JPWO2020054695A1 - Optical filters and their uses - Google Patents

Abstract

An object of the present invention is to provide an optical filter having both low incident angle dependence in the near infrared region and excellent red transmittance characteristics and improved ghosting. The optical filter of the present invention is characterized by satisfying the following requirements (A) to (D): (A) In the wavelength range of 430 to 580 nm, the average value of the transmittance when measured from the vertical direction is 75%. (B) The average value of the transmittance when measured from the vertical direction in the wavelength range of 800 to 1000 nm is 10% or less; (C) The transmittance when measured from the vertical direction in the wavelength range of 700 to 750 nm. (D) The shortest wavelength value (Ya) at which the transmittance is 50% when measured from the vertical direction in the wavelength range of 560 to 800 nm, and 30 ° with respect to the vertical direction. The absolute value of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% when measured from the angle of is less than 15 nm.

Description

The present invention relates to an optical filter and its use. More specifically, the present invention relates to an optical filter having specific optical characteristics (for example, a near-infrared cut filter), and a solid-state imaging device and a camera module using the optical filter.

A CCD or CMOS image sensor, which is a solid-state image sensor for a color image, is used in a solid-state image sensor such as a video camera, a digital still camera, or a mobile phone with a camera function. Since these solid-state image sensors use a sensor that is sensitive to near-infrared rays in the light-receiving part, it is necessary to correct the luminosity factor, and an optical filter (for example, a near-infrared cut filter) is often used. ..

As such an optical filter, those manufactured by various methods have been conventionally used. For example, a near-infrared cut filter having a near-infrared reflective film obtained by laminating a dielectric multilayer film on a norbornene-based resin is known. (See, for example, Patent Document 1). However, in a near-infrared cut filter having such a near-infrared reflecting film, the incident angle dependence of the light transmission characteristics is large, and in a solid-state imaging device having a wide viewing angle, there is a problem that the tint is different between the center and the peripheral part of the image. Was.

As an example of improving the incident angle dependence, an optical filter such as a near-infrared cut filter containing a near-infrared absorber is widely known. Specifically, a near-infrared cut filter is known in which a resin is used as a base material and a near-infrared absorber having a steep absorption characteristic is contained in the resin to improve the dependence on the incident angle in the near-infrared region. (See, for example, Patent Document 2).

In recent years, an image sensing system that detects not only wavelengths of 400 nm to 700 nm, which have high human luminosity, but also near infrared rays, and measures the degree of plant growth and the amount of oxygenated hemoglobin in humans has been studied (for example, Patent Document 3 and 4). For example, in Patent Document 3, it is known that the reflectance of rice leaves at a wavelength of 500 nm to 800 nm changes depending on the nitrogen content, and the reflection intensity of visible light and the reflection intensity of near-infrared light are used to grow plants. A method for obtaining an index has been proposed.

Further, for example, using an ultraviolet laser having a wavelength of 355 nm as a light source, the ratio (F690 / F740) of the fluorescence intensity (F690) having a wavelength of 690 nm to the fluorescence intensity (F740) having a wavelength of 740 nm is a vegetation as an index of the chlorophyll concentration in the living body of a plant. It is known that it can be diagnosed (see, for example, Non-Patent Document 1).

However, in an image sensing system that combines visible light with a wavelength of 400 to 700 nm and near infrared rays, an optical filter such as a conventional near infrared ray absorber containing a conventional near infrared ray absorber has a wavelength of 700 to 700 to be used for detection. The light transmittance at 750 nm was low, and it was difficult to maintain sufficient sensitivity.

In a near-infrared cut filter having a near-infrared reflective film in which a dielectric multilayer film is laminated, it is known that the reflection band is shifted by a long wavelength by increasing the thickness of the laminated dielectric multilayer film. Therefore, it is easy to provide a dielectric multilayer film having a high transmittance at a wavelength of 700 nm to 750 nm, but such a near-infrared cut filter has a large dependence on the incident angle at the time of high-angle incident, and when imaged. In addition, there is a problem that the intensity of light obtained by sensing differs depending on the angle of incidence in the center and the periphery of the image.

Further, the performance of the solid-state image sensor has been improved, and in the conventional optical filter, the image quality may be deteriorated due to the ghost caused by the reflection of the optical filter. In particular, there has been a problem of ghost generation due to the reflection of an optical filter by light rays having a wavelength of 680 to 720 nm, which causes some stray light to re-enter at another position of the sensor. Therefore, it is required to reduce the reflectance at a wavelength of 680 to 720 nm.
However, the conventional optical filter has not sufficiently met the demand for both suppressing the ghost and improving the sensitivity of the red sensor.

Japanese Patent No. 4513420 Japanese Unexamined Patent Publication No. 2012-8532 Japanese Unexamined Patent Publication No. 2016-146784 International Publication No. 2018/123766 Pamphlet

H. K. Richtenthaler et al. : Detection of Vegetation Pressure Via a New High Resolution Fluorescence Imaging System, ". Plant Physiol. , 148,599-612 (1996)

An object of the present invention is an optical filter having both low incident angle dependence in the near-infrared region and excellent light transmittance characteristics of light having a wavelength of 700 to 750 nm required for sensing, and improved ghosting, and the optics thereof. The purpose is to provide an apparatus using a filter.

The optical filter according to one aspect of the present invention is characterized in that it satisfies the following requirements (A) to (D).
(A) In the wavelength range of 430 to 580 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is 75% or more.
(B) In the wavelength range of 800 to 1000 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is 10% or less.
(C) In the wavelength range of 700 to 750 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is more than 46%.
(D) The shortest wavelength value (Ya) at which the transmittance is 50% when measured from the direction perpendicular to the surface of the optical filter in the wavelength range of 560 to 800 nm, and the value perpendicular to the surface of the optical filter. The absolute value of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% when measured from an angle of 30 ° from the direction is less than 15 nm.

According to the present invention, an optical filter having both low incident angle dependence in the near-infrared region and excellent light transmittance characteristics of light having a wavelength of 700 to 750 nm required for sensing and improved ghosting, and the optics thereof. An apparatus using a filter can be provided. The optical filter of the present invention is suitable as a near-infrared cut filter.

It is a schematic diagram which shows an example of the optical filter of this invention. It is a schematic diagram which shows an example of the optical filter of this invention. This is the wavelength-specific intensity data released by the National Research and Development Corporation New Energy and Industrial Technology Development Organization, which standardizes the irradiation dose data of Gifu at a certain date and time with a maximum value of 1.0. This is an example of the wavelength-specific sensitivity of each of the green and near-infrared sensor pixels. It is a figure which shows the optical characteristic of the bi-wavelength region transmission filter which transmits green and near-infrared rays which were made for the sensitivity evaluation of green and the sensitivity of near-infrared rays. It is the schematic which shows the example of the method of measuring the transmittance when measured from the direction perpendicular to the surface of an optical filter. It is the schematic which shows the example of the method of measuring the transmittance when it measured at the angle of 30 ° from the direction perpendicular to the surface of an optical filter. It is the schematic which shows the example of the method of measuring the reflectance of the light incident on the plane of an optical filter at an angle of 5 ° from the vertical direction. It is the schematic which shows an example of a camera module. It is the schematic which shows an example of the ghost generation mechanism in a camera module. It is a schematic diagram which shows an example of a ghost. It is a figure which shows the optical characteristic of the optical filter obtained in Example 1. FIG. It is a figure which shows the optical characteristic of the optical filter obtained in Example 5. It is a figure which shows the optical characteristic of the optical filter obtained in the comparative example 1. FIG. It is a figure which shows the optical characteristic of the optical filter obtained in the comparative example 4. FIG. It is a figure which shows the optical characteristic of the optical filter obtained in the comparative example 7.

Embodiments of the present invention will be described with reference to the drawings as needed, but those drawings are provided solely for illustration purposes and the present invention is not limited to those drawings. Also, please note that the drawings are schematic, and the relationship between the thickness and the plane dimensions, the ratio of the thickness, etc. are different from the actual ones. Further, in the following description, the same reference numerals will be given to the configuration applications having the same or substantially the same function and configuration, and duplicate description will be omitted. As an embodiment of the optical filter of the present invention, as shown in FIG. 1, an embodiment having a base material 10 and near-infrared reflective films 21 and 22 can be mentioned. Further, as shown in FIG. 2, the optical filter of the present invention may have another functional film 13.

[Optical filter]
The optical filter of the present invention satisfies the following requirements (A) to (D).
(A) In the wavelength range of 430 to 580 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is 75% or more.
(B) In the wavelength range of 800 to 1000 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is 10% or less.
(C) In the wavelength range of 700 to 750 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is more than 46%.
(D) The shortest wavelength value (Ya) at which the transmittance is 50% when measured from the direction perpendicular to the surface of the optical filter in the wavelength range of 560 to 800 nm, and the value perpendicular to the surface of the optical filter. The absolute value of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% when measured from an angle of 30 ° from the direction is less than 15 nm.

By using an optical filter that satisfies the requirement (A), the amount of light taken in by the solid-state image sensor can be increased in the wavelength range of 430 nm to 580 nm. The average value of the transmittance in the requirement (A) is preferably 80% or more. If it is 80% or more, imaging is possible even in a darker environment.

By using an optical filter that satisfies the requirement (B), the amount of light taken in by the solid-state image sensor in the wavelength range of 800 nm to 1000 nm can be reduced. This makes it possible to block light that is invisible to the human eye and is unnecessary for sensing. The average value of the transmittance in the requirement (B) is preferably 7% or less, more preferably 6% or less, still more preferably 5% or less.

By using an optical filter that satisfies the requirement (C), the amount of light taken in by the solid-state image sensor is secured in the wavelength range of 700 nm to 750 nm, and the sensing sensitivity is improved. The average value of the transmittance in the requirement (C) is preferably 55% or more, more preferably 65% or more, still more preferably 75% or more. The higher the transmittance, the better, but for example, the upper limit is preferably 100%, more preferably 90%, and even more preferably 80%. Within the above range, the amount of light taken in by the solid-state image sensor is adjusted, and the light required for sensing can be efficiently transmitted.

By using an optical filter that satisfies the requirement (D), the incident angle dependence of the amount of light incident on the solid-state image sensor can be reduced in the wavelength range of 560 nm to 800 nm. As a result, the incident angle dependence of the spectral sensitivity of the solid-state image sensor in this wavelength range can be reduced. By reducing the incident angle dependence, the difference in color tone between the center and the periphery of the image obtained by the solid-state image sensor and the sensor sensitivity is small, and the sensitivity becomes higher.

The optical filter of the present invention preferably further satisfies the following requirement (E).
(E) The wavelength value (Ya) in the requirement (D) is 730 nm or more and 800 nm or less.

By using an optical filter that meets the requirement (E), the visible light transmittance at a wavelength of 400 to 700 nm and the near infrared transmittance at a wavelength of 700 to 750 nm used for sensing can be kept high, and the wavelength 800 unnecessary for sensing can be maintained. It becomes easy to achieve both a low transmittance (high shielding property) of about 1200 nm. The wavelength (Ya) is preferably 740 nm or more and 800 nm or less, and more preferably 745 nm or more and 800 nm or less.

It is preferable that the optical filter of the present invention further satisfies the following requirements (Z1) and (Z2).
(Z1) At a wavelength of 700 nm, the reflectance when measured from an angle of 5 ° from the direction perpendicular to the surface of the optical filter is 10% or less when incident from either surface of the optical filter.
(Z2) Which of the optical filters has the shortest wavelength value (Za) at which the reflectance is 50% when measured from an angle of 5 ° from the direction perpendicular to the surface of the optical filter in the wavelength range of 600 nm or more. It is 730 nm or more even when it is incident from the surface of.
By using an optical filter that satisfies the requirements (Z1) and (Z2), it is possible to suppress the generation of ghosts caused by the light reflected by the optical filter.

The near-infrared reflective film made of a dielectric multilayer film tends to move its reflection band to a shorter wavelength as it is obliquely incident at a higher angle from the surface of the optical filter. Therefore, the wavelength (Za) in the requirement (Z2) is more preferably 740 nm or more, further preferably 750 nm or more, and particularly preferably 780 nm or more. As a result, it is possible to sufficiently suppress the generation of ghosts even in the light incident on the surface of the optical filter at a high angle in the light confirmed by the human eye.
The optical filter of the present invention preferably has a base material containing a near-infrared absorber and a near-infrared reflective film.

An optical filter having a base material containing a near-infrared absorber can suppress the reflection of near-infrared rays of the optical filter and can reduce ghosts. An optical filter having a near-infrared reflective film has excellent near-infrared shielding performance and excellent transmission performance of visible light in the wavelength range of 430 to 580 nm, and can make the obtained solid-state image sensor highly sensitive.

When the near-infrared absorber has an absorption maximum wavelength in the wavelength range of 751 to 950 nm and the near-infrared absorber is contained in an amount such that the transmittance of the base material at the absorption maximum wavelength is 10%. The longest wavelength (Aa) at which the transmittance of the base material is 70% in the wavelength range of 430 nm or more and the absorption maximum wavelength or less, and the longest wavelength (Aa) at which the transmittance of the base material is 30% in the wavelength range of 580 nm or more. The absolute value of the difference from the short wavelength (Ab) is preferably less than 150 nm.

By using an optical filter having a base material containing a near-infrared absorber in which the absolute value of the difference between (Aa) and (Ab) is less than 150 nm, the transmittance of near-infrared rays having a wavelength of 700 to 750 nm is increased. It becomes easy to achieve both the maintenance and the low transmittance (high shielding property) having a wavelength of 800 to 1200 nm, which is unnecessary for sensing. The smaller the absolute value of the difference, the better, more preferably less than 100 nm, still more preferably less than 70 nm. The lower limit is 1 nm.

It is a characteristic of the near-infrared absorber in a preferable range that it has an absorption maximum wavelength at a wavelength of 751 to 950 nm and that the absolute value of the difference between the (Aa) and the (Ab) is less than 150 nm. The characteristics of one type of absorbent may be satisfied, or the characteristics of a mixture of a plurality of types may be used. Further, the near-infrared absorber in which a plurality of types are mixed may include one that does not satisfy the characteristics by itself.

[Base material]
The base material preferably has transparency. Transparency as used in the present invention means that the average value of the transmittance in the wavelength range of 420 to 600 nm is 50% or more. Examples of the material of such a base material include glass, tempered glass, special glass such as phosphoric acid glass, fluorinated glass, alumina glass, yttrium aluminate, and yttrium oxide, and resin.

Further, the base material may be composed of one layer or a plurality of layers, may be composed of one kind of material selected from the above materials, may be composed of a plurality of kinds, or may be an appropriately mixed material. At least one layer constituting the base material preferably contains a near-infrared absorber, and may also contain a near-ultraviolet absorber. The layer containing the near-infrared absorber and the layer containing the near-ultraviolet absorber may be the same layer or different layers.

<Glass>
Examples of the glass include silicate glass, soda-lime glass, borosilicate glass, quartz glass and the like.

<Tempered glass>
Examples of the tempered glass include physically tempered glass, tempered laminated glass, and chemically tempered glass. Among these, chemically strengthened glass having a thin compression layer and being able to process a thin base material is preferable. Specific examples of the chemically strengthened glass include "Dragonrail" manufactured by Asahi Glass Co., Ltd. and "Gorilla Glass" manufactured by Corning Inc.

<Special glass>
Examples of the phosphoric acid glass and the futuric acid glass include BS3, BS4, BS6, BS7, BS8, BS10, BS11, BS12, BS13, BS16, BS17, etc. manufactured by Matsunami Glass Ind. Examples thereof include the fluorinated glass described in 1. Examples of the alumina glass include "High Serum" manufactured by NGK Insulators, Ltd. Examples of the yttrium aluminate and the yttrium oxide include "EXYRIA (registered trademark)" manufactured by CoorsTek.

<Resin>
Examples of the resin include polyester-based resin, polyether-based resin, acrylic-based resin, polyolefin-based resin, polycycloolefin-based resin, norbornene-based resin, polycarbonate-based resin, en-thiol-based resin, epoxy-based resin, and polyamide-based resin. Examples thereof include resins, polyimide resins, polyurethane resins, and polystyrene resins. Among these, norbornene-based resin, polyimide-based resin, and polyether-based resin are preferable.

The refractive index of the resin can be adjusted by a method of adjusting the molecular structure of the raw material component or the like. Specifically, a method of imparting a specific structure to the main chain or side chain of the polymer as a raw material component can be mentioned. The structure imparted into the polymer is not particularly limited, and examples thereof include a norbornene skeleton and a fluorene skeleton.

A commercially available product may be used as the resin. Commercially available products include "Ogsol (registered trademark) EA-F5003" (acrylic resin, refractive index: 1.60) manufactured by Osaka Gas Chemical Co., Ltd. and "Polymethylmethacrylate" (refractive index) manufactured by Tokyo Kasei Kogyo Co., Ltd. 1.49), "Polyisobutylmethacrylate" (refractive index: 1.48) manufactured by Tokyo Kasei Kogyo Co., Ltd., "BR50" (refractive index: 1.56) manufactured by Mitsubishi Rayon Co., Ltd., and the like.

Examples of commercially available polyester-based resins include "OKP4HT" (refraction rate: 1.64), "OKP4" (refraction rate: 1.61), and "B-OKP2" manufactured by Osaka Gas Chemical Co., Ltd. (refraction rate: 1.64). Refraction rate: 1.64), "OKP-850" (refraction rate: 1.65), "Byron (registered trademark) 103" manufactured by Toyo Boseki Co., Ltd. (refraction rate: 1.55), etc. are polycarbonate-based. Examples of commercially available resin products include "LeXan (registered trademark) ML9103" (refractive index: 1.59) manufactured by polycarbonate, "xylex (registered trademark) 7507", and "EP5000" (refraction) manufactured by Mitsubishi Gas Chemicals Co., Ltd. Rate: 1.63), "SP3810" (refraction rate: 1.63), "SP1516" (refraction rate: 1.60), "TS2020" (refraction rate: 1.59), etc. manufactured by Teijin Kasei Co., Ltd. Examples of commercially available products of the norbornene-based resin include "ARTON (registered trademark) (refraction rate: 1.51) manufactured by JSR Co., Ltd. and" ZEONEX (registered trademark) (refraction rate:: 1.51) manufactured by Nippon Zeon Co., Ltd. 1.53) and the like.

The polyether resin is a polymer obtained by a reaction of forming an ether bond in the main chain, and contains at least one structural unit selected from the group consisting of the structural units represented by the following formulas (1) and (2). It is preferably a polymer having. Further, it may have a structural unit represented by the following formula (3).

前記式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に炭素数１〜１２の１価の有機基を示す。ａ〜ｄは、それぞれ独立に０〜４の整数を示し、好ましくは０または１であり、より好ましくは０である。

In the formula (1), R ^{1 to} R ⁴ independently represent monovalent organic groups having 1 to 12 carbon atoms. Each of a to d independently represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

The monovalent organic group having 1 to 12 carbon atoms includes a monovalent hydrocarbon group having 1 to 12 carbon atoms and at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. Examples thereof include monovalent organic groups of ~ 12.

The monovalent hydrocarbon groups having 1 to 12 carbon atoms include linear or branched hydrocarbon groups having 1 to 12 carbon atoms, alicyclic hydrocarbon groups having 3 to 12 carbon atoms, and 6 to 12 carbon atoms. Examples include aromatic hydrocarbon groups.

As the linear or branched hydrocarbon group having 1 to 12 carbon atoms, a linear or branched hydrocarbon group having 1 to 8 carbon atoms is preferable, and a linear or branched hydrocarbon group having 1 to 5 carbon atoms is used. Hydrogen groups are more preferred.

Preferable specific examples of the linear or branched hydrocarbon group include 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 and an n-pentyl group. Groups, n-hexyl groups, n-heptyl groups and the like can be mentioned.

As the alicyclic hydrocarbon group having 3 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 8 carbon atoms is preferable, and an alicyclic hydrocarbon group having 3 or 4 carbon atoms is more preferable.
Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms are cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; cyclobutenyl group, cyclopentenyl group and cyclohexenyl group. Cycloalkenyl groups such as. The binding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group and a naphthyl group. The binding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom include an organic group composed of a hydrogen atom, a carbon atom and an oxygen atom, and among them, a total carbon composed of an ether bond, a carbonyl group or an ester bond and a hydrocarbon group. The organic groups of numbers 1 to 12 can be preferably mentioned.

Examples of the organic group having a total carbon number of 1 to 12 having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and 6 to 12 carbon atoms. Examples thereof include an aryloxy group and an alkoxyalkyl group having 1 to 12 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group and a cyclohexyloxy group. And methoxymethyl group and the like.

Examples of the organic group having a total carbon number of 1 to 12 having a carbonyl group include an acyl group having 2 to 12 carbon atoms, and specific examples thereof include an acetyl group, a propionyl group, an isopropionyl group and a benzoyl group. ..

Examples of the organic group having a total carbon number of 1 to 12 having an ester bond include an acyloxy group having 2 to 12 carbon atoms, and specifically, an acetyloxy group, a propionyloxy group, an isopropionyloxy group and a benzoyloxy group. And so on.

Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom and a nitrogen atom, and specifically, a cyano group, an imidazole group, a triazole group, a benzimidazole group and benz. Examples thereof include a triazole group.

Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom, an oxygen atom, and a nitrogen atom, and specifically, an oxadiazole group and an oxadiazole. Groups, benzoxazole groups, benzoxadiazole groups and the like can be mentioned.

^{As R 1 to} R ⁴ in the formula (1), a monovalent hydrocarbon group having 1 to 12 carbon atoms is preferable from the viewpoint of water absorption (wetness) of the resin (1), and an aromatic group having 6 to 12 carbon atoms is preferable. Hydrocarbon groups are more preferred, and phenyl groups are even more preferred.

In the formula (2), R ^{1 to} R ^{4 and a to d are independently synonymous with R 1 to} R ⁴ and a to d in the formula (1), respectively, and Y is a single bond, −SO. ₂ − or −CO −, R ⁷ and R ⁸ independently represent a halogen atom, a monovalent organic group or a nitro group having 1 to 12 carbon atoms, and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group. g and h each independently represent an integer of 0 to 4, preferably 0.

Examples of the monovalent organic group having 1 to 12 carbon atoms include those similar to the monovalent organic group having 1 to 12 carbon atoms in the formula (1).
The resin (1) has a molar ratio of the structural unit (1) and the structural unit (2) (however, the total of both (the total of the structural unit (1) + the structural unit (2)) is 100). From the viewpoint of optical properties, heat resistance and mechanical properties, structural unit (1): structural unit (2) = 50: 50 to 100: 0 is preferable, and structural unit (1): structural unit (2). = 70:30 to 100: 0 is more preferable, and structural unit (1): structural unit (2) = 80:20 to 100: 0 is even more preferable. In addition, in this specification, a mechanical property means a property such as a tensile strength, a breaking elongation and a tensile elastic modulus of a resin.

Further, the resin (1) is further selected from a group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4) (hereinafter, "structural unit (3)". -4) ”). It is preferable that the resin (1) has such a structural unit (3-4) because the mechanical properties of the base material containing the resin (1) are improved.

In the formula (3), R ⁵ and R ⁶ are each independently a monovalent organic group having 1 to 12 carbon atoms, Z is a single bond, -O -, - S -, - SO 2 -, It represents -CO-, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, and n represents 0 or 1. e and f each independently represent an integer of 0 to 4, preferably 0.

Examples of the monovalent organic group having 1 to 12 carbon atoms include those similar to the monovalent organic group having 1 to 12 carbon atoms in the formula (1).
The divalent organic group having 1 to 12 carbon atoms is a group consisting of a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms containing at least one selected atom, and a divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. Halogenated organic groups and the like.

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a divalent hydrocarbon group having 3 to 12 carbon atoms. Examples thereof include divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms.

Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group and a heptamethylene group.

Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group; cyclobutenylene group, cyclopentenylene group and Examples thereof include a cycloalkenylene group such as a cyclohexenylene group.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group and a biphenylene group.
Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms and a divalent halogenated hydrocarbon group having 3 to 12 carbon atoms. Examples thereof include a cyclic hydrocarbon group and a divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms.

Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a difluoromethylene group, a dichloromethylene group, a tetrafluoroethylene group, a tetrachloroethylene group, a hexafluorotrimethylene group and a hexachlorotrimethylene group. Examples thereof include a group, a hexafluoroisopropylidene group and a hexachloroisopropyridene group.

As the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, at least a part of the hydrogen atoms of the groups exemplified in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms are fluorine atoms. , A group substituted with a chlorine atom, a bromine atom or an iodine atom, and the like.

As the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms, at least a part of the hydrogen atoms of the groups exemplified in the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms are fluorine atoms and chlorine. Examples thereof include groups substituted with an atom, a bromine atom or an iodine atom.

Examples of the organic group having 1 to 12 carbon atoms including at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom and a carbon atom and an oxygen atom and / or a nitrogen atom. Examples thereof include a divalent organic group having 1 to 12 total carbon atoms having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.

The divalent halogenated organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms is specifically selected from the group consisting of oxygen atoms and nitrogen atoms. Examples thereof include a group in which at least a part of hydrogen atoms of the group exemplified in the divalent organic group having 1 to 12 carbon atoms including at least one atom is replaced with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ..

Formula (3) as Z in a single _{bond, -O -, - SO 2 -} , - CO- or preferably a divalent organic group having 1 to 12 carbon atoms, water absorption resin (1) (wet) properties From this point of view, a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferable.

It is preferable that the base material has a resin layer containing a near-infrared absorber, and the resin layer contains at least one selected from the group consisting of a norbornene-based resin, a polyimide-based resin, and a polyether resin.

By having the resin layer, an optical filter having high transparency at a wavelength of 430 to 580 nm, high heat resistance, resistance to warping, resistance to breakage, and _{low in-plane retardation R 0} can be obtained. Therefore, the solid-state image sensor provided with the optical filter having the resin layer has high image quality and can be easily manufactured.

The average value of the transmittance of the resin layer at a wavelength of 430 to 580 nm is preferably 70% or more at a thickness of 1 μm because the solid-state image sensor has high sensitivity.
The glass transition temperature of the resin layer is preferably 140 ° C. or higher because the solid-state image sensor can be manufactured in the low-temperature reflow step.

The Young's modulus of the resin layer is preferably 2 GPa or more from the viewpoint of obtaining an optical filter that does not easily warp.
The in-plane retardation R ₀ of the resin layer is preferably 50 nm or less, more preferably 20 nm or less, still more preferably 10 nm or less, and particularly preferably 5 nm or less. When an optical filter having a small in-plane phase difference R ₀ is provided with an image sensor having different sensitivities depending on the polarization, the polarization characteristics can be accurately detected and the error is reduced.

The resin layer may be one layer or a plurality of layers in the base material, and the base material may be composed of only the resin layer.
The thickness of the base material can be appropriately selected depending on the desired application and is not particularly limited, but the upper limit is preferably 250 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less, and the lower limit is set. It is preferably 30 μm or more, more preferably 40 μm or more. When the thickness is within the above range, the warp of the optical filter is small, and a sufficiently thin solid-state image sensor can be obtained.

<Manufacturing method of resin layer>
The resin layer can be formed by, for example, melt molding or cast molding, and if necessary, is produced by a method of coating a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding. Can be done.

(A) Melt molding The resin layer is a method of melt-molding pellets obtained by melt-kneading a resin and a near-infrared absorber; a resin composition containing a resin and a near-infrared absorber is melt-molded. Method; Alternatively, it can be produced by a method of melt-molding pellets obtained by removing a solvent from a resin composition containing a near-infrared absorber, a resin and a solvent. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding and the like.

(B) Cast molding A method in which a resin composition containing a near-infrared absorber, a resin and a solvent is cast on a suitable support to remove the solvent; an antistatic agent, a hard coat agent and / or A method of casting a resin composition containing a coating agent such as an antistatic agent, a near infrared absorber, and a resin on an appropriate support; or an antireflection agent, a hard coat agent, and / or an antistatic agent, etc. It can also be produced by a method of casting a curable composition containing the coating agent of the above, a dye compound, and a resin on an appropriate support, curing and drying.

The support is not particularly limited, and a support made of glass, tempered glass, special glass or resin mentioned as an example of the material of the base material can be used, and a support other than the material of the base material, For example, a steel belt, a steel drum, or the like may be used.

When the base material is a base material made of a resin substrate, the base material can be obtained by peeling the coating film from the support after cast molding, and the base material is the support. In the case of a base material having a resin layer laminated on the base material, the base material can be obtained by casting and molding without peeling off the coating film.

The amount of residual solvent in the resin layer obtained by the above method should be as small as possible, and is usually 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass, based on the weight of the resin layer. % Or less. When the amount of the residual solvent is within the above range, a resin layer capable of easily exhibiting a desired function can be obtained, in which deformation of the optical filter and change in optical characteristics are unlikely to occur.

[Near infrared absorber]
The near-infrared absorber preferably has an absorption maximum wavelength in the wavelength range of 751-950 nm, more preferably 760 to 940 nm, further preferably 770 to 930 nm, and particularly preferably 775 to 925 nm. When the absorption maximum wavelength is in the above range, the amount of light taken in by the solid-state image sensor is adjusted in the wavelength range of 700 nm to 750 nm, and the light in the wavelength range of 751 nm or more, which has low human visual sensitivity, is transferred to the solid-state image sensor. The amount of light entering can be reduced, and the solid-state image sensor can be brought closer to the human visual sensitivity.

Examples of the near-infrared absorber include cyanine-based pigments, phthalocyanine-based pigments, dithiol-based pigments, diimonium-based pigments, squarylium-based pigments, croconium-based pigments, and copper phosphates. The structure of these dyes is not particularly limited, and generally known ones or commercially available products can be used as long as they do not impair the effects of the present invention. Further, the near-infrared absorber to be added to the optical filter may be one kind or a plurality of kinds as long as the effect of the present invention is not impaired.

The near-infrared absorber is preferably contained in the range of 0.01 to 60.0% by mass with respect to the resin layer. When the content of the near-infrared absorber is within the above range, appropriate optical characteristics can be easily obtained. If it is contained in an amount of more than 60.0% by mass, the above-mentioned high transparency, high heat resistance, resistance to warping, resistance to breakage, and other performances are lost, resulting in deterioration of image quality of the solid-state imaging device and increasing manufacturing difficulty. Become.

Further, the near-infrared absorber preferably satisfies the following conditions (a) and (b).
(A) (absorbance λ ₇₀₀ ) / (absorbance λ _max ) ≤ 0.1
(B) (absorbance λ ₇₅₁ ) / (absorbance λ _max ) ≧ 0.1

Here, the absorbance of the near-infrared absorber at a wavelength of 700 nm is defined as “absorbency λ ₇₀₀ ”, the absorbance at a wavelength of 751 nm is defined as “absorbency λ ₇₅₁ ”, the absorbance at the maximum absorption wavelength _{is defined as “absorbency λ max} ”, and the absorbance λ at wavelength λ is , Calculated from the transmission λ at wavelength λ according to the following commonly used formula.

Absorbance λ = −Log (internal transmittance λ)
For example, when the internal transmittance λ is 0.1 (10%), the absorbance is 1.0. The internal transmittance is a value obtained by subtracting the surface reflectance from the obtained transmittance, and is obtained by dividing the obtained transmittance by the transmittance of the medium excluding the near-infrared absorber.

When the above conditions (a) and (b) are satisfied, it is possible to obtain an optical filter having a high transmittance of a wavelength of 700 to 750 nm required for sensing and sufficiently shielding wavelengths unnecessary for both luminosity factor and sensing. .. By the way, in order to maintain the requirement (C) because the transmittance at a wavelength of 700 to 750 nm required for sensing is high, the absorbance λ ₇₀₀ of the optical filter is preferably 0.25 or less, more preferably 0.2 or less, still more preferable. Is 0.18 or less, particularly preferably 0.16 or less. The lower limit of the absorbance λ _{700 of the optical filter is 0.} By using a near-infrared absorber that satisfies the condition (a), the absorbance λ ₇₀₀ of the optical filter can be set within the above range.

Further, in order to sufficiently block light having a long wavelength from 751 nm, which is unnecessary for both luminosity factor and sensing, and to achieve the requirement (D), the absorbance λ ₇₅₁ of the optical filter is preferably 0.2 or more, more preferably 0.2 or more. Is 0.21 or more, more preferably 0.23 or more, and particularly preferably 0.25 or more. The absorbance λ ₇₅₁ of the optical filter is preferably 0.8 or less, more preferably 0.6 or less, still more preferably 0.5 or less. By using a near-infrared absorber that satisfies the above condition (b), the absorbance λ ₇₅₁ of the optical filter can be set within the above range.

However, the near-infrared absorber satisfying the condition (b) tends to have a smaller _{(absorbance λ 751} ) / (absorbance λ _{max ) as the absorption maximum wavelength λ max} becomes longer from 751 nm to 950 nm. .. Therefore, as the absorption maximum wavelength (λ _max ) becomes longer from 751 nm to 950 nm, it is necessary to increase the concentration of the near-infrared absorber contained in the substrate. On the other hand, if the substrate contains an excessive amount of a near-infrared absorber that satisfies the condition (a), it may be difficult for the optical filter to maintain the requirement (C). Therefore, the near-infrared absorber contained in the base material preferably satisfies the following condition (c).
(C) 1.5 ≧ Σ _{dye (n)} [((950-shortest absorption maximum wavelength) × dye concentration × dye medium thickness)]> 0.2

Here, " _{dye (n)} " in "Σ dye (n)" means each near-infrared absorber contained in the base material. Further, the "shortest absorption maximum wavelength" means the shortest wavelength (nm) among the absorption maximum wavelengths at wavelengths 751 to 950 nm, and the "dye concentration" is the concentration of the near-infrared absorber contained in the substrate. It means (% by mass), and the "dye medium thickness" means the thickness (mm) of the base material containing the near-infrared absorber.

By using a near-infrared absorber that satisfies the conditions (a) and (b) at the concentration of the condition (c), _{it becomes possible to set the absorbance λ 700} and the absorbance λ ₇₅₁ of the optical filter within the above-mentioned preferable ranges. , It becomes easy to meet the requirements (C) and (D).

<Cyanine pigment>
The cyanine-based dye is not particularly limited as long as it does not impair the effects of the present invention, and is described in, for example, JP-A-2009-108267, JP-A-2010-72575, and JP-A-2016-060774. Cyanine pigments can be mentioned.

Some cyanine-based dyes do not have an absorption maximum wavelength at a wavelength of 751-950 nm, but a cyanine-based dye having an absorption maximum wavelength at a wavelength of 751-950 nm is selected, or an absorption maximum at a wavelength of 751-950 nm. A cyanine dye having no wavelength and a cyanine dye having an absorption maximum wavelength at a wavelength of 751 to 950 nm are used in combination, or a cyanine dye having no absorption maximum wavelength at a wavelength of 751 to 950 nm and an absorption maximum wavelength at a wavelength of 751 to 950 nm. It can be used as a near-infrared absorber to obtain the effect of the present invention by using a dye other than the cyanine-based dye having the above.

<Parthalocyanine pigment>
The phthalocyanine dye is not particularly limited as long as it does not impair the effects of the present invention. Japanese Patent Application Laid-Open No. 4-39361, Japanese Patent Application Laid-Open No. 5-78364, Japanese Patent Application Laid-Open No. 5-2222047, Japanese Patent Application Laid-Open No. 5-222301, Japanese Patent Application Laid-Open No. 5-222302, Japanese Patent Application Laid-Open No. 5-345861, Japanese Patent Application Laid-Open No. 6-25548, 6-107663, 6-192584, 6-228533, 7-118551, 7-118552, 8- 120186, 8-225751, Japanese 9-202860, 10-120927, 10-182995, 11-35838, 2000-26748. JP-A-2000-63691, JP-A-2001-106689, JP-A-2004-18561, JP-A-2005-220060, JP-A-2007-169343, JP-A-2013-195480. Examples thereof include the compounds described in paragraphs [0026] to [0027], Table 1 of International Publication No. 2015/025779, and the like.

Some phthalocyanine-based dyes do not have an absorption maximum wavelength at a wavelength of 751-950 nm, but a phthalocyanine-based dye having an absorption maximum wavelength at a wavelength of 751-950 nm is selected, or an absorption maximum at a wavelength of 751-950 nm. A phthalocyanine dye having no wavelength and a phthalocyanine dye having an absorption maximum wavelength at a wavelength of 751 to 950 nm are used in combination, or a phthalocyanine dye having no absorption maximum wavelength at a wavelength of 751 to 950 nm and an absorption maximum wavelength at a wavelength of 751 to 950 nm. It can be used as a near-infrared absorber to obtain the effect of the present invention by using a dye other than the phthalocyanine dye having the above. Phthalocyanine dyes often have steep absorption characteristics near the maximum absorption wavelength, and when a phthalocyanine dye is used in the optical filter of the present invention, it may be used in combination with at least one other near-infrared absorber. preferable.

<Dithiol dye>
The dithiol-based dye is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include the dithiol-based dyes described in JP-A-2006-215395 and WO2008 / 086931.

Some dithiol-based dyes do not have an absorption maximum wavelength at a wavelength of 751-950 nm, but a dithiol-based dye having an absorption maximum wavelength at a wavelength of 751-950 nm is selected, or an absorption maximum at a wavelength of 751-950 nm. A dithiol dye having no wavelength and a dithiol dye having an absorption maximum wavelength at a wavelength of 751 to 950 nm are used in combination, or a dithiol dye having no absorption maximum wavelength at a wavelength of 751 to 950 nm and an absorption maximum wavelength at a wavelength of 751 to 950 nm. It can be used as a near-infrared absorber to obtain the effect of the present invention by using a dye other than the dithiol-based dye having the above.
Further, for example, as described in WO 1998/034988, a counter ionic bond of a dithiol dye may be used.

<Squarylium pigment>
The squarylium dye is not particularly limited as long as it does not impair the effects of the present invention, but for example, squarylium dyes represented by the following formulas (4) to (6), JP-A-2014-074002. , Squalylium-based dyes described in JP-A-2014-052431 and the like, and may be synthesized by a generally known method.

In the formula (4) ~ (6), X is independently an oxygen atom, a sulfur atom, a selenium atom or -NH-, said each independently as R ¹ and R ^{1 ',} a hydrogen atom, a 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, nitro group Preferably, a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and a hydroxyl group are more preferable. R ^{2 to} R ⁸ independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, and an −L ¹ or −NR ^g R ^h group. R ^g and R ^h are independently hydrogen atoms, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e , -L ^f , -L ^g , -L ^h or -C (O). Represents the R ⁱ group (R ⁱ represents -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ), and R ₉ independently represents the hydrogen atom, -L ^a , -L ^b. , -L ^c , -L ^d , -L ^e , -L ^f , -L ^g or -L ^h .
L ¹ is L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h .

The L ^{a to} L ^h represent the following groups.
(L ^a) the substituents L and has also good C1-12 aliphatic hydrocarbon group (L ^b) the substitution with a group L also good C1-12 halogen-substituted alkyl group ( L ^c ) An alicyclic hydrocarbon group ^{having 3 to 14 carbon atoms which may have the substituent L (L d} ) An aromatic hydrocarbon group having 6 to 14 carbon atoms which may have the substituent L. (L ^e ) A heterocyclic group having 3 to 14 carbon atoms which may have the substituent L (L ^f ) An alkoxy group having 1 to 12 carbon atoms which may have the substituent L (L ^g ). Acrylic group having 1 to 12 carbon atoms which may have a substituent L (L ^h ) An alkoxycarbonyl group having 1 to 12 carbon atoms which may have the substituent L (L ⁱ ) Having the substituent L ^{The sulfide or disulfide group R 9} having 1 to 12 carbon atoms may independently represent a hydrogen atom, −L ^a , −L ^b , −L ^c , −L ^d or −L ^e .

The absorption maximum wavelength of the compound (5) can be adjusted by a substituent, but the X is preferably a sulfur atom from the viewpoint that the compound (5) tends to be a compound having a maximum absorption wavelength of 751 to 950 nm.

Some of the squarylium-based dyes do not have an absorption maximum wavelength at a wavelength of 751 to 950 nm, but a squarylium-based dye having an absorption maximum wavelength at a wavelength of 751-950 nm is selected, or an absorption maximum at a wavelength of 751-950 nm. A squarylium dye having no wavelength and a squarylium dye having an absorption maximum wavelength at a wavelength of 751 to 950 nm are used in combination, or a squarylium dye having no absorption maximum wavelength at a wavelength of 751 to 950 nm and an absorption maximum wavelength at a wavelength of 751-950 nm. It can be used as a near-infrared absorber to obtain the effect of the present invention by using a dye other than the squarylium dye having the above.

<Diimonium pigment>
The diimonium-based dye is not particularly limited as long as it does not impair the effects of the present invention, but for example, a diimonium-based dye represented by the following formula (7-1) or (7-2), Patent No. 4168031. No. 4, Patent No. 4252961, Japanese Patent Application Laid-Open No. 63-165392, WO2004 / 048480 and the like can be mentioned, and synthesis may be performed by a generally known method.

In formulas (7-1) and (7-2), Rdi1 to Rdi12 independently contain a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, and a -SR ⁱ group. , -SO ₂ R ⁱ group, or an -OSO ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or the following Represents any of L ^{a to L e , R i} represents any of the following L ^{a to} L ^e ,
(L ^a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L ^b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L ^d) carbon Aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, heterocyclic group (L ^f ) having 3 to 14 carbon atoms, and alkoxy group (L ^g ) substituent L having 1 to 12 carbon atoms may have carbon number. 1-12 acyl groups,
(L ^h ) Alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L

The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and an aromatic hydrocarbon having 6 to 14 carbon atoms. It is at least one selected from the group consisting of a hydrogen group and a heterocyclic group having 3 to 14 carbon atoms.
Adjacent Rdi1 and Rdi2, Rdi3 and Rdi4, Rdi5 and Rdi6, and Rdi7 and Rdi8 may form a ring that may have a substituent L.
X represents the anion needed to neutralize the charge

The Rdi1 to Rdi8 are preferably selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group and a benzyl group. A group selected from an isopropyl group, a sec-butyl group, a tert-butyl group, and a benzyl group.

The Rdi9 to Rdi12 are 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 and phenyl. Group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoro A group selected from a methanoylamino group, a pentafluoroetanoylamino group, a tert-butanoylamino group, a cyclohexinoylamino group, an n-butylsulfonyl group, a methylthio group, an ethylthio group, an n-propylthio group and an n-butylthio group. More preferably, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group. , Trifluoromethanoylamino group, pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, and particularly preferably methyl group, ethyl group, n-propyl group, isopropyl. It is a group selected from the groups.

The X ^- is an anion required to neutralize the electric charge. When the anion is divalent as in the formula (7-2), the anion is 1 ion, and as in the formula (7-1), the anion is 1. In the case of valence, 2 ions are required. In the latter case, the two anions X ^- may be the same or different, but it is preferable that they are the same from the viewpoint of synthesis. X ^- or X ^2-it is not particularly limited as long as such anions.

Among the near-infrared absorbers, the compounds represented by the formulas (4), (5), formulas (7-1) and (7-2) have high visible light transmittance and wavelengths of 700 to 750 nm. It is preferable because of the absorption characteristics in the range and the shielding performance in the wavelength range of 800 to 1100 nm.

[Near infrared reflective film]
The near-infrared reflective film that can be used in the present invention is a film having an ability to reflect near-infrared rays. Examples of such a near-infrared reflective film include an aluminum vapor deposition film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and a small amount of tin oxide are dispersed, or a high refractive index material layer and low refractive index. Examples thereof include a dielectric multilayer film in which rate material layers are alternately laminated. Having such a near-infrared reflective film can cut near-infrared rays more effectively.

In the present invention, the near-infrared reflective film may be provided on one side of the base material or on both sides. When it is provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when it is provided on both sides, it is possible to obtain an optical filter having high strength and less likely to warp.

Among the near-infrared reflective films, there is little scattering, good adhesion, high transmission characteristics of visible light in the wavelength range of 430 to 580 nm, and high light shielding performance in the wavelength range of 800 to 1100 nm. Therefore, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated is preferable. When the near-infrared reflective film is a dielectric multilayer film, the image quality of the obtained solid-state image sensor can be improved.

<Dielectric multilayer film>
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 in the range 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 and tin oxide. And / or those containing a small amount (for example, 0 to 10% with respect to the main component) of cerium oxide or the like can be mentioned.

As a material constituting the low refractive index material layer, a material having a refractive index of less than 1.7 can be used, and a material having a refractive index range of 1.2 or more and less than 1.7 is usually selected. Examples of such a material include resin, silica, alumina, lanthanum fluoride, magnesium fluoride and sodium hexafluoride, and a mixture thereof, and the above-mentioned material is deficient so as to have a refractive index of less than 1.7. For example, the one provided with.

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 high refractive index material layer and low refraction can be obtained directly on the substrate by a CVD method, a vacuum vapor deposition method, a sputtering method, an ion-assisted vapor deposition method, an ion plating method, a radical-assisted sputtering method, an ion beam sputtering method, or the like. A dielectric multilayer film in which ratio material layers are alternately laminated can be formed. The ion-assisted vapor deposition method, the ion plating method, and the radical-assisted sputtering method are preferable because a high-quality film in which the optical film thickness of the obtained multilayer film does not easily change depending on the environment can be obtained. The ion-assisted thin-film deposition method is more preferable because the obtained optical filter is less warped.

The thickness of each of these high-refractive-index material layers and low-refractive-index material layers is usually 0.1 λ except for the two layers adjacent to the base material and the outermost layer, where λ (nm) is the near-infrared wavelength to be shielded. An optical thickness of ~ 0.5λ is preferable. When the optical thickness is in this range, the product (n × d) of the refractive index (n) and the film thickness (d) is calculated by λ / 4, and the optical film thickness, the high refractive index material layer, and the low refractive index are calculated. The thickness of each layer of the material layer becomes almost the same value, and there is a tendency that the shielding / transmission of a specific wavelength can be easily controlled due to the relationship between the optical characteristics of reflection / refraction. The two layers adjacent to the base material preferably have a physical thickness of 5 nm to 45 nm or less. The outermost layer preferably has an optical thickness of 0.05 to 0.2λ. If the thickness of the two layers and the outermost layer adjacent to the base material are in the above range, the reflectance of visible light can be reduced, and ghosting can be reduced by combining with the above requirement (Z).

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 5 to 60 layers, preferably 10 to 50 layers.
Further, when the base material is warped when the dielectric multilayer film is formed, in order to eliminate this, a dielectric multilayer film is formed on both sides of the base material, or a dielectric multilayer film of the base material is formed. It is possible to take a method of irradiating the surface on which the surface is formed with an electromagnetic wave such as ultraviolet rays. When irradiating the electromagnetic wave, it may be irradiated during the formation of the dielectric multilayer film, or it may be irradiated separately after the formation.

However, in the conventional design method as described in Patent Document 1 and Patent Document 2, when a dielectric multilayer film that shields a wavelength of 751 to 1200 nm is formed, the transmittance at a wavelength of 700 to 750 nm required for sensing is formed. May also decrease. Therefore, in order to obtain an optical filter that satisfies the requirements (C) and (Z2), it is preferable that the dielectric multilayer film is designed to satisfy the following condition (e).
(E) The layers other than the two layers adjacent to the base material and the outermost layer do not include a layer having an optical film thickness of 205 nm or less (hereinafter, also referred to as “layer (e1)”).

Here, the optical film thickness represents the physical quantity of the physical film thickness × the refractive index, and the refractive index is the refractive index at a wavelength of 550 nm.
A dielectric multilayer film in which layers having different refractive indexes are laminated is designed to shield wavelengths in the vicinity of the optical film thickness × 4. Since the layers other than the two layers adjacent to the base material and the outermost layer close to the emission medium are layers that contribute to the formation of the shielding layer that reduces the transmittance, the above layers (in order to satisfy the requirement (C)) It is preferable not to include e1).

In order to satisfy the requirement (Z2), it is preferable that all of the dielectric multilayer films formed on both sides of the base material satisfy the condition (e). As a result, an optical filter having a high transmittance at a wavelength of 700 to 750 nm required for sensing and shielding a wavelength of 751 to 1200 nm can be obtained. The optical film thickness of the layer (e1) under the condition (e) is preferably 210 nm or less, more preferably 215 nm or less.
Further, in order to satisfy the requirement (Z1), the dielectric multilayer film is preferably designed to satisfy the following condition (f).
(F) The standard deviation of the optical film thickness is 6 to 20 nm in the layers other than the two layers adjacent to the base material and the outermost layer.

By designing a dielectric multilayer film that satisfies the condition (f), the average value of the transmittance when measured from the direction perpendicular to the surface of the optical filter in the range of the requirement (B) "wavelength 800 to 1000 nm". Is 10% or less ”and the characteristic of the requirement (Z1) can be easily compatible with each other. When the optical filter has dielectric multilayer films on both sides of the base material, it is more preferable that all of the dielectric multilayer films on both sides satisfy the condition (f). The standard deviation of the optical film thickness under the condition (f) is preferably 6 to 18 nm, more preferably 6 to 16 nm.

[Near UV absorber]
Near-ultraviolet absorbers that can be used in the present invention include azomethine-based compounds, indol-based compounds, benzotriazole-based compounds, triazine-based compounds, merophthalocyanine-based compounds, oxazole-based compounds, naphthylimide-based compounds, and oxadiazole-based compounds. It is preferably at least one selected from the group consisting of oxazine-based compounds, oxazolidine-based compounds, and anthracene-based compounds, and it is preferable to have at least one absorption maximum at a wavelength of 300 to 420 nm. By containing such a near-ultraviolet absorber in addition to the near-infrared absorber, an optical filter having a small incident angle dependence can be obtained even in the near-ultraviolet wavelength region.

(A) Azomethine-based compound The azomethine-based compound is not particularly limited, but can be represented by, for example, the following formula (8).

式（８）中、Ｒ^a1〜Ｒ^a5は、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシ基、炭素数１〜１５のアルキル基、炭素数１〜９のアルコキシ基または炭素数１〜９のアルコキシカルボニル基を表す。

In the formula (8), R ^{a1 to} R ^a5 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms. Represents the alkoxycarbonyl group of.

(B) Indole-based compound The indole-based compound is not particularly limited, but can be represented by, for example, the following formula (9).

式（９）中、Ｒ^b1〜Ｒ^b5は、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシ基、シアノ基、フェニル基、アラルキル基、炭素数１〜９のアルキル基、炭素数１〜９のアルコキシ基または炭素数１〜９のアルコキシカルボニル基を表す。

In formula (9), R ^{b1 to} R ^b5 independently contain a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a cyano group, a phenyl group, an alkoxy group, an alkyl group having 1 to 9 carbon atoms, and 1 to 9 carbon atoms. Represents an alkoxy group or an alkoxycarbonyl group having 1 to 9 carbon atoms.

(C) Benzotriazole-based compound The benzotriazole-based compound is not particularly limited, but can be represented by, for example, the following formula (10).

式（１０）中、Ｒ^c1〜Ｒ^c3は、それぞれ独立に水素原子、ハロゲン原子、水酸基、アラルキル基、炭素数１〜９のアルキル基、炭素数１〜９のアルコキシ基、または置換基として炭素数１〜９のアルコキシカルボニル基を有する炭素数１〜９のアルキル基を表す。

In the formula (10), R ^{c1 to} R ^c3 are independently hydrogen atoms, halogen atoms, hydroxyl groups, aralkyl groups, alkyl groups having 1 to 9 carbon atoms, alkoxy groups having 1 to 9 carbon atoms, or carbons as substituents. Represents an alkyl group having 1 to 9 carbon atoms having an alkoxycarbonyl group of 1 to 9.

(D) Triazine-based compound The triazine-based compound is not particularly limited, but can be represented by, for example, the following formulas (11), (12) or (13).

In formulas (11) to (13), R ^d1 is independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an alkenyl group having 3 to 8 carbon atoms. Represents an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group. However, these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups and arylalkyl groups may be substituted with hydroxy groups, halogen atoms, alkyl groups having 1 to 12 carbon atoms or alkoxy groups. It may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. Also, the substitutions and interruptions may be combined. R ^{d2 to} R ^d9 are independently hydrogen atom, halogen atom, hydroxyl group, alkyl group having 1 to 15 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkenyl group having 3 to 8 carbon atoms, and carbon. It represents an aryl group having 6 to 18 atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group.

(E) Commercial products "S0511" manufactured by FewChemicals, "Lumogen (registered trademark) Fviolet 570" manufactured by BASF, "Ubitex (registered trademark) OB", "Hakkol RF-K" manufactured by Showa Chemical Industrial Co., Ltd., Japan Examples thereof include "Nikkafluor EFS" and "Nikkafluor SB-conc" manufactured by Nippon Chemical Industrial Co., Ltd. Exciton's "A BS 407", QCR Solutions Corp. "UV 381A", "UV 381B", "UV 382A", "UV 386A" manufactured by BASF, "TINUVIN 326", "TINUVIN 460", "TINUVIN 479" manufactured by BASF, "BONASORB UA3911" manufactured by Orient Chemical Co., Ltd. Etc. may be used.

<Other ingredients>
The resin layer further contains additives such as antioxidants, dispersants, flame retardants, plasticizers, heat stabilizers, light stabilizers, and metal complex compounds, as long as the effects of the present invention are not impaired. You may. Further, when the resin base material is produced by the above-mentioned cast molding, the production of the resin base material can be facilitated by adding a leveling agent or a defoaming agent. These other components may be used alone or in combination of two or more.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, and the like. Tetrakiss [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)- 1,3,5-triazyl-2,4,6 (1H, 3H, 5H) -trion and the like can be mentioned. These additives may be mixed with a resin or the like when the resin base material is manufactured, or may be added when the resin is manufactured. The amount to be added is appropriately selected according to the desired characteristics, but is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the resin. It is a department.

[Other functional membranes]
In the optical filter of the present invention, a functional film can be appropriately provided as long as the effect of the present invention is not impaired.

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

The method of laminating the functional film is not particularly limited, but is a method of melt-molding or casting a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent on a base material or a near-infrared reflective film. And so on.

The coating agent can also be produced by applying the curable composition on a base material or a near-infrared reflective film with a bar coater or the like, and then curing the curable composition by ultraviolet irradiation and / or heating. It is preferable to have a functional film of a curable composition in order to improve the breaking strength of the obtained base material, prevent scratches, reduce warpage, and the like.

Examples of the curable composition include an ultraviolet (UV) / electron beam (EB) curable resin and a thermosetting resin, and specific examples thereof include vinyl compounds, urethane-based, urethane acrylate-based, and acrylate-based resins. , Epoxy-based and epoxy acrylate-based resins and the like. Examples of the curable composition containing these coating agents include vinyl-based, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxy acrylate-based curable compositions.

Examples of the components contained in the urethane-based or urethane acrylate-based curable composition include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate and bis (2-hydroxyethyl) isocyanurate di (meth) acrylate. Examples thereof include oligourethane (meth) acrylates having two or more (meth) acryloyl groups in the molecule. These components may be used alone or in combination of two or more. Further, an oligomer or polymer such as polyurethane (meth) acrylate or an oligomer or polymer such as polyester (meth) acrylate may be blended.

Examples of the vinyl compounds include vinyl acetate, vinyl propionate, divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like, but are not limited to these examples. No. These components may be used alone or in combination of two or more.

The components contained in the epoxy-based or epoxy-acrylate-based curable composition are not particularly limited, but are glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, and oligo having two or more (meth) acryloyl groups in the molecule. Epoxy (meth) acrylates and the like can be mentioned. These components may be used alone or in combination of two or more. Further, an oligomer or polymer such as polyepoxy (meth) acrylate may be blended.

Commercially available products of the curable composition include "LCH" and "LAS" manufactured by Toyo Ink Mfg. Co., Ltd .; "Beamset" manufactured by Arakawa Chemical Industry Co., Ltd .; "EBECRYL" and "EBECRYL" manufactured by Daicel Cytec Co., Ltd. UVACURE ";" Opstar "," Desolite Z "manufactured by JSR Corporation, and the like.

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

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

Further, an organic solvent may be added to the curable composition as a solvent, and known organic solvents can be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone 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 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 0.7 μm to 5 μm.
In addition, for the purpose of improving the adhesion between the base material and the functional film and / or the near-infrared reflective film and the adhesion between the functional film and the near-infrared reflective film, the surface of the base material and the functional film is treated with corona or plasma. Surface treatment may be performed.

The above materials are used as materials for low-pass filters and wavelength plates to reduce moire and false colors in imaging devices such as digital still cameras, digital video cameras, surveillance cameras, in-vehicle cameras, webcams, and unmanned aircraft. May occur.

[Use of optical filter]
The optical filter of the present invention has a wide viewing angle, high sensitivity to red, and improved ghost characteristics. Therefore, it is useful for correcting the luminosity factor of a solid-state image sensor such as a CCD or CMOS of a camera module. In particular, digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, TVs, car navigation systems, mobile information terminals, personal computers, video game machines, mobile game machines, fingerprint authentication systems, distance measurement sensors , Iridescent authentication system, face authentication system, distance measurement camera, digital music player, etc.

<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 including a solid-state image sensor such as a CCD or CMOS. As a member constituting the solid-state image sensor, a photoelectric conversion element such as a silicon photodiode or an organic semiconductor that converts light having a specific wavelength into an electric charge is used. Further, the pixels constituting the solid-state image sensor include pixels having sensitivity to near infrared rays having a wavelength of at least 700 to 750 nm.

In the solid-state image sensor of the present invention, a polarizing element such as a retardation film or a wire grid may be provided on the entire surface of the solid-state image sensor. When the polarizing element is provided, the phase information of the image can be obtained, and the image excluding the reflected light of the subject and the shape of the subject can be three-dimensionally measured, which is more preferable.

<Wire grid>
As the wire grid provided in the solid-state image sensor of the present invention, aluminum, nickel, silver, platinum, tungsten, alloys containing these metals, or the like can be used, and JP-A-2017-003878 and JP-A-2017-005111 It is preferable to provide the polarizer described in Japanese Patent Application Laid-Open No.

<Camera module>
The camera module of the present invention comprises the optical filter of the present invention. Here, the camera module is a device including an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, and the like, and outputs an image or distance information as an electric signal. Here, a case where the optical filter of the present invention is used in a camera module will be specifically described. FIG. 9 is a schematic cross-sectional view of the camera module 400.

In the case of the optical filter 1 of the present invention, there is no large difference in the transmission wavelength of the light incident from the vertical direction and the light incident from 30 ° with respect to the vertical direction of the filter 1 (dependence of the incident angle of the absorption (transmission) wavelength). Therefore, even if the filter 1 is provided between the lens 301 and the sensor 302, the color change of the entire sensor is small. Therefore, when the optical filter 1 of the present invention is used in a camera module, a lens corresponding to a higher angle of incidence can be used, and the height of the camera module can be reduced.

[ghost]
The ghost that causes image quality deterioration in the present invention means that the light reflected on the front surface or the back surface of the optical component between the subject and the image sensor is reflected by other components or the like and is incident on the image sensor at a position different from the original image pickup position. Image defects caused by light.

As shown in FIG. 10, when the light reflected on the surface of the optical filter 1 is further reflected by the lens, passes through the optical filter 1, and is incident on the sensor 302, it is generated as a ghost 304. Alternatively, when the light reflected from the sensor 302 is further reflected by the back surface of the optical filter 1 and is incident on the sensor 302, it is generated as a ghost 305.

The conventional optical filter has a particularly large reflection near a wavelength of 680 to 720 nm, which causes ghost generation. However, since the optical filter 1 of the present invention has a reflectance of 10% or less on both sides at a wavelength of 700 nm and a (Za) value on both sides of 730 nm or more, reflection at a wavelength of 700 to (Za) nm. The rate will be lower than 50%. Therefore, the reflection on the surface of the filter in the vicinity of the wavelength of 680 to 720 nm is small on both sides. Therefore, ghosts 304 and ghosts 305 that are erroneously incident on the sensor are less likely to occur, and good image quality can be obtained.
FIG. 11 is an example of a ghost.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" mean "part by mass" and "mass%" unless otherwise specified.
The measurement method and evaluation method of various physical properties in the examples are as follows.

<Transmittance>
The transmittance was measured using a spectrophotometer "U-4100" manufactured by Hitachi High-Technologies Corporation. As for the transmittance measured from the direction perpendicular to the surface of the base material and the optical filter, the unpolarized light beam transmitted perpendicularly to the optical filter was measured as shown in FIG. The transmittance when measured from an angle of 30 ° with respect to the surface of the optical filter in the direction perpendicular to the surface of the optical filter is as shown in FIG. The S-polarized rays were measured and calculated from the average of them.

The average value of the transmittances of wavelengths A to Bnm is obtained by measuring the transmittances at each wavelength of Annm or more and Bnm or less in 1 nm increments, and the total of the transmittances is the number of measured transmittances (wavelength range, B). It was calculated by dividing by −A + 1).

<Reflectance>
The spectral reflectance is determined by using a spectrophotometer "U-4100" manufactured by Hitachi High-Technologies Co., Ltd., as shown in FIG. 8, the surface of unpolarized light incident at 5 ° incident from one surface of the optical filter. The intensity of the light reflected from the back surface and the intensity of the light reflected from the front surface and the back surface incident from the other surface were measured by the absolute reflectance measurement method.

The average value of the reflectances of wavelengths A to Bnm is obtained by measuring the reflectances at each wavelength of Annm or more and Bnm or less in 1 nm increments, and the total of the reflectances is the number of measured reflectances (wavelength range, B). It was calculated by the value divided by −A + 1).

<Evaluation of absorbent>
For the evaluation of the absorbent, various absorbents were added to 100 parts by mass of the norbornene resin "ARTON" (refractive index 1.52, glass transition temperature 160 ° C.) manufactured by JSR Corporation, and methylene chloride was further added. A solution having a solid content of 30% on a mass basis was obtained. Next, the obtained solution was cast-molded on a smooth glass plate, dried at 50 ° C. for 8 hours, and further dried at 100 ° C. for 1 hour under reduced pressure, and then peeled off to obtain a substrate having a thickness of 0.1 mm. The amount of the various absorbents added was such that the transmittance of the obtained base material at the maximum absorption wavelength was 10%. From the transmittance of the obtained substrate, the absolute values of the absorption maximum wavelength, the shortest absorption maximum wavelength, the absorbance λ ₇₀₀ , the absorbance λ ₇₅₁ , and the difference between (Aa) and (Ab) were calculated.

<Refractive index>
Unless otherwise specified, the refractive indexes of various materials in the present specification are values having a wavelength of 550 nm.

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

<In-plane phase difference R ₀ >
Using a phase difference meter (“KOBRA-HBR” manufactured by Oji Measuring Instruments Co., Ltd.), the phase difference of the substrate obtained in the example at 550 nm was measured, and the in-plane phase difference was R ₀ .

<Evaluation of green sensitivity and near-infrared sensitivity>
As an effect of the optical filter on the visible light sensitivity and the near-infrared sensitivity, as a numerical value corresponding to the evaluation of the image pickup apparatus configured in FIG. Using T _{0 (λ) and the wavelength-specific transmission T 30} (λ) incident at an angle of 30 degrees from the vertical direction, the sensitivity of green pixels and the sensitivity of near-infrared pixels can be calculated from the following equations (i) to (v). Calculated.

G ₀ represents the sensitivity of the green pixel when the sun's rays are incident from the vertical direction of the optical filter. Specifically, based on the equation (i), the wavelength-specific transmission coefficient T ₀ (λ) of the optical filter. The wavelength-specific intensity I (λ) of the sun's rays, the wavelength-specific sensitivity G (λ) of the green sensor pixel, and the wavelength-specific transmission rate DT (λ) of the two-wavelength region transmission filter that transmits green and near-infrared rays. It was calculated as the sum of the calculated values for each 1 nm of the product of.

IR ₀ represents the sensitivity of the near-infrared pixel when the sun's rays enter from the vertical direction of the optical filter. Specifically, based on the equation (ii), the wavelength-specific transmission coefficient T ₀ (λ) of the optical filter. ), The wavelength-specific intensity I (λ) of the sun's rays, the wavelength-specific sensitivity IR (λ) of the near-infrared sensor pixel, and the wavelength-specific transmission rate DT (λ) of the two-wavelength region transmission filter that transmits green and near-infrared rays. ) And the sum of the calculated values for each 1 nm.

G ₃₀ represents the sensitivity of the green pixel when the sun's rays are incident at an angle of 30 ° from the vertical direction of the optical filter. Specifically, based on the equation (iii), the transmission rate of the optical filter by wavelength. T ₀ (λ), the wavelength-specific intensity I (λ) of the sun's rays, the wavelength-specific sensitivity G (λ) of the green sensor pixel, and the wavelength-specific transmission rate of the two-wavelength region transmission filter that transmits green and near-infrared rays. It was calculated as the sum of the calculated values for each 1 nm of the product with DT (λ).

IR ₃₀ represents the sensitivity of near-infrared pixels when the sun's rays enter at an angle of 30 ° from the vertical direction of the optical filter. Specifically, it is transmitted by wavelength of the optical filter based on equation (iv). Rate T ₀ (λ), intensity I (λ) by wavelength of sunlight, sensitivity IR (λ) by wavelength of near-infrared sensor pixels, and wavelength of two-wavelength region transmission filter that transmits green and near-infrared It was calculated as the sum of the calculated values for each 1 nm of the product with the transmittance DT (λ).

G _N represents the noise of wavelength 800~1200nm in the green pixel, specifically, on the basis of the formula (v), each wavelength transmittance of the optical filter T ₀ and (lambda), wavelength-specific intensity of sunlight Calculation of the product of I (λ), the wavelength-specific sensitivity IR (λ) of the near-infrared sensor pixel, and the wavelength-specific transmission rate DT (λ) of the two-wavelength region transmission filter that transmits green and near-infrared, in 1 nm increments. Calculated as the sum of the values.

As shown in Fig. 3, the intensity I (λ) of the sun's rays by wavelength is the maximum intensity of 1 in the irradiation amount data of Gifu at a certain date and time released by the New Energy and Industrial Technology Development Organization. A value standardized to be 0.0 was used. The values shown in FIG. 4 were used for the wavelength-specific sensitivities of the green and near-infrared sensor pixels based on the description in JP-A-2017-216678.

The two-wavelength region transmission filter that transmits green and near-infrared light is obtained by using an ion-assisted vacuum vapor deposition apparatus on one surface of a glass substrate (D263 manufactured by SCHOTT, thickness 0.1 mm) at a vapor deposition temperature of 120 ° C. Dielectric material of design (0) [silica (SiO ₂ : 550 nm refractive index 1.46) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer are alternately laminated] shown in 2. Obtained by forming a multilayer film. The transmittance DT (λ) for each wavelength of the two-wavelength region transmission filter is shown in FIG.

From the obtained pixel sensitivity, an optical filter that satisfies both the following requirements (Xa) and (Xb) has a small amount of change in sensitivity even at a high incident angle in a green pixel, and has a wavelength of 800 to 1200 nm, which is low in human visual sensitivity. The amount of noise was small, and the sensitivity of green was set to 〇. Those that are not optical filters that satisfy both the requirements (Xa) and (Xb) are rated as green sensitivity ×.
Requirement (Xa) 0.8 ≤ G ₃₀ / G ₀ ≤ 1.2
Requirements _{(Xb) G N / G 0} ≦ 0.05

In addition, an optical filter that satisfies both the following requirements (Y) and (Z) has high near-infrared sensitivity compared to green pixels, and the amount of change in near-infrared sensitivity is small even at a wide viewing angle. bottom. If the requirement (Y) is not satisfied, IR ₀ needs to increase the sensor sensitivity by about 5 times or more as compared with G _{0, and the amount of noise is expected to increase by 5 times or more.} If the requirement (Z) is not satisfied, the _{sensitivity of IR 30} is 0.2 times higher than that of IR _0. That is, if the requirements (Y) and (Z) are not satisfied, it becomes difficult to offset the noise amount _{of IR 30 during sensing under a solar light source.} For this reason, a filter that does not satisfy both the requirements (Y) and (Z) is set as near-infrared sensitivity ×.
Requirement (Y) IR ₀ / G ₀ is 0.21 or more Requirement (Z) 0.8 ≤ IR ₃₀ / IR ₀ ≤ 1.2

<Ghost evaluation>
An image pickup device equipped with the obtained optical filter was constructed between the lens and the sensor used in the image pickup device (“KBCR-M04VG” manufactured by Shikino High Tech Co., Ltd.). Halogen when the image is divided into 5 rows from left to right in 1 to 5 rows and 5 columns from top to bottom when divided into 5 in the vertical direction under an environment that shields ambient stray light. The image was taken so that the light source (“ALA-100” manufactured by Asahi Spectroscopy Co., Ltd.) was located at the position of 2 rows and 4 columns. At that time, among the ghosts generated in the regions of 1 row-5 columns, the region where the red sensitivity was 80 or more was designated as the ghost region, and the area was evaluated. The ghost performance was 0 when it was 20% or less of the area of 1 row-5 columns, and the ghost performance was × when it exceeded 20%.

[Example 1]
The compound (14) represented by the following formula (14) (absorption maximum wavelength; 887 nm, above (absorption maximum wavelength; 887 nm) was added to 100 parts by mass of the norbornene resin “ARTON” (refractive index 1.52, glass transition temperature 160 ° C.) manufactured by JSR Co., Ltd. Absolute value of difference between Aa) and (Ab): 94 nm, Absorbance λ ₇₀₀ / Absorbance λ _max : 0.08, Absorbance λ ₇₅₁ / Absorbance λ _max : 0.31) 0.078 parts by mass, and phenolic antioxidant (“Adecastab AO-20” manufactured by ADEKA) was added in an amount of 0.05 parts by mass, and methylene chloride was further added to dissolve the mixture to obtain a solution having a solid content of 30% on a mass basis. Then, the obtained solution was cast-molded on a smooth glass plate, dried at 50 ° C. for 8 hours, and further dried at 100 ° C. under reduced pressure for 1 hour, and then peeled off. By stretching this resin film at 180 ° C., a substrate having a thickness of 0.1 mm, a side of 60 mm, and an in-plane retardation Ro of 5 nm was obtained. The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 1.3, which satisfied the condition (c).

Using an ion-assisted vacuum vapor deposition apparatus on both sides of the obtained substrate, a near-infrared reflective film composed of a dielectric multilayer film was designed (1) and design (2) [silica (SiO _{2), respectively, at a vapor deposition temperature of 120 ° C.} : 550 nm refractive index 1.46) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer are alternately laminated] to obtain an optical filter with a thickness of 0.107 mm. .. The design (1) and the design (2) are shown in Table 2. The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

Tables 1 and 12 show the results of the above requirements (A) to (E) and (Za) in which the transmittance and reflectance of the obtained optical filter were measured.
As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was 〇. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter was suitable for a solid-state image sensor having sensitivity to near infrared rays.

[Example 2]
The compound (14) in Example 1 is represented by the compound (15) represented by the following formula (15) (absorption maximum wavelength; 898 nm, absolute value of difference between (Aa) and (Ab): 110 nm, absorbance λ ₇₀₀ / absorbance λ. _A substrate was obtained in the same procedure except that max: 0.05, absorbance λ ₇₅₁ / absorbance λ _max : 0.1) was changed to 0.05 parts by mass. The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 0.74, which satisfied the condition (c).

A near-infrared reflective film composed of a dielectric multilayer film was designed on both sides of the obtained substrate by using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C. (2) [Silica (SiO ₂ : Refractive index at 550 nm 1. 46) Layers and titania (TiO ₂ : 550 nm refractive index 2.48) layers were alternately laminated] to obtain an optical filter with a thickness of 0.107 mm. The design (2) is shown in Table 2.

Table 1 shows the results of the above requirements (A) to (E) and (Za) in which the transmittance and reflectance of the obtained optical filter were measured. The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was 〇. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter was suitable for a solid-state image sensor having sensitivity to near infrared rays.

[Example 3]
The compound (14) in Example 1 is represented by the compound (16) represented by the following formula (16) (absorption maximum wavelength; 897 nm, absolute value of difference between (Aa) and (Ab): 134 nm, absorbance λ ₇₀₀ / absorbance λ. _A substrate was obtained in the same procedure except that max: 0.1, absorbance λ ₇₅₁ / absorbance λ _max : 0.2) was changed to 0.064 parts by mass. The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 0.32, which satisfied the condition (c).

A near-infrared reflective film composed of a dielectric multilayer film was designed on both sides of the obtained substrate by using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C. (3) [Silica (SiO ₂ : Refractive index at 550 nm 1. 46) Layers and titania (TiO ₂ : 550 nm refractive index 2.48) layers were alternately laminated] to obtain an optical filter with a thickness of 0.104 mm. The design (3) is shown in Table 2.

Table 1 shows the results of the above requirements (A) to (E) and (Za) in which the transmittance and reflectance of the obtained optical filter were measured. The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was 〇. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter was suitable for a solid-state image sensor having sensitivity to near infrared rays.

[Example 4]
The compound (14) in Example 1 is represented by the compound (17) represented by the following formula (17) (absorption maximum wavelength; 844 nm, absolute value of difference between (Aa) and (Ab): 84 nm, absorbance λ ₇₀₀ / absorbance λ. _A substrate was obtained in the same procedure except that max: 0.08, absorbance λ ₇₅₁ / absorbance λ _max : 0.26) 0.05 parts by mass. The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 0.54, which satisfied the condition (c).

A near-infrared reflective film composed of a dielectric multilayer film was designed on both sides of the obtained substrate by using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C. (3) [Silica (SiO ₂ : Refractive index at 550 nm 1. 46) Layers and titania (TiO ₂ : 550 nm refractive index 2.48) layers were alternately laminated] to obtain an optical filter with a thickness of 0.104 mm. The design (3) is shown in Table 2.

Table 1 shows the results of the above requirements (A) to (E) and (Za) in which the transmittance and reflectance of the obtained optical filter were measured. The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was 〇. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter was suitable for a solid-state image sensor having sensitivity to near infrared rays.

[Example 5]
A substrate was obtained in the same procedure except that the amount of compound (14) in Example 1 was changed to 0.07 parts by mass. The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 1.1, satisfying the condition (c).

_{A near-infrared reflective film composed of a dielectric multilayer film was designed (4) and design (5) [silica (SiO 2} : SiO 2:) on both sides of the obtained substrate by using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C. It was formed of 550 nm refractive index 1.46) layers and titania (TiO ₂ : 550 nm refractive index 2.48) layers alternately laminated] to obtain an optical filter having a thickness of 0.104 mm. The designs (4) and (5) are shown in Table 2.

Tables 1 and 13 show the results of the above requirements (A) to (E) and (Za) in which the transmittance and reflectance of the obtained optical filter were measured. The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was 〇. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter was suitable for a solid-state image sensor having sensitivity to near infrared rays.

[Example 6]
The following resin composition (1) is applied to a glass plate (D263 manufactured by SCHOTT) having a thickness of 0.1 mm by spin coating, and then heated on a hot plate at 80 ° C. for 2 minutes to volatilize and remove the solvent. A layer was formed. At this time, the coating conditions of the spin coater were adjusted so that the film thickness of the cured layer was about 0.8 μm.

Resin composition (1): Isocyanurate ethylene oxide-modified triacrylate (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) A solution obtained by mixing 1 part (manufactured by Chemical Industry Co., Ltd.), dissolving it in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 50% by mass, and then filtering it with a millipore filter having a pore size of 0.2 μm.

100 parts by mass of the norbornene resin "ARTON" (refractive index 1.52, glass transition temperature 160 ° C.) manufactured by JSR Co., Ltd., 0.7 parts by mass of the compound (14) represented by the above formula (14), and a phenolic compound. An antioxidant (“ADEKA STAB AO-20” manufactured by ADEKA) was added in an amount of 0.1 part by mass, and methylene chloride was further added to dissolve the mixture to obtain a solution (A) having a solid content of 10% by mass. The solution (A) is applied onto the cured layer with a spin coater so that the film thickness after drying is 0.01 mm, and the solution is heated on a hot plate at 80 ° C. for 30 minutes to volatilize and remove the solvent. , A resin layer was formed. Next, the glass plate is exposed from the glass plate side using a UV conveyor type exposure machine (exposure amount: 500 mJ / cm ² , illuminance: 200 mW), and then baked in an oven at 210 ° C. for 5 minutes to form a base material composed of a glass substrate and a resin layer. Got The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 1.3, which satisfied the condition (c).

On both sides of the obtained base material, a near-infrared reflective film composed of a dielectric multilayer film was designed (4) and design (5) [Silica (SiO _{2), respectively, using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C.} : 550 nm refractive index 1.46) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer are alternately laminated] to obtain an optical filter with a thickness of 0.104 mm. .. The designs (4) and (5) are shown in Table 2.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was 〇. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter was suitable for a solid-state image sensor having sensitivity to near infrared rays.

[Comparative Example 1]
In 100 parts by mass of the norbornene resin "ARTON" (refractive index 1.52, glass transition temperature 160 ° C.) manufactured by JSR Co., Ltd., the absorbent "NIR829A" manufactured by QCR Solutions (absorption maximum wavelength; 840 nm, said (Aa)). Absolute value of the difference between (Ab) and (Ab): 90 nm, absorbance λ ₇₀₀ / absorbance λ _max : 0.15, absorbance λ ₇₅₁ / absorbance λ _max : 0.38, and condition (a) is not satisfied.) 0. 113 parts by mass and 0.05 parts by mass of a phenolic antioxidant (“Adecastab AO-20” manufactured by ADEKA) are added, and methylene chloride is further added to dissolve the solution, and the solid content is 30% on a mass basis. Got Then, the obtained solution was cast-molded on a smooth glass plate, dried at 50 ° C. for 8 hours, and further dried at 100 ° C. under reduced pressure for 1 hour, and then peeled off. By stretching this resin film at 150 ° C., a substrate having a thickness of 0.1 mm, a side of 60 mm, and an in-plane retardation Ro of 5 nm was obtained. The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 1.2, satisfying the condition (c).

Using an ion-assisted vacuum vapor deposition apparatus on both sides of the obtained substrate, a near-infrared reflective film composed of a dielectric multilayer film was designed (7) and design (6) [Silica (SiO _{2), respectively, at a vapor deposition temperature of 120 ° C.} : 550 nm refractive index 1.46) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer are alternately laminated] to obtain an optical filter with a thickness of 0.106 mm. .. The design (6) and the design (7) are shown in Table 2.

The measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the above requirements (A) to (E) and (Za) are shown in Table 1 and FIG. The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇, but the sensitivity of near infrared rays was ×. Moreover, as a result of ghost evaluation of the obtained optical filter, the ghost performance was 〇. The obtained optical filter had insufficient performance for a solid-state image sensor having sensitivity to near infrared rays.

[Comparative Example 2]
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. -Dimethylbenzyl) Benzene 27.66 g (0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl 7.38 g (0.02 mol) γ-butyrolactone 68.65 g and N, N-dimethyl It was dissolved in 17.16 g of acetoamide. The resulting solution was cooled to 5 ° C. using an ice water bath. While maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride and 0.50 g (0.005 mol) of triethylamine as an imidization catalyst were collectively added to the solution. bottom. 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 completion of the reaction, the mixture was air-cooled until the internal temperature reached 100 ° C., then 143.6 g of N, N-dimethylacetamide was added to dilute the reaction, and the mixture was cooled with stirring to obtain a polyimide resin solution 264 having a solid content concentration of 20% by mass. .16 g was obtained. A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide resin. The polyimide resin separated by filtration was washed with methanol and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powdery polyimide resin. The glass transition temperature of the obtained polyimide resin was 310 ° C.

To 100 parts by weight of the polyimide resin obtained, the formula (4) in which R ¹ is hydrogen group, R ^{1 'is} a methyl group, R ² is hydrogen group, R ³ is iso- propyl group, R ⁴ is hydrogen radical, R ^{Squalylium-based absorber with 5} as hydrogen group and R ⁶ as methyl group (maximum absorption wavelength is 770 nm, absolute value of difference between (Aa) and (Ab) above: 82 nm, absorbance λ ₇₀₀ / absorbance λ _max : 0.4, Absorptivity λ ₇₅₁ / absorbance λ _max : 0.9, which does not satisfy condition (a)) 0.05 parts by mass, and Rdi1 to Rdi8 in the above formula (7-1) are tert-butyl groups, Rdi9 to Rdi12. but hydrogen groups, the anion (X ^-) is bis (trifluoromethanesulfonyl) imide anion in which diimonium absorber (absorption maximum wavelength; 1094Nm, the absolute value of the difference between the (Aa) and (Ab): 124 nm) 0.0005 A part by mass was added, and N, N-dimethylacetamide was further added and dissolved to obtain a solution having a solid content of 30% on a mass basis. Next, the obtained solution was cast-molded on a smooth glass plate, dried at 50 ° C. for 8 hours, and further dried at 140 ° C. under reduced pressure for 1 hour, and then peeled off to obtain a substrate having a thickness of 0.05 mm and a side of 60 mm. rice field. The “(950-shortest absorption maximum wavelength) × dye concentration × dye medium thickness” of the obtained base material was 0.45, which satisfied the condition (c).

An acrylate-based ultraviolet curable hard coat agent (“Desolite Z-7524” manufactured by JSR Corporation) containing 2 parts by mass of a polymerization initiator was diluted with methyl ethyl ketone on both sides of the obtained substrate to reduce the solid content concentration to 45. The solution in mass% was applied by a coater bar (automatic film applicator manufactured by Yasuda Seiki Seisakusho Co., Ltd., model number No. 542-AB). After drying this at 80 ° C. for 3 minutes, UV curing was performed using a UV conveyor UV curing device "US2-X040560Hz" manufactured by Eye Graphics Co., Ltd. with a nitrogen atmosphere, a metal halide lamp illuminance of 270 mW / cm ² , and an integrated light intensity of 150 mJ / cm ^2. By doing so, a laminate having a thickness of 0.052 mm having a hard coat layer having a thickness of 1 μm on both sides of the resin film was obtained.

On both sides of the obtained laminate, a near-infrared reflective film composed of a dielectric multilayer film was designed (8) and design (6) [Silica (SiO _{2), respectively, using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C.} : 550 nm refractive index 1.46) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer are alternately laminated] to obtain an optical filter with a thickness of 0.056 mm. .. The design (8) and the design (6) are shown in Table 2.

Table 1 shows the measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the above requirements (A) to (E) and (Za). The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was ×. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter had insufficient performance for a solid-state image sensor having sensitivity to near infrared rays.

[Comparative Example 3]
35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, and 41.46 g of potassium carbonate in a 3 L four-necked flask. 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask. Then, after 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 polyether resin. The obtained polyether resin had a refractive index of 1.60 and a glass transition temperature of 285 ° C.

100 parts by mass of the obtained polyether resin was added to H. W. Absorbent "SDB4927" manufactured by SANDS (maximum absorption wavelength; 825 nm, absolute value of difference between (Aa) and (Ab): 98 nm, absorbance λ ₇₀₀ / absorbance λ _max : 0.1, absorbance λ ₇₅₁ / absorbance λ _max : 0.3) 0.05 parts by mass was added, and methylene chloride was further added to dissolve the solution to obtain a solution having a solid content of 15% on a mass basis. Next, the obtained solution was spin-coated on a smooth glass plate having a thickness of 0.1 mm (D263 manufactured by SCHOTT), dried at 50 ° C. for 8 hours, and further dried at 150 ° C. under reduced pressure for 1 hour to obtain a thickness of 0. By forming a resin layer of 01 mm, a substrate having a side of 60 mm including a glass plate and a resin layer was obtained. The in-plane retardation Ro of the obtained base material was 8 nm.

Subsequently, a near-infrared reflective film composed of a dielectric multilayer film was designed (7) and design (6) [silica (SiO) on both sides of the obtained base material by using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C. ₂ : 550 nm refractive index 1.46) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer are alternately laminated] to obtain an optical filter with a thickness of 0.116 mm. rice field. The design (7) and the design (6) are shown in Table 2.

Table 3 shows the measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the above requirements (A) to (E) and (Za). The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was ×. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter had insufficient performance for a solid-state image sensor having sensitivity to near infrared rays.

[Comparative Example 4]
In 100 parts by mass of the norbornene resin "ARTON" (refractive index 1.52, glass transition temperature 160 ° C.) manufactured by JSR Co., Ltd., the absorbent "S-2084" manufactured by FewChemicals (absorption maximum wavelength; 667 nm, said (Aa). ) And (Ab) are absolute values: 26 nm, absorbance λ ₇₀₀ / absorbance λ _max : 0.06, absorbance λ ₇₅₁ / absorbance λ _max : 0.0, and condition (b) is not satisfied) 0. 0087 parts by mass was added, and methylene chloride was further added and dissolved to obtain a solution having a solid content of 30% on a mass basis. Next, the obtained solution was cast-molded on a smooth glass plate, dried at 50 ° C. for 8 hours, and further dried at 140 ° C. under reduced pressure for 3 hours, and then peeled off to obtain a substrate having a thickness of 0.1 mm and a side of 60 mm. rice field. The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 1.26, which satisfied the condition (c).

Subsequently, on both sides of the obtained base material, a near-infrared reflective film composed of a dielectric multilayer film was designed (1) and design (9) [silica, respectively, using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C. (SiO ₂ : 550 nm refractive index 1.46) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer are alternately laminated] to form an optical filter with a thickness of 0.106 mm. Got The design (1) and design (9) are shown in Table 2.

The measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the above requirements (A) to (E) and (Za) are shown in Table 1 and FIG. The reflectance at a wavelength of 700 nm exceeded 10%.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was ×. As a result of ghost evaluation, the ghost performance was x. The obtained optical filter had insufficient performance for a solid-state image sensor having sensitivity to near infrared rays.

[Comparative Example 5]
100 parts by mass of norbornene resin "ARTON" (refractive index 1.52, glass transition temperature 160 ° C) manufactured by JSR Co., Ltd., and absorbent "SMP-54" manufactured by Hayashihara Co., Ltd. (absorption maximum wavelength; 721 nm, The absolute value of the difference between (Aa) and (Ab) is 65 nm, the absorbance λ ₇₀₀ / absorbance λ _max : 0.53, and the absorbance λ ₇₅₁ / absorbance λ _max : 0.08. 0.05 parts by mass was added, and methylene chloride was further added to dissolve the mixture to obtain a solution having a solid content of 30% on a mass basis. Next, the obtained solution was cast-molded on a smooth glass plate, dried at 50 ° C. for 3 hours, and further dried at 100 ° C. under reduced pressure for 3 hours, and then peeled off to obtain a substrate having a thickness of 0.1 mm and a side of 60 mm. rice field. The "(950-shortest absorption maximum wavelength) x dye concentration x dye medium thickness" of the obtained base material was 1.15, which satisfied the condition (c).

On both sides of the obtained base material, a near-infrared reflective film composed of a dielectric multilayer film was designed (2) and design (10) [Silica (SiO _{2), respectively, using an ion-assisted vacuum vapor deposition apparatus at a vapor deposition temperature of 120 ° C.} : 550 nm refractive index 1.45, film thickness 37-194 nm) layer and titania (TiO ₂ : 550 nm refractive index 2.45, film thickness 11-108 nm) layers are alternately laminated]. , An optical filter having a thickness of 0.106 mm was obtained.

Table 1 shows the measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the above requirements (A) to (E) and (Za). The reflectance at a wavelength of 700 nm exceeded 10%.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was ×. As a result of ghost evaluation, the ghost performance was x. The obtained optical filter had insufficient performance for a solid-state image sensor having sensitivity to near infrared rays.

[Comparative Example 6]
In addition to 100 parts by mass of the norbornene resin "ARTON" (refractive index 1.52, glass transition temperature 160 ° C.) manufactured by JSR Co., Ltd., 0.05 parts by mass of the compound (15) and the compound represented by the following formula (18) (18) 18) (Maximum absorption wavelength; 1064 nm, absolute value of difference between (Aa) and (Ab): 139 nm, absorbance λ ₇₀₀ / absorbance λ _max : 0.05, absorbance λ ₇₅₁ / absorbance λ _max : 0.1) 0 A solution having a solid content of 30% by mass was obtained by adding .04 parts by mass and further adding methylene chloride to dissolve the mixture. Next, the obtained solution was cast-molded on a smooth glass plate, dried at 50 ° C. for 3 hours, and further dried at 100 ° C. under reduced pressure for 3 hours, and then peeled off to obtain an optical filter having a thickness of 0.1 mm and a side of 60 mm. rice field.

Table 1 shows the measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the above requirements (A) to (E) and (Za). The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was × and the sensitivity of near infrared rays was 〇. In addition, as a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter had insufficient performance for a solid-state image sensor having sensitivity to near infrared rays.

[Comparative Example 7]
Using an ion-assisted vacuum vapor deposition apparatus on both sides of a glass substrate (D263 manufactured by SCHOTT, thickness 0.1 mm), a dielectric multilayer film was formed at a vapor deposition temperature of 120 ° C., respectively, in the design (11) and design (11) shown in Table 2. 12) An optical filter is formed by forming it with [a glass (SiO ₂ : 550 nm refractive index 1.46) layer and a titania (TiO ₂ : 550 nm refractive index 2.48) layer alternately laminated]. Obtained. The measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the above requirements (A) to (E) and (Za) are shown in Table 1 and FIG. The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

As a result of evaluating the sensitivity of this optical filter, the sensitivity of green was 〇 and the sensitivity of near infrared rays was ×. As a result of ghost evaluation, the ghost performance was 〇. The obtained optical filter had insufficient performance for a solid-state image sensor having sensitivity to near infrared rays.

The optical filter of the present invention is useful for sensitivity correction for a solid-state image sensor having a near-infrared sensitivity with a wavelength of 700 to 750 nm, such as a CCD or CMOS of a camera module. In particular, digital still cameras, mobile phone cameras, smartphone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, TVs, car navigation systems, mobile information terminals, personal computers, video game machines, mobile game machines, fingerprint authentication systems. , Iridescent authentication system, face authentication system, distance measurement sensor, distance measurement camera, digital music player, vegetation sensing system, cerebral blood flow sensing system, etc.

1: Example of an optical filter according to the present invention 10: Base material 11: Support 12: Resin layer 13: Other functional film 21: Near infrared reflective film 1
22: Near infrared reflective film 2
201: Detector 301: Lens 302: Sensor 303: Bandpass filter 304: Normal detector 305: Ghost 306: Ghost 400: Camera module 401: Light source 402: Ghost

Examples of the divalent halogenated hydrocarbon group of straight chain or branched chain having 1 to 12 carbon atoms, diphenyl Le Oromechiren group, dichloromethylene group, a tetrafluoroethylene group, tetrachlorethylene group, hexafluoro trimethylene group, hexachloro trimethylene group , Hexafluoroisopropyridene group, hexachloroisopropyridene group and the like.

Table 1 shows the measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the above requirements (A) to (E) and (Za). The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.

Claims (10)

An optical filter characterized by satisfying the following requirements (A) to (D):
(A) In the wavelength range of 430 to 580 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is 75% or more;
(B) In the wavelength range of 800 to 1000 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is 10% or less;
(C) In the wavelength range of 700 to 750 nm, the average value of the transmittance measured from the direction perpendicular to the surface of the optical filter is more than 46%;
(D) The shortest wavelength value (Ya) at which the transmittance is 50% when measured from the direction perpendicular to the surface of the optical filter in the wavelength range of 560 to 800 nm, and the value perpendicular to the surface of the optical filter. The absolute value of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% when measured from an angle of 30 ° from the direction is less than 15 nm. The optical filter according to claim 1, wherein the optical filter further satisfies the following requirement (E):
(E) The wavelength value (Ya) is 730 nm or more and 800 nm or less. The optical filter according to claim 1 or 2, further comprising a base material containing a near-infrared absorber and a near-infrared reflective film. The near-infrared absorber has an absorption maximum wavelength in the wavelength range of 751 to 950 nm, and
When the near-infrared absorber is contained in an amount such that the transmittance of the base material at the absorption maximum wavelength is 10%, the transmittance of the base material is 70% in the range of the wavelength of 430 nm or more and the absorption maximum wavelength or less. The absolute value of the difference between the longest wavelength (Aa) and the shortest wavelength (Ab) at which the transmittance of the substrate is 30% in the wavelength range of 580 nm or more is less than 150 nm. Item 3. The optical filter according to Item 3. 3. The optical filter described. The optical filter according to claim 5, wherein the near-infrared absorber is contained in the range of 0.01 to 60.0% by mass with respect to the resin layer. The optical filter according to any one of claims 3 to 6, wherein the near-infrared reflective film is a dielectric multilayer film. The optical filter according to any one of claims 1 to 7, wherein the optical filter satisfies the following requirements (Z1) and (Z2).
(Z1) At a wavelength of 700 nm, the reflectance when measured from an angle of 5 ° perpendicular to the surface of the optical filter is 10% or less when incident from either surface of the optical filter;
(Z2) In the wavelength range of 600 nm or more, the value (Za) of the wavelength of 600 nm or more at which the reflectance is 50% when measured from an angle of 5 ° from the vertical direction with respect to the surface of the optical filter is the value (Za) of the optical filter. It is 730 nm or more when it is incident from either surface. A solid-state image sensor comprising the optical filter according to any one of claims 1 to 8. A camera module including the optical filter according to any one of claims 1 to 8.

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