JP6791251B2 - Optical filter and equipment using optical filter - Google Patents

Description

The present invention relates to an optical filter and an apparatus using the optical filter. More specifically, the present invention relates to an optical filter containing a compound having absorption in a specific wavelength region, and a solid-state image sensor and a camera module using the optical filter.

CCD and CMOS image sensors, which are solid-state image sensors for color images, are used in solid-state image sensors such as video cameras, digital still cameras, and mobile phones with camera functions. These solid-state image sensors are human beings in their light-receiving parts. A silicon photodiode that is sensitive to near-infrared rays that cannot be perceived by the eye is used. In these solid-state image sensors, it is necessary to perform luminosity factor correction that makes the color tone natural to the human eye, and an optical filter (for example, near-infrared ray cut) that selectively transmits or cuts light in a specific wavelength region is required. Filter) is often used.

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

As a result of diligent studies, the applicant has used a transparent resin substrate containing a near-infrared absorbing dye that has an absorption maximum in a specific wavelength region, so that the optical characteristics do not change much even if the incident angle is changed. Having found that a cut filter can be obtained, Patent Document 2 proposes a near-infrared cut filter having a wide viewing angle and high visible light transmittance. Further, in Patent Document 3, by using a phthalocyanine dye having a specific structure, a near-infrared cut filter that achieves both excellent visible transmittance and long absorption maximum wavelength, which have been problems in the past, at a high level. It is stated that can be obtained. However, in the near-infrared cut filter described in Patent Documents 2 and 3, although the applied base material has an absorption band having sufficient strength in the vicinity of 700 nm, it has a near-infrared wavelength region such as 900 to 1200 nm. Has almost no absorption. Therefore, the light rays in the near-infrared wavelength region are cut almost only by the reflection of the dielectric multilayer film, but in such a configuration, a slight stray light due to the internal reflection in the optical filter and the reflection between the optical filter and the lens. However, it may cause ghosts and flares when shooting in a dark environment. In particular, in recent years, there has been a strong demand for higher image quality of cameras even in mobile devices such as smartphones, and there have been cases where conventional optical filters cannot be used suitably.

On the other hand, an infrared shielding filter as in Patent Document 4 has been proposed as an optical filter using a base material having a wide absorption in the near infrared wavelength region. In Patent Document 4, a wide absorption in the near-infrared wavelength region is achieved by mainly applying a compound having a dithiolene structure, but the absorption intensity near 700 nm is not sufficient. In particular, when used under high incident angle conditions (for example, 45 degree incident) due to the recent reduction in camera module height, image deterioration due to color shading may occur.

Further, Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass base material and a layer containing a near-infrared absorbing dye, but the configuration described in Patent Document 5 also sufficiently improves color shading. (For example, FIG. 5 of Patent Document 5 shows optical characteristic graphs at 0-degree incident and 30-degree incident, but the visible light transmission band is also shown at 30-degree incident. Large wavelength shifts have been observed in the hem region (630-700 nm)).

Japanese Unexamined Patent Publication No. 6-200113 JP-A-2011-100084 International Publication 2015/025779 Pamphlet International Publication 2014/168190 Pamphlet International Publication No. 2014/030628 Pamphlet

An object of the present invention is to provide an optical filter capable of achieving both color shading suppression and ghost suppression of a camera image at a high level, which cannot be sufficiently achieved by a conventional optical filter.

As a result of diligent studies to solve the above problems, the present inventors have a substrate having a sufficiently strong absorption band near a wavelength of 700 nm and a wide absorption band in a near infrared wavelength region of 900 nm or more. By applying the above, it has been found that an optical filter capable of achieving the desired near-infrared cut characteristics, visible light transmittance, color shading suppressing effect and ghost suppressing effect can be obtained, and the present invention has been completed. Examples of aspects of the present invention are shown 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) It has a layer containing the compound (A) having an absorption maximum in a region having a wavelength 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% in the wavelength region of 640 nm or more and the second shortest wavelength (X ₂ ) 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 region of wavelength 430 to 580 nm, the average value of the transmittance measured from the vertical direction of the optical filter is 75% or more;
(E) In the wavelength region of 1100 nm to 1200 nm, the average value of the transmittance 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], which has a dielectric multilayer film on at least one surface of the base material.

[4] The optical filter according to any one of items [1] to [3], wherein the base material further satisfies the following requirement (f).
(F) The minimum value (T ₁ ) of the transmittance in the region of wavelength 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) Contains compound (S) having an absorption maximum in a region having a wavelength of 1050 nm or more and 1200 nm or less.

[6] The item [5], wherein the compound (S) is at least one compound selected from the group consisting of the 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 are independently hydrogen atom, halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R. ^It represents either ⁱ group, -OSO ₂ R ⁱ group or L ^{a to} L ^h below, and R ^g and R ^h are independently hydrogen atom, -C (O) R ⁱ group or L ^{a to} L ^e below. represents either, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L ^b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L ^d) carbon Aromatic hydrocarbon group (L ^e ) of number 6 to 14 Heterocyclic group of carbon number 2 to 14 (L ^f ) Aalkoxy group (L ^g ) substituent L of carbon number 1 to 12 may have carbon number 1-12 acyl groups,
(L ^h ) An alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, and the like. It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.
Adjacent R ³ together may form a ring which may have a substituent L,
n represents an integer from 0 to 4
X represents the anion required to neutralize the charge
M represents a metal atom
Z represents D (R ⁱ ) ₄ , D represents nitrogen atom, phosphorus atom or bismuth atom,
y represents 0 or 1.

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

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

[9] The transparent resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or a polyarylate. Based resin, polysulfone based resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, A term characterized by being at least one resin selected from the group consisting of an allyl ester-based curable resin, a silsesquioxane-based ultraviolet curable resin, an acrylic-based ultraviolet curable resin, and a vinyl-based ultraviolet curable resin [ 2] The optical filter according to any one of [8].

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

[11] The optical filter according to any one of Items [1] to [10] for a solid-state image sensor.

[12] A solid-state image sensor including the optical filter according to any one of items [1] to [11].

[13] A camera module including 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 having excellent near-infrared cut characteristics, less dependence on incident angle, and excellent transmittance characteristics in the visible wavelength region, color shading suppressing effect, and ghost suppressing effect.

1 (a) and 1 (b) are schematic views showing an example of a preferable configuration of the optical filter of the present invention. FIG. 2A is a schematic view showing a method of measuring the transmittance when measured from the vertical direction of the optical filter. FIG. 2B is a schematic view showing a method of measuring the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the 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 base material 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 base material (near infrared absorbing glass substrate) used in Comparative Example 3. FIG. 9 is a spectral transmission spectrum of the base material obtained in Comparative Example 4. FIG. 10 is a spectral transmission spectrum of the base material obtained in Comparative Example 5. It is a schematic diagram for demonstrating the color shading evaluation of the camera image performed in an Example and a comparative example. It is a schematic diagram for demonstrating the ghost evaluation of the camera image performed in an Example and a comparative example.

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

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

[Base material]
The substrate used in the present invention meets the following requirements (a), (b) and (c);
(A) It has a layer containing the compound (A) having an absorption maximum in a region having a wavelength 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% in the wavelength region of 640 nm or more and the second shortest wavelength (X ₂ ) 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.

Further, it is preferable that the base material further satisfies at least one of the following requirements (f) to (h):
(F) The minimum value (T ₁ ) of transmittance in the region of wavelength 690 to 720 nm is 5% or less;
(G) Contains compound (S) having an absorption maximum in the region of wavelength 1050 nm or more and 1200 nm or less;
(H) The shortest wavelength (Xc) at which the transmittance is 50% when the transmittance is more than 50% to 50% or less 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)>
In the requirement (a), the components constituting the layer containing the compound (A) are not particularly limited, and examples thereof include transparent resins, sol-gel materials, low-temperature cured glass materials, etc., but they are easy to handle and the compounds ( From the viewpoint of compatibility with A), a transparent resin is preferable.

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

Squalylium-based compounds have excellent visible light transmittance, steep absorption characteristics, and high molar absorption coefficient, but may generate fluorescence that causes scattered light when absorbing light. In such a case, by using the squarylium compound and the other compound (A) in combination, it is possible to obtain an optical filter with less scattered light and better camera image quality.

The absorption maximum wavelength of 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 further preferably 680 nm or more and 745 nm or less.

When the compound (A) is a combination of two or more kinds of compounds, the difference between the absorption maximum wavelengths of the compound (A) to be applied having the shortest absorption maximum wavelength and the longest absorption maximum wavelength is preferably 10 to 10. It is 60 nm, more preferably 15 to 55 nm, and even more preferably 20 to 50 nm. When the difference in absorption maximum wavelength is within the above range, scattered light due to fluorescence can be sufficiently reduced, and a wide absorption band around 700 nm and excellent visible light transmittance can be compatible with each other, which is preferable.

The content of the entire compound (A) is determined as the base material, for example, a base material made of a transparent resin substrate containing the compound (A) or a curable resin on a transparent resin substrate containing the compound (A). When a base material on which a resin layer such as an overcoat layer made of the above is laminated is used, it is preferably 0.04 to 2.0 parts by weight, more preferably 0.06 to 0.06 to 100 parts by weight of the transparent resin. It is 1.5 parts by weight, more preferably 0.08 to 1.0 parts by weight, and the compound (A) is contained as the base material on a support such as a glass support or a resin support as a base. When a base material on which a transparent resin layer such as an overcoat layer made of a curable resin or the like is laminated is used, it is preferably 0% with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). It is 4 to 5.0 parts by weight, more preferably 0.6 to 4.0 parts by weight, still more preferably 0.8 to 3.5 parts by weight.

<Requirement (b)>
The difference between the wavelengths X ₁ and X ₂ (X _2- X ₁ ) is preferably 53 nm or more, more preferably 55 nm or more, still more preferably 58 nm or more. The upper limit is not particularly limited, but depending on the characteristics of the compound (A) and other near-infrared absorbers, if the value is too large, the visible transmittance may decrease, so that it is preferably 100 nm or less, for example. 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. Color shading can be suppressed even under conditions with a large incident angle, which is preferable.

The wavelength value (X ₁ + X ₂ ) / 2, which is 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, and is 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, light in the wavelength region near the long wavelength end of the visible region can be cut more efficiently, which is preferable.

The X ₁ preferably has 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 further preferably a wavelength of 660 nm or more and 700 nm or less. When X ₁ is in such a range, a camera image with less noise and excellent color reproducibility tends to be obtained, which is preferable.

<Requirement (c)>
The transmittances (c1), (c2) and (c3) are all preferably 60% or less, more preferably 55% or less, 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 value of the transmittance in the near-infrared wavelength region is too low, the visible transmittance may decrease or the thickness of the base material may become extremely thick. Therefore, for example, it is preferably 5% or more. When the transmittances (c1), (c2) and (c3) are within the above ranges, a practically sufficient level of ghost suppressing effect can be obtained, which is preferable.

The base material may be a single layer or a multi-layer as long as it has a layer containing the compound (A). Further, in order to satisfy the requirement (C), the base material preferably contains a near-infrared absorbing agent, and the near-infrared absorbing agent is contained in a different layer even if it is contained in the same layer as the compound (A). It may be.

When the layer containing the compound (A) and the layer containing the near infrared absorber are the same, for example, a base material composed of a transparent resin substrate containing the compound (A) and the near infrared absorber, the compound (A) and the near infrared absorber. A compound (compound) on a base material 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 an infrared absorber, a glass support, or a support such as a base resin support. Examples thereof include a base material on which a transparent resin layer such as an overcoat layer made of a curable resin containing A) and a near-infrared absorber is laminated.

When the layer containing the compound (A) and the layer containing the near-infrared absorber are different, for example, an overcoat layer made of a curable resin or the like containing the compound (A) on a transparent resin substrate containing the near-infrared absorber, etc. Base material on which the resin layer of the above is laminated, a base material on which a resin layer such as an overcoat layer made of a curable resin containing a near infrared absorber is laminated on a transparent resin substrate containing the compound (A), glass support An overcoat layer made of a curable resin containing compound (A) and an overcoat layer made of a curable resin containing a near-infrared absorber are laminated on a support such as a body or a base resin support. Examples thereof include a base material in which a resin layer such as an overcoat layer made of a curable resin containing the compound (A) is laminated on a glass substrate containing a near-infrared absorber.

The near-infrared absorber is not particularly limited as long as it has a wide absorption in the wavelength range of 900 to 1200 nm. For example, a near-infrared absorbing dye, a near-infrared absorbing fine particle, a conductive metal oxide, and a phosphoric acid-based glass. Examples include the transition metal component inside.

<Requirement (f)>
The T ₁ is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less. When T ₁ is in the above range, it can be said that the transmittance cut of the absorption band is sufficient, and flare around the light source can be suppressed in the camera image, which is preferable.

<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 absorption intensity in the near-infrared wavelength region and visible transmittance can be compatible at a high level. It is preferable because it tends to be.

<< Compound (S) >>
The compound (S) is not particularly limited as long as it has an absorption maximum in the region having a wavelength of 1050 nm or more and 1200 nm or less, but is preferably a solvent-soluble dye compound, more preferably a diimonium-based compound or a metal dithiolate complex-based compound. It is at least one compound selected from the group consisting of compounds, pyrolopyrrole compounds, cyanine compounds, croconium compounds and naphthalocyanine compounds, and more preferably selected from the group consisting of diimonium compounds and metal dithiolate complex compounds. It is at least one compound selected from the group consisting of a diimonium-based compound represented by the following formula (I) and a metal dithiolate complex-based compound 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 are independently hydrogen atom, halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R. ^It represents either ⁱ group, -OSO ₂ R ⁱ group or L ^{a to} L ^h below, and R ^g and R ^h are independently hydrogen atom, -C (O) R ⁱ group or L ^{a to} L ^e below. represents either, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L ^b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L ^d) carbon Aromatic hydrocarbon group (L ^e ) of number 6 to 14 Heterocyclic group of carbon number 2 to 14 (L ^f ) Aalkoxy group (L ^g ) substituent L of carbon number 1 to 12 may have carbon number 1-12 acyl groups,
(L ^h ) An alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, and the like. It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.
Adjacent R ³ together may form a ring which may have a substituent L,
n represents an integer from 0 to 4
X represents the anion required to neutralize the charge
M represents a metal atom
Z represents D (R ⁱ ) ₄ , D represents nitrogen atom, phosphorus atom or bismuth atom,
y represents 0 or 1.

The R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, an adamantyl group, or a trifluoromethyl group. , Pentafluoroethyl group, 3-pyridinyl group, epoxy group, phenyl group, benzyl group, fluorenyl group, more preferably isopropyl group, sec-butyl group, tert-butyl group, 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, or 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, pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, more preferably chlorine. Atomic, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group , Pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, particularly preferably methyl group, ethyl group, n-propyl group, isopropyl group. The number of R ² bonded to the same aromatic ring (value of n) is not particularly limited as long as it is 0 to 4, but is preferably 0 or 1.

The X is an anion necessary for neutralizing the electric 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 the same or different, but they are preferably the same from a synthetic point of view. X is not particularly limited as long as it is such an anion, but as an example, those listed in Table 1 below can be mentioned.

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, from the viewpoint of heat resistance, light resistance and spectral characteristics of the diimonium compound, (X-10), (X-16), (X-17), (X-21), (X-21) in Table 1 above. X-22), (X-24), and (X-28) are particularly preferred.

Examples of the diimonium-based compound represented by the above formula (I) include those listed in Tables 2-1 to 2-4 below.

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。

The R ³ is preferably 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 n-pentyl group, an n-hexyl group, and the like. 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, and adjacent Rs. ^{When three} groups form a ring, it is preferably a heterocycle in which at least one sulfur atom or nitrogen atom is contained in the ring.

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

The D is preferably a nitrogen atom or a phosphorus atom, and the ^Ri is preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group or an n-pentyl group. 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 further 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 suppressing effect can be obtained.

The compound (S) may be synthesized by a generally known method. For example, Japanese Patent No. 4168031, Japanese Patent No. 4252961, Japanese Patent Application Laid-Open No. 2010-516823, Japanese Patent Application Laid-Open No. 63-165392. It can be synthesized by referring to the methods described in the above.

The content of the compound (S) is determined as the base material, for example, on a base material made of a transparent resin substrate containing the compound (A) and the compound (S), or on a transparent resin substrate containing the compound (S). When a base material on which a resin layer such as an overcoat layer made of a curable resin containing the compound (A) is laminated is used, it is preferably 0.01 to 2 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 the base material is a glass support, a base resin support, or the like. On a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing the compound (A) and the compound (S) is laminated on a support, or on a transparent resin substrate containing the compound (A). When a base material on which a resin layer such as an overcoat layer made of a curable resin containing the compound (S) is laminated is used, 100 parts by weight of the resin forming the transparent resin layer containing the compound (A) is used. On the other hand, it is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.0 parts by weight, and particularly preferably 0.3 to 3.0 parts by weight. When the content of the compound (S) is within the above range, an optical filter having both good near-infrared absorption characteristics and high visible light transmittance can be obtained.

<Requirement (h)>
The Xc is preferably 630 to 655 nm, more preferably 632 to 652 nm, and even more preferably 634 to 650 nm. If Xc is less than 628 nm, the transmittance in the wavelength region corresponding to red tends to be low, and the color reproducibility tends to be lowered. If it is more than 658 nm, sufficient absorption intensity cannot be secured and the camera image. Color shading tends to occur.

When the base material satisfies the requirement (h), it is possible to reduce the incident angle dependence of the optical characteristics in the vicinity of the visible wavelength to the near infrared wavelength region even when a dielectric multilayer film is formed on the base material. It is preferable because it can achieve both red reproducibility and color shading suppression effect at a high level. Note that Xc indicates a wavelength that satisfies a predetermined condition when the spectral transmittance is evaluated from the short wavelength side to the long wavelength side.

<Other characteristics and physical properties>
The average transmittance of the base material 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. When a substrate having such a transmission characteristic is used, a high light transmission characteristic can be achieved in the visible region, and a highly sensitive camera function can be achieved.

The thickness of the base material 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 further preferably 25 to 150 μm. When the thickness of the base material is within the above range, the optical filter using the base material can be made thinner and lighter, and can be suitably used for various applications such as a solid-state image sensor. In particular, when the base material made of the transparent resin substrate is used for a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height and weight.

<Transparent resin>
The transparent resin used for the transparent resin layer, the transparent resin substrate, and the resin support constituting the base material is not particularly limited as long as it does not impair the effects of the present invention, and is, for example, thermal stability and a film. The glass transition temperature (Tg) is preferably 110 to 380 ° C., in order to obtain a film capable of forming a dielectric multilayer film by high temperature vapor deposition performed at a vapor deposition temperature of 100 ° C. or higher while ensuring moldability to the resin. Examples thereof include resins having a temperature of 110 to 370 ° C, more preferably 120 to 360 ° C. Further, when the glass transition temperature of the resin is 140 ° C. or higher, a film capable of forming a dielectric multilayer film by vapor deposition at a higher temperature can be obtained, which is particularly preferable.

As the transparent resin, when a resin plate having a thickness of 0.1 mm made of the resin is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, More preferably 80 to 95% of the resin can be used. If a resin having a total light transmittance in such a range is used, the obtained substrate exhibits good transparency as an optical film.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of a transparent resin is usually 15,000 to 350,000, preferably 30,000 to 250,000, and is a number. The average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.

Examples of the transparent resin include cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin, and polysalphon. Based resin, polyether sulfone based resin, polyparaphenylene based resin, polyamideimide based resin, polyethylene naphthalate (PEN) based resin, fluorinated aromatic polymer based resin, (modified) acrylic resin, epoxy resin, allyl Examples thereof include ester-based curable resins, silsesquioxane-based UV-curable resins, acrylic-based UV-curable resins, and vinyl-based UV-curable resins.

The transparent resin may be used alone 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。）

Wherein ^{_{(X 0), R x1 ~R}} x4 each independently represents an atom or a group selected from the following (i ') ~ (ix' ), k x, m x and p ^x are each independently 0 Or represents a positive integer.
(I') Hydrogen atom (ii') Halogen atom (iii') Trialkylsilyl group (iv') Substituent or unsubstituted carbon number 1 having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. ~ 30 hydrocarbon group (v') substituted or unsubstituted hydrocarbon group (vi') polar group having 1 to 30 carbon atoms (excluding (iv'))
(Vii') Alkylidene groups formed by mutual bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 (however, R ^{x1 to} R ^x4 not involved in the bond are independently described in (i'). ) ~ (Vi') represents an atom or group selected.)
(Viii') A monocyclic or polycyclic hydrocarbon ring or heterocycle formed by mutually bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 (however, R ^{x1 to} R not involved in the bond). ^x4 represents an atom or group independently selected from the above (i') to (vi').)
(Ix') A monocyclic hydrocarbon ring or heterocycle formed by bonding R ^x2 and R ^x3 to each other (however, R ^x1 and R ^x4 not involved in the bond are independently described in (i). Represents an atom or group selected from') to (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 ), R ^y1 and R ^y2 independently represent atoms or groups selected from the above (i') to (vi'), or R ^y1 and R ^y2 are bonded to each other. It represents a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocycle formed, where k ^y and p ^y 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 the structural unit represented by the following formula (1) and the 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 the formula (1), R ^{1 to} R ⁴ independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d 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 the formula (2), R ^{1 to} R ⁴ and a to d are independently synonymous with R ^{1 to} R ⁴ and a to d in the formula (1), and Y is a single bond, −SO ₂ -Or> C = O, R ⁷ and R ⁸ independently represent a halogen atom, a monovalent organic group or a nitro group having 1 to 12 carbon atoms, and g and h independently represent 0 to 4, respectively. Indicates an integer of, and m indicates 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

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

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 the formula (3), R ⁵ and R ⁶ each independently represents a monovalent organic group having 1 to 12 carbon atoms, 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 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。

In formula (4), R ⁷ , R ⁸ , Y, m, g and h are independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in formula (2), respectively. ⁵ , R ⁶ , Z, n, e and f are independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the above formula (3).

≪Polyimide resin≫
The polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in the repeating unit. For example, the methods described in JP-A-2006-199945 and JP-A-2008-163107 can be used. Can be synthesized.

≪Fluorene polycarbonate resin≫
The fluorene polycarbonate-based resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized by, for example, the method described in JP-A-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 is synthesized by the methods described in, for example, JP-A-2010-285505 and JP-A-2011-197450. Can be done.

≪Fluorinated aromatic polymer resin≫
The fluorinated aromatic polymer resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It 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 ultraviolet curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic groups or methacrylic groups in the molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. What is done can be mentioned. The acrylic ultraviolet curable resin is a base material in which a transparent resin layer containing the compound (A) and a curable resin is laminated on a glass support or a resin support as a base, or a compound ( When a base material 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) is used, it can be particularly preferably used as the curable resin.

≪Epoxy resin≫
The epoxy resin is not particularly limited, but can be roughly classified into an ultraviolet curable type and a thermosetting type. The ultraviolet curable epoxy resin is synthesized from, for example, a composition containing a compound having one or more epoxy groups in the molecule and a compound that generates an acid by ultraviolet rays (hereinafter, also referred to as "photoacid generator"). Examples of the thermosetting epoxy resin include those synthesized from a compound having one or more epoxy groups in the molecule and a composition containing an acid anhydride. Can be done. The epoxy-based ultraviolet curable resin contains, as the base material, a base material in which a transparent resin layer containing the compound (A) is laminated on a glass support or a resin support as a base, or a compound (A). When a base material 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 is used, it can be particularly preferably used as the curable resin.

≪Commercial product≫
Examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic polyolefin resins include Arton manufactured by JSR Corporation, Zeonoa manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available products of the polyether sulfone-based resin include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate-based resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate-based resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available fluorene polyester-based resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include Acryviewer manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available products of the silsesquioxane-based ultraviolet curable resin include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Other pigments (X)>
The base material may further contain a compound (A) and another dye (X) that does not correspond to the compound (S).

The other dye (X) is not particularly limited as long as it is a dye having a maximum absorption wavelength in the region of less than 650 nm or a wavelength of more than 760 nm and less than 1050 nm, but a dye having a maximum absorption wavelength in the region of more than 760 nm and less than 1050 nm is preferable. .. Examples of such dyes include squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, octaphyllin compounds, diimonium compounds, pyrolopyrrole compounds, and borondipyrromethene (BODIPY). Examples thereof include at least one compound selected from the group consisting of a system compound, a perylene system compound and a metal dithiolate system compound.

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

<Other ingredients>
The base material may further contain an antioxidant, a near-ultraviolet absorber, a fluorescent quencher and the like as other components 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-based compounds, indole-based compounds, benzotriazole-based compounds, and triazine-based compounds.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, and tetrakis. [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Methane, tris (2,4-di-t-butylphenyl) phosphite and the like can be mentioned.

These other components may be mixed with a resin or the like when the base material is produced, or may be added when the resin is synthesized. The amount to be added 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, based on 100 parts by weight of the resin. It is a department.

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

The base material is an overcoat made of a curable resin or the like containing the compound (A) on a support such as a glass support or a resin support as a base or a transparent resin substrate containing no compound (A). When the base material has a transparent resin layer such as a layer laminated, for example, a resin solution containing the compound (A) is melt-molded or cast-molded 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 dried and removed, and if necessary, further light irradiation or heating is performed to obtain the compound (A) on the support or the transparent resin substrate. It is possible to produce a base material on which a transparent resin layer containing the above is formed.

≪Melting molding≫
Specifically, the melt molding is a method of melt-molding a pellet obtained by melt-kneading a resin, a compound (A) and, if necessary, other components; a resin, a compound (A) and necessary. A method of melt molding a resin composition containing other components accordingly; or obtained by removing the solvent from compound (A), a resin, a solvent and, if necessary, a resin composition containing other components. Examples thereof include a method of melt molding pellets. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding and the like.

≪Cast molding≫
The cast molding includes a method of casting a resin composition containing the compound (A), a resin, a solvent and, if necessary, other components on a suitable support to remove the solvent; or the compound (A). , Photocurable resin and / or thermosetting resin, and if necessary, other components are cast on a suitable support to remove the solvent, and then UV irradiation, heating, etc. It can also be manufactured by a method of curing by an appropriate method of.

When the base material is a base material made of a transparent resin substrate containing the compound (A), the base material can be obtained by peeling the coating film from the support after cast molding. Further, the base material is made of a curable resin or the like containing the compound (A) on a support such as a glass support or a resin support as a base or a transparent resin substrate containing no compound (A). In the case of a base material on which a transparent resin layer such as an overcoat layer is laminated, the base material can be obtained by casting and molding without peeling the coating film.

As the support, for example, a phosphate containing a copper component such as a near-infrared absorbing glass plate (for example, “BS-11” manufactured by Matsunami Glass Industry Co., Ltd. or “NF-50T” manufactured by AGC Techno Glass Co., Ltd.). Glass plate), transparent glass plate (for example, non-alkali glass plate such as "OA-10G" manufactured by Nippon Electric Glass Co., Ltd. and "AN100" manufactured by Asahi Glass Co., Ltd.), steel belt, steel drum and transparent resin (for example, polyester). A support made of (film, cyclic olefin resin film) can be mentioned.

Further, an optical component made of a glass plate, quartz, transparent plastic, or the like is coated with the resin composition to dry the solvent, or the curable composition is coated to be cured and dried. A transparent resin layer can also be formed on the component.

The amount of residual solvent in the transparent resin layer (transparent resin substrate) 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 (transparent resin substrate). It is as follows. When the amount of the residual solvent is within the above range, a transparent resin layer (transparent resin substrate) that is less likely to be deformed or changes in characteristics and can easily exhibit a desired function can be obtained.

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

Since the optical filter of the present invention satisfies the above requirements (d) and (e), it has excellent transmittance characteristics and near-infrared cut characteristics in the visible wavelength region, has little dependence on the incident angle, has a color shading suppressing effect, and is a ghost. It is an optical filter with an excellent suppressing effect.

<Requirement (d)>
The average value (d1) of the transmittance in the requirement (d) is preferably 78% or more, more preferably 80% or more, and further 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 for a solid-state image sensor.

<Requirement (e)>
The average value (e1) of the transmittance in the requirement (e) is preferably 4% or less, more preferably 3% or less, still more 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 characteristics and physical properties>
Since the optical filter of the present invention has the base material, it is possible to reduce the dependence of the optical characteristics on the incident angle even in the form of having the dielectric multilayer film. Specifically, in the wavelength range of 600 to 800 nm, the shortest wavelength value (Xa) at which the transmittance when measured from the vertical direction of the optical filter is 50% and 30 ° with respect to the vertical direction of the optical filter. The absolute value | Xa-Xb | of the difference from the wavelength value (Xb) at which the transmittance is 50% when measured from the angle of is preferably less than 20 nm, more preferably less than 15 nm, and further preferably less than 10 nm. is there.

The thickness of the optical filter of the present invention is preferably thin in consideration of the recent trend toward thinner and lighter solid-state image sensors. Since the optical filter of the present invention contains the base material, it can be made thinner.

The thickness of the optical filter of the present invention is preferably 210 μm or less, more preferably 190 μm or less, further preferably 160 μm or less, particularly preferably 130 μm or less, and 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 base material. The dielectric multilayer film in the present invention is a film having an ability to reflect near infrared rays or a film having an antireflection effect in the visible region, and having a dielectric multilayer film has more excellent visible light transmittance and near infrared rays. Cut characteristics can be achieved.

In the present invention, the dielectric multilayer film may be provided on one side of the base material or on both sides. When it is provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when it is provided on both sides, it is possible to obtain an optical filter which has high strength and is less likely to warp or twist. When the optical filter is applied to a solid-state image sensor application, it is preferable that the optical filter has a small warp or twist. Therefore, it is preferable to provide a dielectric multilayer film on both sides of the resin substrate.

It is desirable that the dielectric multilayer film preferably has a reflection property over a wavelength range of 700 to 1100 nm, more preferably a wavelength of 700 to 1150 nm, and even more preferably 700 to 1200 nm.

As a form having dielectric multilayer films on both sides of the base material, it is based on the first optical layer having reflection characteristics mainly in the vicinity of a wavelength of 700 to 950 nm when measured from an angle of 5 ° with respect to the vertical direction of the optical filter. With respect to the form in which the second optical layer having one side of the material and having the reflection characteristics mainly in the vicinity of 900 nm to 1150 nm is provided on the other side of the base material (see FIG. 1A) and the vertical direction of the optical filter. When measured from an angle of 5 °, a third optical layer having reflection characteristics mainly in the vicinity of a wavelength of 700 to 1150 nm is provided on one side of the base material, and a fourth optical layer having antireflection characteristics in the visible region is used as a base. Examples thereof include a form having the material on the other surface (see FIG. 1B).

Examples of the dielectric multilayer film include those in which high refractive index material layers and low refractive index material layers are alternately laminated. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of 1.7 to 2.5 is usually selected. Examples of such a material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide and the like as main components, and titanium oxide, tin oxide and /. Alternatively, those containing a small amount of cerium oxide or the like (for example, 0 to 10% by weight based on the main component) can be 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 1.2 to 1.6 is usually selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride and sodium hexafluoride.

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

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

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

In the present invention, the material species 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) and the compound (S). By appropriately selecting the thickness of each layer of the index material layer, the order of lamination, and the number of laminations, it has sufficient light-cutting characteristics in the near-infrared wavelength region while ensuring sufficient transmittance in the visible region. Moreover, it is possible to reduce the refractive index when near infrared rays are incident from an oblique direction.

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

[Other functional membranes]
The optical filter of the present invention has a surface between the base material and the dielectric multilayer film, a surface opposite to the surface on which the dielectric multilayer film is provided, or a dielectric multilayer film, as long as the effects of the present invention are not impaired. Antireflection film, hard, for the purpose of improving the surface hardness of the base material and the dielectric multilayer film, improving chemical resistance, antistatic and scratch erasing, etc. on the surface opposite to the surface on which the base material of the film 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 contain one layer made of the functional film, or may contain two or more layers. When the optical filter of the present invention contains two or more layers made of the functional film, it may contain two or more similar layers or two or more different layers.

The method of laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded or cast on a base material or a dielectric multilayer film in the same manner as described above. Examples thereof include a molding method.

It can also be produced by applying a curable composition containing the coating agent or the like on a base material or a dielectric multilayer film with a bar coater or the like, and then curing by ultraviolet irradiation or the like.

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

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

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

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

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

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

Further, for the purpose of improving the adhesion between the base material and the functional film and / or the dielectric multilayer film and the adhesion between the functional film and the dielectric multilayer film, a corona is formed on the surface of the base material, the functional film or the dielectric multilayer film. Surface treatment such as treatment or plasma treatment may be performed.

[Use of optical filter]
The optical filter of the present invention has a wide viewing angle and has excellent near-infrared ray cutting ability. Therefore, it is useful for correcting the luminosity factor of a solid-state image sensor such as a CCD or CMOS image sensor of a camera module. In particular, digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automobile cameras, televisions, car navigation systems, mobile information terminals, video game machines, portable game machines. , Fingerprint authentication system, digital music player, etc. Further, it is also useful as a heat ray cut filter or the like attached to a glass plate or the like of an automobile or a building.

[Solid image sensor]
The solid-state image sensor of the present invention includes the optical filter of the present invention. Here, the solid-state image sensor is an image sensor provided with a solid-state image sensor such as a CCD or CMOS image sensor, and specifically, a digital still camera, a smartphone camera, a mobile phone camera, a wearable device camera, or a digital camera. 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 described in more detail based on Examples, but the present invention is not limited to these Examples. In addition, "part" means "part by weight" unless otherwise specified. The method for measuring each physical property value and the method for evaluating the physical property are as follows.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent and the like.
(A) Using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS, weight average molecular weight in terms of standard polystyrene. (Mw) and number average molecular weight (Mn) were measured.
(B) Using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: THF), the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured.

For the resin synthesized in Resin Synthesis Example 3 described later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the above method.
(C) A part of the polyimide resin solution was put into anhydrous methanol to precipitate the polyimide resin, which was then filtered to separate it from the unreacted monomer. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. was calculated by the following formula using a Canon-Fenceke viscometer. I asked.

_{μ = {ln (t s /} t 0)} / C
t ₀ : Solvent flow time t _s : Dilute polymer solution flow time C: 0.5 g / dL
<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies Co., Ltd., the temperature was measured at a heating rate of 20 ° C. per minute under a nitrogen stream.

<Spectroscopic transmittance>
The transmittance of the substrate at each wavelength, (T ₁ ), (X ₁ ), (X ₂ ) and (Xc), and the transmittance of the optical filter at each wavelength range, (Xa) and (Xb) are stocks. The measurement was performed using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

Here, in the transmittance measured from the vertical direction of the optical filter, the light transmitted perpendicularly to the filter is measured as shown in FIG. 2 (a), and the angle is 30 ° with respect to the vertical direction of the optical filter. As for the transmittance measured from the above, as shown in FIG. 2B, the light transmitted at an angle of 30 ° with respect to the vertical direction of the filter was measured.

This transmittance was measured using the spectrophotometer under the condition that the light is vertically incident on the substrate and the filter, except when measuring (Xb). (Xb) is measured using the spectrophotometer under the condition that the light is incident at an angle of 30 ° with respect to the vertical direction of the filter.

<Color shading evaluation of camera image>
The color shading evaluation when the optical filter was incorporated into the camera module was performed by the following method. A camera module is created in the same manner as in Japanese Patent Application Laid-Open No. 2016-110067, and a white plate having a size of 300 mm × 400 mm is used as a D65 light source (standard light source device “Macbeth Judge II” manufactured by X-Rite). The image was taken below, and the difference in color between the center and the edge of the white plate in the camera image was evaluated according to the following criteria.

There is no problem at all and the acceptable level is A, a slight difference in color is recognized, but there is no problem in practical use as a high-quality camera module, and the acceptable level is B. The possible level was determined to be C, and the level that was unacceptable for general camera module applications due to a clear difference in color was determined to be D.

As shown in FIG. 11, when shooting, 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 image>
The ghost evaluation when the optical filter was incorporated into the camera module was performed by the following method. A camera module is created in the same manner as in Japanese Patent Application Laid-Open No. 2016-110067, and the camera module is used to take a picture under a halogen lamp light source in a dark room (“Luminer Ace LA-150TX” manufactured by Hayashi Clock Industry Co., Ltd.). The degree of ghost generation around the light source in the image was evaluated according to the following criteria.

There is no problem at all and the acceptable level is A, some ghosts are recognized, but there is no practical problem as a high-quality camera module and the acceptable level is B, ghosts are generated and it is unacceptable for high-quality camera module applications. The possible level was determined to be C, and the level that was unacceptable for general camera module applications with a severe degree of ghost was determined to be D.

As shown in FIG. 12, the light source 122 was adjusted to be the upper right end of the camera image 121 when shooting.

[Synthesis example]
Compound (A) and compound (S) used in the following examples were synthesized by a generally known method. As a general synthesis method, for example, Japanese Patent Application Laid-Open No. 60-228448, Japanese Patent Application Laid-Open No. 1-146846, Japanese Patent Application Laid-Open No. 1-2289960, Japanese Patent No. 4081149, "Parthalocyanine-Chemistry and Function-" (Ai) PC, 1997), Japanese Patent Application Laid-Open No. 2009-108267, Japanese Patent Application Laid-Open No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, and the like.

<Plastic synthesis example 1>
8-Methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] 100 g of 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) are charged in a nitrogen-substituted reaction vessel. , This solution was heated to 80 ° C. Next, 0.2 g of a toluene solution of triethylaluminum (0.6 mol / liter) and 0.9 g of a methanol-modified tungsten hexachloride toluene solution (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 ° 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。

1,000 g of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. The hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, which was dried to obtain a hydrogenated 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>
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") in a 3 L four-necked flask. 443 g and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean Stark tube and a cooling tube were attached to the four-necked flask. Then, after nitrogen substitution in the flask, the obtained solution was reacted at 140 ° C. for 3 hours, and the water produced was removed from the Dean-Stark apparatus at any time. When the formation of water was no longer observed, the temperature was gradually raised to 160 ° C., and the reaction was carried out at the same temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a 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, stirrer, nitrogen introduction tube, dripping funnel with side tube, Dean Stark tube and cooling tube, 1,4-bis (4-amino-α, α) under nitrogen flow. 27.66 g of -dimethylbenzyl) benzene and 7.38 g of 4,4'-bis (4-aminophenoxy) biphenyl were added and dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N, N-dimethylacetamide. The obtained solution was 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 imidization catalyst were added. It was added all at once. After completion of the addition, the temperature was raised to 180 ° C., and the mixture was refluxed for 6 hours while distilling off the distillate as needed. After completion of the reaction, the mixture was air-cooled until the internal temperature reached 100 ° C., then 143.6 g of N, N-dimethylacetamide was added to dilute the mixture, and the mixture was cooled with stirring to obtain 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight. Got A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter, also referred to as “resin 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. The glass transition temperature (Tg) of the resin C was 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 prepared by the following procedure and conditions.

In a container, 100 parts of the resin A obtained in Resin Synthesis Example 1, the compound (a-1) represented by the following formula (a-1) as the compound (A) (absorption maximum wavelength in dichloromethane, 698 nm) 0.04 Part and 0.04 part of the compound (a-2) represented by the following formula (a-2) (absorption maximum wavelength in dichloromethane 733 nm), and the compound (s-) shown in Table 2-2 above as the compound (S). 6) 0.07 parts (maximum absorption wavelength in dichloromethane, 1093 nm) and methylene chloride were added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a substrate made of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. 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, a dielectric multilayer film (I) is formed as a first optical layer on one surface of the obtained substrate, and a dielectric multilayer film (II) is formed as a second optical layer on the other surface of the substrate. An optical filter having a thickness of about 0.105 mm was obtained.

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

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

Regarding the thickness and number of layers of each layer, the wavelength-dependent characteristics of the refractive index of the base material and the applied compounds (S) and compounds so as 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) according to the absorption characteristics of A). When optimizing, in this embodiment, the input parameters (Target values) 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 film configuration optimization, in Example 1, the dielectric multilayer film (I) is formed by alternately laminating silica layers having a film thickness of 31 to 157 nm and titania layers having a film thickness of 10 to 95 nm. The dielectric multilayer film (II) is a multilayer vapor-deposited film having 20 layers, in which silica layers having a film thickness of 37 to 194 nm and titania layers having a film thickness of 12 to 114 nm are alternately laminated. It was. Table 4 below shows an example of the optimized film configuration.

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 in the vertical direction of the obtained optical filter and from an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. 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 evaluation of the camera image were performed. The results are shown in Table 5-1. The resulting camera images gave good results in color shading and ghosting.

[Example 2]
In Example 2, an optical filter having a substrate made of a transparent resin substrate was prepared by the following procedure and conditions.

In Example 1, the compound (A) is represented by 0.04 part of the compound (a-3) represented by the following formula (a-3) (absorption maximum wavelength in dichloromethane 703 nm) and the following formula (a-4). Compound (a-4) (absorption maximum wavelength in dichloromethane, 736 nm) was used in 0.08 parts, and the compound (S) shown in Table 2-3 above was used as the compound (S) (in dichloromethane). 0.06 part of absorption maximum wavelength (1096 nm) was used, and as other dye (X), dye (X-1) represented by the following formula (X-1) (absorption maximum wavelength in dichloromethane 887 nm) 0 A substrate made of a transparent resin substrate containing compound (A) and compound (S) was obtained under the same procedure and conditions as in Example 1 except that 0.01 part was used. 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, silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as the first optical layer on one side of the obtained base material (26 layers in total). A body multilayer film (III) is formed, and silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as a second optical layer on the other surface of the base material (20 layers in total). A dielectric multilayer film (IV) was formed to obtain an optical filter having a thickness of about 0.105 mm. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material. The spectral transmittance measured in the vertical direction of the obtained optical filter and from an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5-1.

[Example 3]
In Example 3, an optical filter having a base material made of a transparent resin substrate having resin layers on both sides was prepared by the following procedure and conditions.

In Example 1, 0.06 part of compound (a-4) and 0.06 of compound (a-5) represented by the following formula (a-5) (absorption maximum wavelength in dichloromethane, 713 nm) 0.06 as compound (A). Except for the fact that 0.08 part of the compound (s-13) (absorption maximum wavelength in dichloromethane, 1096 nm) shown in Table 2-4 above was used as the compound (S). A transparent resin substrate containing the compound (A) and the 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。

The resin composition (1) having the following composition was applied to one side 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, the exposure (exposure 500 mJ / cm ^2, 200 mW) with a conveyor-type exposure apparatus, to cure the resin composition (1), to form a resin layer on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) is formed on the other surface of the transparent resin substrate, and the 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-hydroxycyclohexylphenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%) )
Subsequently, as in Example 1, silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as the first optical layer on one side of the obtained base material (26 layers in total). A body multilayer film (V) is formed, and silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as a second optical layer on the other surface of the base material (20 layers in total). A dielectric multilayer film (VI) was formed to obtain an optical filter having a thickness of about 0.109 mm. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the base material and the like as in Example 1. The spectral transmittance measured in the vertical direction of the obtained optical filter and from an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5-1.

[Example 4]
In Example 4, an optical filter having a substrate having a transparent resin layer containing the compound (A) formed on both sides of a resin support was prepared by the following procedure and conditions.

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

A resin layer composed of the resin composition (2) having the following composition was formed on both sides of the obtained resin support in the same manner as in Example 3, and the compound (A) and the compound (A) were formed on both sides of the resin support. A substrate formed 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-hydroxycyclohexylphenyl ketone, 0.10 parts by weight of compound (a-1), 0.10 parts by weight of compound (a-2). Parts, 1.75 parts by weight of compound (s-6), methyl ethyl ketone (solvent, TSC: 25%)
Subsequently, as in Example 1, silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as the first optical layer on one side of the obtained base material (26 layers in total). A body multilayer film (VII) is formed, and silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as a second optical layer on the other surface of the base material (20 layers in total). A dielectric multilayer film (VIII) was formed to obtain an optical filter having a thickness of about 0.109 mm. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the base material and the like as in Example 1. The spectral transmittance measured in the vertical direction of the obtained optical filter and from an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5-1.

[Example 5]
In Example 5, an optical filter having a base material made of a transparent glass substrate having a transparent resin layer containing the compound (A) on one side was prepared by the following procedure and conditions.

The resin composition (3) having the following composition is applied with a spin coater on a transparent glass substrate "OA-10G (thickness 150 um)" (manufactured by Nippon Electric Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width. The solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes. At this time, the application conditions of the spin coater were adjusted so that the thickness after drying was 2 μm. Next, using a conveyer-type exposure apparatus performs exposure (exposure 500 mJ / cm ^2, 200 mW), cured resin composition (3), a transparent resin layer containing compound (A) and the compound (S) A substrate made 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-hydroxycyclohexylphenylketone, 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, silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as the first optical layer on one side of the obtained base material (26 layers in total). A body multilayer film (IX) is formed, and silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as a second optical layer on the other surface of the base material (20 layers in total). A dielectric multilayer film (X) was formed to obtain an optical filter having a thickness of about 0.107 mm. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the base material and the like as in Example 1. The spectral transmittance measured in the vertical direction of the obtained optical filter and from an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5-1.

[Example 6]
In Example 6, an optical filter having a substrate made of a near-infrared absorbing glass substrate having a transparent resin layer containing the compound (A) on one side was prepared by the following procedure and conditions.

A resin composition (4) having the following composition is applied with a spin coater on a near-infrared absorbing glass substrate "BS-11 (thickness 120 μm)" (manufactured by Matsunami Glass Industry Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width. Then, the solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes. At this time, the application conditions of the spin coater were adjusted so that the thickness after drying was 2 μm. Next, the exposure (exposure 500 mJ / cm ^2, 200 mW) with a conveyor-type exposure apparatus, to cure the resin composition (4), near-infrared-absorbing glass substrate having a transparent resin layer containing the compound (A) A substrate composed of 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. 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-hydroxycyclohexylphenyl 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, silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as the first optical layer on one side of the obtained base material (26 layers in total). A body multilayer film (XI) is formed, and silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as a second optical layer on the other surface of the base material (20 layers in total). A dielectric multilayer film (XII) was formed to obtain an optical filter having a thickness of about 0.107 mm. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the base material and the like as in Example 1. The spectral transmittance measured in the vertical direction of the obtained optical filter and from an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5-1.

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

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

A compound having a resin layer made of the resin composition (5) having the following composition formed on both sides of the obtained resin substrate in the same manner as in Example 3, and having a transparent resin layer containing near-infrared absorbing fine particles on both sides. A substrate made of a transparent resin 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-hydroxycyclohexylphenyl ketone, 35 parts by weight of near-infrared absorbing fine particle dispersion (YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd.) ( Approximately 10 parts by weight in terms of solid content), methyl ethyl ketone (solvent, TSC: 30%)
Subsequently, as in Example 1, silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as the first optical layer on one side of the obtained base material (26 layers in total). A body multilayer film (XIII) is formed, and silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as a second optical layer on the other surface of the base material (20 layers in total). A dielectric multilayer film (XIV) was formed to obtain an optical filter having a thickness of about 0.109 mm. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the base material and the like as in Example 1. The spectral transmittance measured in the vertical direction of the obtained optical filter and from an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5-1.

[Examples 8 to 13]
The basis was the same as in Example 3 except that the resin, the solvent, the drying conditions of the resin substrate, the compound (A), the compound (S) and the other dye (X) were changed as shown in Table 5-1. Materials and optical filters were created. The optical characteristics of the obtained base material and the 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 evaluation of the camera image were performed. The results are shown in Table 5-1.

[Comparative Example 1]
A base material and an optical filter were prepared 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 evaluation of the camera image were performed. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 1 exhibits relatively good visible light transmittance, the optical characteristics are highly dependent on the incident angle, and the base material does not absorb in the vicinity of 700 nm or in the near infrared wavelength region. Therefore, it was confirmed that the effect of suppressing color shading and the effect of suppressing ghosts were inferior.

[Comparative Example 2]
An optical filter was prepared 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 base material, and the optical characteristics were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 2 exhibits relatively good visible light transmittance, the optical characteristics are highly dependent on the incident angle, and the base material does not absorb in the vicinity of 700 nm or in the near infrared wavelength region. Therefore, it was confirmed that the effect of suppressing color shading and the effect of suppressing ghosts were inferior.

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

[Comparative Example 4]
In Example 3, 0.08 part of compound (a-4) and 0.06 part of compound (a-5) were used as compound (A) without using compound (S), and the dye (X-) was used. 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 characteristics were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5-2. The spectral transmission spectrum of the base material is shown in FIG. Although the optical filter obtained in Comparative Example 5 exhibited relatively good optical characteristics, it was confirmed that the absorption intensity of the base material in the near infrared wavelength region was insufficient and the ghost suppressing effect was inferior.

[Comparative Example 5]
A base material and an optical filter were prepared in the same manner as in Example 6 except that the resin composition (6) having the following composition was used instead of the resin composition (4) in Example 6.

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

[Comparative Example 6]
In Example 3, 0.04 part of compound (a-3) and 0.08 part of compound (a-4) were used as compound (A), and compound (s-6) 0.01 as compound (S). A base material and an optical filter were prepared in the same manner as in Example 3 except that the part 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 evaluation of the camera image were performed. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 6 exhibited relatively good optical characteristics, it was confirmed that the absorption intensity of the base material in the near infrared wavelength region was insufficient and the ghost suppressing effect was inferior.

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

[Comparative Example 8]
In Example 3, 0.04 part of compound (a-1) was used as compound (A), and compound (s-14) (absorption in dichloromethane) shown in Table 2-4 above was used as compound (S). A substrate and an optical filter were prepared in the same manner as in Example 3 except that 0.45 parts (maximum wavelength 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 evaluation of the camera image were performed. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 8 exhibited relatively good optical characteristics, it was confirmed that the absorption intensity of the base material near 700 nm was not sufficient and the color shading suppressing effect was inferior.

The composition of the base material, various compounds, etc. applied in Examples and Comparative Examples are as follows.

<Form of base material>
Form (1): Transparent resin substrate containing compound (A) Form (2): Transparent resin substrate containing compound (A) having resin layers on both sides Form (3): Compound on both sides of resin support Form having a transparent resin layer containing (A) (4): Form having a transparent resin layer containing compound (A) on one side of a transparent glass substrate (5): Compound on one side of a near-infrared absorbing glass substrate Form (6) having a transparent resin layer containing (A): Form having a transparent resin layer containing near-infrared absorbing fine particles on both sides of a transparent resin substrate containing compound (A) (7): Containing 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-based resin (resin synthesis example 3)
Resin D: Cyclic olefin resin "Zeonoa 1420R" (manufactured by Zeon Corporation)
<Glass substrate>
Glass substrate (1): Transparent glass substrate "OA-10G (thickness 150 μm)" cut to a size of 60 mm in length and 60 mm in width (manufactured by Nippon Electric Glass Co., Ltd.)
Glass substrate (2): Near-infrared absorbing glass substrate "BS-11 (thickness 120 μm)" cut to a size of 60 mm in length and 60 mm in width (manufactured by Matsunami Glass Industry Co., Ltd.)
<Near infrared absorbing pigment>
≪Compound (A) ≫
Compound (a-1): The above compound (a-1) (absorption maximum wavelength in dichloromethane, 698 nm).
Compound (a-2): The above compound (a-2) (absorption maximum wavelength in dichloromethane, 733 nm).
Compound (a-3): The above compound (a-3) (absorption maximum wavelength in dichloromethane, 703 nm).
Compound (a-4): The above compound (a-4) (absorption maximum wavelength in dichloromethane, 736 nm).
Compound (a-5): The above compound (a-5) (absorption maximum wavelength in dichloromethane, 713 nm).
Compound (a-6): Cyanine-based 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): The above compound (s-6) (absorption maximum wavelength in dichloromethane, 1093 nm)
Compound (s-8): The above compound (s-8) (absorption maximum wavelength in dichloromethane, 1096 nm).
Compound (s-13): The above compound (s-14) (absorption maximum wavelength in dichloromethane, 1096 nm).
Compound (s-14): The above compound (s-15) (absorption maximum wavelength in dichloromethane: 1097 nm)
≪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) (maximum absorption wavelength in dichloromethane 811 nm)

＜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. The coating film was peeled off from the glass plate before drying under reduced pressure.

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

1: Optical filter 2: Spectral photometric meter 3: Light 10: Base material 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 the central part of the white plate 114: Example of the edge of the white plate 121: Camera image 122: Light source 123: Example of ghost around the light source

Claims (11)

A base material satisfying the following requirements (a), (b) , (c) and (g) , and a dielectric multilayer film on at least one surface of the base material , and the following requirements (d) and ( An optical filter characterized by satisfying e):
Have a layer containing a compound having an absorption maximum in the following areas (a) Wavelength 650nm or 760nm with (A), the compound (A) is two or more compounds containing a squarylium compound;
(B) The difference (X _2- X ₁ ) between the shortest wavelength (X ₁ ) at which the transmittance is 10% in the wavelength region of 640 nm or more and the second shortest wavelength (X ₂ ) 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 region of wavelength 430 to 580 nm, the average value of the transmittance measured from the vertical direction of the optical filter is 75% or more;
(E) In the wavelength region of 1100 nm to 1200 nm, the average value of the transmittance measured from the vertical direction of the optical filter is 5% or less ;
(G) Contains compound (S) having an absorption maximum in a region having a wavelength of 1050 nm or more and 1200 nm or less . The optical filter according to claim 1, wherein the layer containing the compound (A) is a transparent resin layer. The transparent resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or a polyarylate resin. Polysulfone-based resin, polyether sulfone-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate-based resin, fluorinated aromatic polymer-based resin, (modified) acrylic-based resin, epoxy-based resin, allyl ester-based The second aspect of claim 2, wherein the resin is at least one selected from the group consisting of a curable resin, a silsesquioxane-based ultraviolet curable resin, an acrylic-based ultraviolet-curable resin, and a vinyl-based ultraviolet curable resin. Optical filter. The optical filter according to any one of claims 1 to 3, wherein the base material further satisfies the following requirement (f).
(F) The minimum value (T ₁ ) of the transmittance in the region of wavelength 690 to 720 nm is 5% or less. Any one of claims 1 to 4, wherein the compound (S) is at least one compound selected from the group consisting of compounds represented by the following formulas (I) and (II). The optical filter described in.

[In formula (I) and formula (II),
R ^{1 to} R ³ are independently hydrogen atom, halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R. ^It represents either ⁱ group, -OSO ₂ R ⁱ group or L ^{a to} L ^h below, and R ^g and R ^h are independently hydrogen atom, -C (O) R ⁱ group or L ^{a to} L ^e below. represents either, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L ^b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L ^d) carbon Aromatic hydrocarbon group of number 6 to 14 (L ^e ) Heterocyclic group having 2 to 14 carbon atoms (L ^f ) An alkoxy group having 1 to 12 carbon atoms (L ^g ) Substituent number of carbon atoms may be L. An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L ^h ) substituent L of 1 to 12 The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms and 1 to 12 carbon atoms. At least one selected from the group consisting of a halogen-substituted alkyl group, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms. Yes,
Adjacent R ³ together may form a ring which may have a substituent L,
n represents an integer from 0 to 4
X represents the anion required to neutralize the charge
M represents a metal atom
Z represents D (R ⁱ ) ₄ , D represents nitrogen atom, phosphorus atom or bismuth atom,
y represents 0 or 1. ) The optical filter according to any one of claims 1 to 5 , wherein the dielectric multilayer film is formed on both surfaces of the base material. Said compound (A), 2 or more kinds of squarylium compounds, or a combination of at least one squarylium compound, and at least one compound selected from the group consisting of phthalocyanine-based compound and a cyanine compound The optical filter according to any one of claims 1 to 6 , wherein the optical filter is characterized. The optical filter according to any one of claims 1 to 7 , wherein the base material contains a transparent resin substrate containing the compound (A) and the compound (S). The optical filter according to any one of claims 1 to 8 , which is for a solid-state image sensor. A solid-state image sensor comprising the optical filter according to any one of claims 1 to 9 . A camera module including the optical filter according to any one of claims 1 to 9 .

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