JP6650040B2 - Near-infrared cut filter, solid-state imaging device, camera module, and image display device - Google Patents

Description

  The present invention relates to a near-infrared cut filter, a solid-state imaging device, a camera module, and an image display device.

  2. Description of the Related Art A video camera, a digital still camera, a mobile phone with a camera function, and the like use a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), and the like, which are solid-state imaging devices for color images. These solid-state imaging devices use silicon photodiodes having a sensitivity to near-infrared rays in their light receiving sections. For this reason, a near-infrared cut filter is often used for visibility correction.

  Patent Document 1 has a transparent resin body having a one-layer or multilayer structure, and the transparent resin contains a specific near-ultraviolet absorbing dye and a near-infrared absorbing dye having an absorption maximum at a wavelength of 600 to 800 nm. A near infrared cut filter is described. As a near-infrared absorbing dye having an absorption maximum at a wavelength of 600 to 800 nm, a squarylium dye, a phthalocyanine dye, and a cyanine dye are mentioned.

  Patent Document 2 describes a near-infrared absorbing agent obtained from a phosphonic acid compound, a phosphoric ester compound, and a copper salt, and a near-infrared cut filter formed from a resin.

International Publication WO2016 / 043166 JP 2011-203467 A

  It is desired that a near-infrared cut filter has good visible transparency and infrared shielding properties. In Patent Document 1, a squarylium dye is used as a near-infrared absorbing dye having an absorption maximum at a wavelength of 600 to 800 nm. However, according to studies by the present inventors, it has been found that the near-infrared cut filter described in Patent Document 1 does not have sufficient visible transparency and infrared shielding properties.

  On the other hand, a near-infrared cut filter using a copper complex as an infrared absorber has good visible transparency and infrared shielding properties. However, when the present inventor studied a near-infrared cut filter using a copper complex, the image obtained by imaging with a camera module or the like incorporating a near-infrared cut filter using a copper complex was referred to as purple fringe. It has been found that purple outline blurring may be recognized. Further, according to the study by the present inventors, it was found that purple fringing easily occurs even in the near-infrared cut filter described in Patent Document 2.

  Accordingly, an object of the present invention is a near-infrared cut filter that has good visible transparency and infrared shielding properties, and can obtain an image in which purple fringes are suppressed when incorporated in a solid-state imaging device or the like, An object of the present invention is to provide a solid-state imaging device, a camera module, and an image display device.

As a result of intensive studies by the present inventors, the present inventors have found that in a near-infrared cut filter containing a copper complex, it is possible to suppress purple fringing by increasing the shielding property of ultraviolet rays near the visible region, and have completed the present invention. . The present invention provides the following.
<1> A near-infrared cut filter containing a copper complex,
The transmittance T _{450 at} a wavelength of 450 nm measured from the vertical direction of the near-infrared cut filter is 85% or more;
T ₃₅₀ / T _450, which is the ratio of the transmittance T _{350 at} a wavelength of 350 nm measured from the vertical direction of the near-infrared cut filter to the transmittance T _{450 at} a wavelength of 450 nm measured from the vertical direction of the near-infrared cut filter. Is 0 to 0.3,
T ₇₀₀ / T ₅₅₀ which is the ratio of the transmittance T _{700 at} a wavelength of 700 nm measured from the vertical direction of the near-infrared cut filter to the transmittance T _{550 at} a wavelength of 550 nm measured from the vertical direction of the near-infrared cut filter. Is 0 to 0.2,
A near-infrared cut filter in which the average value of the reflectance of the near-infrared cut filter is 80% or less in a wavelength range of 800 to 1000 nm.
<2> The near-infrared cut filter according to <1>, wherein the average value of the transmittance when measured from the vertical direction of the near-infrared cut filter is 85% or more in a wavelength range of 430 to 580 nm.
<3> Within the wavelength range of 350 to 450 nm, the wavelength at the longest wavelength side where the transmittance is 70% when measured from the vertical direction of the near-infrared cut filter, and the wavelength when measured from the vertical direction of the near-infrared cut filter. The near-infrared cut filter according to <1> or <2>, wherein the absolute value of the difference from the shortest wavelength side at which the transmittance is 30% is 25 nm or less.
<4> The one according to any one of <1> to <3>, wherein the average value of the transmittance when measured from the vertical direction of the near-infrared cut filter is 20% or less in the wavelength range of 800 to 1000 nm. Near infrared cut filter.
<5> The near-infrared cut filter according to any one of <1> to <4>, comprising an ultraviolet absorber having a maximum absorption wavelength in a wavelength range of 280 to 425 nm.
<6> The near-infrared cut filter according to <5>, comprising a layer containing a copper complex and a layer containing an ultraviolet absorber.
<7> The near-infrared cut filter according to <5>, having a layer containing a copper complex and an ultraviolet absorber.
<8> The near-infrared cut filter according to any one of <1> to <7>, having a layer containing a copper complex and a dielectric multilayer film.
<9> The copper complex according to any one of <1> to <8>, wherein the copper complex is a copper complex having, as a ligand, a compound having four or five coordination sites with respect to copper. Infrared cut filter.
<10> A solid-state imaging device having the near-infrared cut filter according to any one of <1> to <9>.
<11> A camera module having the near-infrared cut filter according to any one of <1> to <9>.
<12> An image display device having the near-infrared cut filter according to any one of <1> to <9>.

  Advantageous Effects of Invention According to the present invention, a near-infrared cut filter that has good visible transparency and infrared shielding properties, and can obtain an image in which purple fringe is suppressed when incorporated in a solid-state imaging device or the like, a solid-state imaging device An element, a camera module, and an image display device can be provided.

FIG. 2 is a schematic cross-sectional view illustrating a configuration of a camera module having a near-infrared cut filter. It is a schematic sectional drawing which shows an example of the peripheral part of a near-infrared cut filter in a camera module. It is a schematic sectional drawing which shows an example of the peripheral part of a near-infrared cut filter in a camera module. It is a schematic sectional drawing which shows an example of the peripheral part of a near-infrared cut filter in a camera module.

Hereinafter, the contents of the present invention will be described in detail.
In this specification, “to” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) allyl” represents allyl and methallyl, “(meth) acryl” represents acryl and methacryl, and “(meth) acrylate” ) "Acryloyl" refers to acryloyl and methacryloyl.
In the description of the group (atomic group) in the present specification, the notation of not indicating substituted or unsubstituted includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, near-infrared rays refer to light (electromagnetic waves) having a wavelength range of 700 to 2500 nm.
In the present specification, the term “total solids” refers to the total mass of components excluding the solvent from all components of the composition.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as values in terms of polystyrene measured by gel permeation chromatography (GPC).

<Near infrared cut filter>
The near-infrared cut filter of the present invention is a near-infrared cut filter containing a copper complex,
The transmittance T _{450 at} a wavelength of 450 nm measured from the vertical direction of the near-infrared cut filter is 85% or more;
T ₃₅₀ / T _450, which is the ratio of the transmittance T _{350 at} a wavelength of 350 nm measured from the vertical direction of the near-infrared cut filter to the transmittance T _{450 at} a wavelength of 450 nm measured from the vertical direction of the near-infrared cut filter. Is 0 to 0.3,
T ₇₀₀ / T ₅₅₀ which is a ratio of the transmittance A _{700 at} a wavelength of 700 nm measured from the vertical direction of the near-infrared cut filter to the transmittance T _{550 at} a wavelength of 550 nm measured from the vertical direction of the near-infrared cut filter. Is 0 to 0.2,
In the wavelength range of 800 to 1000 nm, the average value of the reflectance of the near-infrared cut filter is 80% or less.

Generally, near-infrared cut filter containing copper complex has low reflectance in the wavelength range of 800 to 1000 _{nm, T 700} is _{low, T 550} tends to be higher. The near-infrared cut filter of the present invention contains a copper complex and has a T ₇₀₀ / T _{550 of 0} to 0.2, and thus has good visible transparency and infrared shielding properties. _Further, it is _{T 450} is less than _85%, since T 350 _{/ T 450} is 0 to 0.3, and has good transparency in the visible light in the ultraviolet region near and has good shielding of ultraviolet . Further, since the average value of the reflectance in the wavelength range of 800 to 1000 nm is 80% or less, interference due to reflected light can be suppressed. Since the average value of the reflectance is 80% or less while being excellent in the shielding property of ultraviolet rays, the influence of axial chromatic aberration due to ultraviolet rays can be reduced, and purple fringing can be effectively suppressed. For this reason, according to the near-infrared cut filter of the present invention, the visible transparency and infrared shielding properties are good, and when incorporated in a near-infrared cut filter solid-state imaging device or the like, an image in which purple fringe is suppressed is reduced. Obtainable.
Moreover, since the near-infrared cut filter of the present invention contains a copper complex, the near-infrared reflectivity can be reduced, the viewing angle is wide, and the near-infrared cut filter having excellent infrared shielding properties can be obtained. .
Further, by setting T _{450 of the} near-infrared cut filter to 85% or more and T ₃₅₀ / T ₄₅₀ to 0 to 0.3, the heat resistance of the near-infrared cut filter can be improved. The reason why such an effect is obtained is presumed to be as follows. When a near-infrared cut filter containing a copper complex is heated, radicals generated by the decomposition of components such as a resin contained in the near-infrared cut filter may act on the copper complex and discolor the copper complex. However, it is presumed that the generation of radicals at the time of heating can be suppressed by enhancing the shielding property of the near-infrared cut filter against ultraviolet rays, and as a result, discoloration of the copper complex at the time of heating can be suppressed, and excellent heat resistance can be obtained. When a near-infrared cut filter having a layer containing a copper complex and an ultraviolet absorber is used, particularly excellent heat resistance is easily obtained.

  The near-infrared cut filter having the above-mentioned properties is provided by (1) a method of adjusting the type and content of a copper complex, (2) a method of adjusting the type and content of both by using a copper complex and an ultraviolet absorber in combination, (3) It can be achieved by a method such as a method using a combination of a layer containing a copper complex and an ultraviolet cut layer. Examples of the ultraviolet cut layer include a layer containing an ultraviolet absorber, a dielectric multilayer film, and the like.

  The near-infrared cut filter of the present invention preferably has a copper complex content of 5 to 90% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is preferably equal to or less than 70% by mass, more preferably equal to or less than 60% by mass, and still more preferably equal to or less than 50% by mass. When the near-infrared cut filter of the present invention has an ultraviolet cut layer in addition to a layer containing a copper complex (hereinafter, also referred to as a copper complex layer), the content of the copper complex in the copper complex layer is It is preferably from 10 to 90% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is preferably equal to or less than 70% by mass, more preferably equal to or less than 60% by mass, and still more preferably equal to or less than 50% by mass. Details of the copper complex will be described later. Especially, it is preferable that a copper complex has a compound which has four or five coordination sites with respect to copper as a ligand. According to this aspect, the visible transparency and the infrared shielding property of the near-infrared cut filter can be further improved.

In the near-infrared cut filter of the present invention, T ₃₅₀ / T ₄₅₀ is 0 to 0.3, preferably 0 to 0.25, and more preferably 0 to 0.2. Further, T ₇₀₀ / T ₅₅₀ is 0 to 0.2, preferably 0 to 0.15, and more preferably 0 to 0.10. It is preferable that the values of T ₃₅₀ / T _{450 and} the values of T ₇₀₀ / T ₅₅₀ are both low, but the lower limit may be a value larger than 0.

Near infrared cut filter of the present invention _{is T 450} 85% or more, preferably 87% or more, and more preferably 90% or more.
In the near-infrared cut filter of the present invention, T ₃₅₀ is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less.
Near infrared cut filter of the present invention preferably has a T ₅₅₀ is 85% or more, more preferably 87% or more, more preferably 90% or more.
In the near-infrared cut filter of the present invention, T ₇₀₀ is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less.

In the near-infrared cut filter of the present invention, the transmittance T _{360 at} a wavelength of 360 nm, measured from the vertical direction of the near-infrared cut filter, is preferably 20% or less, more preferably 10% or less, and more preferably 5%. It is more preferred that: Further, T ₃₆₀ / T ₄₅₀ is preferably 0 to 0.3, more preferably 0 to 0.25, and further preferably 0 to 0.2.
In the near-infrared cut filter of the present invention, the transmittance T _{370 at} a wavelength of 370 nm measured from the vertical direction of the near-infrared cut filter is preferably 20% or less, more preferably 10% or less, and more preferably 5%. It is more preferred that: Further, T ₃₇₀ / T ₄₅₀ is preferably 0 to 0.3, more preferably 0 to 0.25, and further preferably 0 to 0.2.
In the near-infrared cut filter of the present invention, the transmittance T _{380 at} a wavelength of 380 nm measured from the vertical direction of the near-infrared cut filter is preferably 20% or less, more preferably 10% or less, and more preferably 5%. It is more preferred that: Further, T ₃₈₀ / T ₄₅₀ is preferably 0 to 0.3, more preferably 0 to 0.25, and further preferably 0 to 0.2.
In the near-infrared cut filter of the present invention, the transmittance T _{390 at} a wavelength of 390 nm measured from the vertical direction of the near-infrared cut filter is preferably 20% or less, more preferably 10% or less, and more preferably 5%. It is more preferred that: Further, T ₃₉₀ / T ₄₅₀ is preferably 0 to 0.3, more preferably 0 to 0.25, and further preferably 0 to 0.2.

  The near-infrared cut filter of the present invention preferably has an average transmittance of 85% or more when measured from the vertical direction of the near-infrared cut filter in the wavelength range of 430 to 580 nm, and more preferably 87% or more. Is more preferable, and 90% or more is further preferable. Further, the near-infrared cut filter of the present invention preferably has a transmittance of 85% or more, and preferably 87% or more, when measured from the vertical direction of the near-infrared cut filter in the entire wavelength range of 430 to 580 nm. Is more preferable, and 90% or more is further preferable. According to this aspect, a near-infrared cut filter having excellent visible transparency can be obtained.

  The near-infrared cut filter of the present invention preferably has an average transmittance of 20% or less, preferably 10% or less when measured from the vertical direction of the near-infrared cut filter in the wavelength range of 800 to 1000 nm. Is more preferable, and 5% or less is further preferable. In addition, the near-infrared cut filter of the present invention preferably has a transmittance of 20% or less, preferably 10% or less when measured from the vertical direction of the near-infrared cut filter in the entire wavelength range of 800 to 1000 nm. Is more preferable, and 5% or less is further preferable. According to this aspect, a near-infrared cut filter having excellent infrared shielding properties can be obtained.

  The near-infrared cut filter of the present invention includes a wavelength at the longest wavelength side where the transmittance when measured from the vertical direction of the near-infrared cut filter is 70% in a wavelength range of 350 to 450 nm, and a vertical wavelength of the near-infrared cut filter. The absolute value of the difference from the shortest wavelength side at which the transmittance is 30% when measured from the direction is preferably 25 nm or less, more preferably 20 nm or less, and further preferably 15 nm or less. preferable. According to this aspect, since the transmittance has a steep gradient near the boundary between the visible region and the ultraviolet region, it is possible to effectively block ultraviolet light while improving visible transparency.

  The near-infrared cut filter of the present invention has an average reflectance of 80% or less, preferably 70% or less, and more preferably 60% or less in the wavelength range of 800 to 1000 nm. Further, the near-infrared cut filter of the present invention preferably has a reflectance of 80% or less, more preferably 70% or less, even more preferably 60% or less in the entire wavelength range of 800 to 1000 nm. . According to this aspect, a near-infrared cut filter having a wide viewing angle and excellent infrared shielding properties can be obtained. The reflectance was measured using U-4100 (manufactured by Hitachi High-Technologies Corporation) with the normal direction of the surface of the near-infrared cut filter set to 0 ° and the incident angle set to 5 °.

  The near-infrared cut filter of the present invention preferably contains an ultraviolet absorber. According to this aspect, the ability to block ultraviolet rays can be improved. The ultraviolet absorber may be contained in the copper complex layer or may be contained in the ultraviolet cut layer. As the ultraviolet absorber, a compound having a maximum absorption wavelength in a wavelength range of 280 to 425 nm is preferable, and a compound having a maximum absorption wavelength in a wavelength range of 300 to 400 nm is more preferable. Details of the ultraviolet absorbent will be described later.

In the near-infrared cut filter of the present invention, when the copper complex layer contains an ultraviolet absorber, the content of the ultraviolet absorber in the copper complex layer is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass. Preferably, it is more preferably 1 to 30% by mass. Moreover, it is preferable to contain 0.1-20 mass parts of an ultraviolet absorber with respect to 100 mass parts of copper complexes, it is more preferable that it contains 1-15 mass parts, and it is more preferable that it contains 1-10 mass parts. .
In the near-infrared cut filter of the present invention, when the ultraviolet cut layer contains an ultraviolet absorber, the content of the ultraviolet absorber in the ultraviolet cut layer is preferably from 1 to 90% by mass, more preferably from 5 to 80% by mass. Preferably, it is 5 to 70% by mass.

  In the near-infrared cut filter of the present invention, the content of unreacted monomer in the copper complex layer is preferably 1% by mass or less, more preferably 500% by mass or less, and further preferably 100% by mass or less. preferable. According to this aspect, the heat resistance of the near-infrared cut filter can be further improved.

  In the near-infrared cut filter of the present invention, the content of the solvent in the copper complex layer is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. According to this aspect, the heat resistance of the near-infrared cut filter can be further improved.

  The near-infrared cut filter of the present invention preferably further includes a dielectric multilayer film in addition to the copper complex layer. The dielectric multilayer film is preferably an ultraviolet cut layer. In the present invention, the dielectric multilayer film is a film that shields ultraviolet light or the like by utilizing the effect of light interference. Specifically, it is a film formed by alternately laminating two or more dielectric layers (high-refractive-index material layer and low-refractive-index material layer) having different refractive indexes.

  As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more (preferably, a material having a refractive index of 1.7 to 2.5) can be used. For example, it contains titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide or indium oxide as a main component and contains a small amount of titanium oxide, tin oxide and / or cerium oxide. Materials.

  As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less (preferably, a material having a refractive index of 1.2 to 1.6) can be used. Examples include silica, alumina, lanthanum fluoride, magnesium fluoride and sodium aluminum hexafluoride.

  The method for forming the dielectric multilayer film is not particularly limited. For example, a high-refractive-index material layer and a low-refractive-index material layer are alternately formed by a CVD (chemical vapor deposition) method, a sputtering method, a vacuum deposition method, or the like. A method of laminating a laminated dielectric multilayer film and bonding it to a copper complex layer or the like with an adhesive, and alternately laminating a high refractive index material layer and a low refractive index material layer on the surface of the copper complex layer or the like. To form a dielectric multilayer film.

  The thickness of each of the high-refractive-index material layer and the low-refractive-index material layer is preferably １ ／ λ to λ with respect to the wavelength λ (nm) of the ultraviolet light to be cut off, and preferably で λ. More preferably, there is. The number of layers in the dielectric multilayer film is preferably 3 to 41 layers, more preferably 11 to 41 layers, and still more preferably 21 to 41 layers.

  The near-infrared cut filter of the present invention may further include a resin, a crosslinked product of a compound having a crosslinkable group, a catalyst, a thermal stability imparting agent, a surfactant, and the like. Details of these will be described later.

Preferred embodiments of the near-infrared cut filter of the present invention include the following embodiments (1) to (4). In the case of the mode (1), there is an advantage that only a single layer is required. In any of the following embodiments, each layer may be laminated on a support. The support is not particularly limited as long as the support is made of a material having high transmittance of visible light. For example, glass, crystal, resin, and the like can be given. Examples of the glass include soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Examples of the crystal include quartz, lithium niobate, and sapphire. Examples of the resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyolefin resins such as polyethylene, polypropylene and ethylene-vinyl acetate copolymer; acrylic resins such as norbornene resin, polyacrylate and polymethyl methacrylate; urethane resins; and vinyl chloride resins. , Fluorine resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin and the like.
(1) Near infrared cut filter including a layer containing a copper complex and an ultraviolet absorber (2) Near infrared cut filter including a copper complex layer and a layer containing an ultraviolet absorber (3) Copper complex layer and dielectric Near infrared cut filter having a multilayer film (4) A near infrared cut filter having a copper complex layer, a layer containing an ultraviolet absorber, and a dielectric multilayer film.

  In the above embodiment (1), the layer containing the copper complex and the ultraviolet absorber preferably has a thickness of 10 to 500 μm, more preferably 50 to 300 μm. The layer containing the copper complex and the ultraviolet absorber may be formed on a support.

  The near-infrared cut filter of the embodiment (1) can be formed using a composition containing at least a copper complex and an ultraviolet absorber. The composition may further include a resin, a compound having a crosslinkable group, a catalyst, a polymerization initiator, a thermal stability imparting agent, a surfactant, and the like. Details of these will be described later.

  The near-infrared cut filter of the embodiment (1) is manufactured through, for example, a step of forming a film by applying a composition containing at least a copper complex and an ultraviolet absorber on a support, a step of drying the film, and the like. it can. Further, a step of forming a pattern may be further performed.

  In the step of forming a film, a known method can be used as a method for applying the composition. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Publications); inkjet (eg, on-demand method, piezo method, thermal method), discharge printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; a transfer method using a mold or the like; a nanoimprint method, and the like. The method of application by inkjet is not particularly limited as long as the composition can be ejected, and is described in, for example, "Spreading and usable inkjet-Infinite possibilities seen in patents", published in February 2005, Sumibe Techno Research. JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261727, JP-A-2012-126830 The method described in JP-A-2006-169325 can be used.

  In the case of the dropping method (drop casting), it is preferable to form a dropping region of a composition using a photoresist as a partition on a support so that a uniform film having a predetermined thickness is obtained. A desired film thickness can be obtained by adjusting the amount of the composition to be dropped, the solid content concentration, and the area of the dropping region. The thickness of the film after drying is not particularly limited, and can be appropriately selected depending on the purpose.

  The support may be a transparent substrate such as glass. Further, it may be a solid-state imaging device. Further, another substrate provided on the light receiving side of the solid-state imaging device may be used. Further, it may be a layer such as a flattening layer provided on the light receiving side of the solid-state imaging device.

  In the step of drying the film, the drying conditions vary depending on the type and the amount of each component. For example, a temperature of 60 to 150 ° C. for 30 seconds to 15 minutes is preferable.

  Examples of the pattern forming step include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method. In the pattern forming method using the photolithography method, an alkaline aqueous solution obtained by diluting an alkaline agent with pure water is preferably used as a developer. The concentration of the alkaline agent in the alkaline aqueous solution is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass. The developer may be once produced as a concentrated solution and diluted to a necessary concentration at the time of use, from the viewpoint of convenience of transportation and storage. The dilution ratio is not particularly limited, but can be set, for example, in a range of 1.5 to 100 times.

  The manufacturing method of the near-infrared cut filter may include other steps. The other steps are not particularly limited and can be appropriately selected depending on the purpose. For example, a surface treatment step of the base material, a pre-heating step of the film (pre-bake step), a curing treatment step of the film, a post-heating step of the film (post-bake step) and the like can be mentioned.

  The heating temperature in the preheating step and the postheating step is preferably from 80 to 200C. The upper limit is preferably 150 ° C. or less. The lower limit is preferably 90 ° C. or higher. The heating time in the preheating step and the postheating step is preferably 30 to 240 seconds. The upper limit is preferably 180 seconds or less. The lower limit is preferably 60 seconds or more.

  The hardening process is a process of performing a hardening process on the formed film as needed. By performing this process, the mechanical strength of the near-infrared cut filter is improved. The curing step is not particularly limited and can be appropriately selected depending on the purpose. For example, exposure treatment, heat treatment, and the like are preferably mentioned. Here, in the present invention, “exposure” is used to mean not only irradiation of light of various wavelengths but also irradiation of radiation such as an electron beam and X-ray.

Exposure is preferably performed by irradiation with radiation, and as the radiation that can be used for exposure, ultraviolet rays such as electron beams, KrF, ArF, g lines, h lines, and i lines, and visible light are particularly preferable. Examples of the exposure method include stepper exposure and exposure using a high-pressure mercury lamp. The exposure amount is preferably 5 to 3000 mJ / cm ² . The upper limit is preferably 2000 mJ / cm ² or less, 1000 mJ / cm ² or less being more preferred. The lower limit is preferably 10 mJ / cm ² or more, and more preferably 50 mJ / cm ² or more. As a method of the exposure treatment, for example, there is a method of exposing the entire surface of the formed film. The exposure apparatus is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an ultraviolet exposure apparatus such as an ultra-high pressure mercury lamp is preferably used.

  As a method of the heat treatment, a method of heating the entire surface of the formed film is given. The heat treatment increases the film strength of the pattern. The heating temperature is preferably from 100 to 260C. The lower limit is preferably at least 120 ° C, more preferably at least 160 ° C. The upper limit is preferably 240 ° C or lower, more preferably 220 ° C or lower. When the heating temperature is in the above range, a film having excellent strength is easily obtained. The heating time is preferably from 1 to 180 minutes. The lower limit is preferably 3 minutes or more. The upper limit is preferably 120 minutes or less. The heating device is not particularly limited and may be appropriately selected from known devices according to the purpose. Examples thereof include a dry oven, a hot plate, and an infrared heater.

In the above embodiment (2), the thickness of the copper complex layer is preferably from 10 to 500 μm, more preferably from 50 to 300 μm. The thickness of the layer containing the ultraviolet absorbent is preferably from 1 to 200 μm, more preferably from 1 to 100 μm.
In the above embodiment (2), the copper complex layer may further contain an ultraviolet absorber. In the above embodiment (2), the layer containing the ultraviolet absorbent may be provided on only one side of the copper complex layer, or may be provided on both sides of the copper complex layer. Further, a layer containing an ultraviolet absorber may be formed on one surface of the support, and a copper complex layer may be formed on the other surface. Examples of the near-infrared cut filter according to the above aspect (2) include the following aspects.
(2-1) Copper complex layer / layer containing ultraviolet absorber (2-2) Layer containing ultraviolet absorber / copper complex layer / layer containing ultraviolet absorber (2-3) Support / copper complex layer / UV Layer containing absorber (2-4) support / layer containing ultraviolet absorber / copper complex layer (2-5) support / layer containing ultraviolet absorber / copper complex layer / layer containing ultraviolet absorber (2 -6) copper complex layer / support / layer containing ultraviolet absorber (2-7) layer containing ultraviolet absorber / support / layer containing ultraviolet absorber / copper complex layer (2-8) ultraviolet absorber Containing layer / support / copper complex layer / layer containing ultraviolet absorber

  The near-infrared cut filter of the above embodiment (2) can be manufactured through a step of forming a layer containing an ultraviolet absorbent and a step of forming a copper complex layer. The order of forming the layer containing the ultraviolet absorber and the copper complex layer is not particularly limited. The copper complex layer can be formed by the method described in the above embodiment (1). Further, the layer containing the ultraviolet absorbent can be formed by the same method as the method of forming the copper complex layer described in the above-mentioned embodiment (1). In the near-infrared cut filter according to the aspect (2), the copper complex layer can be formed using a composition containing at least a copper complex. The layer containing an ultraviolet absorber can be formed using a composition containing at least an ultraviolet absorber. These compositions may further include a resin, a compound having a crosslinkable group, a catalyst, a polymerization initiator, a thermal stability imparting agent, a surfactant, and the like. Details of these will be described later.

In the above embodiment (3), the thickness of the copper complex layer is preferably from 10 to 500 μm, more preferably from 50 to 300 μm. Further, the thickness of the dielectric multilayer film is preferably 0.5 to 10 μm, and more preferably 1 to 5 μm.
In the above embodiment (3), the copper complex layer may further contain an ultraviolet absorber. In the above embodiment (3), the dielectric multilayer film may be provided on only one side of the copper complex layer, or may be provided on both sides of the copper complex layer. Further, a dielectric multilayer film may be formed on one surface of the support, and a copper complex layer may be formed on the other surface. As the near-infrared cut filter according to the aspect (3), for example, the following aspects are exemplified.
(3-1) Copper complex layer / dielectric multilayer film (3-2) Dielectric multilayer film / copper complex layer / dielectric multilayer film (3-3) support / copper complex layer / dielectric multilayer film (3- 4) support / dielectric multilayer / copper complex layer (3-5) support / dielectric multilayer / copper complex layer / dielectric multilayer (3-6) copper complex layer / support / dielectric multilayer (3-7) Dielectric multilayer / support / dielectric multilayer / copper complex layer (3-8) Dielectric multilayer / support / copper complex layer / dielectric multilayer

  The near-infrared cut filter of the embodiment (3) can be manufactured through a step of forming a dielectric multilayer film and a step of forming a copper complex layer. The order of forming the dielectric multilayer film and the copper complex layer is not particularly limited. The copper complex layer can be formed by the method described in the above embodiment (1). In the near-infrared cut filter according to the above aspect (3), the copper complex layer can be formed using a composition containing at least a copper complex. Further, the dielectric multilayer film can be formed by the method described above.

In the above embodiment (4), the thickness of the copper complex layer is preferably from 10 to 500 μm, more preferably from 50 to 300 μm. The thickness of the layer containing the ultraviolet absorbent is preferably from 1 to 200 μm, more preferably from 1 to 100 μm. Further, the thickness of the dielectric multilayer film is preferably 0.5 to 10 μm, and more preferably 1 to 5 μm.
In the above embodiment (4), the copper complex layer may further contain an ultraviolet absorber. In the above embodiment (4), the order of laminating the copper complex layer, the layer containing the ultraviolet absorber, and the dielectric multilayer film is not particularly limited.
(4-1) Copper complex layer / layer containing ultraviolet absorber / dielectric multilayer film (4-2) Copper complex layer / dielectric multilayer film / layer containing ultraviolet absorber (4-3) Dielectric multilayer Membrane / copper complex layer / layer containing ultraviolet absorber (4-4) support / copper complex layer / layer containing ultraviolet absorber / dielectric multilayer film (4-5) support / copper complex layer / dielectric Body multilayer film / layer containing ultraviolet absorber (4-6) support / dielectric multilayer film / copper complex layer / layer containing ultraviolet absorber (4-7) support / dielectric multilayer film / ultraviolet absorption Agent-containing layer / copper complex layer (4-8) support / layer containing ultraviolet absorber / copper complex layer / dielectric multilayer film (4-9) support / layer containing ultraviolet absorber / dielectric Body multilayer film / copper complex layer (4-10) copper complex layer / support / layer containing ultraviolet absorber / dielectric multilayer film (4-11) copper complex layer / support (4-12) Dielectric multilayer film / layer containing ultraviolet absorber (4-12) Dielectric multilayer film / support / copper complex layer / layer containing ultraviolet absorber (4-13) Dielectric multilayer film / support Layer containing absorber / copper complex layer (4-14) Layer containing ultraviolet absorber / support / copper complex layer / dielectric multilayer film (4-15) Layer containing ultraviolet absorber / support / Dielectric multilayer film / copper complex layer (4-16) dielectric multilayer film / support / dielectric multilayer film / copper complex layer / layer containing ultraviolet absorber (4-17) dielectric multilayer film / support / Copper complex layer / Dielectric multilayer film / Layer containing UV absorber

  The near-infrared cut filter according to the above aspect (4) can be manufactured through a step of forming a layer containing an ultraviolet absorber, a step of forming a dielectric multilayer film, and a step of forming a copper complex layer. The order of forming each layer is not particularly limited. The copper complex layer can be formed by the method described in the above embodiment (1). Further, the layer containing the ultraviolet absorbent can be formed by the same method as the method of forming the copper complex layer described in the above-described embodiment (1). Further, the dielectric multilayer film can be formed by the method described above. In the near-infrared cut filter according to the above aspect (4), the copper complex layer can be formed using a composition containing at least a copper complex. The layer containing an ultraviolet absorber can be formed using a composition containing at least an ultraviolet absorber.

  The near-infrared cut filter of the present invention can be used for various devices such as a solid-state imaging device such as a CCD (charge coupled device) and a CMOS (complementary metal oxide semiconductor), an infrared sensor, and an image display device.

<Copper complex layer forming composition>
Next, a composition that can be preferably used for forming the near-infrared cut filter of the present invention will be described. First, a composition that can be used for forming a copper complex layer (hereinafter, also referred to as a composition for forming a copper complex layer) will be described.

<< copper complex >>
The composition for forming a copper complex layer contains a copper complex. As the copper complex, a complex of copper and a compound having a coordination site for copper (ligand) is preferable. Examples of the coordination site for copper include a coordination site that coordinates with an anion and a coordination atom that coordinates with an lone pair. The copper complex may have two or more ligands. When having two or more ligands, each ligand may be the same or different. The copper complex is exemplified by four-coordinate, five-coordinate and six-coordinate, preferably four-coordinate and five-coordinate, more preferably five-coordinate. The copper complex preferably has a 5-membered ring and / or a 6-membered ring formed by copper and a ligand. Such a copper complex is stable in shape and excellent in complex stability.

  The content of the metal other than copper in the copper complex is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less based on the solid content of the copper complex. According to this aspect, it is easy to form a film in which foreign matter defects are suppressed. Further, the lithium content of the copper complex is preferably 100 mass ppm or less. Further, the potassium content of the copper complex is preferably at most 30 mass ppm. Examples of a method for reducing the content of a metal other than copper in the copper complex include a method of purifying the copper complex by a method such as reprecipitation, recrystallization, column chromatography, and sublimation purification. Further, a method in which a copper complex is dissolved in a solvent and then purified by filtering through a filter can also be used. Preferred embodiments of the filter include the filter described in the section of preparation of the composition described below. The content of metals other than copper in the copper complex can be measured by inductively coupled plasma emission spectroscopy.

  The water content in the copper complex is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. According to this aspect, it is easy to prepare a composition having excellent stability over time.

  The total amount of free halogen anions and halogen compounds in the copper complex is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less based on the total solid content of the copper complex. According to this aspect, it is easy to prepare a composition having excellent stability over time.

In the present invention, the copper complex is also preferably a copper complex other than the phthalocyanine copper complex. Here, the phthalocyanine copper complex is a copper complex having a compound having a phthalocyanine skeleton as a ligand. A compound having a phthalocyanine skeleton has a planar structure in which a π-electron conjugate system spreads throughout the molecule. The phthalocyanine copper complex absorbs light at the π-π * transition. In order to absorb light in the infrared region by the π-π * transition, the ligand compound must have a long conjugate structure. However, when the conjugate structure of the ligand is lengthened, the visible transparency tends to decrease. For this reason, the phthalocyanine copper complex may have insufficient visible transparency.
Further, the copper complex is also preferably a copper complex having a compound having no maximum absorption wavelength in a wavelength region of 400 to 600 nm as a ligand. A copper complex having a compound having a maximum absorption wavelength in a wavelength region of 400 to 600 nm as a ligand has an absorption in a visible region (for example, a wavelength region of 400 to 600 nm), and thus may have insufficient visible transparency. is there. Examples of the compound having a maximum absorption wavelength in a wavelength region of 400 to 600 nm include a compound having a long conjugated structure and having a large absorption of π-π * transition light. Specifically, a compound having a phthalocyanine skeleton is exemplified.

  The copper complex can be obtained, for example, by mixing and reacting a copper component (copper or a compound containing copper) with a compound having a coordination site for copper (ligand). The compound having a coordination site for copper (ligand) may be a low molecular compound or a polymer. Both can be used together. The copper component is preferably used after being diluted or dissolved with methanol and then filtered. The pore size of the filter paper or filter used for filtration is preferably 1 μm or less.

  With respect to a ligand in which copper and a ligand are stoichiometrically coordinated in a molar ratio of copper: ligand = 1: p, the molar ratio of the reaction between the copper component and the ligand in the synthesis of the copper complex. Preferably, the ratio is 1: q (where q ≧ p, and q is an arbitrary number). When q <p, the copper component, which is a raw material, easily remains in the copper complex, causing a decrease in visible transparency and causing a foreign matter defect. The residual ratio of the copper component as a raw material in the copper complex (the content of the copper component not coordinated with the ligand) is preferably 10% by mass or less, and more preferably 5% by mass or less based on the solid content of the copper complex. Is more preferable, and 2% by mass or less is further preferable. Further, if the ligand remains excessively in the copper complex, visible transparency may be reduced, the number of foreign matter defects may be increased, and the thermal stability of the composition may be reduced. ≤ 2p, more preferably p ≤ q ≤ 1.5p, even more preferably p ≤ q ≤ 1.2p. The residual ratio of the ligand in the copper complex (the content of the ligand not coordinated with copper) is preferably 10% by mass or less, more preferably 5% by mass or less based on the solid content of the copper complex. The content is more preferably 2% by mass or less. In addition, in producing the copper complex, it is preferable to provide a plurality of crystallization steps. At the time of crystallization, the amount of the good solvent is preferably smaller than that of the poor solvent. When a plurality of crystallization steps are provided, it is preferable to set the solid content of the copper complex to 80% by mass before moving to the next crystallization step.

  The copper component is preferably a compound containing divalent copper. As the copper component, only one type may be used, or two or more types may be used. As the copper component, for example, copper oxide or a copper salt can be used. Copper salts include, for example, copper carboxylate (eg, copper acetate, copper ethyl acetoacetate, copper formate, copper benzoate, copper stearate, copper naphthenate, copper citrate, copper 2-ethylhexanoate), copper sulfonate (For example, copper methanesulfonate), copper phosphate, copper phosphate, copper phosphonate, copper phosphonate, copper phosphinate, amide copper, sulfonamide copper, imide copper, acylsulfonimide copper, bissulfonimide Copper, methide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper perchlorate, copper fluoride, copper chloride, copper bromide are preferred, copper carboxylate, copper sulfonate, Sulfonamide copper, imide copper, acylsulfonimide copper, bissulfonimide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper fluoride, copper chloride, copper sulfate, nitrate Copper is more preferable, copper carboxylate, acyl sulfonimide copper, phenoxy, copper chloride, copper sulfate, copper nitrate are more preferred, copper carboxylate, acyl sulfonimide, copper chloride, copper sulfate particularly preferred.

In the present invention, the copper complex is preferably a compound having a maximum absorption wavelength in a wavelength range of 700 to 1200 nm. The maximum absorption wavelength of the copper complex is more preferably in a wavelength range of 720 to 1200 nm, and further preferably in a wavelength range of 800 to 1100 nm. The maximum absorption wavelength can be measured using, for example, Cary 5000 UV-Vis-NIR (spectrophotometer, manufactured by Agilent Technologies).
The molar extinction coefficient of the copper complex at the maximum absorption wavelength in the above-mentioned wavelength region is preferably 120 (L / mol · cm) or more, more preferably 150 (L / mol · cm) or more, and 200 (L / mol · cm). ) Or more, still more preferably 300 (L / mol · cm) or more, and particularly preferably 400 (L / mol · cm) or more. The upper limit is not particularly limited, but may be, for example, 30000 (L / mol · cm) or less. If the molar extinction coefficient of the copper complex is 100 (L / mol · cm) or more, a near-infrared cut filter having excellent infrared shielding properties can be obtained even if it is a thin film.
The gram extinction coefficient at a wavelength of 800 nm of the copper complex is preferably 0.11 (L / g · cm) or more, more preferably 0.15 (L / g · cm) or more, and 0.24 (L / g · cm). Or more).
In the present invention, the molar extinction coefficient and the gram extinction coefficient of the copper complex are determined by preparing a solution having a concentration of 1 g / L by dissolving the copper complex in a measurement solvent and measuring the absorption spectrum of the solution in which the copper complex is dissolved. You can ask. As a measuring device, UV-1800 (wavelength region 200 to 1100 nm) manufactured by Shimadzu Corporation, Cary 5000 (wavelength region 200 to 1300 nm) manufactured by Agilent, or the like can be used. Examples of the measurement solvent include water, N, N-dimethylformamide, propylene glycol monomethyl ether, 1,2,4-trichlorobenzene, and acetone. In the present invention, a solvent that can dissolve the copper complex to be measured is selected from the above-described measurement solvents. In particular, in the case of a copper complex that dissolves in propylene glycol monomethyl ether, it is preferable to use propylene glycol monomethyl ether as the measurement solvent. The term “dissolve” means a state in which the solubility of the copper complex in a solvent at 25 ° C. exceeds 0.01 g / 100 g Solvent.
In the present invention, the molar extinction coefficient and the gram extinction coefficient of the copper complex are preferably values measured using any one of the measurement solvents described above, and more preferably values in propylene glycol monomethyl ether. .

(Low molecular type copper complex)
As the copper complex, for example, a copper complex represented by the formula (Cu-1) can be used. This copper complex is a copper complex in which a ligand L is coordinated to copper as a central metal, and copper is usually divalent copper. This copper complex can be obtained, for example, by reacting a compound serving as a ligand L or a salt thereof with a copper component.
Cu (L) _n1 · (X) _n2 formula (Cu-1)
In the above formula, L represents a ligand coordinated to copper, and X represents a counter ion. n1 represents an integer of 1 to 4. n2 represents the integer of 0-4.

X represents a counter ion. The copper complex may be a cationic complex or an anionic complex in addition to a neutral complex having no charge. In this case, a counter ion is optionally present to neutralize the charge of the copper complex.
When the counter ion is a negative counter ion (counter anion), for example, it may be an inorganic anion or an organic anion. For example, the counter ion includes a hydroxide ion, a halogen anion (eg, a fluoride ion, a chloride ion, a bromide ion, an iodide ion), a substituted or unsubstituted alkyl carboxylate ion (acetate ion, trifluoro ion, etc.). Acetate ion), substituted or unsubstituted aryl carboxylate ion (benzoate ion, etc.), substituted or unsubstituted alkyl sulfonate ion (methane sulfonic acid ion, trifluoromethane sulfonic acid ion, etc.), substituted or unsubstituted aryl Sulfonic acid ions (for example, p-toluene sulfonic acid ion, p-chlorobenzene sulfonic acid ion, etc.), aryl disulfonic acid ions (for example, 1,3-benzene disulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalene) Disulfonic acid ion), al Sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, nitrate ion, perchlorate ion, borate ion (eg, tetrafluoroborate ion, tetraarylborate ion, tetrakis (pentafluorophenyl)) borate ion ^{_{(B - (C 6 F 5}} ) 4) , etc.), sulfonate ion (e.g., p- toluenesulfonate ion, etc.), imide ion (e.g., a sulfonimide ion, N, N-bis (fluorosulfonyl) imide ion, bis (Trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, N, N-hexafluoro-1,3-disulfonylimide ion, etc., phosphate ion, hexafluorophosphate ion, picric acid ion, amido ion (Including an amide substituted with an acyl group or a sulfonyl group), a methide ion (including a methide substituted with an acyl group or a sulfonyl group), a halogen anion, a substituted or unsubstituted alkyl carboxylate ion, sulfuric acid, Ion, nitrate ion, tetrafluoroborate ion, tetraarylborate ion, hexafluorophosphate ion, amide ion (including amide substituted with acyl group or sulfonyl group), methide ion (substituted with acyl group or sulfonyl group) Including methides).
Further, the counter anion is preferably a low nucleophilic anion. The low nucleophilic anion is an anion obtained by dissociating a proton from an acid having a low pKa, which is generally called a super acid. The definition of superacid is a generic term for an acid having a lower pKa than methanesulfonic acid, although it differs depending on the literature. Org. Chem. 2011, 76, 391-395 The structure described in Equilibrium Acids of Super acids is known. The pKa of the low nucleophilic anion is, for example, preferably -11 or less, and more preferably -11 to -18. pKa is described, for example, in J. Am. Org. Chem. 2011, 76, 391-395. The pKa value in this specification is the pKa in 1,2-dichloroethane unless otherwise specified. When the counter anion is a low nucleophilic anion, the decomposition reaction of the copper complex or the resin hardly occurs and the heat resistance is good. Low nucleophilic anions include tetrafluoroborate ion, tetraarylborate ion (including aryl substituted with halogen atom and fluoroalkyl group), hexafluorophosphate ion, imide ion (substituted with acyl group and sulfonyl group) Amide ions (including amides substituted with an acyl group or a sulfonyl group), methide ions (including aryl substituted with a halogen atom or a fluoroalkyl group), and imide ions (including a sulfonyl group). Particularly preferred are amides (including substituted amides) and methide ions (including methides substituted with a sulfonyl group).
In the present invention, the counter anion is preferably a halogen anion, a carboxylate ion, a sulfonate ion, a borate ion, a sulfonate ion, or an imide ion. Specific examples include chloride ion, bromide ion, iodide ion, acetate ion, trifluoroacetate ion, formate ion, phosphate ion, hexafluorophosphate ion, p-toluenesulfonate ion, tetrafluoroboronate ion, tetrakis ( Pentafluorophenyl) borate ion, N, N-bis (fluorosulfonyl) imide ion, bis (trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, nonafluoro-N-[(trifluoromethane) sulfonyl] butanesulfonylimide Ion, N, N-hexafluoro-1,3-disulfonylimide ion and the like, trifluoroacetate ion, hexafluorophosphate ion, tetrafluborate ion, Trakis (pentafluorophenyl) borate ion, N, N-bis (fluorosulfonyl) imide ion, bis (trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, nonafluoro-N-[(trifluoromethane) sulfonyl] butane Sulfonylimide ion and N, N-hexafluoro-1,3-disulfonylimide ion are preferable, and trifluoroacetate ion, tetrakis (pentafluorophenyl) borate ion, N, N-bis (fluorosulfonyl) imide ion, bis ( Trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, nonafluoro-N-[(trifluoromethane) sulfonyl] butanesulfonylimide ion, N, N-f Safuruoro 1,3-imide ion is more preferable.
When the counter ion is a positive counter ion (counter cation), for example, an inorganic or organic ammonium ion (eg, a tetraalkylammonium ion such as a tetrabutylammonium ion, a triethylbenzylammonium ion, a pyridinium ion, etc.), a phosphonium ion (eg, , A tetraalkylphosphonium ion such as a tetrabutylphosphonium ion, an alkyltriphenylphosphonium ion, a triethylphenylphosphonium ion, etc.), an alkali metal ion or a proton.
The counter ion may be a metal complex ion (eg, a copper complex ion).

  The ligand L is a compound having a coordination site for copper, and is a compound selected from a coordination site for coordinating an anion to copper and a coordination atom for coordinating an unshared electron pair to copper. Compounds having the above are mentioned. The coordination site coordinated by an anion may be dissociated or non-dissociated. The ligand L is preferably a compound having two or more coordination sites for copper (polydentate ligand). Further, it is preferable that a plurality of π-conjugated systems such as aromatics are not continuously bonded to the ligand L in order to improve visible transmittance. As the ligand L, a compound having one coordination site for copper (monodentate ligand) and a compound having two or more coordination sites for copper (polydentate ligand) can be used in combination. Monodentate ligands include monodentate ligands that coordinate with anions or lone pairs. Examples of the ligand coordinated with an anion include a halide anion, a hydroxide anion, an alkoxide anion, a phenoxide anion, an amide anion (including an amide substituted with an acyl group or a sulfonyl group), and an imide anion (an acyl group or a sulfonyl group. (Including substituted imides), anilide anions (including anilides substituted with acyl or sulfonyl groups), thiolate anions, hydrogencarbonate anions, carboxylate anions, thiocarboxylate anions, dithiocarboxylate anions, hydrogensulfate anions, sulfones Acid anion, dihydrogen phosphate anion, phosphate diester anion, phosphonate monoester anion, hydrogen phosphonate anion, phosphinate anion, nitrogen-containing heterocyclic anion, nitrate anion, hypochlorite anion, cyanide anion Cyanate anion, isocyanate anion, thiocyanate anion, isothiocyanate anions, such as azide anions. Monodentate ligands coordinated by lone pairs include water, alcohol, phenol, ether, amine, aniline, amide, imide, imine, nitrile, isonitrile, thiol, thioether, carbonyl compound, thiocarbonyl compound, sulfoxide, Examples include a hetero ring, or carbonic acid, carboxylic acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid, nitric acid, or an ester thereof.

  The anion contained in the ligand L may be any one capable of coordinating to a copper atom, and is preferably an oxygen anion, a nitrogen anion or a sulfur anion. The coordination site coordinated by an anion is preferably at least one selected from the following monovalent functional group group (AN-1) or divalent functional group group (AN-2). In addition, the wavy line in the following structural formulas is a bonding position with an atomic group constituting a ligand.

Group (AN-1)

Group (AN-2)

In the above formula, X represents N or CR, and R independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
The alkyl group represented by R may be linear, branched or cyclic, but is preferably linear. The carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkyl group include a methyl group. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, a carboxyl group, and a heterocyclic group. The heterocyclic group as a substituent may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The number of hetero atoms constituting the hetero ring is preferably 1 to 3, and more preferably 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom. When the alkyl group has a substituent, the alkyl group may further have a substituent.
The alkenyl group represented by R may be linear, branched or cyclic, but is preferably linear. The carbon number of the alkenyl group is preferably 2 to 10, and more preferably 2 to 6. The alkenyl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
The alkynyl group represented by R may be linear, branched or cyclic, but is preferably linear. The carbon number of the alkynyl group is preferably 2 to 10, and more preferably 2 to 6. The alkynyl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
The aryl group represented by R may be monocyclic or polycyclic, but is preferably a monocyclic ring. The carbon number of the aryl group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
The heteroaryl group represented by R may be monocyclic or polycyclic. The number of hetero atoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The carbon number of the heteroaryl group is preferably from 6 to 18, more preferably from 6 to 12. The heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.

  An example of a coordination site coordinated by an anion is a monoanionic coordination site. A monoanionic coordination site represents a site that coordinates with a copper atom via one negatively charged functional group. For example, an acid group having an acid dissociation constant (pKa) of 12 or less can be mentioned. Specific examples include an acid group containing a phosphorus atom (a phosphoric acid diester group, a phosphonic acid monoester group, a phosphinic acid group, and the like), a sulfo group, a carboxyl group, an imido acid group, and the like. preferable.

  The coordinating atom coordinated by the lone pair is preferably an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, still more preferably an oxygen atom, a nitrogen atom, and a nitrogen atom. Is particularly preferred. When the coordinating atom coordinated by the lone pair is a nitrogen atom, the atom adjacent to the nitrogen atom is preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom.

The coordinating atom coordinated by the lone pair is contained in the ring, or the following monovalent functional group (UE-1), divalent functional group (UE-2), and trivalent functional group It is preferable that it is included in at least one kind of partial structure selected from the base group (UE-3). In addition, the wavy line in the following structural formulas is a bonding position with an atomic group constituting a ligand.
Group (UE-1)

Group (UE-2)

Group (UE-3)

In the groups (UE-1) to (UE-3), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² represents a hydrogen atom, an alkyl group, an alkenyl group. Group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group or acyl group.

Coordinating atoms that coordinate with the lone pair may be included in the ring. When a coordinating atom coordinated by a lone pair is included in the ring, the ring containing a coordinating atom coordinated by the lone pair may be monocyclic or polycyclic, It may be aromatic or non-aromatic. The ring containing a coordinating atom coordinated by a lone pair is preferably a 5- to 12-membered ring, more preferably a 5- to 7-membered ring.
The ring containing a coordinating atom coordinated by an unshared electron pair may have a substituent, and the substituent may be a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, Examples thereof include an aryl group having 6 to 12 atoms, a halogen atom, a silicon atom, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, and a carboxyl group.
When the ring containing the coordinating atom coordinated by the lone pair has a substituent, it may further have a substituent, and the ring containing the coordinating atom coordinated by the lone pair Group, a group containing at least one partial structure selected from the above groups (UE-1) to (UE-3), an alkyl group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, hydroxyl Groups.

When the coordinating atom coordinated by the lone pair is included in the partial structures represented by groups (UE-1) to (UE-3), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. , An aryl group or a heteroaryl group, and R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, or an arylthio group. , A heteroarylthio group, an amino group or an acyl group.
The alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group have the same meaning as the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group described in the coordination site coordinated with the anion. The same applies to the preferred range.
The carbon number of the alkoxy group is preferably from 1 to 12, more preferably from 3 to 9.
The carbon number of the aryloxy group is preferably from 6 to 18, more preferably from 6 to 12.
The heteroaryloxy group may be monocyclic or polycyclic. The heteroaryl group constituting the heteroaryloxy group has the same meaning as the heteroaryl group described for the coordination site coordinated with the anion, and the preferred range is also the same.
The carbon number of the alkylthio group is preferably from 1 to 12, and more preferably from 1 to 9.
The carbon number of the arylthio group is preferably from 6 to 18, and more preferably from 6 to 12.
The heteroarylthio group may be monocyclic or polycyclic. The heteroaryl group constituting the heteroarylthio group has the same meaning as the heteroaryl group described for the coordination site coordinated with the anion, and the preferred range is also the same.
The carbon number of the acyl group is preferably 2 to 12, and more preferably 2 to 9.
R ¹ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. By making the substituent on the N atom, that is, R ¹ an alkyl group, the ligand contribution to the molecular orbital of the copper complex is improved, the molar extinction coefficient at the maximum absorption wavelength is improved, and the infrared shielding property is improved. In addition, the transparency tends to be further improved. In particular, an alkyl group is preferable in terms of the balance between heat resistance, infrared shielding properties, and visible transparency.

  When the ligand has, in one molecule, a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair, the coordination site coordinated by an anion and the uncoordinated electron pair are coordinated. The number of atoms connecting the coordinating atom is preferably 1 to 6, and more preferably 1 to 3. With such a configuration, the structure of the copper complex is more easily distorted, so that the color value can be further improved, and the molar extinction coefficient can be easily increased while increasing the visible transparency. One or more kinds of atoms may be used to connect the coordination site coordinated by the anion and the coordination atom coordinated by the lone pair. A carbon atom or a nitrogen atom is preferred.

  When the ligand has two or more coordinating atoms coordinated by a lone pair in one molecule, the ligand may have three or more coordinating atoms coordinated by a lone pair. It is preferable to have 5 to 5, more preferably 4. The number of atoms connecting the coordinating atoms coordinated by the lone pair is preferably 1 to 6, more preferably 1 to 3, still more preferably 2 to 3, and particularly preferably 3. With such a configuration, the structure of the copper complex is more likely to be distorted, so that the color value can be further improved. The number of atoms connecting the coordinating atoms coordinated by the lone pair may be one or more. The atom connecting the coordinating atoms coordinated by the lone pair is preferably a carbon atom.

  In the present invention, the ligand is preferably a compound having at least two coordination sites (also referred to as a polydentate ligand). The ligand preferably has at least three coordination sites, more preferably has three to five coordination sites, and particularly preferably has four to five coordination sites. The polydentate ligand acts as a chelating ligand for the copper component. In other words, when at least two coordination sites of the polydentate ligand are coordinated with copper, the structure of the copper complex is distorted, and excellent visible transparency is obtained. Can be improved, and the color value is also considered to be improved. Thus, even if the near-infrared cut filter is used for a long time, its characteristics are not impaired, and the camera module can be manufactured stably.

  A polydentate ligand is a compound containing at least one coordination site coordinated by an anion and at least one coordination atom coordinated by an unshared electron pair, a coordination coordinated by an unshared electron pair. Compounds having two or more atoms, compounds having two coordination sites coordinated by anions, and the like can be given. These compounds can be used alone or in combination of two or more. Further, as the compound to be a ligand, a compound having only one coordination site can be used.

The polydentate ligand is preferably a compound represented by the following formulas (IV-1) to (IV-14). For example, when the ligand is a compound having four coordination sites, compounds represented by the following formulas (IV-3), (IV-6), (IV-7), and (IV-12) Preferably, the compound represented by (IV-12) is more preferable because it is more likely to form a stable pentacoordinate complex having high heat resistance and more firmly coordinated with the metal center. Further, for example, when the ligand is a compound having five coordination sites, the following formulas (IV-4), (IV-8) to (IV-11), (IV-13), and (IV- The compound represented by the formula (14) is preferable, and is more strongly coordinated to the metal center and easily forms a stable pentacoordination complex having high heat resistance, and thus, (IV-9) to (IV-10), Compounds represented by (IV-13) and (IV-14) are more preferred, and compounds represented by (IV-13) are particularly preferred.

In Formulas (IV-1) to (IV-14), X ^{1 to} X ⁵⁹ each independently represent a coordination site, and L ^{1 to} L ²⁵ each independently represent a single bond or a divalent linking group. ^represents, L 26 ^{~L 32} each independently represents a trivalent linking ^group, representing the L 33 ^{~L 34} are each independently a tetravalent linking group.
X ^{1 to} X ⁴² are each independently selected from the group consisting of a ring containing a coordinating atom coordinated by a lone pair, the group (AN-1), or the group (UE-1) described above. It is preferred to represent at least one.
X ^{43 to} X ⁵⁶ are each independently selected from a group consisting of a ring containing a coordinating atom coordinated by a lone pair, the group (AN-2), or the group (UE-2) described above. It is preferred to represent at least one.
It is preferable that X ^{57 to} X ⁵⁹ each independently represent at least one selected from the group (UE-3) described above.
L ^{1 to} L ²⁵ each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, -SO -, - O -, - SO 2 - or, preferably a group consisting of combinations, carbon number 1-3 alkylene group, a phenylene group, -SO ₂ - or more preferably a group comprising a combination thereof.
L ^{26 to} L ³² each independently represent a trivalent linking group. Examples of the trivalent linking group include groups obtained by removing one hydrogen atom from the above-described divalent linking group.
L ^{33 to} L ³⁴ each independently represent a tetravalent linking group. Examples of the tetravalent linking group include groups obtained by removing two hydrogen atoms from the above-described divalent linking group.
Here, the group (AN-1) R in ~ (AN-2), and, ^{R 1} in group (UE-1) ~ (UE -3) is, R to each other, ^{R 1} or between, and R R ¹ may be linked to form a ring. For example, specific examples of the formula (IV-2) include the following compound (IV-2A). ^{Incidentally, X 3, X 4, X} 43 is a group shown ^below, L 2, ^{L 3} is a methylene group, but ^{R 1} is a methyl group, forms a ring by connecting this ^{R 1} together, (IV-2B) or (IV-2C).

  Specific examples of the compound forming the ligand include the compounds shown below, compounds shown as preferable specific examples of the polydentate ligand described below, and salts of these compounds. Examples of the atoms constituting the salt include a metal atom and tetrabutylammonium. As the metal atom, an alkali metal atom or an alkaline earth metal atom is more preferable. Examples of the alkali metal atom include sodium and potassium. Examples of the alkaline earth metal atom include calcium and magnesium. In addition, the description of paragraphs 0022 to 0042 of JP-A-2014-41318 and the description of paragraphs 0021 to 0039 of JP-A-2015-43063 can be referred to, and the contents thereof are incorporated in the present specification.

As the copper complex, for example, the following embodiments (1) to (5) are mentioned as preferable examples, (2) to (5) are more preferable, (3) to (5) are more preferable, and (4) or (5) is more preferred.
(1) A copper complex having one or two compounds having two coordination sites as ligands.
(2) A copper complex having a compound having three coordination sites as a ligand.
(3) A copper complex having a compound having three coordination sites and a compound having two coordination sites as ligands.
(4) A copper complex having a compound having four coordination sites as a ligand.
(5) A copper complex having a compound having five coordination sites as a ligand.

In the above embodiment (1), the compound having two coordination sites is a compound having two coordination atoms coordinating with an unshared electron pair, or a coordination site coordinating with an anion and an unshared electron pair. And a coordination atom coordinating with the above. When two of the compounds having two coordination sites are used as ligands, the ligand compounds may be the same or different.
In the embodiment (1), the copper complex may further have a monodentate ligand. The number of monodentate ligands can be 0 or 1 to 3. As the kind of the monodentate ligand, both a monodentate ligand coordinated by an anion and a monodentate ligand coordinated by an unshared electron pair are preferable. In the case where the compound having two coordination sites has two coordination atoms coordinating with an unshared electron pair, a monodentate ligand coordinating with an anion is more preferable because of a strong coordination force. When the compound having two coordination sites has a coordination site coordinating with an anion and a coordination atom coordinating with an unshared electron pair, the compound is not shared because the entire copper complex has no charge. Monodentate ligands that coordinate with electron pairs are more preferred.

  In the above embodiment (2), the compound having three coordination sites is preferably a compound having a coordination atom coordinating with an unshared electron pair, and having three coordination atoms coordinating with an unshared electron pair. Compounds are more preferred. Further, in the embodiment (2), the copper complex may further have a monodentate ligand. The number of monodentate ligands can be zero. In addition, the number may be one or more, preferably one to three or more, more preferably one or two, and even more preferably two. As the kind of the monodentate ligand, any of a monodentate ligand coordinated by an anion and a monodentate ligand coordinated by an unshared electron pair is preferable, and the monodentate ligand coordinated by an anion for the above-described reason is preferable. More preferred.

  In the above embodiment (3), the compound having three coordination sites is preferably a compound having a coordination site coordinating with an anion and a coordination atom coordinating with an unshared electron pair. Compounds having two coordinating sites and one coordinating atom coordinating with a lone pair are more preferred. Further, it is particularly preferred that the two anions coordinate different coordination sites. Further, the compound having two coordination sites is preferably a compound having a coordination atom coordinated by a lone pair, and more preferably a compound having two coordination atoms coordinating by a non-shared pair. Among them, a compound having three coordination sites is a compound having two coordination sites coordinating with an anion and one coordination atom coordinating with an unshared electron pair, Particularly preferred is a combination in which the compound having a moiety is a compound having two coordinating atoms coordinated by an unshared electron pair. In the embodiment (3), the copper complex may further have a monodentate ligand. The number of monodentate ligands can be zero or one or more. Zero is more preferred.

  In the above embodiment (4), the compound having four coordinating sites is preferably a compound having a coordinating atom coordinated by an unshared electron pair, and has two or more coordinating atoms coordinated by an unshared electron pair. Compounds are more preferred, and compounds having four coordinating atoms coordinated by lone pairs are more preferred. In the embodiment (4), the copper complex may further have a monodentate ligand. The number of monodentate ligands can be zero, one or more, or two or more. One is preferred. As the kind of the monodentate ligand, both a monodentate ligand coordinated by an anion and a monodentate ligand coordinated by an unshared electron pair are preferable.

  In the above embodiment (5), the compound having five coordination sites is preferably a compound having a coordination atom coordinating with a lone pair, and having two or more coordination atoms coordinating with a non-shared pair. Compounds are more preferred, and compounds having five coordinating atoms coordinated by lone pairs are even more preferred. In the embodiment (5), the copper complex may further have a monodentate ligand. The number of monodentate ligands can be zero or one or more. The number of monodentate ligands is preferably 0.

Examples of the polydentate ligand include compounds having two or more coordination sites and compounds shown below among the compounds described in the specific examples of the ligand described above.

[Phosphate ester copper complex]
In the present invention, a copper phosphate complex can also be used as the copper complex. The phosphate copper complex has copper as a central metal and a phosphate compound as a ligand. As the phosphate compound serving as a ligand of the phosphate copper complex, a compound represented by the following formula (L-100) or a salt thereof is preferable.
_{(HO) n -P (= O} ) - (OR 1) 3-n Formula (L-100)
In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms, or —OR ¹ represents Represents a polyoxyalkyl group having 4 to 100 carbon atoms, a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or a (meth) acryloylpolyoxyalkyl group having 4 to 100 carbon atoms, and n is 1 or 2 Represents When n is 1, R ² may be the same or different.

  Specific examples of the phosphate compound include the ligands described above. In addition, descriptions of paragraphs 0022 to 0042 of JP-A-2014-41318 can be referred to, and the contents thereof are incorporated in the present specification.

[Copper sulfonic acid complex]
In the present invention, a copper sulfonate complex may be used as the copper complex. The copper sulfonic acid complex has copper as a central metal and a sulfonic acid compound as a ligand. The sulfonic acid compound serving as a ligand of the copper sulfonic acid complex is preferably a compound represented by the following formula (L-200) or a salt thereof.
R ² —SO ₂ —OH Formula (L-200)

In the formula, R ² represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, and a heteroaryl group.
The alkyl group, the aryl group, and the heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include a polymerizable group (preferably, a vinyl group, a (meth) acryloyloxy group), a group having an ethylenically unsaturated bond such as a (meth) acryloyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom). atom, iodine atom), an alkyl group, a carboxylic acid ester group (e.g., -CO ₂ CH _3), halogenated alkyl group, an alkoxy group, methacryloyloxy group, acryloyloxy group, an ether group, an alkylsulfonyl group, an arylsulfonyl group, a sulfide Groups, an amide group, an acyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an acid group containing a phosphorus atom, an amino group, a carbamoyl group, and a carbamoyloxy group.

  Specific examples of the sulfonic acid compound include the ligands described above. In addition, descriptions of paragraph numbers 0021 to 0039 of JP-A-2015-43063 can be referred to, and the contents thereof are incorporated in the present specification.

[Other copper complexes]
In the present invention, a phthalocyanine copper complex or a naphthalocyanine copper complex may be used as the copper complex. Examples of the naphthalocyanine copper complex include the following compounds. In the following structural formula, Bu is a butyl group. In the present invention, a polynuclear copper complex can also be used as the copper complex. Specific examples include a binuclear copper complex having a carboxylate ion or the like as a ligand, and these may be in an equilibrium state with a mononuclear copper complex in the composition.

<<<< Copper complex of polymer type >>>>
In the present invention, a copper-containing polymer having a copper complex site in a polymer side chain can be used as the copper complex.

  Examples of the copper complex site include those having copper and a site coordinating to copper (coordination site). Examples of the site that coordinates with copper include a site that coordinates with an anion or an unshared electron pair. Further, the copper complex site preferably has a site that is tetradentate or pentadentate with respect to copper. The details of the coordination site include those described for the low molecular weight copper compound described above, and the preferred range is also the same.

  The copper-containing polymer is a polymer containing a coordination site (also referred to as polymer (B1)) and a polymer obtained by a reaction with a copper component, or a polymer having a reactive site in a polymer side chain (hereinafter also referred to as polymer (B2)). ) And a copper complex having a functional group capable of reacting with a reactive site of the polymer (B2). The weight average molecular weight of the copper-containing polymer is preferably 2000 or more, more preferably 2000 to 2,000,000, and still more preferably 6000 to 200,000.

  The copper-containing polymer may contain another repeating unit in addition to the repeating unit having a copper complex site. Examples of the other repeating unit include a repeating unit having a crosslinkable group.

  The composition for forming a copper complex layer preferably has a copper complex content of 5 to 95% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is preferably equal to or less than 70% by mass, more preferably equal to or less than 60% by mass, and still more preferably equal to or less than 50% by mass.

<< other infrared absorbers >>
The composition for forming a copper complex layer may contain an infrared absorber other than the copper complex (also referred to as another infrared absorber). Other infrared absorbers include cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, diiminium compounds, thiol complex compounds, transition metal oxides, quaterylene compounds, croconium compounds, and the like.

  Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, compounds described in paragraphs 0037 to 0052 of JP 2011-68731 A, and the like. The contents are incorporated herein. Examples of the squarylium compound include the compounds described in Paragraph Nos. 0044 to 0049 of JP-A-2011-208101, the contents of which are incorporated herein. Examples of the cyanine compound include the compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267 and the compounds described in paragraphs 0026 to 0030 of JP-A-2002-194040. Incorporated herein. Examples of the diiminium compound include the compounds described in JP-T-2008-528706, the contents of which are incorporated herein. Examples of the phthalocyanine compound include compounds described in paragraph No. 0093 of JP-A-2012-77153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraphs 0013 to 0029 of JP-A-2013-195480. And the contents of which are incorporated herein. Examples of the naphthalocyanine compound include the compounds described in paragraph No. 0093 of JP-A-2012-77153, the contents of which are incorporated herein. Further, as the cyanine compound, the phthalocyanine compound, the diiminium compound, the squarylium compound and the croconium compound, the compounds described in paragraphs 0010 to 0081 of JP-A-2010-111750 may be used, the contents of which are incorporated herein. It is. In addition, as for the cyanine compound, for example, “Functional Dye, Shin Okawara / Ken Matsuoka / Teijiro Kitao / Tsunaki Hirashima, Kodansha Scientific” can be referred to, and the contents thereof are incorporated herein. It is.

In addition, inorganic fine particles can be used as another infrared absorber. As the inorganic fine particles, metal oxide fine particles or metal fine particles are preferable because infrared shielding properties are more excellent. Examples of the metal oxide fine particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped). SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like. Examples of the metal fine particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. As the inorganic fine particles, a tungsten oxide compound can be used. The tungsten oxide-based compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, paragraph 0080 of JP-A-2006-006476 can be referred to, and the contents are incorporated herein. The shape of the inorganic fine particles is not particularly limited, and may be sheet-like, wire-like, or tube-like regardless of spherical or non-spherical shape.

  The average particle diameter of the inorganic fine particles is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average particle diameter of the inorganic fine particles is in such a range, visible transparency is good. From the viewpoint of avoiding light scattering, the average particle diameter is preferably as small as possible. However, the average particle diameter of the inorganic fine particles is usually 1 nm or more for reasons such as easy handling during production.

  When the composition for forming a copper complex layer contains another infrared absorbing agent, the content of the other infrared absorbing agent is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the copper complex. The lower limit is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, even more preferably at least 1 part by mass. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less.

<< Resin >>
The composition for forming a copper complex layer preferably contains a resin. The type of resin is not particularly limited as long as it can be used for an optical material. The resin is preferably a highly transparent resin. Specifically, polyolefin resins such as polyethylene, polypropylene, carboxylated polyolefin, chlorinated polyolefin, and cycloolefin polymers; polystyrene resins; (meth) acrylic resins such as (meth) acrylic ester resins and (meth) acrylamide resins; vinyl acetate Resin; vinyl halide resin; polyvinyl alcohol resin; polyamide resin; polyurethane resin; polyester resin such as polyethylene terephthalate (PET) and polyarylate (PAR); polycarbonate resin; epoxy resin; polymaleimide resin; polyurea resin; Polyvinyl acetal resin and the like. Among them, (meth) acrylic resin, polyurethane resin, polyester resin, polymaleimide resin and polyurea resin are preferable, (meth) acrylic resin, polyurethane resin and polyester resin are more preferable, and (meth) acrylate resin is particularly preferable. It is also preferable to use a sol-gel cured product of a compound having an alkoxysilyl group as the resin. Examples of the compound having an alkoxysilyl group include the materials described below in the section of the crosslinkable compound. The weight average molecular weight of the resin is preferably from 1,000 to 300,000. The lower limit is more preferably 2000 or more, and still more preferably 3000 or more. The upper limit is more preferably 100,000 or less, and even more preferably 50,000 or less. The number average molecular weight of the resin is preferably from 500 to 150,000. The lower limit is more preferably 1,000 or more, and even more preferably 2,000 or more. The upper limit is more preferably 200,000 or less, and even more preferably 100,000 or less. In the case of an epoxy resin, the weight average molecular weight (Mw) of the epoxy resin is preferably 100 or more, and more preferably 200 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 100 or more, more preferably 200 or more, still more preferably 2,000 or more, and particularly preferably 5,000 or more.

  Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester resin. Epoxy resin, glycidylamine-based epoxy resin, epoxy resin obtained by glycidylation of halogenated phenols, condensate of silicon compound with epoxy group and other silicon compound, polymerizable unsaturated compound with epoxy group and other Copolymers with other polymerizable unsaturated compounds and the like can be mentioned.

  Epoxy resins that are glycidyl etherified phenol compounds include, for example, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-hydroxy) ) Phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) Phenyl] propane, 2,2′-methylene- (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglucinol, diisopropylene Phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene;

  Examples of epoxy resins that are glycidyl etherified novolak resins include various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and naphthols. Glycidyl ethers of various novolak resins such as a novolak resin, a phenol novolak resin having a xylylene skeleton, a phenol novolak resin having a dicyclopentadiene skeleton, a phenol novolak resin having a biphenyl skeleton, and a phenol novolak resin having a fluorene skeleton.

Examples of the alicyclic epoxy resin include an alicyclic epoxy resin having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. Epoxy resins are mentioned.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
Examples of the heterocyclic epoxy resin include a heterocyclic epoxy resin having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester epoxy resin include an epoxy resin composed of a carboxylic acid ester such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine-based epoxy resin include an epoxy resin obtained by glycidylation of amines such as aniline and toluidine.
Epoxy resins obtained by glycidylation of halogenated phenols include, for example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like. Epoxy resins obtained by glycidylation of halogenated phenols are exemplified.

  Examples of copolymers of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds include Marproof G-0150M, G-0105SA, G-0130SP, and commercially available products. G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by NOF CORPORATION) and the like. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, and 4-vinyl-1-cyclohexene-1,2-epoxide. Examples of the copolymer of another polymerizable unsaturated compound include, for example, methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane, and the like. Particularly, methyl (meth) acrylate, Benzyl (meth) acrylate and styrene are preferred.

  The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and still more preferably 310 to 1000 g / eq. Epoxy resins may be used alone or in combination of two or more.

Commercial products can also be used as the epoxy resin. Examples of commercially available products include the following.
As bisphenol A type epoxy resins, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (all above) )).
As bisphenol F type epoxy resins, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (all manufactured by DIC Corporation), LCE-21, RE-602S ( As described above, Nippon Kayaku Co., Ltd.) and the like.
Examples of phenol novolak type epoxy resins include JER152, JER154, JER157S70, JER157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation) and the like. No.
As a cresol novolak type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all manufactured by DIC Corporation) And EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).
As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation), celloxide 2021P, celloxide 2081, celloxide 2083, celloxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) and the like.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Mitsubishi Chemical Corporation) and the like.

式中、Ｒ^１は水素原子またはアルキル基を表し、Ｌ^１〜Ｌ^４はそれぞれ独立に、単結合または２価の連結基を表し、Ｒ^１０〜Ｒ^１３はそれぞれ独立にアルキル基またはアリール基を表す。Ｒ^１４およびＲ^１５は、それぞれ独立に、水素原子または置換基を表す。The resin is also preferably a resin having at least one of the repeating units represented by the following formulas (A1-1) to (A1-7).

In the formula, R ¹ represents a hydrogen atom or an alkyl group, L ^{1 to} L ⁴ each independently represent a single bond or a divalent linking group, and R ^{10 to} R ¹³ each independently represent an alkyl group or an aryl group. Represent. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a substituent.

The carbon number of the alkyl group represented by R ¹ is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R ¹ is preferably a hydrogen atom or a methyl group.

L ^{1 to} L ⁴ each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, -O -, - S -, - SO -, - CO -, - COO -, - OCO -, - SO 2 -, - NR a - (R a Represents a hydrogen atom or an alkyl group), or a combination thereof. 1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched, or cyclic. Further, the cyclic alkylene group may be either monocyclic or polycyclic. The carbon number of the arylene group is preferably from 6 to 18, more preferably from 6 to 14, and even more preferably from 6 to 10.

The alkyl group represented by R ¹⁰ may be linear, branched or cyclic, and is preferably cyclic. The alkyl group may have a substituent or may be unsubstituted. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, 1-10 are still more preferable. The carbon number of the aryl group represented by R ¹⁰ is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. R ¹⁰ is preferably a cyclic alkyl group or an aryl group.

The alkyl group represented by R ¹¹ and R ¹² may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. The carbon number of the aryl group represented by R ¹¹ and R ¹² is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. R ¹¹ and R ¹² are preferably a linear or branched alkyl group.

The alkyl group represented by R ¹³ may be linear, branched, or cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. The carbon number of the aryl group represented by R ¹³ is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. R ¹³ is preferably a linear or branched alkyl group or an aryl group.

The substituent represented by R ¹⁴ and R ¹⁵ is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, Alkylthio group, arylthio group, heteroarylthio group, -NR ^a1 R ^a2 , -COR ^a3 , -COOR ^a4 , -OCOR ^a5 , -NHCOR ^a6 , -CONR ^a7 R ^a8 , -NHCONR ^a9 R ^a10 , -NHCOOR ^a11 , -NH SO ₂ R ^a12 , —SO ₂ OR ^a13 , —NHSO ₂ R ^a14 or —SO ₂ NR ^a15 R ^a16 . R ^{a1 to} R ^a16 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Among them, at least one of R ¹⁴ and R ¹⁵ preferably represents a cyano group or —COOR ^a4 . ^Ra4 preferably represents a hydrogen atom, an alkyl group or an aryl group.

  Commercial products of the resin having a repeating unit represented by the formula (A1-7) include ARTON F4520 (manufactured by JSR Corporation). For details of the resin having a repeating unit represented by the formula (A1-7), paragraphs 0053 to 0075 and 0127 to 0130 of JP-A-2011-100084 can be referred to, and the contents are described in the present specification. Will be incorporated into the book.

  The resin is preferably a resin having a repeating unit represented by Formula (A1-1) and / or (A1-4), and is a resin having a repeating unit represented by Formula (A1-4). Is more preferable. According to this aspect, the thermal shock resistance of the obtained cured film tends to be improved. Further, the compatibility between the copper complex and the resin is improved, and a cured film with few precipitates and the like can be produced. The resin containing a repeating unit having a crosslinkable group is preferably stored and used at a low temperature (for example, 25 ° C. or lower, more preferably 0 ° C. or lower).

  The resin is also preferably a resin containing a repeating unit having a crosslinkable group. According to this aspect, it is easy to obtain a cured film having excellent solvent resistance, thermal shock resistance, and the like. In particular, a resin containing a repeating unit represented by the formula (A1-1) and / or the formula (A1-4) and a repeating unit having a crosslinkable group is more preferable.

  The crosslinkable group is preferably a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group, or an alkoxysilyl group, more preferably a group having an ethylenically unsaturated bond, a cyclic ether group, or an alkoxysilyl group, and a cyclic ether group. , An alkoxysilyl group is more preferred, and an alkoxysilyl group is particularly preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the cyclic ether group include an epoxy group (oxiranyl group), an oxetanyl group, and an alicyclic epoxy group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group.

Examples of the repeating unit having a crosslinkable group include repeating units represented by the following formulas (A2-1) to (A2-4), and represented by the formulas (A2-1) to (A2-3). Repeating units are preferred.

R ² represents a hydrogen atom or an alkyl group. The carbon number of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R ² is preferably a hydrogen atom or a methyl group.

L ⁵¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include the divalent linking groups described for L ^{1 to} L ⁴ in the above formulas (A1-1) to (A1-7). L ⁵¹ is preferably an alkylene group or a group obtained by combining an alkylene group and —O—. The number of atoms constituting the chain of L ⁵¹ is 2 or more, more preferably 3 or more, more preferably 4 or more. The upper limit can be, for example, 200 or less.

P ¹ represents a crosslinkable group. Examples of the crosslinkable group include a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group, and an alkoxysilyl group.A group having an ethylenically unsaturated bond, a cyclic ether group, and an alkoxysilyl group are preferable. Ether groups and alkoxysilyl groups are more preferred, and alkoxysilyl groups are even more preferred. Details of the group having an ethylenically unsaturated bond, the cyclic ether group, and the alkoxysilyl group include the groups described above. The carbon number of the alkoxy group in the alkoxysilyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

  When the resin is a resin containing a repeating unit having a crosslinkable group, the resin preferably contains 10 to 90% by mass of the repeating unit having a crosslinkable group in all the repeating units of the resin, and 10 to 80% by mass. %, More preferably 30 to 80% by mass. According to this aspect, a cured film having excellent solvent resistance is easily obtained.

  The resin may contain other repeating units in addition to the above-mentioned repeating units. As the components constituting other repeating units, descriptions in paragraphs 0068 to 0075 of JP-A-2010-106268 (paragraphs 0112 to 0118 of the corresponding U.S. Patent Application Publication No. 2011/0124824) can be referred to. , The contents of which are incorporated herein.

Specific examples of the resin include resins having the following structures. In addition, the numerical value described together with the repeating unit is a mass ratio.

  When the composition for forming a copper complex layer contains a resin, the content of the resin is preferably 1 to 90% by mass based on the total solid content of the composition for forming a copper complex layer. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less. The resin may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

<<< Compound Having Crosslinkable Group (Crosslinkable Compound) >>>
The composition for forming a copper complex layer may contain a compound having a crosslinkable group (hereinafter, also referred to as a crosslinkable compound). Examples of the crosslinkable compound include a compound having a group having an ethylenically unsaturated bond, a compound having a cyclic ether group, a compound having a methylol group, and a compound having an alkoxysilyl group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the cyclic ether group include an epoxy group (oxiranyl group), an oxetanyl group, and an alicyclic epoxy group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group.

  The crosslinkable compound may be in any form of a monomer or a polymer, but is preferably a monomer. The monomer type crosslinkable compound preferably has a molecular weight of 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. Further, the crosslinkable compound is preferably a compound having substantially no molecular weight distribution. Here, it is preferable that the compound has substantially no molecular weight distribution, in which the degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the compound is 1.0 to 1.5, and 1 to 1.5. 0.0 to 1.3 is more preferable.

  The crosslinkable group equivalent of the crosslinkable compound is preferably from 3.0 to 8.0 mmol / g, more preferably from 3.5 to 8.0 mmol / g, even more preferably from 4.0 to 7.0 mmol / g. The crosslinkable compound preferably has two or more crosslinkable groups in one molecule. The upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less. The crosslinkable group equivalent of the crosslinkable compound is defined by the amount (mmol) of the crosslinkable group contained in 1 g of the sample.

  In the present invention, the crosslinkable compound is preferably a compound having a group having an ethylenically unsaturated bond, a compound having a cyclic ether group, or a compound having an alkoxysilyl group, and more preferably a compound having an alkoxysilyl group. Further, the compound having an alkoxysilyl group preferably has a silicon value of 3.0 to 8.0 mmol / g, more preferably 3.5 to 8.0 mmol / g, and more preferably 4.0 to 7.0 mmol / g. Is more preferred. The silicon value of the crosslinkable compound is defined by the amount (mmol) of silicon contained in 1 g of the sample.

(Compound having a group having an ethylenically unsaturated bond)
In the present invention, a compound having a group having an ethylenically unsaturated bond can be used as the crosslinkable compound. The compound having a group having an ethylenically unsaturated bond is preferably a monomer. The molecular weight of the above compound is preferably from 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. The compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.

As examples of the compound having a group having an ethylenically unsaturated bond, the description of paragraphs 0033 to 0034 of JP-A-2013-253224 can be referred to, and the contents thereof are incorporated herein. Examples of the compound having a group having an ethylenically unsaturated bond include ethyleneoxy-modified pentaerythritol tetraacrylate (a commercially available product is NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and dipentaerythritol triacrylate (a commercially available product is , KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product) Is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexa (meth) acrylate (as commercial products, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) ), And these Meth) acryloyl groups is ethylene glycol, structures linked via a propylene glycol residue are preferable. These oligomer types can also be used. In addition, descriptions of paragraphs 0034 to 0038 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. In addition, polymerizable monomers described in paragraph No. 0477 of JP-A-2012-208494 (corresponding to paragraph No. 0585 of U.S. Patent Application Publication No. 2012/0235099), and the like, are described in the present specification. Incorporated in
Diglycerin EO (ethylene oxide) -modified (meth) acrylate (commercially available: M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol Diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like are also preferable.

  The compound having a group having an ethylenically unsaturated bond may have an acid group such as a carboxyl group, a sulfo group, and a phosphate group. Examples of the compound having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A compound obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group is particularly preferable. In this ester, the aliphatic polyhydroxy compound is preferably pentaerythritol. And / or dipentaerythritol. Examples of commercially available products include Alonix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. The acid value of the compound having an acid group is preferably 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

  As the compound having a group having an ethylenically unsaturated bond, a compound having a caprolactone structure is also a preferred embodiment. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, Ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Can be. As the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, and the contents thereof are incorporated herein. The compound having a caprolactone structure may be, for example, an ethyleneoxy chain manufactured by Sartomer Co., such as DPCA-20, DPCA-30, DPCA-60, or DPCA-120, which is commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd. Examples include SR-494, which is a tetrafunctional acrylate having four, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

  Compounds having a group having an ethylenically unsaturated bond are described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Classes are also suitable. It is also preferable to use the compounds described in JP-A-63-277563, JP-A-63-260909, and JP-A-1-105238. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA -306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

(Compound having cyclic ether group)
In the present invention, a compound having a cyclic ether group may be used as the crosslinkable compound. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable.
Examples of the compound having a cyclic ether group include a polymer having a cyclic ether group in a side chain, and a monomer or oligomer having two or more cyclic ether groups in a molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin and the like can be mentioned. Further, a monofunctional or polyfunctional glycidyl ether compound can also be used. The weight average molecular weight of the compound having a cyclic ether group is preferably from 500 to 5,000,000, more preferably from 1,000 to 500,000.

  As a commercially available product of the compound having a cyclic ether group, for example, description of paragraph 0191 of JP-A-2012-155288 can be referred to, and the contents thereof are incorporated in the present specification. In addition, polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (all manufactured by Nagase ChemteX Corp.) are exemplified. These are low-chlorine products, but not low-chlorine products, such as EX-212, EX-214, EX-216, EX-321, and EX-850. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), JER1031S, celoxide 2021P, celoxide 2081, celoxide 2083, celoxide 2085, EHPE3150, EPOLED PB 3600, PB 4700 (manufactured by Daicel), Cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (all manufactured by Daicel Corporation) and the like. Further, commercially available phenol novolak type epoxy resins include JER-157S65, JER-152, JER-154, and JER-157S70 (all manufactured by Mitsubishi Chemical Corporation). Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule include Alonoxetane OXT-121, OXT-221, OX-SQ, and PNOX ( Manufactured by Toagosei Co., Ltd.).

(Compound having an alkoxysilyl group)
In the present invention, a compound having an alkoxysilyl group can be used as the crosslinkable compound. The carbon number of the alkoxy group in the alkoxysilyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2. The number of alkoxysilyl groups in a molecule is preferably two or more, and more preferably two or three. Specific examples of the compound having an alkoxysilyl group include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltrimethoxysilane. Propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyl Trimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glyciyl Xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) pro Amine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3- Examples include ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane. In addition to the above, an alkoxy oligomer can be used. The following compounds can also be used.

  As commercially available products, KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM-3066 manufactured by Shin-Etsu Silicone Co., Ltd. KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM- 403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, K M-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A, X-41-1056, X-41-1805, X- 41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40-9225, X-40-9246, X-40- 9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X-40-9238 and the like.

  When the composition for forming a copper complex layer contains a crosslinkable compound, the content of the crosslinkable compound is preferably 1 to 30% by mass relative to the total solid content of the composition for forming a copper complex layer, and is 1 to 25%. % By mass is more preferable, and 1 to 20% by mass is further preferable. The crosslinkable compound may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.

<< Dehydrating agent >>
The composition for forming a copper complex layer also preferably contains a dehydrating agent. When the composition for forming a copper complex layer contains a dehydrating agent, the storage stability of the liquid can be improved. Specific examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; Methyl acrylate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate, trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthoisobutyrate, orthoisobutyrate Orthoester compounds such as triethyl butyrate; acetone dimethyl ketal, diethyl ketone dimethyl ketal, acetophenone dimethyl ketal, cycle Hexanone dimethyl digits - le, cyclohexanone diethyl digits - le, benzophenone dimethyl digits - ketal, such as Le compounds; methanol, such as lower alcohols having 1 to 4 carbon atoms such as ethanol. These may be used alone or in combination of two or more.

The dehydrating agent may be added, for example, to a component before polymerizing the resin, may be added during polymerization of the resin, or may be added at the time of mixing the obtained resin with other components, and there is no particular limitation. .
The content of the dehydrating agent is not particularly limited, but is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the resin.

<< polymerization initiator >>
The composition for forming a copper complex layer may include a polymerization initiator. The polymerization initiator is not particularly limited as long as it has a capability of initiating polymerization of the polymerizable compound by one or both of light and heat, but a photopolymerization initiator is preferable. When the polymerization is initiated by light, those having photosensitivity to light in the ultraviolet region to the visible region are preferred. When the polymerization is started by heat, a polymerization initiator that decomposes at 150 to 250 ° C. is preferable.

  As the polymerization initiator, a compound having an aromatic group is preferable. For example, acylphosphine compounds, acetophenone compounds, α-hydroxyketone compounds, α-aminoketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, Examples include organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, onium salt compounds such as azinium compounds, metallocene compounds, organic boron salt compounds, disulfone compounds, thiol compounds, and the like. The description of paragraphs 0217 to 0228 of JP-A-2013-253224 can be referred to for the polymerization initiator, and the contents thereof are incorporated herein.

  The polymerization initiator is preferably an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound. As the α-hydroxyketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF) can be used. As the α-aminoketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF) can be used. As the acylphosphine compound, IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF) can be used. Examples of the oxime compound include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and ADEKA ARKLES NCI-831. (Made by ADEKA Corporation), Adeka Arculs NCI-930 (made by ADEKA Corporation), Adeka Optomer N-1919 (made by ADEKA Corporation, photopolymerization initiator 2 described in JP-A-2012-14052) ) Etc. can be used.

  The content of the polymerization initiator is preferably 0.01 to 30% by mass based on the total solid content of the composition for forming a copper complex layer. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. The polymerization initiator may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.

<< Solvent >>
The composition for forming a copper complex layer preferably contains a solvent. The solvent is not particularly limited, and may be appropriately selected depending on the purpose as long as the components can be uniformly dissolved or dispersed. For example, water and an organic solvent can be used.
Preferred examples of the organic solvent include alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, and dimethylformamide, dimethylacetamide, dimethylsulfoxide, and sulfolane. These may be used alone or in combination of two or more.
Specific examples of alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in paragraph 0136 of JP-A-2012-194534, the contents of which are incorporated herein.
Specific examples of the esters, ketones and ethers include those described in paragraph 0497 of JP-A-2012-208494 ([0609] of the corresponding US Patent Application Publication No. 2012/0235099). . Further, acetic acid-n-amyl, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate and the like can be mentioned.
As the solvent, at least one selected from 1-methoxy-2-propanol, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, ethyl lactate and propylene glycol monomethyl ether It is preferable to use

  In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 parts by mass ppb (parts per billion) or less. If necessary, a solvent having a level of parts per trillion (ppt) may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

  Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

  The solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one isomer may be contained, or a plurality of isomers may be contained.

  The content of the solvent is preferably such that the total solid content of the composition for forming a copper complex layer is 5 to 60% by mass. The lower limit is more preferably 10% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less. The solvent may be only one kind or two or more kinds, and in the case of two or more kinds, the total amount is preferably in the above range.

<< catalyst >>
The composition for forming a copper complex layer may include a catalyst. For example, when a resin containing a repeating unit having a crosslinkable group such as an alkoxysilyl group is used as a resin, or when a crosslinkable compound is used, the composition for forming a copper complex layer contains a catalyst, resulting in crosslinking. The near-infrared cut filter excellent in solvent resistance and heat resistance is easily obtained by promoting crosslinking of the functional group.

  Examples of the catalyst include an organometallic catalyst, an acid catalyst, an amine catalyst, and the like, and an organometallic catalyst is preferable. The organometallic catalyst includes at least one metal selected from the group consisting of Na, K, Ca, Mg, Ti, Zr, Al, Zn, Sn, and Bi, and includes oxides, sulfides, halides, and carbonates. At least one selected from the group consisting of a salt, a carboxylate, a sulfonate, a phosphate, a nitrate, a sulfate, an alkoxide, a hydroxide, and an acetylacetonate complex which may have a substituent. Preferably, there is. Among them, at least one selected from the group consisting of a halide, a carboxylate, a nitrate, a sulfate, a hydroxide, and an acetylacetonate complex which may have a substituent, of the above metal Is preferable, and an acetylacetonate complex is more preferable. In particular, an acetylacetonate complex of Al is preferable. Specific examples of the organometallic catalyst include, for example, aluminum tris (2,4-pentanedionato).

  When the composition for forming a copper complex layer contains a catalyst, the content of the catalyst is preferably 0.01 to 5% by mass based on the total solid content of the composition for forming a copper complex layer. The upper limit is preferably 3% by mass or less, more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more.

<< thermal stability imparting agent >>
The composition for forming a copper complex layer may also contain a thermal stability imparting agent. An oxime compound is mentioned as a thermal stability imparting agent. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), and ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation), ADEKA ARKULS NCI-930 (manufactured by ADEKA Corporation), Adeka Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization described in JP-A-2012-14052) Initiators 2) and the like can be used.
In the present invention, an oxime compound having a fluorine atom can be used as the oxime compound. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471. (C-3). This content is incorporated herein.
In the present invention, an oxime compound having a nitro group can be used as the oxime compound. The oxime compound having a nitro group is preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 of JP2014-137466A, and 0070 to 0079, Compounds described in Paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, Adeka Aquels NCI-831 (manufactured by ADEKA Corporation) may be mentioned.

  In the present invention, an oxime compound having a fluorene ring can be used as the oxime compound. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.

  In the present invention, an oxime compound having a benzofuran skeleton can be used as the oxime compound. Specific examples include compounds OE-01 to OE-75 described in International Publication WO2015 / 036910.

  The content of the thermal stability imparting agent is preferably 0.01 to 30% by mass based on the total solid content of the composition for forming a copper complex layer. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less.

<< Surfactant >>
The composition for forming a copper complex layer may include a surfactant. One surfactant may be used alone, or two or more surfactants may be used in combination. The content of the surfactant is preferably 0.0001 to 5% by mass based on the total solid content of the composition for forming a copper complex layer. The lower limit is preferably 0.005% by mass or more, more preferably 0.01% by mass or more. The upper limit is preferably 2% by mass or less, more preferably 1% by mass or less.

  As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The near-infrared absorbing composition preferably contains at least one of a fluorine-based surfactant and a silicone-based surfactant. The interfacial tension between the coating surface and the coating liquid is reduced, and the wettability to the coating surface is improved. For this reason, the liquid properties (in particular, fluidity) of the composition are improved, and the uniformity of the coating thickness and the liquid saving property are further improved. As a result, even when a thin film of about several μm is formed with a small amount of liquid, it is possible to form a uniform thickness film with small thickness unevenness.

  The fluorine content of the fluorinated surfactant is preferably from 3 to 40% by mass. The lower limit is preferably 5% by mass or more, more preferably 7% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. When the fluorine content is within the above-mentioned range, it is effective in terms of uniformity of the thickness of the coating film and liquid saving, and the solubility is good.

  Specific examples of the fluorine-based surfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-41318 (paragraphs 0060 to 0064 of the corresponding WO 2014/17669). The surfactants described in paragraph Nos. 0117 to 0132 of JP2011-132503A are exemplified, and the contents thereof are incorporated in the present specification. Commercially available fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) and the like.

  In addition, the fluorine-based surfactant is a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off when heat is applied to volatilize the fluorine atom is also preferable. Can be used. Examples of such a fluorinated surfactant include Megafac DS series (manufactured by DIC Corporation, Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafac DS. -21, and these can be used.

上記の化合物の重量平均分子量は、好ましくは３，０００〜５０，０００であり、例えば、１４，０００である。上記の化合物中、繰り返し単位の割合を示す％は質量％である。As the fluorine-based surfactant, a block polymer can also be used. For example, compounds described in JP-A-2011-89090 can be mentioned. The fluorinated surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and has 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group and propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of the repeating unit is% by mass.

  Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. As specific examples, compounds described in paragraphs [0050] to [0090] and paragraphs [0289] to [0295] of JP-A-2010-164965, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation , RS-72-K and the like. As the fluorinated surfactant, compounds described in Paragraph Nos. 0015 to 0158 of JP-A-2015-117327 can also be used.

Specific examples of the nonionic surfactant include a nonionic surfactant described in paragraph 0553 of JP-A-2012-208494 ([0679] of the corresponding US Patent Application Publication No. 2012/0235099). And their contents are incorporated herein.
Specific examples of the cationic surfactant include a cationic surfactant described in paragraph 0554 of JP-A-2012-208494 ([0680] of the corresponding US Patent Application Publication No. 2012/0235099). And their contents are incorporated herein.
Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).
Examples of the silicone-based surfactant include a silicone-based surfactant described in paragraph 0556 of JP-A-2012-208494 ([0682] of the corresponding US Patent Application Publication No. 2012/0235099). And their contents are incorporated herein.

<<<< UV absorber >>
The composition for forming a copper complex layer may contain an ultraviolet absorber. According to this aspect, it is also possible to form a near-infrared cut filter that satisfies the above-described spectral characteristics with one layer.

  As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, or the like can be used. Above all, benzotriazole is preferred because it has good compatibility with copper complexes and the like, and furthermore, it is suitable for absorption wavelengths with copper complexes and can enhance the shielding property of ultraviolet rays while maintaining excellent visible transparency. Compounds and hydroxyphenyltriazine compounds are preferred. For details thereof, the descriptions of paragraphs 0052 to 0072 of JP-A-2012-208374 and paragraphs 0317 to 0334 of JP-A-2013-68814 can be referred to, and the contents thereof are incorporated in the present specification.

Further, the conjugated diene compound is preferably a compound represented by the following formula (UV-1).

In the formula (UV-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² And may be the same or different, but do not represent a hydrogen atom at the same time.
R ¹ and R ² may form a cyclic amino group together with the nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazepino group, a piperazino group, and the like.
R ¹ and R ² are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms.
R ³ and R ⁴ represent an electron-withdrawing group. R ³ and R ⁴ are preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group, and an acyl group, carbamoyl Groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, cyano groups, alkylsulfonyl groups, arylsulfonyl groups, sulfonyloxy groups, and sulfamoyl groups. Further, R ³ and R ⁴ may combine with each other to form a cyclic electron withdrawing group. Examples of the cyclic electron withdrawing group formed by combining R ³ and R ⁴ with each other include a 6-membered ring containing two carbonyl groups.
At least one of the above R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.

  The description of the substituent of the ultraviolet absorbent represented by the formula (UV-1) can be referred to the description of paragraphs 0320 to 0327 of JP-A-2013-68814, the contents of which are incorporated herein. Examples of commercially available products of the ultraviolet absorber represented by the formula (UV-1) include UV503 (manufactured by Daito Chemical Co., Ltd.).

  Examples of the benzotriazole compound include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2′-hydroxy-3′-tert-butyl-5). '-Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3' -Isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) Benzotriazole, 2- [2′-hydroxy-5 ′-(1,1,3,3-tetramethyl) phenyl] benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzo Triazole, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, 2- (2H-benzotriazol-2-yl) -4,6-bis (1 -Methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl ) Phenol and the like. Commercial products include TINUVIN PS, TINUVIN 99-2, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, and TINUVIN 1130 (all manufactured by BASF). As the benzotriazole compound, MYUA series (manufactured by Chemical Industry Daily, February 1, 2016) manufactured by Miyoshi Oil & Fats may be used.

  Examples of the hydroxyphenyltriazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3. , 5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 Mono (hydroxyphenyl) triazine compounds such as 5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; Bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy- -Methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6 Bis (hydroxyphenyl) triazine compounds such as (2,4-dimethylphenyl) -1,3,5-triazine; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-diazine (Butoxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy And tris (hydroxyphenyl) triazine compounds such as -4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine. A reaction product of 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and alkyloxymethyloxirane; It is also possible to use a reaction product of 2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine with (2-ethylhexyl) -glycidic acid ester. it can. Commercial products include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (all manufactured by BASF).

  The content of the ultraviolet absorber is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content of the composition for forming a copper complex layer.

<< other components >>
The composition for forming a copper complex layer further includes a dispersant, a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter and other auxiliaries (for example, a conductive agent). Particles, fillers, defoamers, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.). By appropriately containing these components, properties such as the stability and physical properties of the target near-infrared cut filter can be adjusted. These components can be referred to the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of JP-A-2008-250074, the contents of which are incorporated herein. In addition, examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. Phenol compounds having a molecular weight of 500 or more, phosphite compounds having a molecular weight of 500 or more, or thioether compounds having a molecular weight of 500 or more are more preferred. These may be used as a mixture of two or more. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. Particularly, a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable, and a methyl group, an ethyl group, a propionyl group, an isopropionyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl Groups, t-pentyl groups, hexyl groups, octyl groups, isooctyl groups, and 2-ethylhexyl groups are more preferred. Further, a compound having a phenol group and a phosphite group in the same molecule (an antioxidant) is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be suitably used. As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl )] Oxy] ethyl] amine, and at least one compound selected from the group consisting of ethyl bis (2,4-di-tert-butyl-6-methylphenyl) phosphite. These are easily available as commercial products, and ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO -80, ADK STAB AO-330 (ADEKA Corporation) and the like. The content of the antioxidant is preferably from 0.01 to 20% by mass, more preferably from 0.3 to 15% by mass, based on the total solid content of the composition. The antioxidant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.

  The viscosity of the composition for forming a copper complex layer is preferably from 1 to 3000 mPa · s when a near-infrared cut filter is formed by coating. The lower limit is preferably at least 10 mPa · s, more preferably at least 100 mPa · s. The upper limit is preferably equal to or less than 2000 mPa · s, and more preferably equal to or less than 1500 mPa · s.

  The content of the metal other than copper in the composition for forming a copper complex layer is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less based on the solid content of the copper complex. According to this aspect, it is easy to form a film in which foreign matter defects are suppressed. Further, the lithium content in the composition for forming a copper complex layer is preferably 100 ppm by mass or less. Further, the potassium content in the composition for forming a copper complex layer is preferably 30 mass ppm or less. The content of metals other than copper in the composition for forming a copper complex layer can be measured by inductively coupled plasma emission spectroscopy.

  The content of water in the composition for forming a copper complex layer is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less based on the solid content of the copper complex.

  The total amount of free halogen anions and halogen compounds in the composition for forming a copper complex layer is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass, based on the total solid content of the copper complex. The following are more preferred.

  The residual ratio of the copper component, which is a raw material of the copper complex in the composition for forming a copper complex layer (content of the copper component not coordinated with the ligand), is 10% by mass based on the solid content of the copper complex. Is preferably 5% by mass or less, more preferably 2% by mass or less. In addition, the residual ratio of the ligand, which is the raw material of the copper complex in the composition for forming a copper complex layer (content of the ligand not coordinated with copper), is 10 mass% with respect to the solid content of the copper complex. %, Preferably 5% by mass or less, more preferably 2% by mass or less.

<Composition for forming an ultraviolet cut layer>
Next, a composition that can be used for forming an ultraviolet cut layer (hereinafter, also referred to as a composition for forming an ultraviolet cut layer) will be described.

<<<< UV absorber >>
It is preferable that the composition for forming an ultraviolet cut layer contains an ultraviolet absorber. Examples of the ultraviolet absorber include the ultraviolet absorber described in the composition for forming a copper complex layer described above. The content of the ultraviolet absorber is preferably from 0.1 to 50% by mass, more preferably from 1 to 30% by mass, based on the total solid content of the composition for forming an ultraviolet cut layer.

<< other components >>
The composition for forming an ultraviolet cut layer may contain a resin, a crosslinkable compound, a polymerization initiator, a solvent, a catalyst, a surfactant, an antioxidant, and the like. For these details, the materials described in the composition for forming a copper complex layer described above can be used. It is preferable that the composition for forming an ultraviolet cut layer contains a solvent. It is also preferable that the composition for forming an ultraviolet cut layer contains a resin and / or a crosslinkable compound.

When the composition for forming an ultraviolet cut layer contains a resin, the content of the resin is preferably from 1 to 90% by mass based on the total solid content of the composition for forming an ultraviolet cut layer. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less. The resin may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.
When the composition for forming an ultraviolet cut layer contains a crosslinkable compound, the content of the crosslinkable compound is preferably from 1 to 30% by mass, and more preferably from 1 to 25% by mass, based on the total solid content of the composition for forming an ultraviolet cut layer. % By mass is more preferable, and 1 to 20% by mass is further preferable. The crosslinkable compound may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.
When the composition for forming an ultraviolet cut layer contains a polymerization initiator, the content of the polymerization initiator is preferably from 0.01 to 30% by mass based on the total solid content of the composition for forming an ultraviolet cut layer. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. The polymerization initiator may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.
When the composition for forming an ultraviolet cut layer contains a catalyst, the content of the catalyst is preferably 0.01 to 5% by mass based on the total solid content of the composition for forming an ultraviolet cut layer. The upper limit is preferably 3% by mass or less, more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more. The catalyst may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.
When the composition for forming an ultraviolet cut layer contains a surfactant, the content of the surfactant is preferably from 0.0001 to 5% by mass based on the total solid content of the composition for forming an ultraviolet cut layer. The lower limit is preferably 0.005% by mass or more, more preferably 0.01% by mass or more. The upper limit is preferably 2% by mass or less, more preferably 1% by mass or less. The surfactant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.
When the ultraviolet ray cut layer forming composition contains a solvent, the content of the solvent is preferably such that the total solid content of the ultraviolet ray cut layer forming composition is 5 to 60% by mass. The lower limit is more preferably 10% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less. The solvent may be only one kind or two or more kinds, and in the case of two or more kinds, the total amount is preferably in the above range.

<Method for preparing composition>
The above composition can be prepared by mixing the components. In producing the composition, it is preferable to use a kettle whose inner wall is coated with a metal. In preparing the composition, the components of the composition may be mixed together, or the components may be dissolved and / or dispersed in a solvent and then mixed sequentially. In addition, the order of addition and working conditions at the time of compounding are not particularly limited, but it is preferable to add a high-viscosity component last from the viewpoint of ensuring stirring properties. In addition, the preparation of the composition is preferably performed in a closed system to prevent volatilization. The composition is preferably prepared in an atmosphere of dried air or nitrogen gas (preferably nitrogen gas).

  When the composition includes particles such as a pigment, the composition preferably includes a process of dispersing the particles. In the process of dispersing particles, examples of mechanical force used for dispersing particles include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like. In the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter or to increase the filling rate of the beads, for example, to increase the pulverization efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. The process and the disperser for dispersing particles are described in "Dispersion Technology Taizen, published by Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology mainly for suspensions (solid / liquid dispersion system) and industrial applications. The process and the dispersing machine described in Paragraph No. 0022 of JP-A-2015-157893 can be suitably used. In the process of dispersing the particles, the particles may be refined in a salt milling step. For the materials, equipment, processing conditions, and the like used in the salt milling process, for example, descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

  In producing the composition, it is preferable to use a kettle whose inner wall is coated with metal. The order of addition during the preparation of the composition is appropriately set, but it is preferable to add the high-viscosity component last from the viewpoint of ensuring the stirring property. In addition, the preparation of the composition is preferably performed in a closed system to prevent volatilization. The composition is preferably prepared in an atmosphere of dried air or nitrogen gas (preferably nitrogen gas).

In the present invention, it is preferable to filter with a filter for the purpose of removing foreign substances and reducing defects. The filter can be used without any particular limitation as long as it has been conventionally used for filtration and the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6, nylon-6,6), a polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight (Including polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. Within this range, fine foreign matter can be reliably removed. The thickness of the filter is preferably 25.4 mm or more, more preferably 50.8 mm or more. It is also preferable to use a fibrous filter medium. Examples of the filter medium include a polypropylene fiber, a nylon fiber, and a glass fiber. , TPR005, etc.) and SHPX type series (SHPX003, etc.) filter cartridges.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Further, first filters having different hole diameters within the above-described range may be combined. The pore diameter here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Co., Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.) or Kitz Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as that of the above-described first filter can be used. The pore size of the second filter is preferably from 0.2 to 10.0 μm, more preferably from 0.2 to 7.0 μm, even more preferably from 0.3 to 6.0 μm.

In filling the composition into the container, the filling rate of the composition into the container is preferably 70 to 100% for the purpose of avoiding contact between the composition and moisture in the container. It is also preferable that the space in the storage container is made of dry air or dry nitrogen.
The container for containing the composition is not particularly limited, and a known container can be used. For example, a container made of various resins such as polypropylene can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into the raw materials and the composition, a multilayer bottle in which the inner wall of the container is formed of six types and six layers of resin or a bottle in which six types of resins are formed in a seven-layer structure are used. It is also preferred to use. Examples of such a container include the container described in JP-A-2015-123351.
When the composition contains a resin containing a repeating unit having a crosslinkable group, the composition is preferably stored at a low temperature (preferably 25 ° C. or lower, more preferably 0 ° C. or lower). According to this aspect, the composition can be prevented from thickening.

<Solid-state imaging device, camera module>
The solid-state imaging device of the present invention includes the near-infrared cut filter of the present invention. Further, the camera module of the present invention includes the near-infrared cut filter of the present invention.

FIG. 1 is a schematic cross-sectional view illustrating a configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention.
A camera module 10 shown in FIG. 1 includes a solid-state imaging device 11, a flattening layer 12 provided on the main surface side (light receiving side) of the solid-state imaging device, a near-infrared cut filter 13, and a near-infrared cut filter. A lens holder 15 which is disposed and has an imaging lens 14 in an internal space. The camera module 10 is configured such that the incident light hν from the outside sequentially passes through the imaging lens 14, the near-infrared cut filter 13, and the flattening layer 12, and then reaches the imaging element unit of the solid-state imaging element 11.

  The solid-state imaging device 11 includes, for example, a photodiode, an interlayer insulating film (not shown), a base layer (not shown), a color filter 17, an overcoat (not shown), and a micro lens 18 on a main surface of a substrate 16. Are provided in this order. The color filters 17 (red color filter, green color filter, blue color filter) and the micro lens 18 are arranged so as to correspond to the solid-state imaging device 11. Note that, instead of providing the near-infrared cut filter 13 on the surface of the flattening layer 12, the near-infrared cut filter 13 is provided on the surface of the microlens 18, between the base layer and the color filter 17, or between the color filter 17 and the overcoat. The form in which the infrared cut filter 13 is provided may be used. For example, the near-infrared cut filter 13 may be provided at a position within 2 mm (more preferably, within 1 mm) from the microlens surface. By providing the near-infrared cut filter 13 at this position, the process of forming the near-infrared cut filter can be simplified. Furthermore, unnecessary incidence of near-infrared rays to the microlens can be sufficiently cut, and infrared ray shielding properties can be further improved.

Since the near-infrared cut filter of the present invention has excellent heat resistance, it can be subjected to a solder reflow process. By manufacturing the camera module by the solder reflow process, it becomes possible to automatically mount electronic component mounting boards, etc., which need to be soldered, and to significantly improve productivity compared to the case where the solder reflow process is not used. Can be improved. In addition, the cost can be reduced because it can be performed automatically. When subjected to the solder reflow process, the near-infrared cut filter is exposed to a temperature of about 250 to 270 ° C., so that the near-infrared cut filter has heat resistance that can withstand the solder reflow process (hereinafter, also referred to as “solder reflow resistance”). ) Is preferable. In the present specification, “having solder reflow resistance” means that the property as a near-infrared cut filter is maintained even after heating at 180 ° C. for 1 minute. More preferably, the property is maintained even after heating at 230 ° C. for 10 minutes. More preferably, the property is maintained even after heating at 250 ° C. for 3 minutes. In the case where solder reflow resistance is not provided, when heated under the above conditions, the near-infrared cut filter may have a reduced infrared shielding property or may have an insufficient function as a film.
The camera module of the present invention may further have an ultraviolet absorbing layer. According to this aspect, the ultraviolet shielding property can be improved. The description of the ultraviolet absorbing layer can be referred to, for example, paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO2015 / 099060, and the contents thereof are incorporated herein.

  2 to 4 are schematic cross-sectional views illustrating an example of a peripheral portion of a near-infrared cut filter in a camera module.

  As shown in FIG. 2, the camera module includes a solid-state imaging device 11, a planarizing layer 12, an ultraviolet / infrared light reflecting film 19, a transparent substrate 20, a near-infrared cut filter 21, and an anti-reflection layer 22. May be provided in this order. The ultraviolet / infrared light reflection film 19 can be referred to, for example, paragraphs 0033 to 0039 of JP2013-68888A and paragraphs 0110 to 0114 of WO2015 / 099906. Incorporated herein. The transparent substrate 20 transmits light having a wavelength in the visible region. For example, paragraphs 0026 to 0032 of JP-A-2013-68688 can be referred to, and the contents thereof are incorporated herein. . The anti-reflection layer 22 has a function of improving transmittance by preventing reflection of light incident on the near-infrared cut filter 21, and having a function of efficiently using incident light. The description in paragraph number 0040 of the gazette can be taken into consideration, and the contents are incorporated herein.

  As shown in FIG. 3, the camera module includes a solid-state imaging device 11, a near-infrared cut filter 21, an anti-reflection layer 22, a flattening layer 12, an anti-reflection layer 22, a transparent substrate 20, an ultraviolet / light An infrared light reflection film 19 may be provided in this order.

  As shown in FIG. 4, the camera module includes a solid-state imaging device 11, a near-infrared cut filter 21, an ultraviolet / infrared light reflection film 19, a planarization layer 12, an antireflection layer 22, and a transparent substrate 20. And the antireflection layer 22 in this order.

<Image display device>
The image display device of the present invention has the near-infrared cut filter of the present invention. The near-infrared cut filter of the present invention can also be used for an image display device such as a liquid crystal display device and an organic electroluminescence (organic EL) display device. For the definition of the display device and details of each display device, see, for example, “Electronic Display Device (by Akio Sasaki, published by the Industrial Research Institute, Inc., 1990)”, “Display Device (by Junsho Ibuki, Heisei Sangyo Co., Ltd.) (Published the first year). Further, the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by the Industrial Research Institute, Inc., 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned “next-generation liquid crystal display technology”.

  The image display device may have a white organic EL element. The white organic EL device preferably has a tandem structure. For a tandem structure of an organic EL device, see JP-A-2003-45676, supervised by Akiyoshi Mikami, "The Forefront of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection", Technical Information Association, 326-328, 2008 and the like. The spectrum of white light emitted from the organic EL element preferably has strong maximum emission peaks in a blue region (430 nm to 485 nm), a green region (530 nm to 580 nm), and a yellow region (580 nm to 620 nm). Those having a maximum emission peak in a red region (650 nm to 700 nm) in addition to these emission peaks are more preferable.

  Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below. Unless otherwise specified, “parts” and “%” are based on mass.

<Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) by the following method.
Equipment: HLC-8220 GPC (Tosoh Corporation)
Detector: RI (Refractive Index) detector Column: Guard column HZ-L, TSK gel Super HZM-M, TSK gel Super HZ4000, TSK gel Super HZ3000, TSK gel Super HZ2000 (Tosoh Corporation) Eluent connected with: tetrahydrofuran (containing stabilizer)
Column temperature: 40 ° C
Injection volume: 10 μL
Analysis time: 26 minutes Flow rate: flow rate 0.35 mL / min (sample pump) 0.20 mL / min (reference pump)
Calibration curve base resin: polystyrene

<Preparation of composition for forming copper complex layer>
(Compositions 1-1 to 1-12, 1-R1)
The materials shown below were mixed in the amounts shown below to prepare the respective compositions. In addition, composition 1-1, 1-2, 1-3, 1-6, 1-7, 1-8, 1-9, 1-10 are the following B-1 and B-2 as a copper complex. Were mixed and used at a ratio of B-1 / B-2 = 1/3 by mass. Composition 1-11 was used as a copper complex by mixing the following B-1 and B-2a at a mass ratio of B-1 / B-2a = 1/3. Composition 1-12 was used as a copper complex by mixing the following B-1 and B-2b at a mass ratio of B-1 / B-2b = 1/3. Composition 1-6 used cyclopentanone and butyl acetate as solvents in a ratio of cyclopentanone / butyl acetate = 2/1 by mass.

Ａ−４：特開２０１１−１０００８４号公報の段落番号０１２７〜０１３０に記載の方法に従って合成した樹脂を用いた。すなわち、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１^２，５．１^７，１０］ドデカ−３−エン１００質量部と、１−ヘキセン１８質量部と、トルエン３００質量部とを、窒素置換した反応容器に仕込み、この溶液を８０℃に加熱した。次いで、反応容器内の溶液に、重合触媒として、トリエチルアルミニウムのトルエン溶液（０．６ｍｏｌ／リットル）０．２質量部と、メタノール変性の六塩化タングステンのトルエン溶液（濃度０．０２５ｍｏｌ／リットル）０．９質量部とを添加し、この溶液を８０℃で３時間加熱撹拌することにより開環重合反応させて開環重合体溶液を得た。この重合反応における重合転化率は９７％であった。このようにして得られた開環重合体溶液１，０００質量部をオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ_６Ｈ_５）_３］_３を０．１２質量部添加し、水素ガス圧１００ｋｇ／ｃｍ^２、反応温度１６５℃の条件下で、３時間加熱撹拌して水素添加反応を行った。得られた反応溶液（水素添加重合体溶液）を冷却した後、水素ガスを放圧した。この反応溶液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添加重合体（樹脂Ａ−４）を得た。樹脂Ａ−４の分子量は、数平均分子量（Ｍｎ）が３２，０００、重量平均分子量（Ｍｗ）が１３７，０００であり、ガラス転移温度（Ｔｇ）は１６５℃であった。
Ａ−５：特開２０１４-２０３０４４号公報の段落００７９〜００８８に記載の方法に従って合成したゾルゲル硬化物を用いた。すなわち、フェニルトリエトキシシランとテトラエトキシシランの配合比を５０：５０に設定したものをゾルゲル膜の原料とした。溶媒はいずれもシクロペンタノンを用いた。酸性触媒としては１モル／リットルの塩酸を用い、Ｓｉ１モルに対し６モルの水を投与し、室温にて４時間程度撹拌してゾルゲル硬化物を得た。The raw materials described in the above table are as follows.
(resin)
A-1: Resin having the following structure (Mw = 15000, the numerical value added to the repeating unit is a mass ratio)
A-2: Resin having the following structure (Mw = 14500, the numerical value added to the repeating unit is a mass ratio)
A-3: Resin having the following structure (Mw = 14000, the numerical value added to the repeating unit is a mass ratio)

A-4: A resin synthesized according to the method described in paragraphs 0127 to 0130 of JP-A-2011-100084 was used. That is, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] Dodeca-3-ene (100 parts by mass), 1-hexene (18 parts by mass), and toluene (300 parts by mass) were charged into a nitrogen-purged reaction vessel, and the solution was heated to 80 ° C. Then, 0.2 parts by mass of a toluene solution of triethylaluminum (0.6 mol / l) and a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol / l) were added to the solution in the reaction vessel as a polymerization catalyst. Then, the solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opened polymer solution. The polymerization conversion in this polymerization reaction was 97%. 1,000 parts by mass of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 mass% of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the mixture was heated and stirred for 3 hours under a condition of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. to perform a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), the pressure of hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and collect a coagulated product, which was dried to obtain a hydrogenated polymer (resin A-4). Regarding the molecular weight of the resin A-4, the number average molecular weight (Mn) was 32,000, the weight average molecular weight (Mw) was 137,000, and the glass transition temperature (Tg) was 165 ° C.
A-5: A sol-gel cured product synthesized according to the method described in paragraphs 0079 to 0088 of JP-A-2014-203044 was used. That is, a material in which the mixing ratio of phenyltriethoxysilane and tetraethoxysilane was set to 50:50 was used as a raw material for the sol-gel film. All solvents used cyclopentanone. 1 mol / liter hydrochloric acid was used as an acidic catalyst, and 6 mol of water was administered to 1 mol of Si, followed by stirring at room temperature for about 4 hours to obtain a cured sol-gel.

Ｂ−３：下記化合物を配位子として有する銅錯体

Ｂ−２ａ：塩化銅（ＩＩ）一水和物とトリス［２−（ジメチルアミノ）エチル］アミンを１：０．９５のモル比率で反応させて銅錯体Ｂ−２ａを合成した。
Ｂ−２ｂ：銅錯体Ｂ−２について、メタノール／水＝１／２（体積比）を用いて晶析して銅錯体Ｂ−２ｂを得た。銅錯体Ｂ−２ｂのカリウム含有量を誘導結合プラズマ発光分光分析法（ＩＣＰ−ＯＥＳ、パーキンエルマー製 Ｏｐｔｉｍａ７３００ＤＶ）により測定したところ、３質量ｐｐｍであった。
Ｂ’−１：下記化合物を配位子として有する銅錯体

(Copper complex)
B-1, B-2, B-4: the following compounds

B-3: Copper complex having the following compound as a ligand

B-2a: A copper complex B-2a was synthesized by reacting copper (II) chloride monohydrate and tris [2- (dimethylamino) ethyl] amine at a molar ratio of 1: 0.95.
B-2b: The copper complex B-2 was crystallized using methanol / water = 1/2 (volume ratio) to obtain a copper complex B-2b. The potassium content of the copper complex B-2b measured by inductively coupled plasma emission spectroscopy (ICP-OES, Optima7300DV manufactured by PerkinElmer) was 3 ppm by mass.
B'-1: Copper complex having the following compound as a ligand

(Crosslinkable compound)
M-1: The following compound M-2: The following compound (manufactured by Daicel Corporation, EHPE 3150)
M-3: The following compound (KBM-3066, manufactured by Shin-Etsu Silicone Co., Ltd.)

(UV absorber)
E-1: The following compound (manufactured by BASF, TINUVIN 928, a compound having a maximum absorption wavelength in a wavelength range of 280 to 425 nm)
E-2: The following compound (TISFIN 400 manufactured by BASF, a compound having a maximum absorption wavelength in a wavelength range of 280 to 425 nm)

(solvent)
Cyclopentanone Butyl acetate (catalyst)
Al (acac) 3: Tris (2,4-pentanedionato) aluminum (III) (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Preparation of composition for forming ultraviolet cut layer>
(Composition 2-1)
11.01 parts by mass of resin A-1, 2.38 parts by mass of ultraviolet absorber E-1 (the compound described above), and 1.72 of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a crosslinkable compound. Parts by mass, 1.89 parts by mass of IRGACURE-OXE-01 (manufactured by BASF) as a photopolymerization initiator, and 83.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were mixed and stirred. Thereafter, the mixture was filtered with a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.5 μm to prepare Composition 2-1.
(Composition 2-2)
Composition 2-2 was prepared in the same manner as composition 2-1 except that in composition 2-1 ultraviolet absorber E-2 (the compound described above) was used instead of ultraviolet absorber E-1. .

<Preparation of near infrared cut filter>
(Examples 1, 3, 8 to 16, Comparative Example 2)
A near-infrared cut filter was prepared using the composition for forming a copper complex layer (compositions 1-1, 1-2, 1-4 to 1-12, and 1-R1). That is, each composition for forming a copper complex layer is applied on a glass wafer using a spin coater so that the film thickness after drying becomes 100 μm, and heat-treated using a hot plate at 150 ° C. for 1.5 hours. Then, a near-infrared cut filter was manufactured.

(Example 2)
The composition 2-1 (composition for forming an ultraviolet ray cut layer) is applied on a glass wafer by using a spin coater (manufactured by Mikasa Corporation) to form a coating film, and pre-heated at 100 ° C. for 120 seconds ( After performing (prebaking), the entire surface was exposed at 1000 mJ / cm 2 using an i-line stepper. Next, post-baking was performed at 220 ° C. for 300 seconds to produce an ultraviolet cut layer having a thickness of 1.0 μm.
The above composition 1-3 (composition for forming a copper complex layer) was applied on the obtained ultraviolet cut layer using a spin coater so that the film thickness after drying was 100 μm, and using a hot plate at 150 ° C. A heat treatment was performed for 1.5 hours to form a copper complex layer, thereby producing a near-infrared cut filter.

(Example 4)
The above composition 1-3 (a composition for forming a copper complex layer) is applied on a glass wafer using a spin coater so that the film thickness after drying becomes 100 μm, and is applied using a hot plate at 150 ° C. for 1.5 hours. The heat treatment was performed for a time to form a copper complex layer. On the obtained copper complex layer, a SiO ₂ film as a low-refractive-index material layer and a TiO ₂ film as a high-refractive-index material layer are alternately laminated by vapor deposition to form a 33-layer dielectric multilayer film (ultraviolet reflective film, half value). (Wavelength: 405 nm) to produce a near-infrared cut filter.

(Example 5)
The above composition 1-3 (composition for forming a copper complex layer) is applied on a glass wafer using a spin coater so that the film thickness after drying becomes 100 μm, and is applied using a hot plate at 150 ° C. for 1.5 hours. Heat treatment was performed for a time to form a copper complex layer. On the copper complex layer and the glass wafer on the back surface, a SiO ₂ film as a low-refractive-index material layer and a TiO ₂ film as a high-refractive-index material layer are alternately laminated by vapor deposition, and 17 layers on one side (both sides). A 34-layer) dielectric multilayer film (ultraviolet reflective film, half-value wavelength 405 nm) was formed to produce a near-infrared cut filter.

(Example 6)
The above composition 1-1 (composition for forming a copper complex layer) is applied on a glass wafer using a spin coater so that the film thickness after drying becomes 100 μm, and is applied using a hot plate at 150 ° C. for 1.5 hours. Heat treatment was performed for a time to form a copper complex layer. A SiO ₂ film as a low refractive index material layer and a TiO ₂ film as a high refractive index material layer are alternately laminated on the copper complex layer by vapor deposition, and a 33-layer dielectric multilayer film (ultraviolet reflective film, half-value wavelength 405 nm) Was formed to produce a near infrared cut filter.

(Example 7)
On the copper complex layer of the near-infrared cut filter obtained in Example 2, a SiO ₂ film as a low refractive index material layer and a TiO ₂ film as a high refractive index material layer are alternately laminated by vapor deposition, and a 17-layer dielectric film is formed. A near-infrared cut filter was manufactured by forming a body multilayer film (ultraviolet reflection film, half-wavelength 410 nm).

(Comparative Example 1)
A SiO ₂ film as a low-refractive-index material layer and a TiO ₂ film as a high-refractive-index material layer are alternately laminated on a glass substrate by vapor deposition. 685 nm) to produce a near infrared cut filter.

<Evaluation of spectral characteristics>
The transmittance of the near infrared cut filter obtained above was measured using U-4100 (manufactured by Hitachi High-Technologies Corporation). Specifically, the measurement wavelength range was 400 to 1300 nm, and the transmittance was measured every 5 nm. The average transmittance was calculated by dividing the sum of the transmittance for each 5 nm by the wavelength range. The reflectance was measured using U-4100 (manufactured by Hitachi High-Technologies Corporation). The measurement was performed by setting the surface normal direction of the near-infrared cut filter to 0 ° and setting the incident angle to 5 °.

T ₃₅₀ in the above table is the transmittance at a wavelength of 350 nm measured from the vertical direction of the near-infrared cut filter, and T ₄₅₀ is the transmittance at a wavelength of 450 nm measured from the vertical direction of the near-infrared cut filter. , T ₅₅₀ is the transmittance at a wavelength of 550 nm when measured from the vertical direction of the near infrared cut filter, and T ₇₀₀ is the transmittance at a wavelength of 700 nm when measured from the vertical direction of the near infrared cut filter. Λ (U70) is the wavelength (nm) at the longest wavelength side where the transmittance when measured from the vertical direction of the near-infrared cut filter is 70% in the wavelength range of 350 to 450 nm. Λ (U30) is the shortest wavelength side wavelength (nm) at which the transmittance when measured from the vertical direction of the near-infrared cut filter is 30%.

The near-infrared cut filter of the example had good visible transparency and infrared shielding properties. In addition, it was a near-infrared cut filter having a low near-infrared reflectance and a wide viewing angle. In Comparative Example 1, the near-infrared reflectance was high, and the viewing angle was narrower than in the Examples.
Each near-infrared cut filter was incorporated into a camera module, and an image was taken. Observing the obtained image and observing the presence or absence of purple fringe (purple outline blur), when the near-infrared cut filter of the example was used, the purple fringe could be more effectively suppressed than in Comparative Examples 1 and 2. Was.
Further, even when the composition 2-2 is used instead of the composition 2-1 in the near-infrared cut filters of Examples 2 and 7, the same effects as those of the near-infrared cut filters of Examples 2 and 7 are obtained. was gotten.
Further, in the composition 2-1, similar effects were obtained even when the resin A-1 was changed to the resin A-2 or the resin A-3.

Reference Signs List 10 camera module, 11 solid-state imaging device, 12 flattening layer, 13 near-infrared cut filter, 14 imaging lens, 15 lens holder, 16 silicon substrate, 17 color filter, 18 micro lens, 19 ultraviolet / infrared light reflection film, 20 Transparent base material, 21 near-infrared cut filter, 22 antireflection layer

Claims (15)

A near-infrared ray which is a complex of copper and a compound having a coordination site for copper, the layer containing a copper complex having a maximum absorption wavelength in a wavelength range of 700 to 1200 nm, and a layer containing an ultraviolet absorber. A cut filter,
A transmittance T _{390 at} a wavelength of 390 nm measured from a vertical direction of the near-infrared cut filter is 10% or less;
A transmittance T _{450 at} a wavelength of 450 nm as measured from the vertical direction of the near-infrared cut filter is 85% or more;
The transmittance _{T 350} at a wavelength of 350nm as measured from the vertical direction near infrared cut filter, which is the ratio between the transmittance _{T 450} at a wavelength of 450nm as measured from the vertical direction of the near infrared cut filter _{T 350} / T ₄₅₀ is 0 to 0.3,
T ₃₉₀ / which is the ratio of the transmittance T _{390 at} a wavelength of 390 nm measured from the vertical direction of the near infrared cut filter to the transmittance T _{450 at} a wavelength of 450 nm measured from the vertical direction of the near infrared cut filter. T ₄₅₀ is 0 to 0.3,
T ₇₀₀ / which is the ratio of the transmittance T _{700 at} a wavelength of 700 nm measured from the vertical direction of the near-infrared cut filter to the transmittance T _{550 at} a wavelength of 550 nm measured from the vertical direction of the near-infrared cut filter. T ₅₅₀ is 0 to 0.2,
A near-infrared cut filter in which the average value of the reflectance of the near-infrared cut filter is 80% or less in a wavelength range of 800 to 1000 nm. A near-infrared cut filter having a layer containing copper and a compound having a coordination site for copper, a copper complex having a maximum absorption wavelength in a wavelength range of 700 to 1200 nm, and a UV absorber. ,
A transmittance T _{390 at} a wavelength of 390 nm measured from a vertical direction of the near-infrared cut filter is 10% or less;
A transmittance T _{450 at} a wavelength of 450 nm as measured from the vertical direction of the near-infrared cut filter is 85% or more;
The transmittance _{T 350} at a wavelength of 350nm as measured from the vertical direction near infrared cut filter, which is the ratio between the transmittance _{T 450} at a wavelength of 450nm as measured from the vertical direction of the near infrared cut filter _{T 350} / T ₄₅₀ is 0 to 0.3,
T ₃₉₀ / which is the ratio of the transmittance T _{390 at} a wavelength of 390 nm measured from the vertical direction of the near infrared cut filter to the transmittance T _{450 at} a wavelength of 450 nm measured from the vertical direction of the near infrared cut filter. T ₄₅₀ is 0 to 0.3,
T ₇₀₀ / which is the ratio of the transmittance T _{700 at} a wavelength of 700 nm measured from the vertical direction of the near-infrared cut filter to the transmittance T _{550 at} a wavelength of 550 nm measured from the vertical direction of the near-infrared cut filter. T ₅₅₀ is 0 to 0.2,
A near-infrared cut filter in which the average value of the reflectance of the near-infrared cut filter is 80% or less in a wavelength range of 800 to 1000 nm. A layer containing the copper and a compound having a coordination site for copper, the copper complex having a maximum absorption wavelength in a wavelength range of 700 to 1200 nm, and a layer containing an ultraviolet absorber, the layer containing 100 mass of the copper complex 3. The near-infrared cut filter according to claim 2, wherein the ultraviolet absorber is contained in an amount of 0.1 to 20 parts by mass with respect to parts. The complex of copper and a compound having a coordination site for copper, the copper complex having a maximum absorption wavelength in a wavelength range of 700 to 1200 nm, and the ultraviolet absorber contained in a layer containing the ultraviolet absorber. The near-infrared cut filter according to claim 2, wherein the amount is 0.1 to 50% by mass. The near-infrared cut filter according to any one of claims 1 to 4, wherein the copper complex has a 5-membered ring and / or a 6-membered ring formed of copper and a compound having a coordination site for copper. . The near-infrared cut filter according to any one of claims 1 to 5, wherein the ultraviolet absorber is at least one selected from a benzotriazole compound and a hydroxyphenyltriazine compound. The near-infrared cut filter according to any one of claims 1 to 6 , wherein an average value of transmittance when measured from a vertical direction of the near-infrared cut filter is 85% or more in a wavelength range of 430 to 580 nm. . In the wavelength range of 350 to 450 nm, the wavelength on the longest wavelength side where the transmittance when measured from the vertical direction of the near-infrared cut filter is 70%, and the transmission when measured from the vertical direction of the near-infrared cut filter The near-infrared cut filter according to any one of claims 1 to 7 , wherein the absolute value of the difference from the shortest wavelength side at which the ratio is 30% is 25 nm or less. The near-infrared cut filter according to any one of claims 1 to 8 , wherein an average value of transmittance when measured from a vertical direction of the near-infrared cut filter is 20% or less in a wavelength range of 800 to 1000 nm. . The near-infrared cut filter according to any one of claims 1 to 9 , wherein the ultraviolet absorber is a compound having a maximum absorption wavelength in a wavelength range of 280 to 425 nm. The near-infrared cut filter according to any one of claims 1 to 10 , further comprising a dielectric multilayer film . The near-infrared cut filter according to any one of claims 1 to 11 , wherein the copper complex is a copper complex having, as a ligand, a compound having four or five coordination sites with respect to copper. Solid-state imaging device having a near infrared cut filter according to any one of claims 1 to 12. A camera module comprising the near-infrared cut filter according to any one of claims 1 to 12 . An image display device having a near infrared cut filter according to any one of claims 1 to 12.

Images