JP2020173294A - Optical filter and application thereof - Google Patents

Abstract

To provide an optical filter that can contain near-infrared absorbers with a wide range of structures in a high concentration in a thin resin layer, has low haze, and has good and uniform optical characteristics, can meet the demand for low profile of a solid-state image sensor, an ambient light sensor device, or a TOF range image device, and can be manufactured by a simple method.SOLUTION: An optical filter of the present invention includes a laminate having a substrate and a resin layer made of a thermoplastic resin provided on at least one surface of the substrate. A solubility parameter value of the resin constituting the resin layer is 9.0 (cal/cm3)1/2 or more. The resin layer contains two or more near-infrared absorbers selected from a group consisting of squarylium compounds, cyanine compounds, and phthalocyanine compounds. The ratio of the content (parts by mass) of each near-infrared absorber to 100 parts by mass of the resin and the film thickness (μm) of the resin layer is in a range of 0.005 to 1.0.SELECTED DRAWING: None

Description

The present invention relates to an optical filter and its use. More specifically, an optical filter that can be thinned, has low haze, and has good and uniform optical characteristics, a solid-state image sensor and a solid-state image sensor using the optical filter, an ambient light sensor element, and an ambient light sensor device. , TOF (Time of Flat) distance image sensor element and TOF distance image sensor.

In recent years, information terminal devices such as smartphones and tablet terminals have been rapidly thinned, and there is a demand for lowering the height of camera modules and ambient light sensor modules incorporated in these devices. In order to reduce the height of these modules, it is required to reduce the thickness of optical filters such as near-infrared cut filters (hereinafter, also referred to as "IRCF") installed in the modules.

As the IRCF, conventionally, a hybrid glass IRCF in which a fluoride-based glass or an absorbent glass obtained by adding copper oxide or the like to a phosphate-based glass and a dielectric multilayer film is attached is well known. However, such a hybrid glass IRCF is extremely brittle because it contains copper oxide in the glass, and it is difficult to make a thin film. Therefore, it is sufficient for miniaturization and reduction of height of an imaging device, which has been strongly demanded by the market in recent years. There was a problem that it was not possible to respond to.

On the other hand, a resin substrate type IRCF that can be thinned by attaching a dielectric multilayer film to a resin substrate containing a light absorber that absorbs near-infrared light in the resin has been developed. Such a resin substrate type IRCF is highly evaluated for its features such as thin film, high toughness, and excellent optical characteristics, and is installed in many camera modules, ambient light sensor modules, and the like.

On the other hand, in a resin substrate type IRCF in which a light absorber is contained in a resin, a mixed solution in which the light absorber and the resin are dissolved in a solvent is generally cast or applied onto a metal belt or a film substrate. After drying, the film is peeled off from the base material to produce the film. In this case, it is necessary to dry the film at a high temperature in order to keep the amount of solvent remaining in the film low. However, since the light absorber may decompose and deteriorate in the drying process at a high temperature, it is necessary to select a light absorber having high heat resistance, and the types of light absorbers applicable to IRCF applications are limited. There was a problem. In addition, in order to industrially produce the high-quality film required for IRCF, a long drying furnace is required to volatilize the solvent at low temperature, and expensive manufacturing equipment and advanced manufacturing technology are required. There was a challenge.

In response to the above problem, an IRCF having a structure in which a resin layer containing a near-infrared absorber and a dielectric multilayer film are laminated on a white plate glass having a higher toughness than an absorbent glass has been proposed (for example, a patent). Document 1). The laminate having this structure can be an IRCF having toughness, thin wall thickness, and good optical characteristics by laminating a resin layer having high toughness on a brittle thin film glass. Further, as an IRCF having a similar form, an IRCF having a structure in which a resin layer containing a near-infrared absorber and a dielectric multilayer film are laminated on a transparent resin base material has been proposed (for example, Patent Document 2).

These forms of IRCF are produced by applying a resin solution containing a near-infrared absorber onto glass or a resin base material, but since the strength of IRCF can be borne by the base material, near-infrared ray absorption The thickness of the resin layer containing the agent can be set thin. As a result, the solvent easily volatilizes from the resin layer, and the drying temperature can be set low, so that there is an advantage that the selection criteria of the absorbent from the viewpoint of heat resistance can be relaxed. Further, since IRCF can be produced on a commercially available glass or resin substrate by using a simple coating device, there is an advantage that the production cost can be reduced.

In the IRCF of the above form, in order to thin the resin layer containing the near-infrared absorber, it is necessary to contain a high-concentration near-infrared absorber in the thin resin layer. However, near-infrared absorbers have low solubility (compatibility) in solvents and resins, and many compounds easily aggregate. Therefore, when a high-concentration near-infrared absorber is contained in a thin resin layer, the resin layer There are problems such as the resin layer becoming cloudy due to insufficient compatibility with and the optical properties such as transparency and haze deteriorate, and the optical properties change due to the aggregation of the near-infrared absorber. ..

In this way, when the near-infrared absorber is not uniformly compatible with the resin layer, the near-infrared absorber is unevenly dispersed in the resin layer, so that the concentration of the near-infrared absorber in the resin layer and the concentration of the near-infrared absorber in the resin layer Problems such as large variations in film thickness and high haze of the optical filter may occur. When such an optical filter is used, the color unevenness of the camera image quality becomes large, and the flare phenomenon (a phenomenon in which the surrounding image looks whitish when a strong light source such as a fluorescent lamp is used when using an optical filter with a high haze). In some cases, image defects such as the occurrence of the phenomenon may occur, or malfunction of the ambient light sensor may occur.

In order to avoid these problems, it is necessary to select a near-infrared absorber having high compatibility with the resin layer or limit the content of the near-infrared absorber to a low concentration, and it is necessary to use near-infrared rays. There was a problem that the type and structure of the absorbent were greatly limited. Further, depending on the resin type, it may be necessary to select a solvent having a high boiling point in order to dissolve both the near-infrared absorber and the resin well, and it is difficult to remove the solvent in the drying step during film production. Therefore, the amount of residual solvent in the resin layer may increase. When the dielectric multilayer film is processed using a film having a large amount of residual solvent, the amount of outgas during processing increases, which causes deterioration of the characteristics of the dielectric multilayer film (deterioration of haze value, deterioration of optical characteristics). There was a case.

Japanese Unexamined Patent Publication No. 2013-05593 Japanese Unexamined Patent Publication No. 2013-210585

An object of the present invention is that a thin resin layer can contain a near-infrared absorber having a wide range of structures at a high concentration, has low haze, has good and uniform optical characteristics, and has a solid-state image sensor and an ambient light sensor. It is an object of the present invention to provide an optical filter that can meet the demand for lowering the height of an apparatus or a TOF distance imaging apparatus and can be manufactured by a simple method.

The present inventors have conducted diligent studies to solve the above problems. As a result, a thermoplastic resin having a solubility parameter in a specific range is used as the resin constituting the resin layer, and the ratio of the amount of the near infrared absorber added to the resin layer and the film thickness of the resin layer is set in the specific range. By doing so, good compatibility of the near-infrared absorber with the resin layer is ensured, there is no problem of white turbidity of the resin layer, low haze, and thinning is possible while maintaining good and uniform optical characteristics. We have found that an optical filter can be obtained and have completed the present invention.

An example of an embodiment of the present invention is shown below.
[1] An optical filter including a laminate (X) having a substrate and a resin layer made of a thermoplastic resin provided on at least one surface of the substrate.
The solubility parameter value of the resin constituting the resin layer is 9.0 (cal / cm ³ ) ^1/2 or more.
The resin layer contains two or more kinds of near-infrared absorbers (A) selected from the group consisting of squarylium compounds, cyanine compounds and phthalocyanine compounds.
The ratio (content / film thickness) of the content (parts by mass) of each near-infrared absorber (A) to 100 parts by mass of the resin and the film thickness (μm) of the resin layer is 0.005 to 1. An optical filter characterized by being in the range of 0.
[2] The item is characterized in that the substrate is a glass substrate or a resin substrate having a thickness of 300 μm or less, and the thickness of the resin layer containing the near-infrared absorber (A) is 20 μm or less [1]. ] The optical filter described in.
[3] The optical filter according to Item [1] or [2], wherein the haze value of the laminated body (X) is 0.20% or less.
[4] The optical filter according to any one of Items [1] to [3], wherein the laminated body (X) has a dielectric multilayer film on at least one surface.
[5] The optical filter according to any one of Items [1] to [3], wherein the in-plane variation in the thickness of the resin layer or the laminated body (X) is within 10%.
[6] A solid-state imaging device comprising the optical filter according to any one of items [1] to [5].
[7] A solid-state image pickup apparatus comprising the optical filter according to any one of items [1] to [5].
[8] An ambient light sensor element comprising the optical filter according to any one of items [1] to [5].
[9] An ambient light sensor device comprising the optical filter according to any one of items [1] to [5].
[10] A TOF distance image sensor element comprising the optical filter according to any one of items [1] to [5].
[11] A TOF distance imaging apparatus comprising the optical filter according to any one of items [1] to [5].

According to the present invention, a near-infrared absorber having a wide range of structures can be contained in a thin resin layer at a high concentration, has low haze, has good and uniform optical characteristics, and is a simple device and method. An optical filter that can be manufactured can be provided. Further, by using the optical filter of the present invention, it is possible to meet the demand for lowering the height of the camera module, the ambient light sensor module, the TOF distance image sensor module, the solid-state image sensor, the optical sensor device, and the TOF distance image device. .. Further, by using the optical filter of the present invention, a camera module and a solid that can obtain camera image quality with improved flare phenomenon, which has been a problem in IRCF having a structure in which a near-infrared absorber-containing resin layer is laminated on a transparent base material. An image sensor can be obtained.

It is a schematic diagram which shows the structural example of the laminated body (X) in the optical filter of this invention. It is a schematic diagram which shows the structural example of the laminated body (Y) in the optical filter of this invention. It is sectional drawing which shows an example of the camera module of this invention. It is a schematic diagram which shows the structural example of the ambient light sensor of this invention. It is a schematic diagram which shows the structural example of the ambient light sensor of this invention. It is a schematic diagram which shows the method of measuring the transmittance of the optical filter of this invention.

Hereinafter, the present invention will be specifically described.
[Optical filter]
The optical filter of the present invention is an optical filter including a laminate (X) having a substrate and a resin layer provided on at least one surface of the substrate, and the solubility parameter value of the resin constituting the resin layer is 9. It is 0.0 (cal / cm ³ ) ^1/2 or more, and the resin layer contains two or more kinds of near-infrared absorbers (A) selected from the group consisting of squarylium-based compounds, cyanine-based compounds and phthalocyanine-based compounds. The ratio (content / film thickness) of the content (parts by mass) of each near-infrared absorber (A) to 100 parts by mass of the resin and the film thickness (μm) of the resin layer is 0.005 to 1 in each case. It is characterized in that it is within the range of 0.0.

<Board>
As the substrate, a glass substrate or a resin substrate can be used. The thickness of the glass substrate and the resin substrate is preferably 300 μm or less, more preferably 50 to 210 μm, and further preferably 100 to 210 μm. In the case of a glass substrate, it becomes very brittle when it becomes thin, and there are problems such as cracking and cracking during handling. Therefore, it is preferable to use a glass substrate having a thickness of 210 μm or more. The resin substrate is superior in toughness to a glass substrate and is advantageous for thinning, and the thickness is preferably 30 to 300 μm, more preferably 50 to 200 μm, and further preferably 70 to 100 μm. If the thickness of the resin substrate is too thin, there is a problem that the warp becomes large when the dielectric multilayer film is laminated, and it is preferable to use a resin substrate having a film thickness of 30 μm or more.

The glass substrate used in the present invention is not particularly limited, but a non-absorbent glass substrate (white plate glass) and an absorbent glass substrate containing CuO as an absorbent can be used. The glass substrate having no absorption is not particularly limited as long as it contains a silicate as a main component, and examples thereof include a quartz glass substrate having a crystal structure. In addition, borosilicate glass substrate, soda glass substrate, colored glass substrate and the like can be used, but in particular, glass substrates such as non-alkali glass substrate and low α-ray glass substrate have little influence on the sensor element. preferable.

As the absorbent glass substrate, CuO-containing futurate glass or CuO-containing phosphate glass (hereinafter, these are collectively referred to as "CuO-containing glass") can be used. By using CuO-containing glass, it is possible to obtain an optical filter having a high shielding property against near infrared rays. It should be noted that the phosphate glass also includes a silicate glass in which a part of the glass skeleton is composed of SiO ₂ . Examples of the CuO-containing glass include those having the following composition.

(I) P ₂ O ₅ 46 to 70%, AlF ₃ 0.2 to 20%, LiF + NaF + KF 0 to 25%, MgF ₂ + CaF + SrF ₂ + BaF ₂ + PbF ₂ 1 to 50%, but F 0.5 to 32%, A glass containing 0.5 to 7 parts by mass of CuO by external division with respect to 100 parts by mass of the base glass containing 26 to 54% of O.

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

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

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

(V) In cation% display. P ⁵⁺ 23-41%, Al ³⁺ 4-16%, Li ⁺ 11-40%, Na ⁺ 3-13%, R ²⁺ (Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn content of ²⁺⁾ 12-53%, and Cu ²⁺ comprises 2.6 to 4.7%, further anionic% in ^F - 25 to 48% and O ^2-fifty-two to seventy-five% glass containing.

(Vi) In terms of mass%, P ₂ O ₅ 70 to 85%, Al ₂ O ₃ 8 to 17%, B ₂ O ₃ 1 to 10%, Li ₂ O 0 to 3%, Na ₂ O 0 to 5% , K ₂ O 0 to 5%, however, CuO is 0.1 to 100 parts of the base glass consisting of Li ₂ O + Na ₂ O + K ₂ O 0.1 to 5% and SiO _{20 to} 3%. Glass containing 5 parts by mass.

Commercially available products include, for example, (i) NF50-E, NF50-EX (manufactured by Asahi Glass Co., Ltd.), (ii) BG-60, BG-61 (manufactured by SCHOTT), (v) CD5000 (manufactured by HOYA), etc. Can be mentioned.

Further, the CuO-containing glass may further contain a metal oxide. When one or more of, for example, Fe ₂ O ₃ , MoO ₃ , WO ₃ , CeO ₂ , Sb ₂ O ₃ , V ₂ O _5, etc. are contained as the metal oxide, the CuO-containing glass has an ultraviolet absorbing property. .. Regarding the content of the metal oxide, at least one selected from the group consisting of Fe ₂ O ₃ , MoO ₃ , WO ₃ and CeO _{2 with} respect to 100 parts by mass of the CuO-containing glass is selected as Fe ₂ O _30. .6 to 5 parts by mass, MoO ₃ 0.5 to 5 parts by mass, WO _{3 to} 1 to 6 parts by mass, CeO ₂ 2.5 to 6 parts by mass, or Fe ₂ O ₃ and Sb ₂ O ₃ Fe ₂ O ₃ 0.6 to 5 parts by mass + Sb ₂ O ₃ 0.1 to 5 parts by mass, or V ₂ O ₅ and CeO ₂ 2 types V ₂ O ₅ 0.01 to 0.5 parts by mass + CeO It is preferably _{2 to} 6 parts by mass.

As the glass substrate, it is preferable to use a glass substrate having no absorption. In the case of fluoric acid-based crow or phosphoric acid-based glass containing CuO, it is necessary to increase the CuO content in order to obtain the desired optical characteristics when the thickness of the glass substrate is reduced, but the toughness increases as the CuO content increases. There is a problem that it is significantly reduced, and even a slight stimulus may cause cracking and chipping. Further, the CuO-containing borosilicate glass has low adhesion to the resin layer laminated on the glass substrate, and it is necessary to provide a special adhesion layer between the borosilicate glass and the resin layer, which causes a problem of increasing cost. There is a point.

Further, when the glass substrate containing CuO is used as the base material of the optical filter (for example, IRCF) of the present invention, the absorption of the base material by CuO and the absorption of the near infrared ray absorber added to the resin layer overlap. Therefore, the absorption of the red region of the base material becomes larger than that of the normal IRCF, the transmittance of the red region of the IRCF decreases, and the RGB balance of the camera image may deteriorate.

The resin substrate used in the present invention is not particularly limited as long as it does not contain a dye, and is, for example, an acrylic resin, a polycarbonate resin, a polyester resin, an aromatic polyester (polyarylate) resin, a cyclic polyolefin resin, or an aromatic polyether. System resin, polysulfone resin (PSF), polyether sulfone resin (PES), polyparaphenylene resin (PPP), polyimide resin (PPI), polyamideimide resin (PAI), transparent polyamide (aramid) resin, polyethylene naphthalate ( A resin substrate made of one or more resins selected from PEN), fluorene polyester-based resin, fluorene polycarbonate-based resin, fluorinated aromatic polymer, epoxy resin, and polyvinyl butyral-based resin can be used.

Examples of the commercially available resin substrate and the resin for the resin substrate include the following commercially available products. Examples of commercially available cyclic (poly) olefin resins include Arton manufactured by JSR Corporation, Zeonex and Zeonoa manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Co., Ltd. Can be done. Examples of commercially available products of the polyether sulfone-based resin include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of the aromatic polyester-based resin film include Unitika's unifier. Examples of commercially available polycarbonate-based resins include Pure Ace manufactured by Teijin Chemicals Ltd. Examples of commercially available fluorene polycarbonate-based resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available fluorene polyester-based resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include Acryviewer manufactured by Nippon Shokubai Co., Ltd. As the resin substrate, the above-mentioned resin substrate can be used alone, or two or more kinds of resin substrates can be laminated and used.

In the present invention, the resin substrate may contain a dye, but it is preferable to use a resin substrate that does not contain the dye. When a dye is contained in both the resin substrate and the resin layer, factors related to the optical characteristics of the optical filter (concentration of the dye in the resin substrate and the resin layer and the thickness of each layer) increase, and the optical characteristics can be controlled. It can be difficult. A commercially available resin substrate (film) can be used as the dye-free resin substrate, but when a dye-containing resin substrate is used, it is necessary to manufacture a dedicated resin substrate, which is costly. May cause.

Additives such as antioxidants, fluorescent quenchers, and UV absorbers can be contained in the resin substrate of the present invention as long as the effects of the present invention are not impaired.
The resin substrate of the present invention can be produced by melt molding, melt extrusion molding or solvent cast molding. When manufactured by the melt molding or melt extrusion molding method, a high temperature is required to melt the resin, and the near infrared absorber may be decomposed at the melt molding temperature. Therefore, the near infrared absorber is placed in the resin substrate. It is not preferable to include it.

<Resin layer>
The resin layer is provided on at least one surface of the substrate, and the solubility parameter value (SP value) of the resin constituting the resin layer is 9.0 (cal / cm ³ ) ^1/2 or more.

The solubility parameter (SP value) of the resin can be calculated from the following formula.
SP value (δ) = (Ev / v) ^1/2 = (ΣΔei / ΣΔvi) ^1/2
Ev: Evaporation energy v: Molar volume Δei: Evaporation energy of atoms or atomic groups of each component Δvi: Molar volume of each atom or atomic group The evaporation energy and molar volume of each atom or atomic group used in the calculation of the above formula is R. F. Fedors, Polym. Eng. Sci. , 14, 147 (1974) can be referred to.

Examples of resins having a solubility parameter value of 9.0 (cal / cm ³ ) ^1/2 or more that can be used in the present invention include polar group-containing cyclic (poly) olefin resins, aromatic polyether resins, and polyimide resins. Resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfone resins, polyether sulfone resins, polyparaphenylene resins, polyamideimide resins, Examples thereof include polyethylene naphthalate (PEN) -based resin, polyvinyl butyral-based resin, fluorinated aromatic polymer-based resin, and (modified) acrylic-based resin. As for the ultraviolet curable resin and the thermosetting resin, the near-infrared absorber may be decomposed by radicals generated during curing, and it is preferable to use a thermoplastic resin.

In the present invention, a resin having a solubility parameter value of 9.0 (cal / cm ³ ) ^1/2 or more is used from the viewpoint of compatibility with the near-infrared absorber (A), but the solubility parameter value is 9. If it is less than 0 (cal / cm ³ ) ^1/2 , the compatibility with the near-infrared absorber (A) is insufficient, and the near-infrared absorber (A) having a concentration satisfying the required optical characteristics is added to the resin layer. Then, a problem such as cloudiness of the resin layer occurs. On the other hand, if the solubility parameter value is too large, the water resistance and chemical resistance of the resin itself are lowered, which is not preferable because it causes a problem that the durability of the optical filter is lowered. The preferable range of the solubility parameter value is preferably in the range of 9.00 to 12.5 (cal / cm ³ ) ^1/2 , and is preferably in the range of 9.0 to 12.0 (cal / cm ³ ) ^1/2 . It is more preferably in the range.

In order to ensure the compatibility between the near-infrared absorber (A) and the resin layer, the ratio of the amount of the near-infrared absorber (A) added and the thickness of the resin layer is important together with the solubility parameter of the resin. Since it is preferable to make the optical filter thinner, it is preferable to reduce the film thickness of the resin layer. However, when the film thickness of the resin layer is reduced, a near-infrared ray absorber per film thickness is obtained in order to obtain the desired optical characteristics. It is necessary to set the concentration of (A) high, and aggregation and association of the near-infrared absorber (A) are likely to occur, and uniform compatibility of the near-infrared absorber (A) in the resin becomes difficult. As a result of examining in detail the relationship between the compatibility between the near-infrared absorber (A) used in the present invention and the resin and the thickness of the resin layer, the content (resin) of each near-infrared absorber (A). The ratio of (parts by mass per 100 parts by mass) to the thickness of the resin layer (μm) [content of near infrared absorber (parts by mass) / thickness of resin layer (μm)] is preferably 0.005. By setting the content in the range of ~ 1.0, more preferably 0.01 to 1.0, still more preferably 0.015 to 0.95, good compatibility between the near infrared absorber (A) and the resin is ensured. It turned out that it could be done.

If the above ratio is less than 0.005, sufficient optical characteristics may not be obtained due to insufficient addition of the near-infrared absorber (A). When the above ratio exceeds 1.0, the amount of the near-infrared absorber (A) added to the amount of the resin is too large, and the near-infrared absorber (A) is not uniformly compatible with the resin layer. Becomes non-uniform, and the concentration of the near-infrared absorber (A) in the resin layer and the thickness variation of the resin layer become large, so that the variation in the optical characteristics in the film surface becomes large, the haze becomes high, and the like. Problems may occur.

As described above, the thickness of the resin layer in the present invention is preferably a thin film layer from the viewpoint of thinning the entire optical filter, but if the film thickness is too thin, the near-infrared absorber (A) is used. It is necessary to add it at a high concentration, and there is a problem that the compatibility of the near-infrared absorber (A) with the resin layer is lowered and the variation in optical characteristics is large. The thickness of the resin layer is preferably 20 μm or less, more preferably 1 to 15 μm, still more preferably 2 to 10 μm, and particularly preferably 3 to 10 μm. The resin layer may be arranged on one side or both sides of the glass substrate or the resin substrate, but is arranged on one side from the viewpoint of thinning the near-infrared cut filter and controlling the optical characteristics. Is preferable. However, when a plurality of near-infrared absorbers (A) are used and the compatibility with the resin layer differs depending on the type of the near-infrared absorber (A), the resin layers made of different resin types are used on both sides. It can also be placed in.

Specific examples of the resin used for the resin layer include the following resins.
≪Polar group-containing cyclic (poly) olefin resin≫
As the polar group-containing cyclic (poly) olefin resin, at least one single amount selected from the group consisting of the monomer represented by the following formula (1) and the monomer represented by the following formula (2). A resin obtained from the body and a resin obtained by hydrogenating the resin are preferable.

式（１）中、Ｒ^x1〜Ｒ^x4はそれぞれ独立に下記（i'）〜（ix'）より選ばれる原子または基を表し、Ｒ^x1〜Ｒ^x4のいずれか１つ以上は下記（iv'）または（vi'）より選ばれる原子または基であり、ｋ^x、ｍ^xおよびｐ^xは、それぞれ独立に０〜４の整数を表す。
（i'）水素原子
（ii'）ハロゲン原子
（iii'）トリアルキルシリル基
（iv'）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１〜３０の炭化水素基
（v'）置換または非置換の炭素数１〜３０の炭化水素基
（vi'）極性基（但し、（ii'）および（iv'）を除く。）
（vii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが相互に結合して形成されたアルキリデン基（但し、前記結合に関与しないＲ^x1〜Ｒ^x4はそれぞれ独立に前記（ｉ'）〜（vi'）より選ばれる原子または基を表す。）
（viii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが相互に結合して形成された単環もしくは多環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1〜Ｒ^x4はそれぞれ独立に前記（i'）〜（vi'）より選ばれる原子または基を表す。）
（ix'）Ｒ^x2とＲ^x3とが相互に結合して形成された単環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1とＲ^x4はそれぞれ独立に前記（i'）〜（vi'）より選ばれる原子または基を表す。）

In the formula (1), R ^{x1 to} R ^x4 each independently represent an atom or group selected from the following (i') to (ix'), and any one or more of R ^{x1 to} R ^x4 is the following (iv'). ) or (vi ') from an atom or group selected, k ^x, m ^x and p ^x each independently represent an integer of 0 to 4.
(I') Hydrogen atom (ii') Halogen atom (iii') Trialkylsilyl group (iv') Substituent or unsubstituted carbon number 1 having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. ~ 30 hydrocarbon group (v') substituted or unsubstituted hydrocarbon group (vi') polar groups with 1 to 30 carbon atoms (excluding (ii') and (iv'))
(Vii') Alkylidene groups formed by mutual bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 (however, R ^{x1 to} R ^x4 not involved in the bond are independently described in (i') to Represents an atom or group selected from (vi').)
(Viii') Monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by mutual bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 (however, R ^{x1 to} R ^x4 not involved in the bond) Represents an atom or group independently selected from the above (i') to (vi').)
(Ix') A monocyclic hydrocarbon ring or heterocycle formed by mutually bonding R ^x2 and R ^x3 (however, R ^x1 and R ^x4 not involved in the bond are independently described in (i'). Represents an atom or group selected from ~ (vi').)

式（２）中、Ｒ^y1およびＲ^y2はそれぞれ独立に前記（i'）〜（vi'）より選ばれる原子または基を表すか、Ｒ^y1とＲ^y2とが相互に結合して形成された単環もしくは多環の脂環式炭化水素、芳香族炭化水素または複素環を表し、Ｒ^y1およびＲ^y2のいずれか１つ以上は前記（iv'）または（vi'）より選ばれる原子または基であり、ｋ^yおよびｐ^yはそれぞれ独立に、０〜４の整数を表す。極性基含有環状（ポリ）オレフィン系樹脂としては、例えば、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−エンの開環重合体の水素添加体（溶解度パラメーター値：９．７(ｃａｌ／ｃｍ³)^1/2）を好適に使用することができる。

In formula (2), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i') to (vi'), or R ^y1 and R ^y2 are formed by being bonded to each other. Represents a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocycle, and any one or more of R ^y1 and R ^y2 is an atom or group selected from the above (iv') or (vi'). And ^ky and p ^y each independently represent an integer from 0 to 4. Examples of the polar group-containing cyclic (poly) olefin resin include 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] A hydrogenated product of a ring-opening polymer of dodeca-3-ene (solubility parameter value: 9.7 (cal / cm ³ ) ^1/2 ) can be preferably used.

≪Aromatic polyether resin≫
The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (3) and the structural unit represented by the following formula (4).

式（３）中、Ｒ¹〜Ｒ⁴はそれぞれ独立に炭素数１〜１２の１価の有機基を示し、ａ〜ｄはそれぞれ独立に０〜４の整数を示す。

In the formula (3), R ^{1 to} R ⁴ independently represent monovalent organic groups having 1 to 12 carbon atoms, and a to d independently represent integers 0 to 4.

式（４）中、Ｒ¹〜Ｒ⁴およびａ〜ｄは、それぞれ前記式（３）中のＲ¹〜Ｒ⁴およびａ〜ｄと同義であり、Ｙは、単結合、−ＳＯ₂−または−ＣＯ−を示し、Ｒ⁵およびＲ⁶はそれぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、eおよびfはそれぞれ独立に０〜４の整数を示し、ｍは０または１を示す。但し、ｍが０のとき、Ｒ⁶はシアノ基ではない。

In formula (4), R ^{1 to} R ⁴ and a to d are synonymous with R ^{1 to} R ⁴ and a to d in the formula (3), respectively, and Y is a single bond, −SO ₂ − or -CO-, R ⁵ and R ⁶ independently represent a halogen atom, a monovalent organic group or a nitro group having 1 to 12 carbon atoms, and e and f each independently represent an integer of 0 to 4. m represents 0 or 1. However, when m is 0, R ⁶ is not a cyano group.

Further, the aromatic polyether resin further has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (5) and the structural unit represented by the following formula (6). Is preferable.

式（５）中、Ｒ⁷およびＲ⁸はそれぞれ独立に炭素数１〜１２の１価の有機基を示し、Ｚは、単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｇおよびｈはそれぞれ独立に０〜４の整数を示し、ｎは０または１を示す。

Wherein (5), R ⁷ and R ⁸ is each independently a monovalent organic group having 1 to 12 carbon atoms, Z is a single bond, -O -, - S -, - SO 2 -, - CO -, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, g and h each independently represent an integer of 0 to 4, and n represents 0 or 1.

式（６）中、Ｒ⁵、Ｒ⁶、Ｙ、m、eおよびfは、それぞれ前記式（３）中のＲ⁵、Ｒ⁶、Ｙ、ｍ、eおよびfと同義であり、Ｒ⁷、Ｒ⁸、Ｚ、ｎ、gおよびhは、それぞれ前記式（５）中のＲ⁷、Ｒ⁸、Ｚ、ｎ、gおよびhと同義である。芳香族ポリエステル系樹脂としては、例えば、２，６−ジフルオロベンゾニトリルと９，９−ビス（４−ヒドロキシフェニル）フルオレンから得られる重合体（溶解度パラメーター値：１１．０(cal/cm³)^1/2）を好適に使用することができる。

In formula (6), R ⁵ , R ⁶ , Y, m, e and f are synonymous with R ⁵ , R ⁶ , Y, m, e and f in formula (3), respectively, and R ⁷ , R ⁸ , Z, n, g and h are synonymous with R ⁷ , R ⁸ , Z, n, g and h in the above formula (5), respectively. Examples of the aromatic polyester resin include a polymer obtained from 2,6-difluorobenzonitrile and 9,9-bis (4-hydroxyphenyl) fluorene (solubility parameter value: 11.0 (cal / cm ³ ) ¹ ). ^{/ 2} ) can be preferably used.

≪Polyimide resin≫
The polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in the repeating unit. For example, JP-A-2006-199945, JP-A-2008-163107, and WO2013-69725, public relations. The compounds described in can be used. Examples of the polyimide resin include 1,2,4,5-sixhexanetetracarboxylic acid, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene and 1,3-bis (4-amino). A copolymer (solubility parameter value: 12.0 (cal / cm ³ ) ^1/2 ) obtained from −α, α-dimethylbenzyl) benzene can be preferably used.

≪Polycarbonate resin≫
The polycarbonate resin is not particularly limited, and a bisphenol type polycarbonate resin or a polycarbonate resin containing a fluorene moiety can be used. As the bisphenol type polycarbonate, those using bisphenol A and those using bisphenol Z can be used as the bisphenol component. Polycarbonate containing bisphenol Z can be synthesized, for example, by the method described in Japanese Patent Application Laid-Open No. 2010-126647. Further, a polycarbonate resin containing a fluorene moiety can be used, and for example, it can be synthesized by the method described in JP-A-2008-163194. For example, a polymer obtained from 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and diphenyl carbonate (solubility parameter value: 10.5 (cal / cm ³ ) ^1/2 ) is preferably used. be able to.

≪Polyester resin≫
The polyester resin is not particularly limited, and a polyester resin obtained by reacting a phthalic acid derivative with a bisphenol compound or a polyester resin containing a fluorene moiety can be used. The polyester resin can be synthesized, for example, by the method described in Japanese Patent Publication No. 55-027577. For example, a polymer obtained from terephthalic acid dichloride, isophthalic acid dichloride and 2,2-bis (4-hydroxyphenyl) propane (solubility parameter value 9.8 (cal / cm ³ ) ^1/2 ) is preferably used. Can be done. Further, the polyester resin containing the fluorene moiety can be synthesized by, for example, the methods described in JP-A-2010-285505 and JP-A-2011-197450. For example, a polymer (solubility parameter value: 10.6 (cal / cm ³ ) ^1/2 ) obtained from 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and dimethyl isophthalate is preferably used. can do.

≪Polyvinyl butyral resin≫
The polyvinyl butyral-based resin is not particularly limited, and a polymer obtained by butyraldehyde-forming polyvinyl alcohol with butyraldehyde can be used. Although the solubility parameter value differs depending on the degree of butyralization, a polymer having a solubility parameter value in the range of 10.0 to 16.0 (cal / cm ³ ) ^1/2 can be preferably used. Further, the hydroxyl group in the polymer can be crosslinked with a diisocyanate compound such as TDI or MDI before use.

In addition to the above resins, polyethylene naphthalate (solubility parameter value: 11.5 (cal / cm ³ ) ^1/2 ), polysulfone resin (solubility parameter value: 9.1 (cal / cm ³ ) ^1/2 ), etc. Can be used.

<Near infrared absorber (A)>
The near-infrared absorber (A) used in the present invention is two or more compounds selected from a squarylium-based compound, a phthalocyanine-based compound, and a cyanine-based compound. As the near-infrared absorber (A), it is preferable to use a compound having maximum absorption in the region of 600 to 800 nm. By using these near-infrared absorbing compounds (A), the compatibility with the resin is good in the resin layer of the thin film, and the optical characteristics are less dependent on the incident angle for cameras, ambient light sensors, and TOF distance image sensors. A suitable optical filter can be obtained.
As the two or more kinds of near-infrared absorbers (A), two or more kinds of compounds of the same system can be used, or compounds of different systems can be mixed and used.

≪Squarylium compound≫
The squarylium-based compound is not particularly limited, but is at least one selected from the group consisting of the squarylium-based compound represented by the following formula (I) and the squarylium-based compound represented by the following formula (II). It is preferable to use the compound of. Hereinafter, they are also referred to as “Compound (I)” and “Compound (II)”, respectively.

式（Ｉ）中、Ｒ^a、Ｒ^bおよびＹａは、下記条件（Ｉ−ａ）または（Ｉ−ｂ）を満たす。

In formula (I), R ^a , R ^b and Ya satisfy the following conditions (Ia) or (Ib).

Condition (Ia):
Plural R ^a each independently represents a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a -L ¹ or -NR ^e R ^f group;
The plurality of R ^bs independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^g R ^h group;
Multiple Yas independently represent -NR ^{jR k} groups;
L ¹ represents L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h ;
R ^e and R ^f each independently represents a hydrogen ^{atom, -L a, -L b, -L} c, a -L ^d or -L ^e;
R ^g and R ^h are independently hydrogen atoms, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C (O) R ⁱ group (R ⁱ is -L ^a , Represents -L ^b , -L ^c , -L ^d or -L ^e );
R ^j and R ^k each independently represent a hydrogen ^{atom, -L a, -L b, -L} c, a -L ^d or -L ^e;
L ^a represents an aliphatic hydrocarbon group of good 1 to 12 carbon atoms have a substituent L;
L ^b represents a halogen-substituted alkyl group having 1 to 12 carbon atoms which may have a substituent L;
L ^c represents an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L;
L ^d represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L;
L ^e represents a heterocyclic group having carbon atoms of 3 to 14 which may have a substituent group L;
L ^f represents an alkoxy group having 1 to 9 carbon atoms which may have a substituent L;
L ^g represents an acyl group having 1 to 9 carbon atoms which may have a substituent L;
L ^h represents an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L;
L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and an aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents at least one substituent selected from the group consisting of a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group and an amino group.

Condition (I-b):
At least one of the two R ^a on one benzene ring, but bonded to each other and Y on the same benzene ring, form a heterocyclic ring-constituting atom number of 5 or 6 comprising at least one nitrogen atom;
The heterocycle may have a substituent, and R ^b and R ^a not involved in the formation of the heterocycle are independently synonymous with R ^b and R ^a of the condition (α), respectively.

Wherein L ^a ~L ^h, the total number of carbon atoms including the substituent is preferably respectively 50 or less, still more preferably a few 40 or less carbon atoms, and particularly preferably 30 or less carbon atoms. If the number of carbon atoms is more than this range, it may be difficult to synthesize the compound, and the light absorption intensity per unit weight tends to be small.

The aliphatic hydrocarbon group having 1 to 12 carbon atoms in the L ^a and L, for example, a methyl group (Me), ethyl (Et), n-propyl group (n-Pr), isopropyl (i-Pr ), N-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Alkyl group of: vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group, octenyl group and other alkenyl groups. ; Also, alkynyl groups such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group and octynyl group can be mentioned.

Examples of the halogen-substituted alkyl groups having 1 to 12 carbon atoms in L ^b and L include trichloromethyl group, trifluoromethyl group, 1,1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group and heptachloro. Propyl groups and heptafluoropropyl groups can be mentioned.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in L ^c and L include a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a norbornan group and an adamantan group. And other polycyclic alicyclic groups can be mentioned.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L ^d and L include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 1-naphthyl group, a 2-naphthyl group and an anthracenyl group. Examples thereof include a phenanthryl group, an acenaphthyl group, a phenalenyl group, a tetrahydronaphthyl group, an indanyl group and a biphenylyl group.

Wherein L Examples of the heterocyclic group having 3 to 14 carbon atoms in the ^e and L, for example, furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, indole, indoline, indolenine, benzofuran , Benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, acrydin, morpholine and phenazine and other heterocyclic groups.

Examples of the alkoxy group having 1 to 12 carbon atoms in L ^f include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group. it can.

Examples of the acyl group having 1 to 9 carbon atoms in L ^g include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group and a benzoyl group.

Examples of the alkoxycarbonyl group having 1 to 9 carbon atoms in L ^h include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group and an octyl. An oxycarbonyl group can be mentioned.

As the L ^a, preferably a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- butyl group, a pentyl group, a hexyl group, an octyl group, 4-phenylbutyl The group is 2-cyclohexylethyl, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.

The L ^b is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, and more preferably a trichloro group. It is a methyl group, a pentachloroethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

The L ^c is preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group or a 4-phenylcycloheptyl group, and more preferably a cyclopentyl group, a cyclohexyl group or a 4-ethylcyclohexyl group. Is.

The L ^d is preferably a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a trill group, a xylyl group, a mesityl group, a cumenyl group, a 3,5-di-tert-butylphenyl group, or a 4-cyclopentylphenyl group. , 2,3,6-triphenylphenyl group, 2,3,4,5,6-pentaphenylphenyl group, more preferably phenyl group, trill group, xsilyl group, mesityl group, cumenyl group, 2,3 , 4, 5, 6-Pentaphenylphenyl group.

The ^Le is preferably a group composed of furan, thiophene, pyrrole, indole, indoline, indoline, benzofuran, benzothiophene and morpholin, and more preferably a group composed of furan, thiophene, pyrrole and morpholin.

The L ^f is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a methoxymethyl group, a methoxyethyl group, a 2-phenylethoxy group, a 3-cyclohexylpropoxy group, a pentyloxy group or a hexyloxy group. The group is an octyloxy group, more preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group.

The L ^g is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group or a trifluoromethylcarbonyl group, and more preferably an acetyl group, a propionyl group or a benzoyl group. ..

The L ^h is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group, and more preferably. It is a methoxycarbonyl group and an ethoxycarbonyl group.

Wherein L ^a ~L ^h further, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, at least one atom or group selected from the group consisting of a phosphate group and an amino group May be. Examples of such are 4-sulfobutyl group, 4-cyanobutyl group, 5-carboxypentyl group, 5-aminopentyl group, 3-hydroxypropyl group, 2-phosphorylethyl group, 6-amino-2,2-dichloro. Hexyl group, 2-chloro-4-hydroxybutyl group, 2-cyanocyclobutyl group, 3-hydroxycyclopentyl group, 3-carboxycyclopentyl group, 4-aminocyclohexyl group, 4-hydroxycyclohexyl group, 4-hydroxyphenyl group, Pentafluorophenyl group, 2-hydroxynaphthyl group, 4-aminophenyl group, 4-nitrophenyl group, group consisting of 3-methylpyrrole, 2-hydroxyethoxy group, 3-cyanopropoxy group, 4-fluorobenzoyl group, 2 -Hydroxyethoxycarbonyl group and 4-cyanobutoxycarbonyl group can be mentioned.

The R ^a in the condition (I-a), preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- Butyl group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, nitro group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group. Is.

The R ^{b under the} above condition (Ia) is preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-. Butyl group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoyl Amino group, t-butanoylamino group, cyclohexinoylamino group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group, dimethylamino group, It is a nitro group, an acetylamino group, a propionylamino group, a trifluoromethanoylamino group, a pentafluoroetanoylamino group, a t-butanoylamino group, and a cyclohexinoylamino group.

The Ya is preferably an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-t-butylamino group, N. -Ethyl-N-methylamino group, N-cyclohexyl-N-methylamino group, more preferably dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group , Di-t-butylamino group.

A nitrogen atom formed by bonding at least one of two ^Ra on one benzene ring with Y on the same benzene ring under the condition (Ib) of the formula (I). Examples of the heterocycle having at least one constituent atom number of 5 or 6 include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine. Among these heterocycles, a heterocycle which constitutes the heterocycle and in which one atom next to the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

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

In formula (II), X is independently O, S, Se, N- R c or C (R ^d R ^d) represents; plural R ^c is independently a hydrogen ^{atom, L a, L b, L} c , L ^d or L ^e ; multiple R ^ds are independently hydrogen atom, halogen atom, sulfonic acid group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -L ¹ or -NR ^e R. It represents an ^f group, R ^d adjacent may form a ring which may have a substituent ^{linked; L a ~L e, L 1} , R e and R ^f, the equation ( L ^a ~L ^e defined in I), and the same meanings as L ^1, R ^e and R ^f.

The R ^c in the formula (II) is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, or an n-pentyl group. , N-hexyl group, cyclohexyl group, phenyl group, tolfluoromethyl group, pentafluoroethyl group, more preferably hydrogen atom, methyl group, ethyl group, n-propyl group and isopropyl group.

The R ^d in the formula (II) is preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl. Group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, 4-aminocyclohexyl group, more preferably hydrogen atom, chlorine atom, fluorine atom. , Methyl group, ethyl group, n-propyl group, isopropyl group, trifluoromethyl group, pentafluoroethyl group.

The X is preferably O, S, Se, N-Me, N-Et, CH ₂ , C-Me ₂ , C-Et ₂ , and more preferably S, C-Me ₂ , C-Et _2. Is.

In the above formula (II), adjacent R ^ds may be connected to each other to form a ring. Examples of such a ring include a benzoindrenin ring, an α-naphthoimidazole ring, a β-naphthoimidazole ring, an α-naphthoxazole ring, a β-naphthoxazole ring, an α-naphthiazole ring, and a β-naphthiathiazole ring. Examples thereof include an α-naphthoselazole ring and a β-naphthoserenazol ring.

Compound (I) and compound (II) have the following formulas (I-2) and the following formula (II-2) in addition to the description methods such as the following formula (I-1) and the following formula (II-1). The structure can also be expressed by a description method that takes a resonance structure as described above. That is, the difference between the following formula (I-1) and the following formula (I-2), and the difference between the following formula (II-1) and the following formula (II-2) is only the method of describing the structure. Represents the same compound. Unless otherwise specified in the present invention, the structure of the squarylium-based compound shall be represented by the description methods such as the following formula (I-1) and the following formula (II-1).

さらに、例えば、下記式（Ｉ−３）で表される化合物と下記式（Ｉ−４）で表される化合物は、同一の化合物であると見なすことができる。

Further, for example, the compound represented by the following formula (I-3) and the compound represented by the following formula (I-4) can be regarded as the same compound.

The structures of the compounds (I) and (II) are not particularly limited as long as they satisfy the requirements of the formulas (I) and (II), respectively. For example, when the structure is expressed as in the above formulas (I-1) and (II-1), the left and right substituents bonded to the central four-membered ring may be the same or different. It is preferable that they are the same because it is easy to synthesize.

Specific examples of the compounds (I) and (II) include the compounds (a-1) shown in Tables 1 to 3 below, which have a basic skeleton represented by the following formulas (IA) to (IH). )-(A-36) can be mentioned. Among these compounds, a compound having a bulky structure as a substituent is preferable from the viewpoint of solubility in the resin layer, (a-5), (a-6), (a-8), (a-9). ), (A-16), (a-17), (a-19), (a-20) are particularly preferable.

The compounds (I) and (II) may be synthesized by a generally known method. For example, JP-A No. 1-2289960, JP-A-2001-40234, Patent No. 3196383, etc. It can be synthesized by referring to the described method and the like.

<< Phthalocyanine compounds >>
Although the phthalocyanine compound is not particularly limited, it is preferable to use a compound represented by the following formula (III) (hereinafter, also referred to as “compound (III)”).

In formula (III), M represents a substituted metal atom containing two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom, and there are a plurality of R's. _a , R _b , R _c and R _d are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -S. -L ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , or a combination of at least one of R _a and R _b , R _b and R _c, and R _c and R _d. Represents at least one group selected from the group consisting of the groups represented by the following formulas (A) to (H) to which is bonded. However, at least one of R _a , R _b , R _c and R _d bonded to the same aromatic ring is not a hydrogen atom.

The amino group, amide group, imide group and silyl group may have the substituent L defined in the above formula (I).
L ¹ is synonymous with L ¹ defined in the above formula (I).
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydroxyl group or the L ^a ~L ^e,
L ⁴ represents represents any of the L ^a ~L ^e.

In formulas (A) to (H), R _x and R _y represent carbon atoms, and a plurality of _{RA to RL} independently represent hydrogen atoms, halogen atoms, hydroxyl groups, nitro groups, amino groups, amide groups, and imides. Represents a group, a cyano group, a silyl group, -L ¹ , -S-L ² , -SS-L ² , -SO _2- L ³ , -N = N-L ⁴ , and the amino group, amide group, and imide group. And the silyl group may have a substituent L defined in the above formula (I), and L ^{1 to} L ⁴ are synonymous with L ^{1 to} L ⁴ defined in the above formula (III).

In the above _{Ra to} R _d and _{RA to RL} , the amino group which may have a substituent L includes an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group and a diisopropylamino. Group etc. can be mentioned.

In the above _{Ra to} R _d and _{RA to RL} , examples of the amide group which may have a substituent L include an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group and a diisopropylamide group. Examples thereof include a dibutylamide group, an α-lactam group, a β-lactam group, a γ-lactam group and a δ-lactam group.

Wherein in R _a to R _d and R _A to R _L, as good imido group which may have a substituent L, an imido group, methylimide group, Echiruimido group, diethyl imido group, dipropyl imido group, diisopropyl imido group, Examples thereof include a dibutylimide group.

Examples of the silyl group which may have a substituent _L in R _{a to} R _d and _{RA to RL} include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a triethylsilyl group and the like. ..

In R _{a to} R _d and _{RA to RL} , -S-L ² includes a thiol group, a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, an isobutyl sulfide group and a sec-butyl sulfide group. , Tart-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butyl phenyl sulfide group, 2,6-diphenyl phenyl sulfide group, 4-cumyl phenyl sulfide group and the like.

In R _{a to} R _d and _{RA to RL} , -SS-L ² includes a disulfide group, a methyl disulfide group, an ethyl disulfide group, a propyl disulfide group, a butyl disulfide group, an isobutyl disulfide group and a sec-butyl disulfide group. , Tert-butyl disulfide group, phenyl disulfide group, 2,6-di-tert-butyl phenyl disulfide group, 2,6-diphenyl phenyl disulfide group, 4-cumyl phenyl disulfide group and the like.

In R _{a to} R _d and _{RA to RL} , examples of -SO _2- L ³ include a sulfo group, a mesyl group, an ethyl sulfonyl group, an n-butyl sulfonyl group, and a p-toluene sulfonyl group.

In the R _a to R _d and R _A to R _L, as the -N = N-L ^4, Mechiruazo group, phenylazo group, p- methylphenyl azo group, p- dimethyl aminophenyl azo group.

In M, examples of the monovalent metal atom include Li, Na, K, Rb, and Cs.

In M, the divalent metal atoms include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, Hg, Sn, Examples include Pb.

In the above M, examples of the substituted metal atom containing a trivalent metal atom include Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga-I, and In. -F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH and the like can be mentioned.

In the above M, examples of the substituted metal atom containing a tetravalent metal atom include TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , ZrCl ₂ , HfCl ₂ , CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , and so on. GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , SnI ₂ , Zr (OH) ₂ , Hf (OH) ₂ , Mn (OH) ₂ , Si (OH) ₂ , Ge ( OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , GeR ₂ , SnR ₂ , Ti (OR) ₂ , Cr (OR) ₂ , Si (OR) ₂ , Ge (OR) ₂ , Sn (OR) ₂ (R represents an aliphatic group or an aromatic group), TiO, VO, MnO and the like can be mentioned.

The M is a divalent transition metal belonging to the 4th to 5th periods of the Periodic Table Group 5 to 11, a trivalent or tetravalent metal halide, or a tetravalent metal oxide. Of these, Cu, Ni, Co and VO are particularly preferable because high visible light transmittance and stability can be achieved.

A method for synthesizing the phthalocyanine compound by a cyclization reaction of a phthalonitrile derivative as shown in the following formula (IV) is generally known, and the obtained phthalocyanine compounds are described in the following formulas (V-1) to (V-1) to ( It is a mixture of four isomers such as V-4). In the present invention, unless otherwise specified, only one isomer is exemplified for one phthalocyanine compound, but the other three isomers can be used in the same manner. Although these isomers can be separated and used as needed, the present invention deals with isomer mixtures collectively.

Specific examples of the compound (III) include (b-1) to (b-61) shown in Tables 4 to 7 below, which have basic skeletons represented by the following formulas (III-A) to (III-J). ) And so on. Among these compounds, a compound having a bulky structure as a substituent is preferable from the viewpoint of compatibility with the resin layer, and (b-33), (b-37), (b-38), and (b-39). ), (B-45) and (b-53) are particularly preferable.

Compound (III) may be synthesized by a generally known method, for example, the method described in Japanese Patent No. 4081149 and "Parthalocyanine-Chemistry and Function-" (IPC, 1997). It can be referenced and synthesized.

≪Cyanine compounds≫
The cyanine-based compound is not particularly limited, but is a compound represented by any of the following formulas (VI-1) to (VI-3) (hereinafter, "Compounds (VI-1) to (VI-3)". ) ”) Is preferably used.

Wherein (VI-1) ~ (VI -3), X a - represents a monovalent anion, a plurality of D is independently a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, a plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group and imide. Group, cyano group, silyl group, -L ¹ , -S-L ² , -SS-L ³ , -SO _2- L ³ , -N = N-L ⁴ , or R _b and R _c , R _d A group represented by the above formulas (A) to (H) in which at least one combination of R _e , R _e and R _f , R _f and R _g , R _g and R _h and R _h and R _i is bound. Representing at least one group selected from the group consisting of, the amino group, the amide group, the imide group and the silyl group may have the substituent L defined in the above formula (I).
L ¹ is synonymous with L ¹ defined in the above formula (I).
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydrogen atom or the L ^a ~L ^e,
L ⁴ are, represents any of the L ^a ~L ^e,
Z _{a to} Z _c and Y _{a to} Y _d are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -. S-L ² , -SS-L ² , -SO _2- L ³ , -N = N-L ⁴ (L ^{1 to} L ⁴ are synonymous with L ^{1 to} L ⁴ in R _{a to} R _i . ) Or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which is formed by bonding Zs or Ys selected from two adjacent twos to each other; a nitrogen atom, an oxygen atom or a sulfur atom. A 5- to 6-membered alicyclic hydrocarbon group which may contain at least one; or a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom. These aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic hydrocarbon groups may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z to each other or Y to each other in Z _{a to} Z _c and Y _{a to} Y _d include the substituent L. Examples thereof include compounds exemplified by aromatic hydrocarbon groups.

A 5- to 6-membered ring of Z _{a to} Z _c and Y _{a to} Y _d , which may contain at least one nitrogen atom, oxygen atom or sulfur atom formed by bonding Z to each other or Y to each other. Examples of the alicyclic hydrocarbon group include the alicyclic hydrocarbon group in the substituent L and the compounds exemplified by the heterocycle (excluding the heteroaromatic hydrocarbon group).

Examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding Z to each other or Y to each other in Z _{a to} Z _c and Y _{a to} Y _d include the substituent L. Examples of the compound exemplified as the heterocyclic group in (excluding an alicyclic hydrocarbon group containing at least one nitrogen atom, oxygen atom or sulfur atom) can be mentioned.

In the above formulas (VI-1) to (VI-3), even if it has -S-L ² , -SS-L ² , -SO _2- L ³ , -N = N-L ⁴ , and the substituent L. Examples of a good amino group, amide group, imide group, and silyl group include groups similar to the group exemplified by the above formula (III).

X _a ^- is not particularly limited as long as it is a monovalent ^{anion, I -, Br -, PF} 6 -, N (SO 2 CF 3) 2 -, B (C 6 F 5) 4 -, nickel dithio alert Examples thereof include a system complex and a copper dithiolate system complex.

Specific examples of the cation structure of the compounds (VI-1) to (VI-3) include (c-1) to (c-24) shown in Table 8 below. Further, specific examples of the anion structure of the compounds (VI-1) to (VI-3) include (Xa-1) to (Xa-31) shown in Table 9 below. Among these compounds, in order to improve the compatibility with the resin layer, it is preferable to use a compound having a bulky anion structure. It is preferable to use a compound having an anion having a molecular weight of 250 or more, preferably 300 or more. Specifically, (Xa-23), (Xa-25), (Xa-26), (Xa-27), and (Xa-30) are particularly preferable.

The compounds (VI-1) to (VI-3) may be synthesized by a generally known method, and can be synthesized, for example, by the method described in JP-A-2009-108267.

It is possible to add a light absorber other than the near-infrared absorber (A) to the resin layer, but from the viewpoint of compatibility with the resin layer, a light absorber having good compatibility with the resin layer. It is necessary to select the amount of the material, and it is necessary to set the amount of addition to an amount that can ensure compatibility with the resin layer. As the light absorber that can be used other than the above, diimonium-based compounds, croconium-based compounds, naphthalocyanine-based compounds, metal dithiolate-based compounds, pyrrolopyrrole-based compounds and the like can be used. These light absorbers can be added to the same resin layer as the squarylium-based compound, cyanine-based compound, and phthalocyanine-based compound, or can be added to separate resin layers.

As the solvent for dissolving the resin and the near-infrared absorber (A) used for forming the resin layer, a solvent having high solubility in both the resin and the near-infrared absorber (A) was selected. It is preferable to do so. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, methylene chloride, Chlorine-based hydrocarbons such as chloroform, dichloroethylene and trichloroethane, and amides such as tetrahydrofuran, dioxane, cyclopentylmethyl ether, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone. A solvent selected from the above can be used. If a large amount of solvent remains in the resin layer, the amount of outgassing increases during processing of the dielectric multilayer film, and the characteristics of the dielectric multilayer film deteriorate (increase in haze value, decrease in adhesion between the resin layer and the dielectric multilayer film, etc.). As the solvent, a solvent having a high volatilization property from the resin layer is preferable, and therefore a solvent having a low boiling point and a high vapor pressure is preferable. From this point of view, it is preferable to use methylene chloride, chloroform, or toluene as the solvent.

In addition to the near-infrared absorber (A), other components such as an antioxidant, an ultraviolet absorber, and a surfactant can be added to the resin layer.

The content of the near-infrared absorber (A) in the resin layer varies depending on the target optical characteristics and the thickness of the resin layer, but is preferably 0.1 with respect to 100 parts by mass of the resin constituting the resin layer. It is ~ 30 parts by mass, more preferably 0.2 to 15 parts by mass, and further preferably 0.3 to 10 parts by mass. When the content of the near-infrared absorber (A) is less than 0.1 parts by mass, the absorption intensity may be insufficient and the desired optical characteristics may not be obtained. When the content of the near-infrared absorber (A) is more than 30 parts by mass, the near-infrared absorber (A) is not uniformly compatible with the resin layer, the resin layer becomes non-uniform, and the haze is high. Poor appearance and poor optical characteristics may occur.

In the present invention, the optical characteristics (absorption characteristics) of the optical filter are determined by the thickness of the resin layer and the content of the near-infrared absorber (A), but in order to ensure the uniformity of the optical characteristics of the optical filter. It is preferable that the thickness of the resin layer and the concentration of the near-infrared absorber (A) in the resin layer be as uniform as possible. In order to keep the variation in optical characteristics within the range usually required for an optical filter such as IRCF, the near-infrared absorber (A) is uniformly compatible with the resin layer, and then the resin layer or the laminate is used. The in-plane film thickness variation of the body (X) is preferably within 10%, more preferably within 8%, further preferably within 6%, and particularly preferably within 5%. In the present invention, the in-plane film thickness variation of the resin layer is the central portion of a sample having a size of 150 mm × 150 mm cut out from the laminate (X) composed of the substrate and the resin layer containing the near-infrared absorber (A). It means the variation in film thickness (Equation 1) at 9 points in the plane in the region of 130 × 130 mm.
Film thickness variation = (maximum value of 9 points-minimum value of 9 points) / average value of 9 points (Equation 1)

In order to make the in-plane film thickness of the resin layer or the laminate (X) uniform, it is necessary to select an appropriate coating method for the resin layer to be applied on the substrate, and a spin coating method is used. In many cases, it is difficult to obtain a uniform film thickness, and for example, a uniform film thickness distribution can be obtained by applying the die coating method. When the film thickness variation of the resin layer or the laminate (X) exceeds 10%, the transmittance of each wavelength and the IR half value (the shortest wavelength at which the transmittance is 50% in the wavelength region of 600 to 800 nm) vary. Will increase, causing variations in camera image quality (color) and deterioration of the color tone sensitivity of the ambient light sensor, making it difficult to meet the characteristics of the optical filter required for camera modules, ambient light sensors, and TOF range image sensor applications. ..

The variation in the in-plane film thickness of the resin layer or the laminate (X) is kept within the above range, and the variation in the concentration of the near-infrared absorber (A) in the resin layer is preferably within 6%, more preferably. By keeping it within 4%, the uniformity of the optical characteristics of the optical filter can be ensured. In order to make the concentration variation of the near-infrared absorber (A) in the resin layer uniform, it is necessary to uniformly dissolve the near-infrared absorber (A) in the resin layer. For that purpose, it is necessary to use a resin in the solubility parameter range of the present invention as the resin of the resin layer and select a solvent type that dissolves both the near-infrared absorber (A) and the resin.

<Adhesion layer>
Since the resin layer and the glass substrate have different chemical compositions and coefficient of linear thermal expansion, it is preferable to provide an adhesion layer between the resin layer and the glass substrate to ensure sufficient adhesion between the two layers. .. The adhesion layer used in the present invention is not particularly limited as long as it is made of a material capable of ensuring adhesion between the resin layer and the glass substrate, and for example, (a) a structural unit derived from a (meth) acryloyl group-containing compound. It is preferable to use a compound having a structural unit derived from (b) a carboxylic acid group-containing compound and (c) a structural unit derived from an epoxy group-containing compound because the adhesion between the resin layer and the glass substrate is high.

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

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

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

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

These commercially available products include, for example, Aronix M-210, M-240, and M-6200 (all manufactured by Toagosei Co., Ltd.); KAYARAD HDDA, HX-220, and R-604 (the same). Above, Nippon Kayaku Co., Ltd.); Viscort 260, 312, 335HP (all manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate 1,9-NDA (manufactured by Kyoeisha Chemical Co., Ltd.); be able to.

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

Commercially available products of trifunctional or higher functional (meth) acrylic acid esters include, for example, Aronix M-309, M-315, M-400, M-405, M-450, and M-7100. , M-8030, M-8060, TO-1450 (all manufactured by Toa Synthetic Co., Ltd.); KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA- 120, DPEA-12 (above, manufactured by Nippon Kayaku Co., Ltd.); Viscort 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); Examples of commercially available products containing polyfunctional urethane acrylate compounds include New Frontier R-1150 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.); KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.).

These (meth) acryloyl group-containing compounds (a) can be used alone or in combination of two or more in the adhesion layer.

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

Examples of monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid. Acid can be mentioned.

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

The polymer having a carboxylic acid group comprises one or more polymerizable compounds selected from, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, etc., which are compounds containing a carboxylic acid group. A polymer or a polymer of these compounds and the (meth) acryloyl group-containing compound can be preferably used.

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

(C) Structural unit derived from the epoxy group-containing compound The structural unit (c) is not particularly limited as long as it is a structural unit derived from the epoxy group-containing compound. Examples of the epoxy group (oxylanyl group) -containing compound include oxylanyl groups such as (meth) acrylate oxylanyl (cyclo) alkyl ester, α-alkyl acrylate oxylanyl (cyclo) alkyl ester, and glycidyl ether compound having an unsaturated bond. Unsaturated compounds having; Examples thereof include unsaturated compounds having an oxetanyl group such as (meth) acrylic acid ester having an oxetanyl group.

Examples of the (meth) acrylic acid oxylanyl (cyclo) alkyl ester include (meth) acrylate glycidyl, (meth) acrylate 2-methylglycidyl, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylate 3,4. -Epoxybutyl, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate can be mentioned.

Examples of α-alkylacrylic acid oxylanyl (cyclo) alkyl esters include α-ethylacrylic acid glycidyl, α-n-propylacrylic acid glycidyl, α-n-butylacrylic acid glycidyl, and α-ethylacrylic acid 6,7-epoxyheptyl. And α-ethylacrylic acid 3,4-epoxycyclohexyl.

Examples of the glycidyl ether compound having an unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether.

Examples of the (meth) acrylic acid ester having an oxetanyl group include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, and 3-((meth) acryloyloxymethyl). ) -2-Methyloxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyloxy Methyloxetane and 3-ethyl-3- (meth) acryloyloxymethyloxetane can be mentioned.

Of these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methylloyloxymethyl-3-ethyloxetane, 3-methyl- 3-Methacrylic oxymethyloxetane or 3-ethyl-3-methyloxetane is preferable from the viewpoint of polymerizable property.

(D) Optional component An optional component such as an acid generator, an adhesion aid, a surfactant, and a polymerization initiator can be added to the adhesion layer as long as the effect of the present invention is not impaired. The amount of these additions is appropriately selected according to the desired properties, but is usually used with respect to a total of 100 parts by mass of the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound, and the epoxy group-containing compound. It is preferably 0.01 to 15.0 parts by mass, preferably 0.05 to 10.0 parts by mass.

The polymerization initiator is a component that produces an active species capable of initiating the polymerization of a monomer component in response to light rays such as ultraviolet rays and electron beams. Such a polymerization initiator is not particularly limited, and examples thereof include an O-acyloxime compound, an acetophenone compound, a biimidazole compound, an alkylphenone compound, and a benzophenone compound. Specific examples of these include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-. 6-Benzoyl-9. H. -Carbazole-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, ethane-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone-1- [9- Ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl) } -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-dimethylamino-2- (4) -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1 -Phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- Examples thereof include (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylbenzophenone, and 1-hydroxycyclohexylphenyl ketone. These polymerization initiators can be used alone or in admixture of two or more.

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

The blending amount of the (meth) acryloyl group-containing compound is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, and the blending of the carboxylic acid group-containing compound per 100 parts by mass of the composition (I). The amount is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and the blending amount of the epoxy group-containing compound is 100 parts by mass of the composition (I). It is preferably 15 to 50 parts by mass, more preferably 20 to 40 parts by mass.

The amount of the optional component to be blended is appropriately selected according to the desired properties, but is preferably 0.01 to 15.0 parts by mass, more preferably 0.05 to 100 parts by mass per 100 parts by mass of the composition (I). It is 10.0 parts by mass.

The thickness of the adhesion layer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.1 to 5.0 μm, and more preferably 0.2 to 3.0 μm.

The haze value of the laminate (X) containing the substrate, the adhesion layer, and the resin layer containing the near-infrared absorber (A) is preferably 0.20% or less, more preferably 0.15% or less. More preferably, it is 0.10% or less. When an optical filter using a laminated body (X) having a haze value of 0.20% or more is used for a camera module, flare occurs in an image of a light source such as a fluorescent lamp, which causes an image defect.

<Dielectric multilayer film>
The optical filter of the present invention preferably has a dielectric multilayer film on at least one surface of the laminated body (X). The dielectric multilayer film in the present invention is a film having an ability to reflect near infrared rays or a film having an antireflection effect in the visible region, and having a dielectric multilayer film has more excellent visible light transmittance and near infrared rays. Cut characteristics can be achieved. Hereinafter, a laminate in which a dielectric multilayer film is formed on at least one surface of the laminate (X) is also referred to as a “laminate (Y)”.

2A to 2C are schematic views showing a configuration example of the optical filter (laminated body (Y)) of the present invention. The optical filter 100a shown in FIG. 2A has a dielectric multilayer film 103 on one surface of the substrate 130. The dielectric multilayer film 103 has a property of reflecting near infrared rays. Further, the optical filter 100b shown in FIG. 2B has a first dielectric multilayer film 103a on one surface of the substrate 130 and on the other surface. The second dielectric multilayer film 103b is provided. As described above, the dielectric multilayer film that reflects near infrared rays may be provided on one side of the base material or on both sides. When provided on one side, the manufacturing cost and An optical filter that is easy to manufacture, has high strength when provided on both sides, and is less likely to warp or twist can be obtained. When the optical filter is applied to a camera module or an ambient light sensor application, the warp of the optical filter can be obtained. It is preferable to provide a dielectric multilayer film on both sides of the base material because it is preferable that the twist and the twist are small.

As another form, the optical filter 100c shown in FIG. 1C has a dielectric multilayer film 103 having a property of reflecting near infrared rays on one surface of the substrate 130, and has a visible region on the other surface of the substrate 130. It has an antireflection film 104 having antireflection characteristics. By combining a dielectric multilayer film and an antireflection film on a substrate, it is possible to reflect near infrared rays while increasing the light transmittance in the visible region.

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

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

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

The thickness of each of the high refractive index material layer and the low refractive index material layer is usually preferably 0.1λ to 0.5λ, where λ (nm) is the near-infrared wavelength to be blocked. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is in this range, the optical film thickness in which the product (n × d) of the refractive index (n) and the film thickness (d) is calculated by λ / 4, the high refractive index material layer, and the low refraction The thickness of each layer of the index material layer becomes almost the same value, and there is a tendency that the blocking / transmitting of a specific wavelength can be easily controlled due to the relationship between the optical characteristics of reflection / refraction.

The total number of layers of the high-refractive index material layer and the low-refractive index material layer in the dielectric multilayer film is preferably 16 to 70 layers as a whole, and more preferably 20 to 60 layers. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and warpage of the optical filter and cracks of the dielectric multilayer film are reduced. can do.

In the present invention, the material types constituting the high refractive index material layer and the low refractive index material layer according to the absorption characteristics of the absorbent, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, the order of lamination, and the lamination By properly selecting the number, it has sufficient light-cutting characteristics in the near-infrared wavelength region while ensuring sufficient transmittance in the visible region, and has a refractive index when near-infrared light is incident from an oblique direction. Can be reduced.

Here, in order to optimize the above conditions, for example, optical thin film design software (for example, Essential Macleod, manufactured by Thin Film Center) can be used to achieve both an antireflection effect in the visible region and a light ray cutting effect in the near infrared region. You can set the parameters as follows. In the case of the above software, for example, when designing the first optical layer, the target transmittance at a wavelength of 400 to 700 nm is set to 100%, the value of Target Tolerance is set to 1, and the target transmittance at a wavelength of 705 to 950 nm is set to 0%. Parameter setting methods such as setting the value of Target Tolerance to 0.5 can be mentioned. These parameters can also change the value of Target Tolerance by further dividing the wavelength range according to various characteristics of the base material and the like.

The in-plane film thickness variation of the laminated body (Y) is preferably 9% or less, more preferably 7% or less, and further preferably 6% or less. The in-plane film thickness variation of the laminated body (Y) can be measured in the same manner as the in-plane film thickness variation of the resin layer or the laminated body (X).

<Other functional membranes>
In the optical filter of the present invention, a dielectric multilayer film is provided between the substrate and the dielectric multilayer film, between the resin layer and the dielectric multilayer film, and on the substrate or the resin layer as long as the effects of the present invention are not impaired. Improved surface hardness, improved chemical resistance, and antistatic properties of the substrate and dielectric multilayer film on the surface opposite to the surface opposite to the surface on which the substrate and the resin layer are provided. A functional film such as an antireflection film, a hard coat film, or an antistatic film can be appropriately provided for the purpose of erasing scratches and the like.

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

The method for laminating the functional film is not particularly limited, but a coating agent containing an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded or cast-molded on the substrate or the dielectric multilayer film in the same manner as described above. The method and the like can be mentioned.

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

Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resin and thermosetting resin. Specific examples of the curable resin include vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxy acrylate-based resins.

In addition, the coating agent may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can be used, and the photopolymerization initiator and the thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more.

The proportion of the polymerization initiator in the coating agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, still more preferably 1 when the total amount of the coating agent is 100% by mass. ~ 5% by mass. When the blending ratio of the polymerization initiator is within the above range, it is possible to obtain a functional film such as an antireflection film, a hard coat film or an antistatic film which has excellent curing characteristics and handleability of the coating agent and has a desired hardness.

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

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

In addition, for the purpose of improving the adhesion between the substrate and the functional film and / or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, the surface of the substrate, the functional film or the dielectric multilayer film is corona-treated. Surface treatment such as plasma treatment may be performed.

[Use of optical filter]
The optical filter of the present invention can contain a near-infrared absorber (A) having a wide range of structures in a thin resin layer at a high concentration, has low haze, good optical characteristics, and uniformity of optical characteristics, and is a solid. It is possible to manufacture IRCF that can meet the demand for lower profile of imaging devices, ambient light sensor devices and TOF range imaging devices without using expensive manufacturing equipment or advanced manufacturing technology, and smartphones and tablets. It is useful as an optical filter for an ambient light sensor module or a camera module in a device having a sensing function such as a terminal, a wearable device, an in-vehicle camera, a television, or a game machine.

[Solid image sensor]
The solid-state image sensor of the present invention includes the optical filter of the present invention. Here, the solid-state image sensor is an image sensor equipped with a solid-state image sensor such as a CCD or CMOS image sensor having both a camera function and a near-infrared sensing function. Specifically, a digital still camera, a smartphone camera, and a portable device. It can be used for applications such as telephone cameras, wearable device cameras, and digital video cameras. For example, the camera module of the present invention comprises the optical filter of the present invention.

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

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

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

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

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

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

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

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

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The method for measuring each physical property value and the method for evaluating the physical property are as follows.

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

(A) Using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Toso Co., Ltd., developing solvent: o-dichlorobenzene) manufactured by Waters Corp., weight equivalent to standard polystyrene. The average molecular weight (Mw) and the number average molecular weight (Mn) were measured.

(B) Using a GPC apparatus (HLC-8220 type, column: TSKgelα-M, developing solvent: tetrahydrofuran) manufactured by Toso Co., Ltd., the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured. ..

For the resin synthesized in Resin Synthesis Example 4 described later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the above method.
(C) A part of the polyimide resin solution was put into anhydrous methanol to precipitate the polyimide resin, and the mixture was filtered to separate unreacted monomers. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. was calculated by the following formula using a Canon-Fenceke viscometer. I asked.

_{μ = {ln (t s /} t 0)} / C
t ₀ : Solvent flow time t _s : Dilute polymer solution flow time C: 0.5 g / dL

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

<Spectroscopic transmittance>
The transmittance of the optical filter in each wavelength region was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

Here, the transmittance when measured from the vertical direction of the laminated body (X) or the laminated body (Y) is as shown in FIG. 6 from the vertical direction with respect to the laminated body (X) or the laminated body (Y): 10. The light incident and transmitted in the vertical direction was measured by the spectrophotometer 20.

When expressed as "average transmittance at a wavelength of 430 to 580 nm" in the present specification, the transmittance at each wavelength of 430 nm or more and 580 nm or less in 1 nm increments was measured, and the total transmittance was measured. It refers to the value calculated by dividing by the number of transmittances (wavelength range, 580-430 + 1). Further, when it is expressed as "IR half value" in the present invention, it means the value of the shortest wavelength in which the transmittance is 50% in the wavelength region of 600 to 800 nm.

<Haze>
The haze values of the laminates (X) and (Y) were measured using a "haze meter HZ-2" manufactured by Suga Test Instruments Co., Ltd.

<Film thickness>
The thickness of the near-infrared absorber (A) -containing resin layer in the laminate (X) was measured using a reflection spectroscopic film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd. The film thicknesses of the laminated body (X) and the laminated body (Y) were measured using "ABS Digimatic Indicator ID-F150" manufactured by Mitutoyo Co., Ltd. The film thickness variation was determined by measuring the film thickness at 9 in-plane points in the 130 mm × 130 mm region in the center of the 150 mm × 150 mm sample.

<Camera module image evaluation>
When the optical filters of the examples and the comparative examples use a resin substrate having a thickness of 100 μm, the optical filters of the camera module of the Sony “Xperia XZ3” main camera are taken out and replaced with the examples and comparisons described later. The optical filter produced in the example was incorporated into the camera module, a photograph was taken, and the quality of the photographic image was evaluated. When the optical filters of the examples and the comparative examples use a glass substrate having a thickness of 210 μm, the optical filters of the camera module of the “iPhone X” main camera manufactured by Apple Inc. are taken out and replaced with the examples and comparisons described later. The optical filter produced in the example was incorporated into the camera module, a photograph was taken, and the photographic image quality (color tone unevenness) was evaluated. The case where the color tone unevenness of the photographic image quality was not good was evaluated as "○", and the case where the color tone unevenness of the photographic image quality was large and the photographic image quality was poor was evaluated as "x". In addition, when observing the flare of the image of the fluorescent lamp, if the flare phenomenon around the fluorescent lamp is not observed and the photographic image quality is good, "○", a clear flare phenomenon is observed, and the photographic image quality is poor. A certain case was designated as "x".

<Ambient light sensor performance>
The optical filter of the ambient light sensor module of "iPhone X" manufactured by Apple Inc. was taken out, and instead, the optical filters produced in the examples and comparative examples described later were incorporated into the ambient light sensor module, and the operating condition of the ambient light sensor was observed. .. The case where the operating condition of the ambient light sensor was good was evaluated as "○", and the case where the operating condition was poor was evaluated as "x".

<Plastic synthesis example 1>
8-Methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] 100 parts of dodeca-3-ene, 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene were placed in a nitrogen-substituted reaction vessel, and the solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (concentration 0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) 0 were added to the solution in the reaction vessel as a polymerization catalyst. .9 parts was added, and the obtained solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

100 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.012 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. The hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, which was dried to obtain a hydrogenated polar group-containing cyclic polyolefin resin (hereinafter, also referred to as “resin A”). The obtained resin A has a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, a glass transition temperature (Tg) of 165 ° C., and a solubility parameter of 9.7 (). It was cal / cm ³ ) ^1/2 .

<Resin synthesis example 2>
228.3 parts of 2,2-bis (4-hydroxyphenyl) propane, 224.9 parts of diphenyl carbonate, and 0.075 parts of an aqueous solution of cesium carbonate having a concentration of 0.65% by mass were charged into a glass reaction vessel equipped with a stirrer. After melting the raw material monomer at 210 ° C. for 40 minutes in a nitrogen atmosphere, the reaction was carried out for 60 minutes under the conditions of 210 ° C. and 100 mmHg, 60 minutes under the conditions of 240 ° C. and 15 mmHg, and 90 minutes under the conditions of 280 ° C. and 0.5 mmHg. Then, a polycarbonate-based resin having a viscosity molecular weight of 23,000 (hereinafter, also referred to as “resin B”) was synthesized. The glass transition temperature of the obtained resin B was 143 ° C., and the solubility parameter was 9.8 (cal / cm ³ ) ^1/2 .

<Resin synthesis example 3>
After mixing and stirring 22.5 parts of 2,2-bis (4-hydroxyphenyl) propane and 450 parts of a 10 mass% NaOH aqueous solution in a 3 L three-necked flask, 8 parts of isophthalic acid dichloride and 12 parts are added to this solution. A 1 L methylene chloride solution in which 1 L of terephthalic acid dichloride was dissolved was added dropwise, and the mixture was vigorously stirred to carry out an interfacial polymerization reaction. After completion of the polymerization reaction, the methylene chloride layer and the aqueous layer were separated, and then the methylene chloride layer was washed and separated three times with 500 parts of distilled water. This methylene chloride solution was slowly added dropwise to 3 L of methanol with vigorous stirring to solidify the polymer. After filtering the polymer, it was added to 1 L of methanol, and the methanol was heated and refluxed with stirring. The polymer was recovered by filtration and drying. The obtained polyester resin (hereinafter, also referred to as "resin C") has a number average molecular weight (Mn) of 20,300, a weight average molecular weight (Mw) of 64,900, and a glass transition temperature (Tg) of 193 ° C. Yes, the solubility parameter was 9.8 (cal / cm ³ ) ^1/2 .

<Resin synthesis example 4>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen introduction tube, dripping funnel with side tube, Dean Stark tube and cooling tube, 1,4-bis (4-amino-α, α) under a nitrogen stream. Add 27.66 parts of -dimethylbenzyl) benzene and 7.38 parts of 4,4'-bis (4-aminophenoxy) biphenyl, 68.65 parts of γ-butyrolactone and N, N-dimethylacetamide (hereinafter "DMAc"). Also referred to as.) Dissolved in 17.16 parts. The obtained solution was cooled to 5 ° C. using an ice-water bath, and while maintaining the same temperature, 22.62 parts of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and triethylamine 0.50 as an imidization catalyst were used. Parts were added all at once. After completion of the addition, the temperature was raised to 180 ° C., and the mixture was refluxed for 6 hours while distilling off the distillate as needed. After refluxing for 6 hours, the mixture is air-cooled until the internal temperature reaches 100 ° C., 143.6 parts of DMAc is added to dilute the mixture, and the mixture is cooled with stirring to obtain 264.16 parts of a polyimide resin solution having a solid content concentration of 20% by weight. Obtained. A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter, also referred to as “resin D”).

The IR spectra of the obtained resin D was measured, the absorption was observed peculiar 1704 cm ^-1 and 1770 cm ^-1 imide group. The glass transition temperature (Tg) of the resin D was 310 ° C., and the logarithmic viscosity was measured to be 0.87 m ³ / kg, and the solubility parameter was 12.0 (cal / cm ³ ) ^1/2 .

<Resin synthesis example 5>
To the reactor, 302.8 parts of 9,9-bis {4- (2-hydroxyethoxy) -3,5-dimethylphenyl} fluorene, 136.6 parts of ethylene glycol and 194.2 parts of dimethyl isophthalate were added and stirred. While gradually heating and melting, the transesterification reaction was carried out. Next, 0.21 part of germanium oxide was added, and ethylene glycol was removed while gradually raising and lowering the temperature until the temperature reached 290 ° C. and 1 Torr or less. After that, the contents were taken out from the reactor to obtain pellets of a fluorene polyester resin (hereinafter, also referred to as "resin E"). The obtained resin E had a number average molecular weight of 40,000, a glass transition temperature of 145 ° C., and a solubility parameter of 10.3 (cal / cm ³ ) ^1/2 .

<Resin synthesis example 6>
35.12 parts of 2,6-difluorobenzonitrile, 87.60 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 parts of potassium carbonate, N, N-dimethylacetamide 443 in a 3 L 4-neck flask. And 111 parts of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean Stark tube and a cooling tube were attached to the four-necked flask. Then, after nitrogen substitution in the flask, the obtained solution was reacted at 140 ° C. for 3 hours, and the water produced was removed from the Dean-Stark apparatus at any time. When the formation of water was no longer observed, the temperature was gradually raised to 160 ° C., and the reaction was carried out at the same temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum-dried at 60 ° C. overnight to obtain a white powdered aromatic polyether resin (hereinafter, also referred to as “resin F”) (yield 95%). The obtained resin F has a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, a glass transition temperature (Tg) of 285 ° C., and a solubility parameter of 11.0 ( It was cal / cm ³ ) ^1/2 .

<Resin synthesis example 7>
8-Ethyltetracyclo [4.4.0.1 ^2,5 .] In a nitrogen-substituted 20 L reactor. 1 ^7,10 ] -Dodeca-3-ene (hereinafter, also referred to as "ETCD") 100 parts and 2,400 parts of cyclohexane were added, and tri-i-butylaluminum (i-Bu ₃ Al) was added as a polymerization catalyst. 8 parts, 2.6 parts of isobutyl alcohol and 1.4 parts of acetone were added as a reaction adjusting agent, and 18.8 parts of 1-hexene diluted with 200 parts of cyclohexane was added as a molecular weight adjusting agent. After raising the temperature of the reaction solution to 40 ° C., a solution prepared by dissolving 1.8 parts of tungsten hexachloride in 1,520 parts of cyclohexane was added. A solution prepared by dissolving 1,900 parts of ETCD and 2.6 parts of tungsten hexachloride in 2,200 parts of cyclohexane was continuously put into the reaction system over 2 hours while cooling so as to maintain the temperature of the reaction solution at 45 ° C. Added. After the addition was completed, stirring was continued at 45 ° C. for another 30 minutes, and then ring-opening polymerization was completed. The polymerization reaction solution was transferred to an autoclave, and 3,400 parts of cyclohexane was added. As a hydrogenation catalyst, 50 parts of a nickel catalyst supported on diatomaceous earth was added, the inside of the reactor was replaced with hydrogen, the pressure was increased to 10 kg / cm ² , and the temperature was raised to 160 ° C. with stirring. When the internal temperature was stable, the hydrogen pressure was maintained at 40 kg / cm ² , and the reaction was carried out for 8 hours while replenishing the hydrogen consumed by the reaction. After completion of the hydrogenation reaction, the hydrogenation catalyst was filtered off, and the solvent was distilled off under reduced pressure at 280 ° C. The obtained cyclic olefin resin (hereinafter, also referred to as “resin G”) has a weight average molecular weight (Mw) of 32,000, a glass transition temperature of 140 ° C., and a solubility parameter of 6.2 (cal / cm ³ ). It was ^1/2 .

<Plastic synthesis example 8>
In a nitrogen atmosphere, 500 parts of dehydrated cyclohexane was mixed with 0.082 parts of 1-hexene, 0.015 parts of dibutyl ether and 0.03 parts of triisobutylaluminum in a reactor at room temperature, and then tricyclo [] was maintained at 45 ° C. 4.3.0.1 ^2,5 ] -Deca-3,7-Diene 8 parts, 7,8-Benzotricyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -Deca-3-ene 50 parts, and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] ^-7 parts of dodeca-3-ene and 4 parts of tungsten hexachloride (0.7% toluene solution) were continuously added over 2 hours to carry out a polymerization reaction. 0.106 parts of butyl glycidyl ether and 0.052 parts of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst and stop the polymerization reaction. Next, 270 parts of cyclohexane was added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and 0.5 parts of a nickel-alumina catalyst was further added as a hydrogenation catalyst to a hydrogen pressure of 50 kg / cm ² . The temperature was raised to 200 ° C. while pressurizing and stirring, and then the reaction was carried out for 4 hours. The obtained cyclic olefin resin (hereinafter, also referred to as “resin H”) has a weight average molecular weight (Mw) of 37,000, a glass transition temperature of 134 ° C., and a solubility parameter of 7.4 (cal / cm ^3). ) It was ^1/2 .

[Example 1]
In Example 1, a resin layer containing a near-infrared absorber (A) was laminated on one side of a glass substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, the following resin composition (1) is applied as an adhesion-imparting layer on one side of a glass substrate "D263 (thickness 210 μm)" manufactured by SCHOTT with a die coater so that the thickness after drying is 0.7 μm. , The solvent was volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes. On this adhesion-imparting layer, 100 parts of resin A having a solubility parameter of 9.7 (cal / cm ³ ) ^1/2 obtained in Resin Synthesis Example 1 and compound (a-16) 1 shown in Table 1 above. A resin composition obtained by dissolving 3 parts and 1.3 parts of the compound (b-3) shown in Table 4 above in methylene chloride so as to have a concentration of 35% was prepared so that the thickness after drying was about 3 μm. It was applied with a tar. Next, the laminate (X) composed of the resin layer containing the compound (a-16) and the compound (b-3) and the glass substrate is removed by volatilizing and removing the solvent by heating on a hot plate at 80 ° C. for 3 minutes. Got

The optical characteristics of the obtained laminate (X) are shown in Table 12. As is clear from this result, in the obtained laminate (X), the compounds (a-16) and (b-3) are uniformly compatible in the resin A layer, and the laminate (X) is It had excellent transparency and low haze. Table 12 shows variations in the film thickness of the resin layer in the plane of the 150 mm × 150 mm size sample (central portion 130 mm × 130 mm) of the laminate (X), IR half values, and variations in the average transmittance at wavelengths of 430 to 580 nm. As is clear from this result, the variation in the film thickness in the surface of the laminated body is suppressed to be small, the variation in the IR half value and the variation in the average transmittance at the wavelength of 430 to 580 nm are also small, and the in-plane uniformity of good optical characteristics is good. Had.

Resin composition (1): Ethylene oxide-modified triacrylate of isocyanurate (trade name: Aronix M-315, manufactured by Toa Synthetic Chemical Co., Ltd.) 30 parts, 1,9-nonanediol diacrylate 20 parts, methacrylic acid 20 parts, 30 parts of glycidyl methacrylate, 5 parts of 3-glycidoxypropyltrimethoxysilane, 5 parts of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by Ciba Specialty Chemical Co., Ltd.) and Sun Aid SI-110 main agent (Sanshin) Chemical Industry Co., Ltd.) 1 part is mixed, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 50 wt%, and then filtered through a millipore filter having a pore size of 0.2 μm to form a resin composition (1). Was prepared.

Subsequently, a dielectric multilayer film (α) is formed on one side of the obtained laminate (X), and a dielectric multilayer film (β) is further formed on the other surface of the laminate (X) to obtain a thickness. An optical filter composed of a laminate (Y) in which a 4.6 μm dielectric multilayer film was laminated was obtained.

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

Regarding the thickness and number of layers of each layer, the wavelength-dependent characteristics of the refractive index of the base material and the applied compounds (A) and (B) so as to achieve the antireflection effect in the visible region and the selective transmission and reflection performance in the near infrared region. ) And (C) and other absorption characteristics were optimized using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When optimizing, in this example, the input parameters (Target values) to the software are as shown in Table 10 below.

As a result of film configuration optimization, in Example 1, the dielectric multilayer film (α) is formed by alternately laminating silica layers having a film thickness of about 32 to 158 nm and titania layers having a film thickness of about 10 to 96 nm. The 22-layer multi-layer deposition film is formed, and the dielectric multi-layer film (β) is a multi-layer with 18 layers in which silica layers having a film thickness of about 38 to 192 nm and titania layers having a film thickness of about 10 to 112 nm are alternately laminated. It was a vapor-deposited film. An example of the optimized film configuration is shown in Table 11 below.

続いて、得られた光学フィルター（積層体（Ｙ））の光学特性を測定した。結果を表１２に示す。この結果から明らかなように、得られた光学フィルターは優れた光学特性を有していた。また、本光学フィルターの光学有効範囲（中央部１３０ｍｍ×１３０ｍｍ）内のＩＲ半値、４３０〜５８０ｎｍ領域の平均透過率のばらつきを表１２に示す。この結果から明らかなように、ＩＲ半値、４３０〜５８０ｎｍ平均透過率のばらつきが小さく抑えられており、良好な光学特性の面内均一性を有していた。さらに、得られた光学フィルターを組み込んだカメラモジュールの写真画像評価と環境光センサーの作動状況評価を実施した。評価結果を表１２に示す。この結果から明らかなように、カメラモジュールの写真画像は良好であり、環境光センサーの作動状況は良好であった。

Subsequently, the optical characteristics of the obtained optical filter (laminated body (Y)) were measured. The results are shown in Table 12. As is clear from this result, the obtained optical filter had excellent optical characteristics. Table 12 shows variations in the IR half value within the optical effective range (central portion 130 mm × 130 mm) of this optical filter and the average transmittance in the 430 to 580 nm region. As is clear from this result, the variation in IR half value and average transmittance of 430 to 580 nm was suppressed to be small, and the in-plane uniformity of good optical characteristics was obtained. Furthermore, we evaluated the photographic image of the camera module incorporating the obtained optical filter and evaluated the operating status of the ambient light sensor. The evaluation results are shown in Table 12. As is clear from this result, the photographic image of the camera module was good, and the operating condition of the ambient light sensor was good.

[Example 2]
In Example 2, a resin layer containing a near-infrared absorber (A) was laminated on one side of a glass substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, the resin composition (1) as an adhesion-imparting layer is applied to one side of a glass substrate "D263 (thickness 210 μm)" manufactured by SCHOTT with a die coater so that the thickness after drying is 0.7 μm. , The solvent was volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes. On this adhesion-imparting layer, 100 parts of resin B having a solubility parameter of 9.8 (cal / cm ³ ) ^1/2 obtained in Resin Synthesis Example 2, 0.8 parts of the compound (a-16) and the above. A resin composition prepared by dissolving 0.8 parts of compound (b-1) in methylene chloride so as to have a concentration of 35% was applied with a die coater so that the thickness after drying was about 5 μm. Then, the solvent is volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes to remove the laminate (X) composed of the resin layer containing the compound (a-16) and the compound (b-3) and the glass substrate. ) Was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 12 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). As is clear from this result, in the obtained laminate (X), the compounds (a-16) and (b-3) are uniformly compatible with the resin B layer, and the film thickness variation of the resin layer is small. , The haze value of the laminated body (X) showed a small value. Further, the variations in the optical characteristics of the laminated bodies (X) and (Y) were small, and they had good in-plane uniformity.
Further, Table 12 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this embodiment and the operation status evaluation of the ambient light sensor. As is clear from this result, the photographic image of the camera module was good, and the operating condition of the ambient light sensor was good.

[Example 3]
In Example 3, an optical filter having a resin layer containing a near-infrared absorber (A) on both sides of a resin substrate and a dielectric multilayer film was produced. The specific procedure is shown below.

First, a Zeonoa ZF16 film (100 μm thickness) is used as the resin substrate, and the solubility parameter obtained in Resin Synthesis Example 3 is 9.8 (cal / cm ³ ) ^1/2 on one surface of the resin substrate. A resin composition obtained by dissolving 100 parts of the resin C and 1.3 parts of the compound (a-16) in methylene chloride so as to have a concentration of 35% was applied with a die coater so that the thickness after drying was 3 μm. Then, the solvent was volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes. Further, a resin composition obtained by dissolving 100 parts of the resin C and 1.0 part of the compound (b-39) shown in Table 6 above in methylene chloride so as to have a concentration of 35% was applied to the other surface of the resin substrate. The coating was applied with a die coater so that the thickness after drying was 3 μm, and the solvent was volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes. As a result, a laminate (X) composed of a resin layer containing the compound (a-16), another resin layer containing the compound (b-39), and the resin substrate was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 12 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). As is clear from this result, in the obtained laminate (X), the compounds (a-16) and (b-39) are uniformly compatible with the resin C layer, and the film thickness variation of the resin layer is small. , The haze value of the laminated body (X) showed a small value. Further, the variations in the optical characteristics of the laminated bodies (X) and (Y) were small, and they had good in-plane uniformity.

Further, Table 12 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this embodiment and the operation status evaluation of the ambient light sensor. As is clear from this result, the photographic image of the camera module was good, and the operating condition of the ambient light sensor was good.

[Example 4]
In Example 4, a resin layer containing a near-infrared absorber (A) was laminated on one side of a resin substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, a Zeonoa ZF16 film (100 μm thick) is used as the resin substrate, and the solubility parameter obtained in Resin Synthesis Example 4 is 12.0 (cal / cm ³ ) ^1/2 on one side of the resin substrate. Concentration of 100 parts, 0.3 part of the compound (a-16) and 0.4 part of the compound (c-6 / Xa-25) represented by the following formula (c-6 / Xa-25) in methylene chloride 35 The resin composition dissolved so as to be% was applied with a die coater so that the thickness after drying was about 10 μm. Then, the solvent is volatilized and removed by heating in a dryer at 80 ° C. for 5 minutes to remove the solvent from the resin layer containing the compound (a-16) and (c-6 / Xa-25) and the resin substrate. (X) was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 12 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). As is clear from this result, in the obtained laminate (X), the compounds (a-16) and (c-6 / Xa-25) are uniformly compatible in the resin D layer, and the film of the resin layer is formed. The thickness variation was small, and the haze value of the laminated body (X) was small. Further, the variations in the optical characteristics of the laminated bodies (X) and (Y) were small, and they had good in-plane uniformity.

Further, Table 12 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this embodiment and the operation status evaluation of the ambient light sensor. As is clear from this result, the photographic image of the camera module was good, and the operating condition of the ambient light sensor was good.

[Example 5]
In Example 5, a resin layer containing a near-infrared absorber (A) was laminated on one side of a resin substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

An ARTON film (100 μm thickness) is used as the resin substrate, and 100 parts of resin E having a solubility parameter of 10.3 (cal / cm ³ ) ^1/2 obtained in Resin Synthesis Example 5 on one side of the resin substrate, The thickness of the resin composition obtained by dissolving 1.0 part of the compound (a-16) and 2.7 parts of the compound (c-6 / Xa-25) in methylene chloride so as to have a concentration of 35% after drying. Was applied with a die coater so that the thickness was about 3 μm. Then, the solvent is volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes to remove the solvent from the resin layer containing the compound (a-16) and (c-6 / Xa-25) and the resin substrate. (X) was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 12 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). As is clear from this result, in the obtained laminate (X), the compounds (a-16) and (c-6 / Xa-25) were uniformly compatible in the resin E layer, and the resin layer was formed. The film thickness variation was small, and the haze value of the laminated body (X) was small. Further, the variations in the optical characteristics of the laminated bodies (X) and (Y) were small, and they had good in-plane uniformity.

Further, Table 12 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this embodiment and the operation status evaluation of the ambient light sensor. As is clear from this result, the photographic image of the camera module was good, and the operating condition of the ambient light sensor was good.

[Example 6]
In Example 6, an optical filter having a resin layer containing a near-infrared absorber (A) on one side on a resin substrate and having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, an ARTON film (100 μm thickness) is used as the resin substrate, and the solubility parameter obtained in Resin Synthesis Example 1 is 9.7 (cal / cm ³ ) ^1/2 on one side of the resin substrate. After drying, 1.2 parts of the compound (a-19) shown in Table 1 above and 1.0 part of the compound (b-3) were dissolved in methylene chloride so as to have a concentration of 35%. Was applied with a die coater so that the thickness of the mixture was 5 μm. Then, the solvent is volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes to remove the solvent, thereby forming a laminate composed of the resin layer containing the compounds (a-19) and (b-3) and the resin substrate ( X) was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 13 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). As is clear from this result, in the obtained laminate (X), the compounds (a-19) and (b-3) are uniformly compatible in the resin layer, and the film thickness variation of the resin layer is small. , The haze value of the laminated body (X) showed a small value. Further, the variations in the optical characteristics of the laminated bodies (X) and (Y) were small, and they had good in-plane uniformity.

Further, Table 13 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this embodiment and the operation status evaluation of the ambient light sensor. As is clear from this result, the photographic image of the camera module was good, and the operating condition of the ambient light sensor was good.

[Example 7]
In Example 7, an optical filter having a resin layer containing a near-infrared absorber (A) on both sides of a glass substrate and a dielectric multilayer film was produced. The specific procedure is shown below.

First, the resin composition (1) as an adhesion-imparting layer was applied to one surface of a glass substrate "D263 (thickness 210 μm)" manufactured by SCHOTT with a die coater so that the thickness after drying was 0.7 μm. After that, the solvent was volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes. An adhesion-imparting layer made of the resin composition (1) having a thickness of 0.7 μm after drying was formed on the other surface of the glass substrate by the same method. On one surface of this adhesion-imparting layer, 100 parts of the resin F having a solubility parameter of 11.0 (cal / cm ³ ) ^1/2 obtained in Resin Synthesis Example 6 and the compound (a-19) 1. A resin composition obtained by dissolving two parts in methylene chloride so as to have a concentration of 35% is applied with a die coater so that the thickness after drying is about 5 μm, and heated on a hot plate at 80 ° C. for 2 minutes to form a solvent. Was volatilized and removed. Further, a resin composition obtained by dissolving 100 parts of resin F and 0.6 part of the compound (c-6 / Xa-25) in methylene chloride so as to have a concentration of 35% on the other surface of the adhesion-imparting layer. Was applied with a die coater so that the thickness after drying was about 5 μm, and the solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes. As a result, a laminate (X) having a resin layer containing the compound (a-19) and another resin layer containing the compound (c-6 / Xa-25) on both sides of the glass substrate was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 13 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). As is clear from this result, in the obtained laminate (X), the compounds (a-19) and (c-6 / Xa-25) are uniformly compatible with each other in the resin layer, and the film of the resin layer is formed. The thickness variation was small, and the haze value of the laminated body (X) was small. Further, the variations in the optical characteristics of the laminated bodies (X) and (Y) were small, and they had good in-plane uniformity.
Further, Table 13 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this embodiment and the operation status evaluation of the ambient light sensor. As is clear from this result, the photographic image of the camera module was good, and the operating condition of the ambient light sensor was good.

[Example 8]
In Example 8, a resin layer containing a near-infrared absorber (A) was laminated on one side of the resin substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, an ARTON film (100 μm thickness) is used as the resin substrate, and the solubility parameter obtained in Resin Synthesis Example 1 is 9.7 (cal / cm ³ ) ^1/2 on one side of the resin substrate. A resin composition obtained by dissolving 1.2 parts of the compound (a-19) and 1.0 part of the compound (b-3) in methylene chloride so as to have a concentration of 35% is about 5 μm in thickness after drying. It was applied with a spin coater so as to become. Then, by heating on a hot plate at 80 ° C. for 2 minutes to volatilize and remove the solvent, a laminate (X) composed of the resin layer containing the compounds (a-19) and (b-3) and the resin substrate. ) Was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 13 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). As is clear from this result, in the obtained laminate (X), the compounds (a-19) and (b-3) are uniformly compatible in the resin layer, and the laminate (X) is good. The haze value is shown. On the other hand, since the resin layer was coated with a spin coater, the film thickness variation of the resin layer became large, so that the in-plane variation of the optical characteristics was large. Therefore, the in-plane variation in the optical characteristics of the laminated body (Y) is also large.

Further, Table 13 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this embodiment and the operation status evaluation of the ambient light sensor. As is clear from this result, the color tone unevenness of the photographic image quality was large and the photographic image quality was poor, but the flare phenomenon was not observed. In addition, the ambient light sensor did not function well in changing the color tone of the screen in response to the change in external light, and the operating condition was poor.

[Example 9]
In Example 9, a resin layer containing a near-infrared absorber (A) was laminated on one side of a glass substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, the resin composition (1) as an adhesion-imparting layer is applied to one side of a glass substrate "D263 (thickness 210 μm)" manufactured by SCHOTT with a die coater so that the thickness after drying is 0.7 μm. , The solvent was volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes. On this adhesion-imparting layer, 100 parts of resin B having a solubility parameter of 9.8 (cal / cm ³ ) ^1/2 obtained in Resin Synthesis Example 2, 0.8 parts of the compound (a-16), and A resin composition obtained by dissolving 0.8 part of the compound (b-3) in methylene chloride so as to have a concentration of 35% was applied with a spin coater so that the thickness after drying was about 5 μm. Then, by heating on a hot plate at 80 ° C. for 2 minutes to volatilize and remove the solvent, a laminate (X) composed of the resin layer containing the compounds (a-16) and (b-3) and the glass substrate. ) Was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 13 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). As is clear from this result, in the obtained laminate (X), the compounds (a-16) and (b-3) are uniformly compatible in the resin layer, and the laminate (X) is good. The haze value is shown. On the other hand, since the resin layer was coated with a spin coater, the film thickness variation of the resin layer became large, so that the in-plane variation of the optical characteristics was large. Therefore, the in-plane variation in the optical characteristics of the laminated body (Y) is also large.

Further, Table 13 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this comparative example and the operation status evaluation of the ambient light sensor. As is clear from this result, the color tone unevenness of the photographic image quality was large and the photographic image quality was poor, but the flare phenomenon was not observed. In addition, the ambient light sensor did not function well in changing the color tone of the screen in response to the change in external light, and the operating condition was poor.

[Comparative Example 1]
In Comparative Example 1, a resin layer containing a near-infrared absorber (A) was laminated on one side of a glass substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, the resin composition (1) as an adhesion-imparting layer is applied to one side of a glass substrate "D263 (thickness 210 μm)" manufactured by SCHOTT with a die coater so that the thickness after drying is 0.7 μm. , The solvent was volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes. On this adhesion-imparting layer, 100 parts of resin G having a solubility parameter of 6.2 (cal / cm ³ ) ^1/2 obtained in Resin Synthesis Example 7, 0.8 parts of the compound (a-16), and A resin composition in which 0.8 part of compound (b-3) was dissolved in chlorobenzene to a concentration of 25% was applied with a die coater so that the thickness after drying was about 5 μm. Next, the compound (a-16) and the above (b-3) are contained by heating on a hot plate at 80 ° C. for 10 minutes and then heating in a vacuum dryer at 80 ° C. for 3 hours to volatilize and remove the solvent. A laminate (X) composed of a resin layer and the glass substrate was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 14 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). In the obtained laminate (X), the near-infrared absorber (A) is not uniformly compatible with the resin layer, so that the haze value of the laminate (X) is high and the resin layer is inhomogeneous, so that the resin layer Due to the large in-plane variation in film thickness and optical characteristics, it had characteristics that could not be put into practical use. Therefore, the in-plane variation in the optical characteristics of the laminated body (Y) is also large.

Further, Table 14 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this comparative example and the operation status evaluation of the ambient light sensor. As is clear from this result, the color tone unevenness of the photographic image quality was large, the color tone unevenness of the photographic image quality was large, and the flare phenomenon around the fluorescent lamp was observed. In addition, the ambient light sensor did not function well in changing the color tone of the screen in response to the change in external light, and the operating condition was poor.

[Comparative Example 2]
In Comparative Example 2, a resin layer containing a near-infrared absorber (A) was laminated on one side of a resin substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, a Zeonoa ZF16 film substrate (thickness of 100 μm) is used as the resin substrate, and a resin having a solubility parameter of 7.4 (cal / cm ³ ) ^1/2 obtained in Resin Synthesis Example 8 on one side of the resin substrate. A resin composition obtained by dissolving 100 parts of H, 1.2 parts of the compound (a-19) and 1.0 part of the compound (b-3) in chlorobenzene so as to have a concentration of 25% is about the thickness after drying. It was applied with a die coater so as to have a thickness of 5 μm. Next, the resin containing the compounds (a-19) and (b-3) is removed by volatilizing and removing the solvent by heating on a hot plate at 80 ° C. for 10 minutes and then heating in a vacuum dryer at 80 ° C. for 3 hours. A laminate (X) composed of a layer and the resin substrate was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 14 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). In the obtained laminate (X), the near-infrared absorber (A) is not uniformly compatible with the resin layer, so that the haze value of the laminate (X) is high and the resin layer is inhomogeneous, so that the resin layer Due to the large in-plane variation in film thickness and optical characteristics, it had characteristics that could not be put into practical use. Therefore, the in-plane variation in the optical characteristics of the laminated body (Y) is also large.

Further, Table 14 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this comparative example and the operation status evaluation of the ambient light sensor. As is clear from this result, the color tone unevenness of the photographic image quality was large, the photographic image quality was poor, and the flare phenomenon around the fluorescent lamp was observed. In addition, the ambient light sensor did not function well in changing the color tone of the screen in response to the change in external light, and the operating condition was poor.

[Comparative Example 3]
In Comparative Example 3, a resin layer containing a near-infrared absorber (A) was laminated on one side of the resin substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, an ARTON film (100 μm thickness) is used as the resin substrate, and the solubility parameter obtained in Resin Synthesis Example 2 is 9.8 (cal / cm ³ ) ^1/2 on one side of the resin substrate. A resin composition obtained by dissolving 3.2 parts of the compound (a-16) and 0.5 part of the compound (b-3) in chlorobenzene so as to have a concentration of 25% is about 3 μm in thickness after drying. It was applied with a die coater so as to become. Next, the resin containing the compounds (a-16) and (b-3) is removed by volatilizing and removing the solvent by heating on a hot plate at 80 ° C. for 10 minutes and then heating in a vacuum dryer at 80 ° C. for 3 hours. A laminate (X) composed of a layer and the resin substrate was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 14 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). In the obtained laminate (X), the near-infrared absorber (A) is not uniformly compatible with the resin layer, so that the haze value of the laminate (X) is high and the resin layer is inhomogeneous, so that the resin layer Due to the large in-plane variation in film thickness and optical characteristics, it had characteristics that could not be put into practical use. Therefore, the in-plane variation in the optical characteristics of the laminated body (Y) is also large.

Further, Table 14 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this comparative example and the operation status evaluation of the ambient light sensor. As is clear from this result, the color tone unevenness of the photographic image quality was large, the photographic image quality was poor, and the flare phenomenon around the fluorescent lamp was observed. In addition, the ambient light sensor did not function well in changing the color tone of the screen in response to the change in external light, and the operating condition was poor.

[Comparative Example 4]
In Comparative Example 4, a resin layer containing a near-infrared absorber (A) was laminated on one side of a glass substrate, and an optical filter having a dielectric multilayer film on both sides of the laminated body was produced. The specific procedure is shown below.

First, the following resin composition (1) is applied as an adhesion-imparting layer on one side of a glass substrate "D263 (thickness 210 μm)" manufactured by SCHOTT with a die coater so that the thickness after drying is 0.7 μm. , The solvent was volatilized and removed by heating in a dryer at 80 ° C. for 3 minutes. On this adhesion-imparting layer, 100 parts of the resin A obtained in Resin Synthesis Example 1, 1.0 part of the compound (a-16) and 3.2 parts of the compound (b-3) are concentrated in methylene chloride at a concentration of 35. The resin composition dissolved so as to be% is applied with a die coater so that the thickness after drying becomes about 3 μm, and then heated in a dryer at 80 ° C. for 3 minutes to volatilize and remove the solvent. A laminate (X) composed of a resin layer containing the compounds (a-16) and (b-3) and the glass substrate was obtained. Subsequently, by the same method as in Example 1, an optical filter made of a laminate (Y) in which dielectric multilayer films (α) and (β) were formed on both sides of the obtained laminate (X) was obtained. ..

Table 14 shows variations in the film thickness of the resin layer, haze values of the laminate (X), and variations in the optical characteristics of the laminates (X) and (Y). In the obtained laminate (X), since the near-infrared absorber (A) is not uniformly compatible with the resin layer, the haze value is high and the resin layer is inhomogeneous, so that the film thickness and optical characteristics of the resin layer are high. The in-plane variation was large, and it had characteristics that could not be put into practical use. Therefore, the in-plane variation in the optical characteristics of the laminated body (Y) is also large.

Further, Table 14 shows the results of the photographic image evaluation of the camera module incorporating the optical filter of this comparative example and the operation status evaluation of the ambient light sensor. As is clear from this result, the color tone unevenness of the photographic image quality was large, the photographic image quality was poor, and the flare phenomenon around the fluorescent lamp was observed. In addition, the ambient light sensor did not function well in changing the color tone of the screen in response to the change in external light, and the operating condition was poor.

1: Camera module 2: Lens barrel 3: Flexible substrate 4: Hollow package 5: Lens 6: Optical filter 7: (CCD or CMOS) Image sensor 10: Laminated body (X) or Laminated body (Y)
20: Spectrophotometer 100: Optical filter 101: Substrate 103: Dielectric multilayer film 104: Antireflection film 110: Near-infrared absorber (A) -containing resin layer 111: Near-infrared absorber (A) -containing resin layer 120: Near Absorbent-containing resin layer 130 other than infrared absorber (A): Laminated body (X)
200: Ambient light sensor 202: Photoelectric conversion element 204: Housing 206: First electrode 208: Photoelectric conversion layer 210: Second electrode 212: Color filter 214: Element separation insulating layer 216: Passivation film

Claims (11)

An optical filter including a laminate (X) having a substrate and a resin layer made of a thermoplastic resin provided on at least one surface of the substrate.
The solubility parameter value of the resin constituting the resin layer is 9.0 (cal / cm ³ ) ^1/2 or more.
The resin layer contains two or more kinds of near-infrared absorbers (A) selected from the group consisting of squarylium compounds, cyanine compounds and phthalocyanine compounds.
The ratio (content / film thickness) of the content (parts by mass) of each near-infrared absorber (A) to 100 parts by mass of the resin and the film thickness (μm) of the resin layer is 0.005 to 1. An optical filter characterized by being in the range of 0. The first aspect of the present invention, wherein the substrate is a glass substrate or a resin substrate having a thickness of 300 μm or less, and the thickness of the resin layer containing the near-infrared absorber (A) is 20 μm or less. Optical filter. The optical filter according to claim 1 or 2, wherein the haze value of the laminated body (X) is 0.20% or less. The optical filter according to any one of claims 1 to 3, further comprising a dielectric multilayer film on at least one side of the laminated body (X). The optical filter according to any one of claims 1 to 3, wherein the in-plane variation in the thickness of the resin layer or the laminate (X) is within 10%. An element for solid-state imaging, which comprises the optical filter according to any one of claims 1 to 5. A solid-state imaging device comprising the optical filter according to any one of claims 1 to 5. An ambient light sensor element comprising the optical filter according to any one of claims 1 to 5. An ambient light sensor device comprising the optical filter according to any one of claims 1 to 5. A TOF distance image sensor element comprising the optical filter according to any one of claims 1 to 5. A TOF distance imaging apparatus comprising the optical filter according to any one of claims 1 to 5.

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