JPWO2018043564A1 - Optical filter and apparatus using the optical filter - Google Patents

Abstract

It is an object of the present invention to provide an optical filter which can achieve both color shading suppression and ghost suppression of a camera image at a high level, which can not be sufficiently achieved by the conventional optical filter. The optical filter of the present invention is characterized by having a substrate satisfying the requirements (a) to (c): (a) a layer containing a compound (A) having an absorption maximum in a region of wavelengths of 650 nm to 760 nm (B) the difference (X2-X1) between the shortest wavelength (X1) and the second shortest wavelength (X2) at which the transmittance is 10% in the region of 640 nm or more, is 50 nm or more; The transmittances at wavelengths of 900 nm, 1000 nm and 1100 nm are all 65% or less.

Description

  The present invention relates to an optical filter and an apparatus using the optical filter. In particular, the present invention relates to an optical filter including a compound having absorption in a specific wavelength range, and a solid-state imaging device and a camera module using the optical filter.

  CCDs and CMOS image sensors that are solid-state imaging devices for color images are used in solid-state imaging devices such as video cameras, digital still cameras, cell phones with cameras, etc. These solid-state imaging devices Silicon photodiodes are used that have sensitivity to near infrared rays that can not be detected by the eye. In these solid-state imaging devices, it is necessary to perform luminosity correction to make a natural color tone visible to human eyes, and an optical filter (for example, near-infrared cut) that selectively transmits or cuts light in a specific wavelength range Filter) is often used.

  As such a near infrared cut filter, those manufactured by various methods are conventionally used. For example, there is known a near infrared cut filter in which a transparent resin is used as a base material and a near infrared absorbing dye is contained in the transparent resin (see, for example, Patent Document 1). However, the near infrared cut filter described in Patent Document 1 may not necessarily have sufficient near infrared absorption characteristics.

  As a result of intensive studies, the present applicants use a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength range, whereby near-infrared rays with few changes in optical characteristics even when the incident angle is changed. It has been found that a cut filter can be obtained, and Patent Document 2 proposes a near infrared cut filter having a wide viewing angle and a high visible light transmittance. Moreover, in patent document 3, the near-infrared cut off filter which made the outstanding visible transmittance and the absorption maximum wavelength long wavelength which were the conventional subject compatible by a high level by using the phthalocyanine system pigment which has a specific structure It is stated that it is possible to obtain However, in the near-infrared cut filters described in Patent Documents 2 and 3, although the base material applied has an absorption band of sufficient intensity around 700 nm, for example, a near-infrared wavelength region such as 900 to 1200 nm. Has almost no absorption. For this reason, although light rays in the near infrared wavelength region are almost cut only by reflection of the dielectric multilayer film, in such a configuration, slight stray light due to internal reflection in the optical filter or reflection between the optical filter and the lens However, when shooting in a dark environment, it may cause ghosts and flares. In particular, in recent years, there has been a strong demand for high image quality of cameras even for mobile devices such as smartphones, and there have been cases where conventional optical filters can not be suitably used.

  On the other hand, as an optical filter using a substrate having a wide absorption in the near infrared wavelength region, an infrared shielding filter as disclosed in Patent Document 4 has been proposed. In patent document 4, although the broad absorption of a near-infrared wavelength range is achieved by applying the compound which has a dithiolene structure mainly, the absorption intensity of 700 nm vicinity is not enough. In particular, when used under high incident angle conditions (for example, 45 degrees incident) due to recent reduction in height of camera modules, image degradation due to color shading may occur.

  Moreover, although the near-infrared cut off filter which has a near-infrared absorption glass base material and the layer containing a near-infrared absorption pigment is disclosed by patent document 5, even if it is the structure of patent document 5, color shading is improved sufficiently. In some cases (for example, FIG. 5 of Patent Document 5 shows optical characteristic graphs at 0 degree incidence and 30 degree incidence, but the visible light transmission band also at 30 degrees incidence). A large wavelength shift is observed in the region (630 to 700 nm) of the foot portion of

Japanese Patent Laid-Open No. 6-200113 JP, 2011-100084, A International publication 2015/025779 brochure International Publication 2014/168190 pamphlet International Publication 2014/030628 brochure

  An object of the present invention is to provide an optical filter compatible with color shading suppression and ghost suppression at a high level, which can not be sufficiently achieved by the conventional optical filter.

  As a result of intensive studies to solve the above problems, the present inventors have found that a substrate having an absorption band with a sufficient intensity near a wavelength of 700 nm and a wide absorption band in a near infrared wavelength region of 900 nm or more. It has been found that an optical filter capable of achieving the target near-infrared cut characteristics, visible light transmittance, color shading suppression effect and ghost suppression effect can be obtained by applying the above, and the present invention has been completed. Examples of aspects of the invention are given below.

[1] An optical filter having a base material satisfying the following requirements (a), (b) and (c), and satisfying the following requirements (d) and (e):
(A) having a layer containing a compound (A) having an absorption maximum in a wavelength range of 650 nm or more and 760 nm or less;
(B) The difference (X ₂ −X ₁ ) between the shortest wavelength (X ₁ ) at which the transmittance is 10% and the second shortest wavelength (X ₂ ) in the wavelength range of 640 nm or more is 50 nm or more;
(C) the transmittance at a wavelength of 900 nm, the transmittance at a wavelength of 1000 nm, and the transmittance at a wavelength of 1100 nm are all 65% or less;
(D) In the wavelength region of 430 to 580 nm, the average value of the transmittance when measured from the vertical direction of the optical filter is 75% or more;
(E) In the region of wavelengths 1100 nm to 1200 nm, the average value of the transmittance when measured from the vertical direction of the optical filter is 5% or less.

  [2] The optical filter according to Item [1], wherein the layer containing the compound (A) is a transparent resin layer.

  [3] The optical filter according to Item [1] or [2], having a dielectric multilayer film on at least one surface of the substrate.

[4] The optical filter according to any one of [1] to [3], wherein the base material further satisfies the following requirement (f):
(F) The minimum value (T ₁ ) of the transmittance in the wavelength region of 690 to 720 nm is 5% or less.

[5] The optical filter according to any one of items [1] to [4], wherein the base material further satisfies the following requirement (g):
(G) The compound (S) which has an absorption maximum in the area | region of wavelength 1050 nm-1200 nm is included.

[6] The compound according to item [5], wherein the compound (S) is at least one compound selected from the group consisting of compounds represented by the following formulas (I) and (II) Optical filter.

式（Ｉ）および式（ＩＩ）中、
Ｒ¹〜Ｒ³は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−ＮＲ^gＲ^h基、−ＳＲⁱ基、−ＳＯ₂Ｒⁱ基、−ＯＳＯ₂Ｒⁱ基または下記Ｌ^a〜Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、−Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a〜Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a〜Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１〜１２の脂肪族炭化水素基
（Ｌ^b）炭素数１〜１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３〜１４の脂環式炭化水素基
（Ｌ^d）炭素数６〜１４の芳香族炭化水素基
（Ｌ^e）炭素数２〜１４の複素環基
（Ｌ^f）炭素数１〜１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１〜１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１〜１２のアルコキシカルボニル基
置換基Ｌは、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のハロゲン置換アルキル基、炭素数３〜１４の脂環式炭化水素基、炭素数６〜１４の芳香族炭化水素基および炭素数３〜１４の複素環基からなる群より選ばれる少なくとも１種であり、
隣り合うＲ³同士は、置換基Ｌを有してもよい環を形成してもよく、
ｎは０〜４の整数を表し、
Ｘは電荷を中和させるのに必要なアニオンを表し、
Ｍは金属原子を表し、
ＺはＤ（Ｒⁱ）₄を表し、Ｄは窒素原子、リン原子またはビスマス原子を表し、
ｙは０もしくは１を表す。

In formula (I) and formula (II),
R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a -NR ^g R ^h group, a -SR ⁱ group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any of L ^{a to} L ^h below, R ^g and R ^h each independently represent a hydrogen atom, -C (O) R ⁱ group or L ^{a to} L ^e below R ⁱ represents any one of the following L ^{a to} L ^e ,
(L ^a ) aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) halogen substituted alkyl group having 1 to 12 carbon atoms (L ^c ) alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon Aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, heterocyclic group (L ^f ) having 2 to 14 carbon atoms, and alkoxy group having 1 to 12 carbon atoms (L ^g ) 1 to 12 acyl groups,
(L ^h ) C 1-12 alkoxycarbonyl group 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, At least one selected from the group consisting of alicyclic hydrocarbon groups having 3 to 14 carbon atoms, aromatic hydrocarbon groups having 6 to 14 carbon atoms, and heterocyclic groups having 3 to 14 carbon atoms,
Adjacent R ^{3 's} may form a ring which may have a substituent L,
n represents an integer of 0 to 4;
X represents an anion necessary to neutralize the charge;
M represents a metal atom,
Z represents D (R ⁱ ) ₄ and D represents a nitrogen atom, a phosphorus atom or a bismuth atom,
y represents 0 or 1;

  [7] The optical filter according to any one of [3] to [6], wherein the dielectric multilayer film is formed on both sides of the substrate.

  [8] Any one of the above items [1] to [7], wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds and cyanine compounds. The optical filter according to item 1.

  [9] The transparent resin constituting the transparent resin layer may be cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate Resins, polysulfone resins, polyether sulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, Item characterized in that it is at least one resin selected from the group consisting of allyl ester-based curable resins, silsesquioxane-based UV-curable resins, acrylic UV-curable resins, and vinyl-based UV-curable resins. 2] to [8] Manabu filter.

  [10] The optical filter according to any one of Items [1] to [9], wherein the substrate contains a transparent resin-made substrate containing a compound (A) and a compound (S).

  [11] The optical filter according to any one of [1] to [10] for a solid-state imaging device.

  [12] A solid-state imaging device comprising the optical filter according to any one of [1] to [11].

  [13] A camera module comprising the optical filter according to any one of items [1] to [11].

  According to the present invention, it is possible to provide an optical filter which is excellent in near-infrared cut characteristics, less in incident angle dependency, and excellent in transmittance characteristics in the visible wavelength range, color shading suppression effect and ghost suppression effect.

FIGS. 1 (a) and 1 (b) are schematic views showing an example of a preferable configuration of the optical filter of the present invention. Fig.2 (a) is schematic which shows the method to measure the transmittance | permeability at the time of measuring from the orthogonal | vertical direction of an optical filter. FIG.2 (b) is schematic which shows the method to measure the transmittance | permeability at the time of measuring from an angle of 30 degrees with respect to the orthogonal | vertical direction of an optical filter. FIG. 3 is a spectral transmission spectrum of the substrate obtained in Example 1. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG. 5 is a spectral transmission spectrum of the substrate obtained in Example 2. FIG. 6 is a spectral transmission spectrum of the substrate obtained in Example 6. FIG. 7 is a spectral transmission spectrum of the substrate obtained in Example 7. FIG. 8 is a spectral transmission spectrum of the substrate (near-infrared absorbing glass substrate) used in Comparative Example 3. FIG. 9 is a spectral transmission spectrum of the substrate obtained in Comparative Example 4. FIG. 10 is a spectral transmission spectrum of the substrate obtained in Comparative Example 5. It is a schematic diagram for demonstrating the color shading evaluation of the camera image performed by the Example and the comparative example. It is a schematic diagram for demonstrating the ghost evaluation of the camera image performed by the Example and the comparative example.

  Hereinafter, an optical filter according to the present invention and an apparatus using the optical filter will be described in detail.

  The optical filter of the present invention is characterized by having a base material satisfying requirements (a), (b) and (c) described later, and satisfying requirements (d) and (e) described later. The optical filter of the present invention preferably has a dielectric multilayer film on at least one surface of the substrate.

[Base material]
The substrate used in the present invention satisfies the following requirements (a), (b) and (c);
(A) having a layer containing a compound (A) having an absorption maximum in a wavelength range of 650 nm or more and 760 nm or less;
(B) The difference (X ₂ −X ₁ ) between the shortest wavelength (X ₁ ) at which the transmittance is 10% and the second shortest wavelength (X ₂ ) in the wavelength range of 640 nm or more is 50 nm or more;
(C) The transmittance (c1) at a wavelength of 900 nm, the transmittance (c2) at a wavelength of 1000 nm, and the transmittance (c3) at a wavelength of 1100 nm are all 65% or less.

Preferably, the substrate further satisfies at least one of the following requirements (f) to (h):
(F) The minimum value (T ₁ ) of the transmittance in the wavelength region of 690 to 720 nm is 5% or less;
(G) containing a compound (S) having an absorption maximum in the region of wavelengths of 1050 nm to 1200 nm;
(H) The shortest wavelength (Xc) at which the transmittance is 50% when the transmittance is 50% to 50% in the wavelength region of 600 nm or more is in the wavelength range of 628 to 658 nm.

  Each requirement will be described below.

<Requirement (a)>
Although the component which comprises the layer containing a compound (A) in a requirement (a) is not specifically limited, For example, transparent resin, sol-gel material, low-temperature-hardened glass material etc. are mentioned, The handling is easy and a compound ( It is preferable that it is a transparent resin from a viewpoint of compatibility with A).

<< Compound (A) >>
The compound (A) is not particularly limited as long as it is a compound having an absorption maximum in a wavelength range of 650 nm to 760 nm, but is preferably a solvent-soluble dye compound, and is a squalilium compound, a phthalocyanine compound and a cyanine compound. The compound is more preferably at least one selected from the group consisting of compounds, still more preferably containing a squalilium compound, and particularly preferably two or more containing a squarylium compound. When the compound (A) is two or more kinds including a squarylium compound, two or more kinds of squarylium compounds having different structures may be used, and a combination of the squarylium compound and the other compound (A) may be used. As the other compound (A), phthalocyanine compounds and cyanine compounds are particularly preferable.

  The squarylium-based compounds have excellent visible light transmission, steep absorption characteristics and high molar absorptivity, but may generate fluorescence which causes scattered light upon light absorption. In such a case, by using the squarylium compound and the other compound (A) in combination, an optical filter with less scattered light and better camera image quality can be obtained.

  The absorption maximum wavelength of the compound (A) is preferably 660 nm or more and 755 nm or less, more preferably 670 nm or more and 750 nm or less, and still more preferably 680 nm or more and 745 nm or less.

  When the compound (A) is a combination of two or more compounds, the difference in absorption maximum wavelength of the compound (A) having the shortest absorption maximum wavelength and the longest absorption maximum wavelength among the compounds (A) to be applied is preferably 60 nm, more preferably 15 to 55 nm, still more preferably 20 to 50 nm. When the difference of the absorption maximum wavelength is in the above range, the scattered light due to fluorescence can be sufficiently reduced, and a wide absorption band around 700 nm and excellent visible light transmittance can be achieved, which is preferable.

  The total content of the compound (A) is, for example, a substrate made of a transparent resin substrate containing the compound (A) as the substrate, or a curable resin on the transparent resin substrate containing the compound (A) When using the base material on which resin layers, such as the overcoat layer which consists of etc., were laminated | stacked, Preferably it is 0.04-2.0 weight part with respect to 100 weight part of transparent resin, More preferably, it is 0.06- 1.5 parts by weight, more preferably 0.08 to 1.0 parts by weight, and containing the compound (A) on a support such as a glass support or a resin support as a base as the base In the case of using a base material on which a transparent resin layer such as an overcoat layer made of a curable resin is laminated, preferably 0. 1 to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). 4 to 5.0 parts by weight, more preferably 0. To 4.0 parts by weight, more preferably from 0.8 to 3.5 parts by weight.

<Requirement (b)>
The difference (X ₂ -X ₁ ) between the wavelengths X ₁ and X ₂ is preferably 53 nm or more, more preferably 55 nm or more, and still more preferably 58 nm or more. The upper limit is not particularly limited, but the visible transmittance may decrease if the value is too large depending on the properties of the compound (A) and other near infrared absorbers. When the difference (X ₂ -X ₁ ) is in the above range, it has an absorption band with sufficient intensity (width) in the near-infrared wavelength region close to the visible region, for example, an incident angle of 45 degrees It is preferable because color shading can be suppressed even under conditions where the incident angle is large.

The value (X ₁ + X ₂ ) / 2 of the wavelength corresponding to the middle between X ₁ and X ₂ can be said to be the central wavelength of the absorption band in the near infrared wavelength region close to the visible region, preferably 670 nm or more and 740 nm or less, more preferably Is 680 nm or more and 730 nm or less, more preferably 690 nm or more and 720 nm or less. When the value of the wavelength represented by (X ₁ + X ₂ ) / 2 is in the above range, it is preferable because light in a wavelength range near the long wavelength end of the visible range can be cut more efficiently.

The X ₁ is preferably a wavelength of 650 nm or more and 720 nm or less, more preferably a wavelength of 655 nm or more and 710 nm or less, and still more preferably a wavelength of 660 nm or more and 700 nm or less. It is preferable that X ₁ be in such a range, since it tends to be possible to obtain a camera image with less noise and excellent color reproducibility.

<Requirement (c)>
The transmittances (c1), (c2) and (c3) are all preferably 60% or less, more preferably 55% or less, and still more preferably 50% or less. The lower limit is not particularly limited, but depending on the characteristics of the near-infrared absorber, if the transmittance in the near-infrared wavelength region is too low, the visible transmittance may decrease or the thickness of the substrate may become extremely thick. For example, it is preferably 5% or more. If the transmittances (c1), (c2) and (c3) are in the above-mentioned range, it is preferable because a ghost suppression effect of a practically sufficient level can be obtained.

  The substrate may be a single layer or a multilayer as long as it has a layer containing the compound (A). Moreover, in order to satisfy the requirement (C), the substrate preferably contains a near infrared absorber, and the near infrared absorber is contained in the same layer as the compound (A) but in a different layer. It may be done.

  When the layer containing the compound (A) and the layer containing the near infrared absorber are the same, for example, a substrate comprising the transparent resin substrate containing the compound (A) and the near infrared absorber, the compound (A) and the near The compound is formed on a transparent resin substrate containing an infrared ray absorbing agent, a substrate obtained by laminating a resin layer such as an overcoat layer made of a curable resin or the like, a glass support, a resin support serving as a base The base material on which transparent resin layers, such as overcoat layer which consists of curable resin etc. which contain A) and a near-infrared absorber, etc. can be mentioned.

  When the layer containing the compound (A) is different from the layer containing the near infrared absorber, for example, an overcoat layer comprising a curable resin containing the compound (A) on a transparent resin substrate containing the near infrared absorber, etc. A substrate obtained by laminating a resin layer such as an overcoat layer comprising a curable resin containing a near-infrared absorber on a transparent resin substrate containing the compound (A), a glass support An overcoat layer made of a curable resin containing the compound (A) and an overcoat layer made of a curable resin containing a near infrared ray absorber are laminated on a support such as a body or base resin support. The base material etc. which laminated | stacked resin layers, such as overcoat layers which consist of curable resin etc. which contain a compound (A), on the glass substrate containing the near base material and a near-infrared absorber etc. can be mentioned.

  The near infrared absorber is not particularly limited as long as it has a broad absorption in the wavelength range of 900 to 1200 nm, and for example, a near infrared absorbing dye, a near infrared absorbing fine particle, a conductive metal oxide, and a phosphate glass The transition metal component etc. in can be mentioned.

<Requirement (f)>
The T ₁ is preferably 3% or less, more preferably 2% or less, and further preferably 1% or less. If the range T ₁ is the transmittance cutting absorption band can be said to be sufficient, the preferred order flare around the light source can be suppressed in the camera image.

<Requirement (g)>
The substrate of the present invention preferably contains a near-infrared absorber, but when the near-infrared absorber is the compound (S), both the absorption intensity in the near-infrared wavelength range and the visible transmittance can be compatible at a high level Preferred because it tends to.

«Compound (S)»
The compound (S) is not particularly limited as long as it has an absorption maximum in the wavelength range of 1050 nm to 1200 nm, but is preferably a solvent-soluble dye compound, more preferably a dimonium compound, metal dithiolate complex At least one compound selected from the group consisting of compounds, pyrrolopyrrole compounds, cyanine compounds, croconium compounds and naphthalocyanine compounds, more preferably selected from the group consisting of diimonium compounds and metal dithiolate complex compounds Or at least one compound selected from the group consisting of diimmonium compounds represented by the following formula (I) and metal dithiolate complex compounds represented by the following formula (II): . By using such a compound (S), good near infrared absorption characteristics and excellent visible light transmittance can be achieved.

式（Ｉ）および式（ＩＩ）中、
Ｒ¹〜Ｒ³は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−ＮＲ^gＲ^h基、−ＳＲⁱ基、−ＳＯ₂Ｒⁱ基、−ＯＳＯ₂Ｒⁱ基または下記Ｌ^a〜Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、−Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a〜Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a〜Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１〜１２の脂肪族炭化水素基
（Ｌ^b）炭素数１〜１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３〜１４の脂環式炭化水素基
（Ｌ^d）炭素数６〜１４の芳香族炭化水素基
（Ｌ^e）炭素数２〜１４の複素環基
（Ｌ^f）炭素数１〜１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１〜１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１〜１２のアルコキシカルボニル基
置換基Ｌは、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のハロゲン置換アルキル基、炭素数３〜１４の脂環式炭化水素基、炭素数６〜１４の芳香族炭化水素基および炭素数３〜１４の複素環基からなる群より選ばれる少なくとも１種であり、
隣り合うＲ³同士は置換基Ｌを有してもよい環を形成してもよく、
ｎは０〜４の整数を表し、
Ｘは電荷を中和させるのに必要なアニオンを表し、
Ｍは金属原子を表し、
ＺはＤ（Ｒⁱ）₄を表し、 Ｄは窒素原子、リン原子またはビスマス原子を表し、
ｙは０もしくは１を表す。

In formula (I) and formula (II),
R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a -NR ^g R ^h group, a -SR ⁱ group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any of L ^{a to} L ^h below, R ^g and R ^h each independently represent a hydrogen atom, -C (O) R ⁱ group or L ^{a to} L ^e below R ⁱ represents any one of the following L ^{a to} L ^e ,
(L ^a ) aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) halogen substituted alkyl group having 1 to 12 carbon atoms (L ^c ) alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon Aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, heterocyclic group (L ^f ) having 2 to 14 carbon atoms, and alkoxy group having 1 to 12 carbon atoms (L ^g ) 1 to 12 acyl groups,
(L ^h ) C 1-12 alkoxycarbonyl group 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, At least one selected from the group consisting of alicyclic hydrocarbon groups having 3 to 14 carbon atoms, aromatic hydrocarbon groups having 6 to 14 carbon atoms, and heterocyclic groups having 3 to 14 carbon atoms,
Adjacent R ^{3 's} may form a ring which may have a substituent L,
n represents an integer of 0 to 4;
X represents an anion necessary to neutralize the charge;
M represents a metal atom,
Z represents D (R ⁱ ) ₄ and D represents a nitrogen atom, a phosphorus atom or a bismuth atom,
y represents 0 or 1;

Preferably, R ¹ is 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, an adamantyl group, a trifluoromethyl group Pentafluoroethyl group, 3-pyridinyl group, epoxy group, phenyl group, benzyl group and fluorenyl group, more preferably isopropyl group, sec-butyl group, tert-butyl group and benzyl group.

The R ² is preferably a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a hydroxyl group , 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, trifluoromethanoylamino Group, pentafluoroethanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, 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, pentafluoroethanoylamino group, tert-butanoylamino group, cyclohexene group Sinoylamino, particularly preferably methyl, ethyl, n-propyl or isopropyl. The number (value of n) of R ² bonded to the same aromatic ring is not particularly limited as long as it is 0 to 4, but it is preferably 0 or 1.

  The above-mentioned X is an anion necessary to neutralize the charge, and one molecule is required when the anion is divalent, and two molecules are required when the anion is monovalent. In the latter case, the two anions may be identical or different, but are preferably identical from the viewpoint of synthesis. Although X will not be restrict | limited especially if it is such an anion, The thing of following Table 1 can be mentioned as an example.

Ｘとしては、ジイモニウム系化合物の耐熱性、耐光性および分光特性の観点から、上記表１中の（Ｘ−１０）、（Ｘ−１６）、（Ｘ−１７）、（Ｘ−２１）、（Ｘ−２２）、（Ｘ−２４）、（Ｘ−２８）が特に好ましい。

As X, (X-10), (X-16), (X-17), (X-17), (X-21), (X-21), and (X-21) in the above-mentioned Table 1 from the viewpoints of heat resistance, light resistance and spectral characteristics of dimonium compounds. X-22), (X-24) and (X-28) are particularly preferred.

  As a dimonium type compound represented by the said Formula (I), the thing of following Table 2-1-2-4 can be mentioned, for example.

前記Ｒ³としては、好ましくはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロヘキシル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、フェニル基、メチルチオ基、エチルチオ基、ｎ−プロピルチオ基、ｎ−ブチルチオ基、フェニルチオ基、ベンジルチオ基であり、隣り合うＲ³同士が環を形成する場合、環の中に少なくとも一つ以上の硫黄原子もしくは窒素原子が含まれる複素環であることが好ましい。

As R ³ above, preferably, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, phenylthio group, benzylthio group, adjacent R ^{When 3} forms a ring, it is preferable that it is a heterocyclic ring in which at least one or more sulfur atoms or nitrogen atoms are contained in the ring.

  The M is preferably a transition metal, and more preferably Ni, Pd, Pt.

The above D is preferably a nitrogen atom or a phosphorus atom, and the R ⁱ is preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group. A group, n-hexyl group, n-heptyl group, phenyl group.

  The absorption maximum wavelength of the compound (S) is preferably 1060 nm or more and 1190 nm or less, more preferably 1070 nm or more and 1180 nm or less, and still more preferably 1080 nm or more and 1170 nm or less. When the absorption maximum wavelength of the compound (S) is in such a range, unnecessary near infrared rays can be efficiently cut, and an excellent ghost suppression effect can be obtained.

  The compound (S) may be synthesized by a generally known method, for example, Japanese Patent No. 4168031, Japanese Patent No. 4252621, Japanese Patent Publication No. 2010-516823, Japanese Patent Laid-Open No. 63-165392. It can synthesize | combine with reference to the method etc. which are described in etc.

  The content of the compound (S) is, for example, a substrate comprising a transparent resin substrate containing the compound (A) and the compound (S) as the substrate, or a transparent resin substrate containing the compound (S) In the case of using a substrate on which a resin layer such as an overcoat layer made of a curable resin containing a compound (A) is laminated, preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the transparent resin. It is 0 parts by weight, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight, and as the substrate, a glass support, a resin support to be a base, etc. A substrate on which a transparent resin layer such as an overcoat layer comprising a curable resin containing compound (A) and compound (S) is laminated on a support, or a transparent resin substrate containing compound (A) Curable resin containing compound (S) When using the base material on which resin layers, such as an overcoat layer, were laminated | stacked, Preferably it is 0.1-5.0 weight with respect to 100 weight part of resin which forms the transparent resin layer containing a compound (A) Parts, more preferably 0.2 to 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight. When the content of the compound (S) is in the above range, it is possible to obtain an optical filter in which good near infrared absorption characteristics and high visible light transmittance are compatible.

<Requirement (h)>
The Xc is preferably 630 to 655 nm, more preferably 632 to 652 nm, and still more preferably 634 to 650 nm. When Xc is less than 628 nm, the transmittance in the wavelength range corresponding to red decreases and color reproducibility tends to decrease, and when it is more than 658 nm, sufficient absorption intensity can not be ensured, and a camera image is obtained. Color shading tends to occur.

  When the base material satisfies the requirement (h), even when forming a dielectric multilayer film on the base material, reducing the incident angle dependency of the optical characteristics in the visible wavelength to near infrared wavelength range This is preferable because it can achieve both red reproducibility and color shading suppression effects at high levels. In addition, Xc shows the wavelength which satisfy | fills a predetermined condition, when spectral transmission factor is evaluated toward a long wavelength side from a short wavelength side.

<Other Properties and Properties>
The average transmittance of the substrate in the wavelength region of 430 to 580 nm is preferably 75% or more, more preferably 78% or more, and particularly preferably 80% or more. By using a substrate having such transmission characteristics, high light transmission characteristics can be achieved in the visible region, and a highly sensitive camera function can be achieved.

  The thickness of the substrate can be appropriately selected depending on the desired application and is not particularly limited, but is preferably 10 to 200 μm, more preferably 20 to 180 μm, and still more preferably 25 to 150 μm. When the thickness of the substrate is in the above range, the optical filter using the substrate can be thinned and reduced in weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when the substrate made of the transparent resin substrate is used for a lens unit such as a camera module, the height and weight of the lens unit can be reduced, which is preferable.

<Transparent resin>
The transparent resin used for the transparent resin layer, the transparent resin substrate, and the resin support constituting the substrate is not particularly limited as long as the effects of the present invention are not impaired. The glass transition temperature (Tg) is preferably 110 to 380 ° C. in order to ensure the formability of the film and to form a film capable of forming a dielectric multilayer film by high temperature deposition performed at a deposition temperature of 100 ° C. or higher. The resin which is preferably 110 to 370 ° C., more preferably 120 to 360 ° C. can be mentioned. Further, when the glass transition temperature of the resin is 140 ° C. or more, a film capable of forming a dielectric multilayer film at a higher temperature can be obtained, which is particularly preferable.

  When a 0.1 mm thick resin plate made of the resin is formed as the transparent resin, the total light transmittance (JIS K7105) of this resin plate is preferably 75 to 95%, more preferably 78 to 95 %, More preferably 80 to 95%, may be used. When a resin in which the total light transmittance is in such a range is used, the obtained substrate exhibits good transparency as an optical film.

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

  As transparent resin, for example, cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin, polysulfone Resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl Ester-based curable resins, silsesquioxane-based UV-curable resins, acrylic UV-curable resins, and vinyl-based UV-curable resins can be mentioned.

  The transparent resin may be used singly or in combination of two or more.

«Cyclic polyolefin resin»
The cyclic polyolefin resin is obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ) A resin and a resin obtained by hydrogenating the resin are preferable.

式（Ｘ₀）中、Ｒ^x1〜Ｒ^x4はそれぞれ独立に、下記（i'）〜（ix'）より選ばれる原子または基を表し、ｋ^x、ｍ^xおよびｐ^xはそれぞれ独立に、０または正の整数を表す。
（i'）水素原子
（ii'）ハロゲン原子
（iii'）トリアルキルシリル基
（iv'）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１〜３０の炭化水素基
（v'）置換または非置換の炭素数１〜３０の炭化水素基
（vi'）極性基（但し、（iv'）を除く。）
（vii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成されたアルキリデン基（但し、前記結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（vi'）より選ばれる原子または基を表す。）
（viii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（i'）〜（vi'）より選ばれる原子または基を表す。）
（ix'）Ｒ^x2とＲ^x3とが、相互に結合して形成された単環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1とＲ^x4は、それぞれ独立に前記（i'）〜（vi'）より選ばれる原子または基を表す。）

In formula (X ₀ ), R ^{x1 to} R ^x4 each independently represent an atom or a group selected from the following (i ′) to (ix ′), and k ^x , m ^x and p ^x each independently represent 0 Or represents a positive integer.
(I ') hydrogen atom (ii') halogen atom (iii ') trialkylsilyl group (iv') substituted or unsubstituted C1 having a linking group containing oxygen atom, sulfur atom, nitrogen atom or silicon atom To 30 hydrocarbon group (v ') substituted or unsubstituted hydrocarbon group (vi') having 1 to 30 carbon atoms (with the exception of (iv '))
(Vii ') and R ^x1 and R ^x2 or R ^x3 and R ^x4 are mutually formed bonded to alkylidene group (wherein, R ^x1 to R ^x4 which is not involved in the binding, the independently (i' ) Represents an atom or a group selected from (vi '))
(Viii ') and R ^x1 and R ^x2 or R ^x3 and R ^x4 are mutually formed bonded to the monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring (provided that does not participate in the binding R ^x1 to R Each of ^x4 independently represents an atom or a group selected from (i ') to (vi').)
(Ix ′) A monocyclic hydrocarbon ring or heterocycle formed by mutual bonding of R ^x2 and R ^x3 (with the proviso that R ^x1 and R ^{x4 which} are not involved in the above-mentioned bond are each independently as defined above (i) ') Represents an atom or a group selected from (vi'))

式（Ｙ₀）中、Ｒ^y1およびＲ^y2はそれぞれ独立に、前記（i'）〜（vi'）より選ばれる原子または基を表すか、Ｒ^y1とＲ^y2とが、相互に結合して形成された単環もしくは多環の脂環式炭化水素、芳香族炭化水素または複素環を表し、ｋ^yおよびｐ^yはそれぞれ独立に、０または正の整数を表す。

In formula (Y ₀ ), each of R ^y1 and R ^y2 independently represents an atom or a group selected from the above (i ′) to (vi ′), or R ^y1 and R ^y2 are bonded to each other formed monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or heterocyclic, k ^y and p ^y are each independently, represent 0 or a positive integer.

«Aromatic polyether resin»
The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

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

In formula (1), R ^{1 to} R ⁴ each independently represent a C ^{1 to} C 12 monovalent organic group, and a to d each independently represent an integer of 0 to 4.

式（２）中、Ｒ¹〜Ｒ⁴およびａ〜ｄはそれぞれ独立に、前記式（１）中のＲ¹〜Ｒ⁴およびａ〜ｄと同義であり、Ｙは、単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、Ｒ⁷およびＲ⁸はそれぞれ独立に、ハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｇおよびｈはそれぞれ独立に、０〜４の整数を示し、ｍは０または１を示す。但し、ｍが０のとき、Ｒ⁷はシアノ基ではない。

In formula (2), R ^{1 to} R ⁴ and a to d each independently have the same meaning as R ^{1 to} R ⁴ and a to d in formula (1), and Y is a single bond, —SO ₂ -Or> C = O is shown, R ⁷ and R ⁸ are each independently a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h are each independently 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

  In addition, the aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4) Is preferred.

式（３）中、Ｒ⁵およびＲ⁶はそれぞれ独立に、炭素数１〜１２の１価の有機基を示し、Ｚは、単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｅおよびｆはそれぞれ独立に、０〜４の整数を示し、ｎは０または１を示す。

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

式（４）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈはそれぞれ独立に、前記式（２）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆはそれぞれ独立に、前記式（３）中のＲ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆと同義である。

Wherein ^{(4), R 7, R} 8, Y, m, g and h are each independently, R ⁷ in the formula (2), R ^8, Y, m, has the same meaning as g and h, R ⁵ , R ⁶ , Z, n, e and f each independently have the same meaning as R ⁵ , R ⁶ , Z, n, e and f in the formula (3).

«Polyimide resin»
The polyimide-based resin is not particularly limited as long as it is a polymer compound having an imide bond in the repeating unit, for example, by the method described in JP-A-2006-199945 or JP-A-2008-163107. It can be synthesized.

«Fluorene polycarbonate resin»
The fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in Japanese Patent Application Laid-Open No. 2008-163194.

«Fluorene polyester resin»
The fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety, and for example, it may be synthesized by the method described in JP-A-2010-285505 or JP-A-2011-197450. Can.

«Fluorinated aromatic polymer resin»
The fluorinated aromatic polymer-based resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond The polymer is preferably a polymer containing a repeating unit containing at least one bond, and can be synthesized, for example, by the method described in JP-A-2008-181121.

«Acrylic UV-curable resin»
The acrylic UV-curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic or methacrylic groups in the molecule and a compound which is decomposed by ultraviolet light to generate active radicals. Can be mentioned. The acrylic UV-curable resin is a substrate in which a transparent resin layer containing the compound (A) and a curable resin is laminated on a glass support or a resin support serving as a base as the substrate, a compound ( When using a substrate in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing A), the resin can be particularly suitably used as the curable resin.

«Epoxy resin»
The epoxy resin is not particularly limited, but can be roughly classified into ultraviolet curing type and thermosetting type. The UV curable epoxy resin is synthesized, for example, from a composition containing a compound having one or more epoxy groups in the molecule and a compound that generates an acid by ultraviolet light (hereinafter, also referred to as “photoacid generator”). The thermosetting epoxy resin may be, for example, one synthesized from a compound having one or more epoxy groups in the molecule and a composition containing an acid anhydride. Can. The epoxy-based UV-curable resin contains, as the substrate, a substrate in which a transparent resin layer containing the compound (A) is laminated on a glass support or a resin support serving as a base, or the compound (A) When using a substrate in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate, the resin can be particularly suitably used as the curable resin.

«Commercial item»
As a commercial item of transparent resin, the following commercial item etc. can be mentioned. Examples of commercially available cyclic polyolefin-based resins include Arton manufactured by JSR Corporation, Zeonor manufactured by Nippon Zeon Corporation, APEL manufactured by Mitsui Chemicals, Inc., TOPAS manufactured by Polyplastics Corporation, and the like. As a commercial item of polyether sulfone type resin, Sumitomo Chemical Co., Ltd. product Sumica excel PES etc. can be mentioned. As a commercial item of polyimide resin, Mitsubishi Gas Chemical Co., Ltd. neoprem L etc. can be mentioned. As a commercial item of polycarbonate-type resin, Teijin Ltd. product Pure Ace etc. can be mentioned. As a commercial item of fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. product ピ pizeta EP-5000 etc. can be mentioned. As a commercial item of fluorene polyester resin, Osaka Gas Chemical Co., Ltd. OKP4HT etc. can be mentioned. As a commercial item of acrylic resin, the acclaimer made by Nippon Shokubai Co., Ltd., etc. can be mentioned. As a commercial item of silsesquioxane type ultraviolet curing resin, Nippon Steel Chemical Co., Ltd. sill plus etc. can be mentioned.

<Other pigments (X)>
The base material may further contain other dyes (X) which do not correspond to the compound (A) and the compound (S).

  The other dye (X) is not particularly limited as long as it has a maximum absorption wavelength of less than 650 nm or more than 760 nm and less than 1050 nm, but a dye having an absorption maximum wavelength of more than 760 nm and less than 1050 nm is preferable . As such a dye, for example, squalilium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, octaphilin compounds, diimonium compounds, pyrrolopyrrole compounds, boron dipyrromethene (BODIPY) Examples include at least one compound selected from the group consisting of system compounds, perylene compounds and metal dithiolate compounds.

  The content of the other dye (X) is, for example, when using a substrate made of a transparent resin substrate containing the other dye (X) as the substrate, with respect to 100 parts by weight of the transparent resin, The amount is preferably 0.005 to 1.0 parts by weight, more preferably 0.01 to 0.9 parts by weight, particularly preferably 0.02 to 0.8 parts by weight, and as the substrate, a glass support or a base And a compound (A), and a base material in which a transparent resin layer such as an overcoat layer comprising a curable resin containing another dye (X) is laminated on a support such as a resin support to be When using a base material on which a resin layer such as an overcoat layer made of a curable resin containing other pigment (X) is laminated on a transparent resin substrate, a transparent resin containing the other pigment (X) Relative to 100 parts by weight of the resin forming the layer Is properly 0.05 to 4.0 parts by weight, more preferably 0.1 to 3.0 parts by weight, particularly preferably 0.2 to 2.0 parts by weight.

<Other ingredients>
The substrate may further contain, as other components, an antioxidant, a near ultraviolet light absorber, a fluorescence quencher, and the like as long as the effects of the present invention are not impaired. These other components may be used alone or in combination of two or more.

  Examples of the near-ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, and triazine compounds.

  Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, and tris (2,4-di-t-butylphenyl) phosphite and the like can be mentioned.

  In addition, when manufacturing a base material, these other components may be mixed with resin etc., and may be added when synthesize | combining resin. The addition amount is appropriately selected according to the desired characteristics, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the resin. It is a department.

<Method of manufacturing base material>
When the substrate is a substrate including a transparent resin substrate containing a compound (A), the transparent resin substrate can be formed, for example, by melt molding or cast molding, and further, if necessary, After molding, a base material on which an overcoat layer is laminated can be produced by coating a coating agent such as an antireflective agent, a hard coating agent and / or an antistatic agent.

  An overcoat comprising a curable resin containing the compound (A) on a support such as a glass support or a resin support as a base or a transparent resin substrate not containing the compound (A). In the case of a substrate on which a transparent resin layer such as a layer is laminated, for example, a resin solution containing the compound (A) is melt-molded or cast-formed on the support or the transparent resin substrate, preferably spin After coating by a method such as coating, slit coating, or inkjet, the solvent is removed by drying, and if necessary, light irradiation and heating are further performed, whereby the compound (A) is formed on the support or the transparent resin substrate. The base material in which the transparent resin layer containing these was formed can be manufactured.

«Melt forming»
Specifically, as the melt-molding, a method of melt-molding pellets obtained by melt-kneading a resin, a compound (A) and other components as required; a resin and a compound (A) and necessary Method for melt molding a resin composition containing other components accordingly; or obtained by removing the solvent from a resin composition containing a compound (A), a resin, a solvent and, if necessary, other components The method of melt-molding a pellet etc. are mentioned. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

«Cast molding»
As the cast molding, a method of casting a resin composition containing a compound (A), a resin, a solvent and, if necessary, other components on a suitable support to remove the solvent; or the compound (A) , After casting a curable composition containing a photocurable resin and / or a thermosetting resin and, if necessary, other components on a suitable support to remove the solvent, UV irradiation, heating, etc. It can also be manufactured by a method of curing by an appropriate method of

  When the substrate is a substrate comprising a transparent resin substrate containing a compound (A), the substrate can be obtained by peeling a coating film from a support after cast molding, Further, the substrate is made of a curable resin containing the compound (A) on a support such as a glass support or a resin support serving as the base or on a transparent resin substrate not containing the compound (A). In the case of a substrate on which a transparent resin layer such as an overcoat layer is laminated, the substrate can be obtained by not peeling off the coating film after cast molding.

  The support may be, for example, a near infrared absorbing glass plate (for example, a phosphate containing a copper component such as “BS-11” manufactured by Matsunami Glass Industry Co., Ltd. or “NF-50T” manufactured by AGC Techno Glass Co., Ltd.). Glass plates), transparent glass plates (eg, alkali-free glass plates such as “OA-10G” manufactured by Nippon Electric Glass Co., Ltd. and “AN100” manufactured by Asahi Glass Co., Ltd.), steel belts, steel drums and transparent resins (eg polyesters) Films, cyclic olefin-based resin films) supports.

  Furthermore, an optical component such as a glass plate, quartz or transparent plastic is coated with the resin composition to dry the solvent, or the curable composition is coated to cure and dry. A transparent resin layer can also be formed on the part.

  The amount of residual solvent in the transparent resin layer (substrate made of transparent resin) obtained by the above method should be as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight, based on the weight of the transparent resin layer (substrate made of transparent resin) It is below. When the amount of residual solvent is in the above range, a transparent resin layer (substrate made of transparent resin) which can easily exhibit a desired function, in which deformation or characteristics do not easily change, can be obtained.

[Optical filter]
The optical filter according to the present invention is characterized by having a base material satisfying the requirements (a), (b) and (c) and satisfying the following requirements (d) and (e):
(D) In the wavelength region of 430 to 580 nm, the average value (d1) of the transmittance as measured from the vertical direction of the optical filter is 75% or more;
(E) In the region of wavelengths of 1100 nm to 1200 nm, the average value (e1) of the transmittance when measured from the vertical direction of the optical filter is 5% or less.

  Since the optical filter of the present invention satisfies the requirements (d) and (e), it has excellent transmittance characteristics in the visible wavelength range and near-infrared cut characteristics, less dependency on incident angle, color shading suppression effect and ghost It is an optical filter excellent in the suppression effect.

<Requirement (d)>
The average value (d1) of the transmittances in the requirement (d) is preferably 78% or more, more preferably 80% or more, and still more preferably 82% or more. When the average value (d1) of the transmittance is in this range, excellent imaging sensitivity can be achieved when the optical filter of the present invention is used as a solid-state imaging device application.

<Requirement (e)>
The average value (e1) of the transmittances in the requirement (e) is preferably 4% or less, more preferably 3% or less, and further preferably 2% or less. When the average value (e1) of the transmittance is in this range, good black reproducibility can be achieved near the center of the camera image.

<Other Properties and Properties>
Since the optical filter of the present invention has the above-mentioned base material, it is possible to reduce the incidence angle dependency of the optical characteristics even in the form having a dielectric multilayer film. Specifically, in the wavelength range of 600 to 800 nm, the shortest wavelength value (Xa) at which the transmittance is 50% when measured from the vertical direction of the optical filter, and 30 ° to the vertical direction of the optical filter Is preferably less than 20 nm, more preferably less than 15 nm, still more preferably less than 10 nm. The absolute value | Xa−Xb | is there.

  The thickness of the optical filter of the present invention is preferably thin in consideration of recent trends such as thinning and weight reduction of solid-state imaging devices. The optical filter of the present invention can be thinned because it includes the above-mentioned base material.

  The thickness of the optical filter of the present invention is preferably 210 μm or less, more preferably 190 μm or less, still more preferably 160 μm or less, particularly preferably 130 μm or less. The lower limit is not particularly limited, but is preferably 20 μm or more.

[Dielectric multilayer film]
The optical filter of the present invention preferably has a dielectric multilayer film on at least one surface of the substrate. The dielectric multilayer film in the present invention is a film having the ability to reflect near infrared rays or a film having an antireflection effect in the visible region, and having a dielectric multilayer film provides better visible light transmittance and near infrared rays. Cutting characteristics can be achieved.

  In the present invention, the dielectric multilayer film may be provided on one side or both sides of the substrate. 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 which has high strength and is not easily warped or twisted. When the optical filter is applied to a solid-state imaging device application, it is preferable to provide a dielectric multilayer film on both sides of a resin substrate, since it is preferable that the warp and twist of the optical filter be small.

  The dielectric multilayer film preferably has reflective properties over the entire wavelength range of preferably 700 to 1100 nm, more preferably 700 to 1150 nm, and even more preferably 700 to 1200 nm.

  As a form having a dielectric multilayer film on both sides of a substrate, when measured from an angle of 5 ° with respect to the vertical direction of the optical filter, the first optical layer mainly having a reflection characteristic at a wavelength of 700 to 950 nm (A) on the other side of the substrate (see FIG. 1 (a)), or to the direction perpendicular to the optical filter. Measured from an angle of 5 °, a third optical layer mainly having a reflection characteristic at a wavelength of 700 to 1150 nm on one side of the substrate, and a fourth optical layer having an antireflection characteristic in the visible region The form (refer FIG.1 (b)) etc. which have on the other side of a material are mentioned.

  As a dielectric multilayer film, what laminated | stacked the high refractive index material layer and the low refractive index material layer by turns is mentioned. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected. Such materials include, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide or indium oxide, etc., and titanium oxide, tin oxide and / or Or what made the cerium oxide etc. contain a small amount (for example, 0 to 10 weight% with respect to a main component) is mentioned.

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

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

  The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1 λ to 0.5 λ, where λ (nm) is a near infrared wavelength to be blocked. The value of λ (nm) is, for example, 700 to 1,400 nm, preferably 750 to 1,300 nm. When the thickness is in this range, the optical film thickness calculated by λ / 4 of the product (n × d) of the refractive index (n) and the film thickness (d), the high refractive index material layer and the low refractive index The thickness of each layer of the index material layer becomes almost the same value, and the blocking / transmission of a specific wavelength tends to be easily controlled from the relationship of the optical characteristics of reflection and refraction.

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

  In the present invention, the material type constituting the high refractive index material layer and the low refractive index material layer, the high refractive index material layer and the low refractive index according to the absorption characteristics of the near infrared absorber such as the compound (A) or the compound (S) By appropriately selecting the thickness of each layer of the rate material layer, the order of lamination, and the number of laminations, it has sufficient light transmittance in the visible region and has sufficient light ray-cut characteristics in the near infrared wavelength region, And the reflectance when near infrared rays are incident from an oblique direction can be reduced.

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

[Other functional membranes]
In the optical filter of the present invention, the surface of the substrate opposite to the surface provided with the dielectric multilayer film, or the dielectric multilayer, is within the range not impairing the effects of the present invention. Antireflective film, hard for the purpose of improving the surface hardness of the substrate or dielectric multilayer film, improving chemical resistance, preventing electrification and scratching on the surface opposite to the surface on which the film substrate is provided A functional film such as a coat film or an antistatic film can be appropriately provided.

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

  The method for laminating the functional film is not particularly limited, but a coating agent such as an antireflective agent, a hard coating agent and / or an antistatic agent, etc. may be melt molded or cast on the substrate or dielectric multilayer film as described above. The method etc. which are shape | molded can be mentioned.

  Moreover, after apply | coating the curable composition containing the said coating agent etc. on a base material or a dielectric multilayer by a bar coater etc., it can manufacture also by hardening by ultraviolet irradiation etc.

  The coating agent may, for example, be an ultraviolet (UV) / electron beam (EB) curable resin or a thermosetting resin. Specifically, vinyl compounds, urethanes, urethane acrylates, acrylates, epoxy And epoxy acrylate resins. As said curable composition containing these coating agents, vinyl type, urethane type, urethane acrylate type, acrylate type, epoxy type and epoxy acrylate type curable composition etc. are mentioned.

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

  The content of the polymerization initiator in the curable composition is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, based on 100% by weight of the total amount of the curable composition. More preferably, it is 1 to 5% by weight. When the blending ratio of the polymerization initiator is in the above range, the curing characteristics and handleability of the curable composition are excellent, and a functional film such as an antireflective film, a hardcoat film or an antistatic film having a desired hardness can be obtained. it can.

  Furthermore, 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, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Amides such as methyl pyrrolidone can be mentioned.

  These solvents may be used alone or in combination of two or more.

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

  Also, in order to improve the adhesion between the substrate and the functional film and / or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, corona on the surface of the substrate, the functional film or the dielectric multilayer film Surface treatment such as treatment or plasma treatment may be performed.

[Application of optical filter]
The optical filter of the present invention has a wide viewing angle, and has excellent near infrared ray cutting ability and the like. Accordingly, it is useful for correcting the visibility of a solid-state imaging device such as a CCD of a camera module or a CMOS image sensor. In particular, digital still cameras, cameras for smartphones, cameras for mobile phones, digital video cameras, cameras for wearable devices, PC cameras, surveillance cameras, cameras for automobiles, televisions, car navigation systems, portable information terminals, video game machines, portable game machines , Fingerprint authentication system, digital music player, etc. Furthermore, it is useful also as a heat ray cut filter etc. with which glass plates, such as a car and a building, etc. are equipped.

[Solid-state imaging device]
The solid-state imaging device of the present invention comprises the optical filter of the present invention. Here, the solid-state imaging device is an image sensor provided with a solid-state imaging device such as a CCD or a CMOS image sensor, and more specifically, a digital still camera, a camera for smartphones, a camera for mobile phones, a camera for wearable devices, digital It can be used for applications such as video cameras. For example, the camera module of the present invention comprises the optical filter of the present invention.

  Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. The term "parts" means "parts by weight" unless otherwise noted. Moreover, the measuring method of each physical-property value and the evaluation method of a physical property are as follows.

Molecular weight
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in the solvent and the like.
(A) Gel Permeation Chromatography (GPC) apparatus (150 C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by Waters Corporation, using weight average molecular weight in terms of standard polystyrene (Mw) and number average molecular weight (Mn) were measured.
(B) Tosoh GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF) was used to measure weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene.

In addition, about the resin synthesize | combined by resin synthesis example 3 mentioned later, the measurement of the logarithmic viscosity by the following method (c) instead of the measurement of the molecular weight by the said method was performed.
(C) A part of the polyimide resin solution was introduced into anhydrous methanol to precipitate the polyimide resin, which was separated from unreacted monomer by filtration. 0.1 g of the polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and logarithmic viscosity (μ) at 30 ° C. is measured according to the following equation using a Canon-Fenske viscometer I asked.

μ = {ln (t _s / t ₀ )} / C
t ₀ : Falling time of solvent t _s : Falling time of dilute polymer solution C: 0.5 g / dL
<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC 6200) manufactured by SII Nano Technologies Inc., the heating rate was measured at 20 ° C./min under a nitrogen stream.

<Spectral transmittance>
The transmittance of each wavelength of the substrate, (T ₁ ), (X ₁ ), (X ₂ ) and (Xc), and the transmittance of each of the optical filters in each wavelength range, (Xa) and (Xb) It measured using the spectrophotometer (U-4100) made from the company Hitachi High-Technologies.

  Here, in the transmittance when measured from the vertical direction of the optical filter, as shown in FIG. 2A, the light transmitted perpendicularly to the filter is measured, and an angle of 30 ° with respect to the vertical direction of the optical filter In the case of the transmittance as measured from the above, the light transmitted at an angle of 30 ° with respect to the vertical direction of the filter was measured as shown in FIG. 2 (b).

  In addition, this transmittance | permeability is measured using this spectrophotometer on the conditions which light injects perpendicularly | vertically with respect to a board | substrate and a filter except the case where (Xb) is measured. In the case of measuring (Xb), it is measured using the spectrophotometer under the condition that light is incident at an angle of 30 ° with respect to the vertical direction of the filter.

<Color shading evaluation of camera image>
Color shading evaluation when an optical filter was incorporated into a camera module was performed by the following method. A camera module is created by the same method as Japanese Patent Application Laid-Open No. 2016-110067, and a white plate of 300 mm × 400 mm size is created using the created camera module as a D65 light source (X-Rite standard light source device “Macbeth Judge II”) It photographed below and the difference of the color in the center part and the edge part of the white board in a camera image was evaluated by the following references | standards.

  There is no problem at all, acceptable level is A, slight difference in color is recognized, but there is no problem in practical use as a high quality camera module, B is acceptable level with difference in color and unacceptable for high quality camera module application The possible level was C, and an obvious difference in color was determined, and an unacceptable level for general camera module application was determined as D.

  Note that, as shown in FIG. 11, when photographing, the positional relationship between the white plate 112 and the camera module was adjusted so that the white plate 112 occupies 90% or more of the area in the camera image 111.

<Ghost evaluation of camera images>
Ghost evaluation when an optical filter was incorporated into a camera module was performed by the following method. A camera module is prepared in the same manner as in JP-A-2016-110067, and the camera module is used to capture an image under a halogen lamp light source ("Luminer Ace LA-150TX" manufactured by Hayashi Watch Industry Co., Ltd.) in a dark room The degree of ghosting around the light source in the image was evaluated according to the following criteria.

  There is no problem at all, acceptable level A, some ghosts are recognized, but there is no problem in practical use as a high quality camera module B, acceptable level is generated and ghosting is not acceptable for high quality camera module application The possible level was determined to be C, and the level of ghosts was determined to be unacceptable and a level that would be unacceptable for general camera module applications was determined to be D.

  Note that, as shown in FIG. 12, when shooting was performed, the light source 122 was adjusted to be at the upper right end of the camera image 121.

[Composition example]
Compound (A) and compound (S) used in the following examples were synthesized by generally known methods. As a general synthesis method, for example, JP-A-60-228448, JP-A-1-146846, JP-A-1-228960, JP-A-4081149, "Phthalocyanine-chemistry and function-" (eye) PC, 1997), JP-A-2009-108267, JP-A-2010-241873, JP-B-3699464, JP-A-4740631 and the like can be mentioned.

<Resin Synthesis Example 1>
Represented by the following formula (a) 8- methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} 100 g of ^1,7,10 ] dodeca-3-ene (hereinafter also referred to as "DNM"), 18 g of 1-hexene (molecular weight modifier) and 300 g of toluene (solvent for ring-opening polymerization reaction) were charged in a nitrogen-substituted reaction vessel The solution was heated to 80.degree. Next, 0.2 g of a toluene solution of triethylaluminum (0.6 mol / liter) and 0.9 g of a methanol solution of tungsten hexachloride in toluene (concentration 0.025 mol / liter) were added to the solution in the reaction vessel as a polymerization catalyst. Was added and the solution was heated and stirred at 80.degree. C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

このようにして得られた開環重合体溶液１，０００ｇをオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．１２ｇ添加し、水素ガス圧１００ｋｇ／ｃｍ²、反応温度１６５℃の条件下で、３時間加熱撹拌して水素添加反応を行った。得られた反応溶液（水素添加重合体溶液）を冷却した後、水素ガスを放圧した。この反応溶液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添加重合体（以下「樹脂Ａ」ともいう。）を得た。得られた樹脂Ａは、数平均分子量（Ｍｎ）が３２，０００、重量平均分子量（Ｍｗ）が１３７，０００であり、ガラス転移温度（Ｔｇ）が１６５℃であった。

The autoclave is charged with 1,000 g of the ring-opening polymer solution thus obtained, and 0.12 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ is added to the ring-opening polymer solution. Under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C., heating and stirring were carried out for 3 hours to carry out a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

<Resin synthesis example 2>
In a 3 L four-necked flask, 35.12 g of 2,6-difluorobenzonitrile, 87.60 g of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g of potassium carbonate, N, N-dimethylacetamide (hereinafter referred to as "DMAc" 443 g) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube and a cooling tube were attached to a four-necked flask. Next, after the inside of the flask was purged with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and the generated water was removed from the Dean-Stark tube as needed. When the formation of water was not observed, the temperature was gradually raised to 160 ° C., and the reaction was carried out for 6 hours at the same temperature. After cooling to room temperature (25 ° C.), the formed salt was removed by filter paper, the filtrate was poured into methanol to reprecipitate, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried overnight at 60 ° C. to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

<Resin synthesis example 3>
In a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with a side tube, a Dean-Stark tube and a cooling tube, under a nitrogen stream, 1,4-bis (4-amino-α, α 27.66 g of -dimethylbenzyl) benzene and 7.38 g of 4,4'-bis (4-aminophenoxy) biphenyl were introduced and dissolved in 68.65 g of .gamma.-butyrolactone and 17.16 g of N, N-dimethylacetamide. The resulting solution is cooled to 5 ° C. using an ice water bath, and while maintaining the same temperature, 22.62 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.50 g of triethylamine as an imidation catalyst It added at once. After completion of the addition, the temperature was raised to 180 ° C., and refluxing was carried out for 6 hours while distilling off the distillate as needed. After completion of the reaction, air cooling to an internal temperature of 100 ° C., and then adding 143.6 g of N, N-dimethylacetamide for dilution, followed by cooling while stirring, to give a polyimide resin solution with a solid concentration of 20% by weight of 264.16 g I got A portion of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The filtered polyimide was washed with methanol and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). The IR spectrum of the obtained resin C was measured, 1704 cm ^-1 characteristic of imido group, absorption of 1770 cm ^-1 were observed. Resin C had a glass transition temperature (Tg) of 310 ° C., and the logarithmic viscosity was measured to be 0.87.

Example 1
In Example 1, an optical filter having a substrate made of a transparent resin substrate was produced in the following procedure and conditions.

In a container, 100 parts of resin A obtained in Resin Synthesis Example 1, compound (a-1) represented by the following formula (a-1) as compound (A) (absorption maximum wavelength in dichloromethane: 698 nm) 0.04 And 0.04 part of a compound (a-2) (absorption maximum wavelength 733 nm in dichloromethane) represented by the following formula (a-2), the compound (s-) described in Table 2-2 as a compound (S) 6) 0.07 parts of (absorption maximum wavelength 1093 nm in dichloromethane) and methylene chloride were added to prepare a solution with a resin concentration of 20% by weight. The resulting solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and peeled off from the glass plate. The peeled coating was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate made of a transparent resin substrate of 0.1 mm in thickness, 60 mm in length and 60 mm in width. The spectral transmittance of this substrate was measured, and the transmittances at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength were determined. The results are shown in FIG. 3 and Table 5-1.

続いて、得られた基材の片面に第一光学層として誘電体多層膜（Ｉ）を形成し、さらに基材のもう一方の面に第二光学層として誘電体多層膜（ＩＩ）を形成し、厚さ約０．１０５ｍｍの光学フィルターを得た。

Subsequently, dielectric multilayer film (I) is formed as a first optical layer on one surface of the obtained substrate, and dielectric multilayer film (II) is formed as a second optical layer on the other surface of the substrate. An optical filter with a thickness of about 0.105 mm was obtained.

The dielectric multilayer film (I) is formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer at a deposition temperature of 100 ° C. (total 26 layers). The dielectric multilayer film (II) is formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer at a deposition temperature of 100 ° C. (total 20 layers). In any of the dielectric multilayers (I) and (II), the silica layer and the titania layer are in the order of the titania layer, the silica layer, the titania layer,... The silica layer, the titania layer, the silica layer from the substrate side The layers are alternately laminated, and the outermost layer of the optical filter is a silica layer.

  The design of dielectric multilayer films (I) and (II) was performed as follows.

  With regard to the thickness and the number of layers of each layer, the wavelength dependency of the refractive index of the base material, the applied compound (S) and the compound (S) to achieve the antireflection effect in the visible region and the selective transmission / reflection performance in the near infrared region. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) in accordance with the absorption characteristics of A). When performing optimization, in this example, input parameters (Target value) to the software are as shown in Table 3 below.

膜構成最適化の結果、実施例１では、誘電体多層膜（Ｉ）は、膜厚３１〜１５７ｎｍのシリカ層と膜厚１０〜９５ｎｍのチタニア層とが交互に積層されてなる、積層数２６の多層蒸着膜となり、誘電体多層膜（ＩＩ）は、膜厚３７〜１９４ｎｍのシリカ層と膜厚１２〜１１４ｎｍのチタニア層とが交互に積層されてなる、積層数２０の多層蒸着膜となった。最適化を行った膜構成の一例を下記表４に示す。

As a result of optimizing the film configuration, in Example 1, the dielectric multilayer film (I) is formed by stacking 26 silica layers with a thickness of 31 to 157 nm and titania layers with a thickness of 10 to 95 nm alternately. The multilayer dielectric film (II) is a multilayer vapor deposition film having 20 laminated layers in which silica layers of 37 to 194 nm in film thickness and titania layers of 12 to 114 nm in film thickness are alternately laminated. The An example of the optimized film configuration is shown in Table 4 below.

得られた光学フィルターの垂直方向および垂直方向から３０°の角度から測定した分光透過率を測定し、各波長領域における光学特性を評価した。結果を図４および表５−１に示す。波長４３０〜５８０ｎｍにおける透過率の平均値は８４％、波長１１００〜１２００ｎｍにおける透過率の平均値は１％以下、絶対値｜Ｘａ−Ｘｂ｜は２ｎｍであった。

The spectral transmittance measured from the vertical direction and the angle of 30 ° from the vertical direction of the obtained optical filter was measured to evaluate the optical characteristics in each wavelength region. The results are shown in FIG. 4 and Table 5-1. The average value of the transmittance at a wavelength of 430 to 580 nm was 84%, the average value of the transmittance at a wavelength of 1100 to 1200 nm was 1% or less, and the absolute value | Xa−Xb | was 2 nm.

  In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1. The camera image obtained gave good results in color shading and ghosting.

Example 2
In Example 2, the optical filter which has a base material which consists of a transparent resin-made board | substrate was created in the following procedures and conditions.

In Example 1, a compound (a-3) represented by the following formula (a-3) as a compound (A) (absorption maximum wavelength 703 nm in dichloromethane) 0.04 part and represented by the following formula (a-4) Compound (a-4) (absorption maximum wavelength 736 nm in dichloromethane) using 0.08 parts, compound (s-8) described in Table 2-3 above as compound (S) (in dichloromethane Dye (X-1) (Absorption maximum wavelength 887 nm in dichloromethane) represented by the following Formula (X-1) as the other dye (X) using 0.06 parts of absorption maximum wavelength 1096 nm) Under the same procedure and conditions as in Example 1 except that .01 part was used, a base material comprising a transparent resin substrate containing the compound (A) and the compound (S) was obtained. The spectral transmittance of this substrate was measured, and the transmittances at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength were determined. The results are shown in FIG. 5 and Table 5-1.

続いて、実施例１と同様に、得られた基材の片面に第一光学層としてシリカ（ＳｉＯ₂）層とチタニア（ＴｉＯ₂）層とが交互に積層されてなる（合計２６層）誘電体多層膜（ＩＩＩ）を形成し、さらに基材のもう一方の面に第二光学層としてシリカ（ＳｉＯ₂）層とチタニア（ＴｉＯ₂）層とが交互に積層されてなる（合計２０層）誘電体多層膜（ＩＶ）を形成し、厚さ約０．１０５ｍｍの光学フィルターを得た。誘電体多層膜の設計は、基材屈折率の波長依存性を考慮した上で、実施例１と同じ設計パラメーターを用いて行った。得られた光学フィルターの垂直方向および垂直方向から３０°の角度から測定した分光透過率を測定し、各波長領域における光学特性を評価した。また、得られた光学フィルターを用いてカメラモジュールを作成し、カメラ画像の色シェーディングおよびゴーストの評価を行った。結果を表５−１に示す。

Subsequently, as in Example 1, on one surface of the obtained substrate, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer (total 26 layers) dielectric Body multilayer film (III), and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the substrate (total 20 layers) A dielectric multilayer film (IV) was formed to obtain an optical filter with a thickness of about 0.105 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the refractive index of the substrate. The spectral transmittance measured from the vertical direction and the angle of 30 ° from the vertical direction of the obtained optical filter was measured to evaluate the optical characteristics in each wavelength region. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Example 3]
In Example 3, an optical filter having a base made of a transparent resin substrate having a resin layer on both sides was produced in the following procedure and conditions.

  In Example 1, 0.06 parts of compound (a-4) as compound (A) and compound (a-5) represented by the following formula (a-5) (absorption maximum wavelength in dichloromethane: 713 nm) 0.06 Example 1 and Example 1 except that the compound (s-13) described in Table 2-4 (the absorption maximum wavelength in dichloromethane 1096 nm) 0.08 part was used as the compound (S). A transparent resin substrate containing Compound (A) and Compound (S) was obtained under the same procedure and conditions.

得られた透明樹脂製基板の片面に、下記組成の樹脂組成物（１）をバーコーターで塗布し、オーブン中７０℃で２分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが２μｍとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光（露光量５００ｍＪ／ｃｍ²，２００ｍＷ）を行い、樹脂組成物（１）を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物（１）からなる樹脂層を形成し、化合物（Ａ）および化合物（Ｓ）を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。この基材の分光透過率を測定し、（Ｔ₁）、（Ｘ₁）、（Ｘ₂）、（Ｘｃ）および各波長における透過率を求めた。結果を表５−１に示す。

A resin composition (1) of the following composition was coated on one surface of the obtained transparent resin substrate with a bar coater, and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, exposure (exposure amount 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1), and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) is formed on the other surface of the transparent resin substrate, and resin layers are provided on both sides of the transparent resin substrate containing the compound (A) and the compound (S). A substrate was obtained. The spectral transmittance of this substrate was measured, and the transmittances at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength were determined. The results are shown in Table 5-1.

Resin composition (1): 60 parts by weight of tricyclodecanedimethanol diacrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30% )
Subsequently, as in Example 1, on one surface of the obtained substrate, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer (total 26 layers) dielectric Body multilayer film (V), and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the substrate (total 20 layers) The dielectric multilayer film (VI) was formed to obtain an optical filter with a thickness of about 0.109 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the refractive index of the substrate and the like as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 ° from the vertical direction of the obtained optical filter was measured to evaluate the optical characteristics in each wavelength region. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

Example 4
In Example 4, an optical filter having a base formed by forming a transparent resin layer containing the compound (A) on both sides of a resinous support was produced according to the following procedure and conditions.

  Resin A and methylene chloride obtained in Resin Synthesis Example 1 were added to a container to prepare a solution having a resin concentration of 20% by weight, and the resin substrate of Example 1 was used except that the obtained solution was used. A resin support was prepared in the same manner as the preparation.

In the same manner as in Example 3, a resin layer composed of the resin composition (2) having the following composition is formed on both sides of the obtained resinous support, and the compound (A) and the compound (A) A substrate obtained by forming a transparent resin layer containing S) was obtained. The spectral transmittance of this substrate was measured, and the transmittances at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength were determined. The results are shown in Table 5-1.

Resin composition (2): 100 parts by weight of tricyclodecanedimethanol diacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.10 parts by weight of compound (a-1), 0.10 parts by weight of compound (a-2) Part, 1.75 parts by weight of compound (s-6), methyl ethyl ketone (solvent, TSC: 25%)
Subsequently, as in Example 1, on one surface of the obtained substrate, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer (total 26 layers) dielectric Body multilayer film (VII), and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the substrate (total 20 layers) A dielectric multilayer film (VIII) was formed to obtain an optical filter with a thickness of about 0.109 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the refractive index of the substrate and the like as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 ° from the vertical direction of the obtained optical filter was measured to evaluate the optical characteristics in each wavelength region. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Example 5]
In Example 5, the optical filter which has a base material which consists of a transparent glass substrate which has a transparent resin layer which contains a compound (A) in single side | surface was produced in the following procedures and conditions.

A resin composition (3) of the following composition is applied on a transparent glass substrate “OA-10G (thickness 150 μm)” (manufactured by Nippon Electric Glass Co., Ltd.) cut to a size of 60 mm long and 60 mm wide by a spin coater, The solvent was evaporated by heating on a hot plate at 80 ° C. for 2 minutes. Under the present circumstances, the coating conditions of the spin coater were adjusted so that the thickness after drying might be 2 micrometers. Next, exposure (exposure dose 500 mJ / cm ² , 200 mW) is performed using a conveyor type exposure machine to cure the resin composition (3), and a transparent resin layer containing the compound (A) and the compound (S) is provided. The base material which consists of a transparent glass substrate was obtained. The spectral transmittance of this substrate was measured, and the transmittances at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength were determined. The results are shown in Table 5-1.

Resin composition (3): 20 parts by weight of tricyclodecanedimethanol diacrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.20 parts by weight of compound (a-1), compound (A-2) 0.20 parts by weight, compound (s-6) 3.50 parts by weight, methyl ethyl ketone (solvent, TSC: 35%)
Subsequently, as in Example 1, on one surface of the obtained substrate, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer (total 26 layers) dielectric Body multilayer film (IX), and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the substrate (total 20 layers) A dielectric multilayer film (X) was formed to obtain an optical filter with a thickness of about 0.107 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the refractive index of the substrate and the like as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 ° from the vertical direction of the obtained optical filter was measured to evaluate the optical characteristics in each wavelength region. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Example 6]
In Example 6, the optical filter which has a base material which consists of a near-infrared absorption glass substrate which has a transparent resin layer which contains a compound (A) in single side | surface was produced in the following procedures and conditions.

A resin composition (4) of the following composition is applied on a near infrared absorbing glass substrate “BS-11 (120 μm thick)” (manufactured by Matsunami Glass Industry Co., Ltd.) cut to a size of 60 mm long and 60 mm wide using a spin coater Then, the solvent was removed by heating at 80 ° C. for 2 minutes on a hot plate. Under the present circumstances, the coating conditions of the spin coater were adjusted so that the thickness after drying might be 2 micrometers. Next, exposure (exposure amount 500 mJ / cm ² , 200 mW) is performed using a conveyor type exposure machine to cure the resin composition (4), and a near infrared absorbing glass substrate having a transparent resin layer containing the compound (A) The base material which consists of The spectral transmittance of this substrate was measured, and the transmittances at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength were determined. The results are shown in FIG. 6 and Table 5-1.

Resin composition (4): 20 parts by weight of tricyclodecanedimethanol diacrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.15 parts by weight of compound (a-3), compound (A-4) 0.30 parts by weight, methyl ethyl ketone (solvent, TSC: 35%)
Subsequently, as in Example 1, on one surface of the obtained substrate, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer (total 26 layers) dielectric Body multilayer film (XI), and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the substrate (total 20 layers) A dielectric multilayer film (XII) was formed to obtain an optical filter with a thickness of about 0.107 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the refractive index of the substrate and the like as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 ° from the vertical direction of the obtained optical filter was measured to evaluate the optical characteristics in each wavelength region. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Example 7]
In Example 7, an optical filter having a base made of a transparent resin substrate containing a compound (A) having a transparent resin layer containing near infrared absorbing fine particles on both sides was produced according to the following procedure and conditions.

  A transparent resin-made substrate containing compound (A) was obtained in the same manner as in Example 2 except that the compound (S-8) and the other dye (X-1) were not used in Example 2. The

In the same manner as in Example 3, a resin layer comprising a resin composition (5) having the following composition is formed on both sides of the obtained resinous substrate, and a compound having a transparent resin layer containing near infrared absorbing fine particles on both sides The base material which consists of a transparent resin-made board | substrate containing (A) was obtained. The spectral transmittance of this substrate was measured, and the transmittances at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength were determined. The results are shown in FIG. 7 and Table 5-1.

Resin composition (5): 100 parts by weight of tricyclodecanedimethanol diacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 35 parts by weight of a near-infrared absorbing fine particle dispersion (YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd.) About 10 parts by weight in terms of solid content), methyl ethyl ketone (solvent, TSC: 30%)
Subsequently, as in Example 1, on one surface of the obtained substrate, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer (total 26 layers) dielectric Body multilayer film (XIII), and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the substrate (total 20 layers) A dielectric multilayer film (XIV) was formed to obtain an optical filter with a thickness of about 0.109 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the refractive index of the substrate and the like as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 ° from the vertical direction of the obtained optical filter was measured to evaluate the optical characteristics in each wavelength region. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Examples 8 to 13]
The same procedure as in Example 3 was repeated except that the resin, the solvent, the drying condition of the resin substrate, and the compound (A), the compound (S) and the other dye (X) were changed as shown in Table 5-1. Material and optical filters were made. The optical properties of the obtained substrate and optical filter are shown in Table 5-1. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

Comparative Example 1
A substrate and an optical filter were produced in the same manner as in Example 1 except that the compound (S) and the compound (A) were not used in Example 1, and the optical properties were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 1 exhibits relatively good visible light transmittance, the incident angle dependency of the optical characteristics is large, and the base material has no absorption in the vicinity of 700 nm or near infrared wavelength region. From these results, it was confirmed that the color shading suppressing effect and the ghost suppressing effect were inferior.

Comparative Example 2
An optical filter was produced in the same manner as in Example 1 except that a transparent glass substrate "OA-10G (thickness 150 um)" (manufactured by Nippon Electric Glass Co., Ltd.) was used as a substrate, and the optical characteristics were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 2 exhibits relatively good visible light transmittance, the incident angle dependency of the optical characteristics is large, and the base material has no absorption in the vicinity of 700 nm or near infrared wavelength region. From these results, it was confirmed that the color shading suppressing effect and the ghost suppressing effect were inferior.

Comparative Example 3
An optical filter is prepared in the same manner as in Example 1 except that a near infrared absorbing glass substrate "BS-11 (thickness 120 um)" (manufactured by Matsunami Glass Industry Co., Ltd.) is used as a substrate, and the optical characteristics are evaluated. did. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. The spectral transmission spectrum of the substrate is shown in FIG. Although the optical filter obtained in Comparative Example 3 exhibits relatively good optical characteristics, it has been confirmed that the absorption intensity around 700 nm of the substrate is not sufficient and the color shading suppression effect is inferior.

Comparative Example 4
In Example 3, 0.08 parts of compound (a-4) and 0.06 parts of compound (a-5) were used as compound (A) without using compound (S), and dye (X-) 1) A substrate and an optical filter were prepared in the same manner as in Example 3 except that 0.01 part was used, and the optical properties were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. The spectral transmission spectrum of the substrate is shown in FIG. Although the optical filter obtained in Comparative Example 5 exhibits relatively good optical characteristics, it has been confirmed that the absorption intensity in the near infrared wavelength region of the substrate is not sufficient and the ghost suppressing effect is inferior.

Comparative Example 5
A substrate and an optical filter were produced in the same manner as in Example 6, except that, in Example 6, a resin composition (6) having the following composition was used instead of the resin composition (4).

Resin composition (6): 20 parts by weight of tricyclodecanedimethanol diacrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.15 parts by weight of compound (a-1), methyl ethyl ketone (Solvent, TSC: 35%)
The optical properties of the obtained substrate and optical filter were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. The spectral transmission spectrum of the substrate is shown in FIG. Although the optical filter obtained in Comparative Example 5 exhibits relatively good optical characteristics, it has been confirmed that the absorption intensity around 700 nm of the substrate is not sufficient and the color shading suppression effect is inferior.

Comparative Example 6
In Example 3, 0.04 part of compound (a-3) and 0.08 parts of compound (a-4) were used as compound (A), and compound (s-6) 0.01 as compound (S) A substrate and an optical filter were prepared in the same manner as in Example 3 except that a part was used, and the optical properties were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 6 exhibits relatively good optical characteristics, it has been confirmed that the absorption intensity in the near infrared wavelength region of the substrate is not sufficient and the ghost suppressing effect is inferior.

Comparative Example 7
Example 3 except that 0.04 part of the compound (a-1) was used as the compound (A) and 0.07 part of the compound (s-6) was used as the compound (S) in Example 3 A substrate and an optical filter were prepared in the same manner as in the above, and the optical properties were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 7 shows relatively good optical characteristics, it is confirmed that the absorption intensity around 700 nm of the base is not sufficient and the color shading suppression effect is inferior.

Comparative Example 8
In Example 3, 0.04 parts of Compound (a-1) was used as Compound (A), and Compound (s-14) described in Table 2-4 above as Compound (S) (absorption in dichloromethane A substrate and an optical filter were produced in the same manner as in Example 3 except that 0.45 part of a maximum wavelength of 1097 nm was used, and the optical characteristics were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 8 exhibits relatively good optical characteristics, it has been confirmed that the absorption intensity around 700 nm of the substrate is not sufficient and the color shading suppression effect is inferior.

  The structure of the base material applied by the Example and the comparative example, various compounds, etc. are as follows.

<Form of base material>
Form (1): Transparent resin substrate containing compound (A) Form (2): A resin layer is provided on both sides of a transparent resin substrate containing compound (A) Form (3): Compounds on both sides of resin support Having a transparent resin layer containing (A) Form (4): Having a transparent resin layer containing a compound (A) on one side of a transparent glass substrate Form (5): Compound on one side of a near infrared absorbing glass substrate Having a transparent resin layer containing (A) Form (6): Having a transparent resin layer containing near infrared absorbing fine particles on both sides of a transparent resin substrate containing a compound (A) Form (7): containing a compound (A) No transparent resin substrate (comparative example)
Form (8): Transparent glass substrate (comparative example)
Form (9): Near-infrared absorbing glass substrate (comparative example)
<Transparent resin>
Resin A: Cyclic Polyolefin Resin (Resin Synthesis Example 1)
Resin B: Aromatic polyether resin (Resin synthesis example 2)
Resin C: Polyimide Resin (Resin Synthesis Example 3)
Resin D: Cyclic olefin resin "Zeonor 1420R" (manufactured by Nippon Zeon Co., Ltd.)
<Glass substrate>
Glass substrate (1): Transparent glass substrate “OA-10G (thickness 150 μm)” (manufactured by Nippon Electric Glass Co., Ltd.) cut to a size of 60 mm long and 60 mm wide
Glass substrate (2): Near infrared ray absorbing glass substrate “BS-11 (120 μm in thickness)” cut into a size of 60 mm long and 60 mm wide (manufactured by Matsunami Glass Industry Co., Ltd.)
<Near-infrared absorbing dye>
<< Compound (A) >>
Compound (a-1): Compound (a-1) described above (absorption maximum wavelength in dichloromethane: 698 nm)
Compound (a-2): Compound (a-2) above (absorption maximum wavelength in dichloromethane: 733 nm)
Compound (a-3): Compound (a-3) above (absorption maximum wavelength in dichloromethane: 703 nm)
Compound (a-4): Compound (a-4) above (absorption maximum wavelength in dichloromethane: 736 nm)
Compound (a-5): Compound (a-5) above (absorption maximum wavelength in dichloromethane: 713 nm)
Compound (a-6): Cyanine compound represented by the following formula (a-6) (absorption maximum wavelength 681 nm in dichloromethane)

≪化合物（Ｓ）≫
化合物（ｓ−６）：上記の化合物（ｓ−６）（ジクロロメタン中での吸収極大波長１０９３ｎｍ）
化合物（ｓ−８）：上記の化合物（ｓ−８）（ジクロロメタン中での吸収極大波長１０９６ｎｍ）
化合物（ｓ−１３）：上記の化合物（ｓ−１４）（ジクロロメタン中での吸収極大波長１０９６ｎｍ）
化合物（ｓ−１４）：上記の化合物（ｓ−１５）（ジクロロメタン中での吸収極大波長１０９７ｎｍ）
≪その他の色素（Ｘ）≫
色素（Ｘ−１）：上記の色素（Ｘ−１）（ジクロロメタン中での吸収極大波長８８７ｎｍ）
色素（Ｘ−２）：下記式（Ｘ−２）で表される色素（ジクロロメタン中での吸収極大波長８１１ｎｍ）

«Compound (S)»
Compound (s-6): Compound (s-6) described above (absorption maximum wavelength 1093 nm in dichloromethane)
Compound (s-8): Compound (s-8) described above (absorption maximum wavelength 1096 nm in dichloromethane)
Compound (s-13): Compound (s-14) described above (absorption maximum wavelength 1096 nm in dichloromethane)
Compound (s-14): Compound (s-15) described above (absorption maximum wavelength 1097 nm in dichloromethane)
«Other pigments (X)»
Dye (X-1): the above dye (X-1) (absorption maximum wavelength in dichloromethane: 887 nm)
Dye (X-2): Dye represented by the following formula (X-2) (absorption maximum wavelength 811 nm in dichloromethane)

＜溶媒＞
溶媒（１）：塩化メチレン
溶媒（２）：Ｎ，Ｎ−ジメチルアセトアミド
溶媒（３）：シクロヘキサン／キシレン（重量比：７／３）
表５−１および表５−２における、実施例および比較例の（透明）樹脂製基板の乾燥条件は以下の通りである。なお、減圧乾燥前に、塗膜をガラス板から剥離した。

<Solvent>
Solvent (1): methylene chloride solvent (2): N, N-dimethylacetamide solvent (3): cyclohexane / xylene (weight ratio: 7/3)
The drying conditions of the (transparent) resin substrates of Examples and Comparative Examples in Tables 5-1 and 5-2 are as follows. In addition, the coating film was peeled from the glass plate before drying under reduced pressure.

<Film drying conditions>
Condition (1): 20 ° C./8 hr → under reduced pressure 100 ° C./8 hr
Condition (2): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 140 ° C./8 hr
Condition (3): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 100 ° C./24 hr

1: Optical filter 2: Spectrophotometer 3: Light 10: Substrate 11: First optical layer 12: Second optical layer 13: Third optical layer 14: Fourth optical layer 111: Camera image 112: White plate 113: Example of center part of white plate 114: Example of end of white plate 121: camera image 122: light source 123: example of ghost around light source

Claims (13)

An optical filter comprising a substrate satisfying the following requirements (a), (b) and (c), and satisfying the following requirements (d) and (e):
(A) having a layer containing a compound (A) having an absorption maximum in a wavelength range of 650 nm or more and 760 nm or less;
(B) The difference (X ₂ −X ₁ ) between the shortest wavelength (X ₁ ) at which the transmittance is 10% and the second shortest wavelength (X ₂ ) in the wavelength range of 640 nm or more is 50 nm or more;
(C) the transmittance at a wavelength of 900 nm, the transmittance at a wavelength of 1000 nm, and the transmittance at a wavelength of 1100 nm are all 65% or less;
(D) In the wavelength region of 430 to 580 nm, the average value of the transmittance when measured from the vertical direction of the optical filter is 75% or more;
(E) In the region of wavelengths 1100 nm to 1200 nm, the average value of the transmittance when measured from the vertical direction of the optical filter is 5% or less.   The optical filter according to claim 1, wherein the layer containing the compound (A) is a transparent resin layer.   The optical filter according to claim 1, further comprising a dielectric multilayer film on at least one surface of the substrate. The optical filter according to any one of claims 1 to 3, wherein the substrate further satisfies the following requirement (f):
(F) The minimum value (T ₁ ) of the transmittance in the wavelength region of 690 to 720 nm is 5% or less. The optical filter according to any one of claims 1 to 4, wherein the substrate further satisfies the following requirement (g):
(G) The compound (S) which has an absorption maximum in the area | region of wavelength 1050 nm-1200 nm is included. The optical filter according to claim 5, wherein the compound (S) is at least one compound selected from the group consisting of compounds represented by the following formulas (I) and (II).

[In the formula (I) and the formula (II),
R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a -NR ^g R ^h group, a -SR ⁱ group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any of L ^{a to} L ^h below, R ^g and R ^h each independently represent a hydrogen atom, -C (O) R ⁱ group or L ^{a to} L ^e below R ⁱ represents any one of the following L ^{a to} L ^e ,
(L ^a ) aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) halogen substituted alkyl group having 1 to 12 carbon atoms (L ^c ) alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon Aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms, heterocyclic group (L ^f ) having 2 to 14 carbon atoms, and alkoxy group having 1 to 12 carbon atoms (L ^g ) 1 to 12 acyl groups,
(L ^h ) C 1-12 alkoxycarbonyl group 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, At least one selected from the group consisting of alicyclic hydrocarbon groups having 3 to 14 carbon atoms, aromatic hydrocarbon groups having 6 to 14 carbon atoms, and heterocyclic groups having 3 to 14 carbon atoms,
Adjacent R ^{3 's} may form a ring which may have a substituent L,
n represents an integer of 0 to 4;
X represents an anion necessary to neutralize the charge;
M represents a metal atom,
Z represents D (R ⁱ ) ₄ and D represents a nitrogen atom, a phosphorus atom or a bismuth atom,
y represents 0 or 1; )   The optical filter according to any one of claims 3 to 6, wherein the dielectric multilayer film is formed on both sides of the substrate.   The optical system according to any one of claims 1 to 7, wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds and cyanine compounds. filter.   The transparent resin constituting the transparent resin layer is cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, Polysulfone resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin The resin is at least one resin selected from the group consisting of a curable resin, a silsesquioxane ultraviolet curable resin, an acrylic ultraviolet curable resin, and a vinyl ultraviolet curable resin. Optical filter according to any one of .   The optical filter according to any one of claims 1 to 9, wherein the base material comprises a transparent resin substrate containing the compound (A) and the compound (S).   The optical filter according to any one of claims 1 to 10 for a solid-state imaging device.   A solid-state imaging device comprising the optical filter according to any one of claims 1 to 11.   A camera module comprising the optical filter according to any one of claims 1 to 11.

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