the transmittance of compound (A) to light of an arbitrary wavelength X nm in the wavelength range of 600 to (λA-1) nm is TaA and the transmittance of compound (A) to light of a wavelength (X+1) nm is TbA, the compound (A) has a wavelength X nm that satisfies TbA-TaA>0 within a portion of the wavelength range of 600 to (λA-1) nm.

3. 2. The optical member according to claim 1, wherein the minimum transmittance of light having a wavelength of λA to λB nm incident from a direction perpendicular to the surface direction of the resin layer is 3% or less.

4. 2. The optical member according to claim 1, wherein Wmin is the shortest wavelength at which the transmittance is 50% for light having a wavelength of 600 to 900 nm incident from a direction perpendicular to the surface direction of the resin layer, and Wmin is in the range of 650 to 750 nm.

5. 2. The optical element according to claim 1, wherein the shortest wavelength Wmin at which the transmittance is 50% and the longest wavelength Wmax at which the transmittance is 50% are Wmax-Wmin≧130 nm for light having a wavelength of 600 to 900 nm incident from a direction perpendicular to the surface direction of the resin layer.

6. 2. The optical member according to claim 1, wherein the compounds (A) and (B) are compounds selected from the group consisting of phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, croconium compounds, cyanine compounds, polymethine compounds (provided that the polymethine compounds are compounds other than squarylium compounds, croconium compounds, and cyanine compounds), diimonium compounds, dithiol metal complex compounds, and pyrrolopyrrole compounds.

7. 2. The optical member according to claim 1, wherein the average transmittance of light having a wavelength of 450 to 570 nm incident from a direction perpendicular to the surface direction of the resin layer is 80% or more.

8. 2. The optical member according to claim 1, wherein the resin layer comprises at least one resin selected from the group consisting of cyclic (poly)olefin-based resins, aromatic polyether-based resins, polyimide-based resins, polyester-based resins, polycarbonate-based resins, polyamide-based resins, polyarylate-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorinated aromatic polymer-based resins, (modified) acrylic-based resins, epoxy-based resins, allyl ester-based curable resins, silsesquioxane-based ultraviolet-curable resins, acrylic-based ultraviolet-curable resins, and vinyl-based ultraviolet-curable resins.

9. An optical filter comprising the optical member according to any one of claims 1 to 8 and a dielectric multilayer film.

10. 10. The optical filter according to claim 9, which is a near-infrared cut filter, a dual bandpass filter, or a single bandpass filter.

11. A solid-state imaging device comprising the optical member according to any one of claims 1 to 8.

12. An optical sensor device comprising the optical member according to any one of claims 1 to 8.

Images