WO2016158461A1 - Optical filter and device using optical filter - Google Patents

Abstract

The present invention addresses the problem of providing an optical filter that has little incidence angle dependency, and that is capable of reducing multiple reflections when a near-infrared light comes in from an oblique direction. The optical filter according to the present invention has a basal material and a dielectric multilayer film provided on at least one surface of the basal material. The basal material is characterized by having a transparent resin layer containing a compound (A) that has an absorption maximum at a wavelength equal to or higher than 600 nm but lower than 750 nm and a compound (S) that has a absorption maximum at a wavelength of 750-1050 nm, or having a transparent resin layer containing the compound (A) and a transparent resin layer containing the compound (S). The basal material is also characterized by satisfying the following requirement (a): (a) the average value of transmittance when a measurement is made in the vertical direction to the optical filter within a wavelength range of 800-1000 nm is equal to or less than 5%.

Description

Optical filter and device using optical filter

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

A solid-state image pickup device such as a video camera, a digital still camera, or a mobile phone with a camera function uses a CCD or CMOS image sensor, which is a solid-state image pickup device for a color image. Silicon photodiodes that are sensitive to near infrared rays that cannot be sensed by the eyes are used. These solid-state image sensors need to be corrected for visibility so that they appear natural to the human eye. Optical filters that selectively transmit or cut light in a specific wavelength region (for example, near-infrared cut) Filter) is often used.

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

The present applicant has proposed a near-infrared cut filter having a norbornene-based resin substrate and a near-infrared reflective film in Patent Document 2. The near-infrared cut filter described in Patent Document 2 is excellent in near-infrared cut characteristics, moisture absorption resistance and impact resistance, but cannot take a wide viewing angle.

In addition, as a result of intensive studies, the present applicant uses a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength region, so that there is little change in optical characteristics even when the incident angle is changed. It has been found that a near-infrared cut filter can be obtained, and Patent Document 3 proposes a near-infrared cut filter having both a wide viewing angle and high visible light transmittance.

Japanese Patent Laid-Open No. 6-200113 JP 2005-338395 A JP 2011-100084 A

In recent years, the image quality level required for camera images has become very high even in mobile devices. According to the study by the present inventors, in order to satisfy the demand for high image quality, in addition to a wide viewing angle and high visible light transmittance, a high light-cut characteristic is required even in a relatively long wavelength region in the optical filter. It becomes. Furthermore, with the miniaturization of camera modules, the incident angle of light rays tends to be larger than before, especially at the edge of the screen, but with conventional optical filters, multiple reflections between the optical filter and the lens, and multiple reflections inside the optical filter In some cases, ghosts caused by multiple reflections between the optical filter and the solid-state imaging device may become a problem (see FIGS. 1- (a) to (d)).

It is an object of the present invention to provide an optical filter that is less dependent on an incident angle and can reduce multiple reflections when near infrared light is incident from an oblique direction.

As a result of intensive studies to solve the above problems, the present inventors have applied a combination of two or more compounds having an absorption maximum in a specific wavelength range, thereby achieving the desired near-infrared cut characteristics and visible transmission. The present inventors have found that an optical filter that can achieve a reduction in the ratio and multiple reflected light in the near-infrared wavelength region can be obtained, and the present invention has been completed. Examples of embodiments of the present invention are shown below.

[1] A substrate and a dielectric multilayer film on at least one surface of the substrate;
The substrate has a transparent resin layer containing a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm and a compound (S) having an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less, or the compound ( A transparent resin layer containing A) and a transparent resin layer containing the compound (S),
An optical filter characterized by satisfying the following requirement (a):
(A) In the wavelength region of 800 to 1000 nm, the average transmittance when measured from the vertical direction of the optical filter is 5% or less.

[2] The optical filter according to item [1], which further satisfies the following requirement (b):
(B) In the wavelength range of 430 to 580 nm, the average transmittance when measured from the vertical direction of the optical filter is 75% or more.

[3] The item [1] or [3], wherein the compound (S) is at least one selected from the group consisting of squarylium compounds, cyanine compounds, pyrrolopyrrole compounds, and metal dithiolate compounds. 2].

[4] The optical filter according to any one of items [1] to [3], wherein the compound (S) is a squarylium compound represented by the following formula (Z).

　式（Ｚ）中、置換ユニットＡおよびＢは、それぞれ独立に下記式（Ｉ）および（ＩＩ）で表される置換ユニットのいずれかを表す。

In the formula (Z), the substitution units A and B each independently represent any of the substitution units represented by the following formulas (I) and (II).

　式（Ｉ）および（ＩＩ）中、波線で表した部分が中央四員環との結合部位を表し、
　Ｘは、独立に酸素原子、硫黄原子、セレン原子、テルル原子または－ＮＲ⁸－を表し、
　Ｒ¹～Ｒ⁸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３～１４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種である。

In formulas (I) and (II), the portion represented by the wavy line represents the binding site with the central four-membered ring,
X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or —NR ⁸ —;
R ¹ to R ⁸ are each independently a 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 ⁱ group, —OSO ₂ R ⁱ group or any of the following L ^a to L ^h , wherein R ^g and R ^h are each independently a hydrogen atom, —C (O) R ⁱ group or the following L ^a to L ^e It represents either, R ⁱ represents any of the following L ^a ~ L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon C ^6-14 aromatic hydrocarbon group (L ^e ) C ^3-14 heterocyclic group (L ^f ) C ^1-12 alkoxy group (L ^g ) carbon number optionally having substituent L 1 to 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, 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.

[5] The optical filter according to any one of items [1] to [4], wherein a dielectric multilayer film is provided on both surfaces of the substrate.
[6] Any one of items [1] to [5], wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. The optical filter according to item.

[7] The transparent resin is a cyclic (poly) olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin Item [1]-characterized in that it is at least one resin selected from the group consisting of curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins. The optical filter according to any one of [6]

[8] The optical filter according to any one of items [1] to [7], wherein the base material contains a transparent resin substrate containing the compound (A) and the compound (S).
[9] The optical filter according to any one of items [1] to [8], which is for a solid-state imaging device.

[10] A solid-state imaging device comprising the optical filter according to any one of items [1] to [8].
[11] A camera module comprising the optical filter according to any one of items [1] to [8].

According to the present invention, it is possible to provide an optical filter that has excellent near-infrared cut characteristics, is less dependent on incident angle, and has excellent transmittance characteristics in the visible wavelength region and multiple reflected light reduction effect in the near-infrared wavelength region. it can.

FIG. 1A is a schematic diagram illustrating that light beams that are multiple-reflected between an optical filter and a lens are incident on a solid-state imaging device. FIG. 1- (b) is a schematic diagram showing that light beams that have been multiple-reflected inside the optical filter enter the solid-state imaging device. FIG. 1- (c) is a schematic diagram showing that light beams that are multiple-reflected between the optical filter and the solid-state image sensor enter the solid-state image sensor. FIG. 1- (d) is a schematic diagram showing that light beams that have been multiple-reflected between the optical filter and the solid-state image sensor enter the solid-state image sensor. FIG. 2A is a schematic diagram illustrating a method for measuring the transmittance when measured from the vertical direction of the optical filter. FIG. 2B is a schematic diagram illustrating a method of measuring the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter. FIG. 2C is a schematic diagram illustrating a method of measuring the reflectance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter. FIG.2 (d) is schematic which shows the method of measuring the reflectance at the time of measuring from an angle of 5 degrees with respect to the perpendicular direction of the glass for vapor deposition monitors. FIGS. 3A and 3B are schematic views showing an example of a preferable configuration of the optical filter of the present invention. FIG. 4 is a spectral transmission spectrum of the substrate obtained in Example 1. FIG. 5A is a spectral reflection spectrum measured from an angle of 5 ° with respect to the vertical direction of the dielectric multilayer film (I) prepared in Example 1, and FIG. 2 is a spectral reflection spectrum measured from an angle of 5 ° with respect to the vertical direction of the dielectric multilayer film (II) prepared in 1. FIG. 6 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG. 7 shows the optical filter obtained in Example 1 at 30 ° with respect to the vertical direction of the optical filter when the light incident surface is on the dielectric multilayer film (II) (second optical layer) side. It is a spectral reflection spectrum measured from an angle. FIG. 8 is a spectral transmission spectrum of the base material obtained in Example 2. FIG. 9 is a spectral transmission spectrum of the optical filter obtained in Example 2. FIG. 10 shows the optical filter obtained in Example 2 at 30 ° with respect to the vertical direction of the optical filter when the light incident surface is on the dielectric multilayer film (IV) (second optical layer) side. It is a spectral reflection spectrum measured from an angle.

Hereinafter, the present invention will be specifically described.
[Optical filter]
The optical filter according to the present invention has a transparent resin layer containing at least one compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm and one or more compounds (S) having an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less. Formed on at least one surface of the substrate (i) or the substrate (i) having the transparent resin layer containing the compound (A) and the transparent resin layer containing the compound (S), and the substrate (i) And a dielectric multilayer film. For this reason, the optical filter of the present invention is an optical filter that has excellent near-infrared cut characteristics, low incidence angle dependency, and excellent transmittance characteristics in the visible wavelength region and multiple reflected light reduction effect in the near-infrared wavelength region. is there.

When the optical filter of the present invention is used for a solid-state imaging device, it is preferable that the transmittance in the near infrared wavelength region is low. In particular, it is known that the light receiving sensitivity of the solid-state imaging device is relatively high in the wavelength region of 800 to 1000 nm. By reducing the transmittance in this wavelength region, it is effective to correct the visibility of the camera image and the human eye. And excellent color reproducibility can be achieved.

The optical filter of the present invention has an average transmittance of 5% or less, preferably 4% or less, more preferably 3% or less, particularly preferably 2 when measured from the vertical direction of the optical filter in a wavelength region of 800 to 1000 nm. % Or less. When the average transmittance at a wavelength of 800 to 1000 nm is in this range, it is preferable because near infrared rays can be sufficiently cut and excellent color reproducibility can be achieved.

When the optical filter of the present invention is used for a solid-state imaging device or the like, it is preferable that the visible light transmittance is high. Specifically, in the wavelength range of 430 to 580 nm, the average transmittance when measured from the vertical direction of the optical filter is preferably 75% or more, more preferably 80% or more, still more preferably 83% or more, particularly preferably. 85% or more. When the average transmittance is within this range in this wavelength region, excellent imaging sensitivity can be achieved when the optical filter of the present invention is used as a solid-state imaging device.

The optical filter of the present invention has the shortest wavelength value (Xa) at which the transmittance when measured from the vertical direction of the optical filter is 50% in the wavelength range of 560 to 800 nm and the vertical direction of the optical filter. It is preferable that the absolute value of the difference from the wavelength value (Xb) at which the transmittance when measured from an angle of 30 ° is 50% is smaller. The absolute value of the difference between (Xa) and (Xb) is preferably less than 20 nm, more preferably less than 15 nm, and particularly preferably less than 10 nm. Such an optical filter can be obtained by forming a dielectric multilayer film on the substrate (i).

The optical filter of the present invention has a dielectric multilayer film on at least one surface of the substrate (i). The dielectric multilayer film of the present invention is a film having the ability to reflect near infrared rays. In the present invention, the near-infrared reflective film may be provided on one side of the substrate (i) or may be provided on both sides. When it is provided on one side, it is possible to obtain an optical filter that is excellent in production cost and manufacturability and has high strength and is less likely to warp or twist when provided on both sides. When the optical filter is applied to a solid-state imaging device, it is preferable that the optical filter is less warped or twisted. Therefore, it is preferable to provide a dielectric multilayer film on both surfaces of the resin substrate.

The dielectric multilayer film preferably has a reflection characteristic over the entire wavelength range of 700 to 1100 nm, more preferably has a reflection characteristic over the entire wavelength range of 700 to 1150 nm, and particularly preferably 700 to 1200 nm. A first optical layer mainly having reflection characteristics 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 as a form having dielectric multilayer films on both surfaces of the substrate (i) On one side of the substrate (i), and the reflection characteristics mainly in the vicinity of 900 nm to 1150 nm when measured from the angle of 5 ° to the vertical direction of the optical filter on the other surface of the substrate (i). A second optical layer having a second optical layer (see FIG. 3 (a)), or a third optical device mainly having reflection characteristics in the vicinity of a wavelength of 700 to 1150 nm when measured from an angle of 5 ° with respect to the vertical direction of the optical filter. Examples include a layer having a layer on one side of the substrate (i) and a fourth optical layer having an antireflection property in the visible region on the other surface of the substrate (i) (see FIG. 3B). It is done.

Since the optical filter of the present invention contains the compound (S) in the substrate (i), at least one surface of the optical filter is inclined even if it has a dielectric multilayer film having near-infrared reflection characteristics. The reflectance when near infrared rays are incident from the direction can be reduced. In particular, when the first optical layer is provided on one side of the optical filter and the second optical layer is provided on the other side, or the third optical layer is provided on the other side of the optical filter. This tendency becomes remarkable when the fourth optical layer is provided. As a result of diligent study, the applicant of the present invention is that near-infrared wavelength light incident from an oblique direction with respect to the vertical direction, particularly oblique incident light with a wavelength of 815 to 935 nm, is a major cause of various ghosts during multiple reflection. I found. In the wavelength region of 815 to 935 nm, the minimum reflectance measured from at least one surface when measured from an angle of 30 ° with respect to the vertical direction of the optical filter is preferably 80% or less, more preferably 75. % Or less, particularly preferably 70% or less. When the reflectance is in such a range, it is preferable when used for a solid-state imaging device, because various ghosts derived from multiple reflected light tend to be reduced particularly when shooting a scene including a light source in a dark place. .

The thickness of the optical filter of the present invention may be appropriately selected according to the desired application. However, according to the recent trend of thinning and weight reduction of solid-state imaging devices, the thickness of the optical filter of the present invention is also thin. Is preferred. Since the optical filter of the present invention includes the substrate (i), it can be thinned.

The thickness of the optical filter of the present invention is preferably, for example, preferably 200 μm or less, more preferably 180 μm or less, further preferably 150 μm or less, particularly preferably 120 μm or less, and the lower limit is not particularly limited, but for example, 20 μm It is desirable to be.

[Base material (i)]
The substrate (i) may be a single layer or a multilayer, and has a transparent resin layer containing at least one compound (A) and one compound (S), or a compound (A). What is necessary is just to have a transparent resin layer containing the transparent resin layer and compound (S) which contain. In the case where the substrate (i) is a single layer, for example, a substrate composed of a transparent resin substrate (ii) containing the compound (A) and the compound (S) can be mentioned, and this transparent resin substrate (ii) Becomes the transparent resin layer. In the case of a multilayer, for example, a transparent resin layer such as an overcoat layer made of a curable resin containing the compound (A) and the compound (S) on a support such as a glass support or a base resin support. 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 transparent resin substrate (iii) containing the compound (S), a compound ( A base material in which a resin layer such as an overcoat layer made of a curable resin containing a compound (S) is laminated on a transparent resin substrate (iv) containing A), the compound (A) and the compound (S) Examples thereof include a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on the transparent resin substrate (ii). From the viewpoints of manufacturing cost and ease of optical property adjustment, and further, it is possible to achieve the scratch-removing effect of the resin support and the transparent resin substrate (ii) and the improvement of scratch resistance of the substrate (i). And a substrate in which a resin layer such as an overcoat layer made of a curable resin is laminated on a transparent resin substrate (ii) containing the compound (S). In addition, when using a glass support body as a support body of a base material (i), the glass support body which does not contain a near-infrared absorber from a viewpoint of the intensity | strength of a base material or thickness reduction correspondence is especially preferable.

Hereinafter, a layer containing at least one selected from the compound (A) and the compound (S) and a transparent resin is also referred to as a “transparent resin layer”, and the other resin layers are also simply referred to as “resin layers”.
In the region of wavelength 600 nm or more and less than 750 nm, the lowest transmittance (Ta) measured from the vertical direction of the substrate (i) is preferably 40% or less, more preferably 25% or less, and particularly preferably 10% or less. is there.

The shortest wavelength (Xc) at which the transmittance measured in the vertical direction of the substrate (i) in the region of wavelength 600 nm or more is more than 50% to 50% is preferably 610 to 670 nm, more preferably 620 to 665 nm. Particularly preferred is 630 to 660 nm.

If (Ta) and (Xc) of the substrate (i) are in such a range, unnecessary near infrared rays can be selectively and efficiently cut, and a dielectric multilayer film is formed on the substrate (i). When the film is formed, it is possible to reduce the incident angle dependency of the optical characteristics in the visible wavelength to near infrared wavelength region.

In the region of wavelength 800 nm or more and 1050 nm or less, the lowest transmittance (Tb) measured from the vertical direction of the substrate (i) is preferably 80% or less, more preferably 70% or less, and particularly preferably 60% or less. is there.

If (Tb) of the substrate (i) is within such a range, the visible light transmittance is kept high, and when the dielectric multilayer film is formed on the substrate (i), the oblique direction is approached. The reflectance when infrared rays are incident can be reduced.

The average transmittance of the substrate (i) at a wavelength 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 transmission characteristics is used, high light transmission characteristics can be achieved in the visible range, and a highly sensitive camera function can be achieved.

The thickness of the base material (i) can be appropriately selected according to a desired application, and is not particularly limited. However, it is desirable and preferably selected appropriately so as to reduce the incident angle dependency of the obtained optical filter. Is 10 to 200 μm, more preferably 15 to 180 μm, particularly preferably 20 to 150 μm.

When the thickness of the substrate (i) is in the above range, the optical filter using the substrate (i) can be thinned and reduced in weight, and can be suitably used for various applications such as a solid-state imaging device. it can. In particular, when the base material (i) made of the transparent resin substrate (ii) is used in a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height and weight.

<Compound (A)>
The compound (A) is not particularly limited as long as it has an absorption maximum at a wavelength of 600 nm or more and less than 750 nm, but is preferably a solvent-soluble dye compound, and is a group consisting of a squarylium compound, a phthalocyanine compound, and a cyanine compound. More preferably, it is at least one selected from the above, more preferably contains a squarylium compound, more preferably contains at least one squarylium compound and another compound (A), and other compound (A). Particularly preferred are phthalocyanine compounds and cyanine compounds.

The squarylium-based compound has excellent visible light permeability, steep absorption characteristics, and a high molar extinction coefficient, but may generate fluorescence that causes scattered light during light absorption. In such a case, an optical filter with less scattered light and better camera image quality can be obtained by using a combination of the squarylium compound and the other compound (A).

The absorption maximum wavelength of the compound (A) is preferably 620 nm or more and 748 nm or less, more preferably 650 nm or more and 745 nm or less, and particularly preferably 660 nm or more and 740 nm or less.

The content of the compound (A) includes, as the base material (i), for example, a base material made of a transparent resin substrate (ii) containing the compound (A) and the compound (S), or the compound (A). When using a base material in which a resin layer such as an overcoat layer made of a curable resin containing the compound (S) is laminated on the transparent resin substrate (iv) to be used, with respect to 100 parts by weight of the transparent resin , Preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. A substrate in which a transparent resin layer such as an overcoat layer composed of a curable resin containing the compound (A) and the compound (S) is laminated on a resin support as a support or a base, or a compound (S) Curable tree containing compound (A) on transparent resin substrate (iii) In the case of using a base material on which a resin layer such as an overcoat layer made of, etc. is used, it is preferably 0.1 to 5. with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). The amount is 0 part by weight, more preferably 0.2 to 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight.

<Compound (S)>
The compound (S) is not particularly limited as long as it has an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less, but is preferably a solvent-soluble dye compound, and is preferably a squarylium compound, a phthalocyanine compound, a cyanine compound, or a naphthalocyanine. It is more preferable that it is at least one selected from the group consisting of a series compound, a pyrrolopyrrole compound, a croconium compound, a hexaphyrin compound, a metal dithiolate compound, and a ring extended BODIPY (boron dipyrromethene) compound. It is more preferable that the compound is at least one selected from the group consisting of a compound based on a compound, a cyanine compound, a pyrrolopyrrole compound, and a metal dithiolate compound, and particularly a squarylium compound represented by the following formula (Z). preferable By using such a compound (S), it is possible to simultaneously achieve high near-infrared cut characteristics near the absorption maximum and good visible light transmittance.

　式（Ｚ）中、置換ユニットＡおよびＢは、それぞれ独立に下記式（Ｉ）および（ＩＩ）で表される置換ユニットのいずれかを表す。

In the formula (Z), the substitution units A and B each independently represent any of the substitution units represented by the following formulas (I) and (II).

　式（Ｉ）および（ＩＩ）中、波線で表した部分が中央四員環との結合部位を表し、
　Ｘは、独立に酸素原子、硫黄原子、セレン原子、テルル原子または－ＮＲ⁸－を表し、
　Ｒ¹～Ｒ⁸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３～１４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種である。

In formulas (I) and (II), the portion represented by the wavy line represents the binding site with the central four-membered ring,
X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or —NR ⁸ —;
R ¹ to R ⁸ are each independently a 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 ⁱ group, —OSO ₂ R ⁱ group or any of the following L ^a to L ^h , wherein R ^g and R ^h are each independently a hydrogen atom, —C (O) R ⁱ group or the following L ^a to L ^e It represents either, R ⁱ represents any of the following L ^a ~ L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon C ^6-14 aromatic hydrocarbon group (L ^e ) C ^3-14 heterocyclic group (L ^f ) C ^1-12 alkoxy group (L ^g ) carbon number optionally having substituent L 1 to 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, 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.

R ¹ is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, phenyl group. Group, hydroxyl group, amino group, dimethylamino group and nitro group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group and hydroxyl group.

R ² to R ⁷ are preferably each independently a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, or tert-butyl. Group, cyclohexyl group phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetyl Amino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio More preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an Group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, a t-butanoylamino group, a cyclohexinoylamino group, a methylthio group, and an ethylthio group;

R ⁸ is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, more preferably hydrogen atom, methyl group, ethyl group, n-propyl group , Isopropyl group, n-butyl group, tert-butyl group and n-decyl group.

X is preferably an oxygen atom, a sulfur atom or —NR ⁸ —, particularly preferably an oxygen atom or a sulfur atom in the substitution unit of the formula (I), and — in the substitution unit of the formula (II). NR ⁸ - is.

The squarylium-based compound can also represent the structure by a description method such as the following formula (S2) and a description method that takes a resonance structure as the following formula (S2). That is, the difference between the following formula (S1) and the following formula (S2) is only the structure description method, and both represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium compound is represented by a description method such as the following formula (S1).

Furthermore, for example, the compound represented by the following formula (S1) and the compound represented by the following formula (S3) can be regarded as the same compound.

In the compound represented by the formula (Z), the left and right units bonded to the central four-membered ring are the same or different as long as they are represented by the formula (I) or the formula (II), respectively. However, it is preferable that they are the same including the substituents in the unit because they are easy to synthesize. That is, among the compounds represented by the formula (Z), those represented by the following formula (III) or formula (IV) are preferable.

　式（Ｚ）で表される化合物の具体例としては、例えば、下記表１および表２に記載の化合物（ｓ－１）～（ｓ－５８）、ならびに、下記化学式で表わされる化合物（ｓ－５９）および化合物（ｓ－６０）を挙げることができる。

Specific examples of the compound represented by the formula (Z) include, for example, the compounds (s-1) to (s-58) described in the following Tables 1 and 2, and the compound (s- 59) and the compound (s-60).

The squarylium compound, cyanine compound, pyrrolopyrrole compound, and metal dithiolate compound other than the squarylium compound represented by the formula (Z) are not particularly limited as long as they have an absorption maximum at a wavelength of 750 nm to 1050 nm. Examples thereof include the following compounds (s-61) to (s-67).

The absorption maximum wavelength of the compound (S) is 750 nm or more and 1050 nm or less, preferably 770 nm or more and 1000 nm or less, more preferably 780 nm or more and 970 nm or less, further preferably 790 nm or more and 960 nm or less, and particularly preferably 800 nm or more and 950 nm or less. When the absorption maximum wavelength of the compound (S) is in such a range, unnecessary near infrared rays that cause various ghosts can be efficiently cut.

The compound (S) may be synthesized by a generally known method. For example, JP-A-1-228960, JP-A-2001-40234, JP-A-3094037, JP-A-3196383, etc. Can be synthesized with reference to the method described in the above.

The content of the compound (S) includes, as the base material (i), for example, a base material composed of a transparent resin substrate (ii) containing the compound (A) and the compound (S), or the compound (S). When using a base material in which a resin layer such as an overcoat layer composed of a curable resin containing the compound (A) is laminated on the transparent resin substrate (iii) to be used, with respect to 100 parts by weight of the transparent resin , Preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. A substrate in which a transparent resin layer such as an overcoat layer composed of a curable resin containing the compound (A) and the compound (S) is laminated on a resin support as a support or a base, or a compound (A) Curability containing compound (S) on transparent resin substrate (iv) When using a base material on which a resin layer such as an overcoat layer made of fat is laminated, it is preferably 0.1 to 5 with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). 0.0 parts by weight, more preferably 0.2 to 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight. When the content of the compound (S) is within the above range, an optical filter having both good near infrared absorption characteristics and high visible light transmittance can be obtained.

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

Other dyes (X) are not particularly limited as long as the absorption maximum wavelength is less than 600 nm or more than 1050 nm, but those having an absorption maximum wavelength of more than 1050 nm are preferable. Examples of such dyes include squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, octaphyrin compounds, diimonium compounds, pyrrolopyrrole compounds, and boron dipyrromethene (BODIPY). And at least one compound selected from the group consisting of a compound, a perylene compound, and a metal dithiolate compound.

<Transparent resin>
The transparent resin layer and the transparent resin substrates (ii) to (iv) to be laminated on the resin support or the glass support can be formed using a transparent resin.
As transparent resin used for the said base material (i), 1 type may be individual and 2 or more types may be sufficient.

The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, it ensures thermal stability and moldability to a film, and dielectrics are formed by high-temperature deposition performed at a deposition temperature of 100 ° C. or higher. For example, a resin having a glass transition temperature (Tg) of preferably 110 to 380.degree. C., more preferably 110 to 370.degree. C., and still more preferably 120 to 360.degree. Further, it is particularly preferable that the glass transition temperature of the resin is 140 ° C. or higher because a film capable of depositing a dielectric multilayer film at a higher temperature can be obtained.

As the transparent resin, when a resin plate made of the resin having a thickness of 0.1 mm is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, Particularly 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 resulting substrate exhibits good transparency as an optical film.

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

Examples of transparent resins include cyclic (poly) olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, and polyarylate resins. Resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins Examples thereof include resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins.

≪Cyclic (poly) olefin resin≫
The cyclic (poly) olefin resin is 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 ) And a resin obtained by hydrogenating the resin are preferred.

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

In the formula (X ₀ ), R ^x1 to R ^x4 each independently represents an atom or group selected from the following (i ′) to (ix ′), and k ^x , ^mx and p ^x are each independently 0 Or represents a positive integer.
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom 30 to 30 hydrocarbon group (v ′) substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi ′) polar group (excluding (iv ′))
(Vii ′) an alkylidene group formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other (provided that R ^x1 to R ^x4 not involved in the bonding are independently the above (i ′ )-(Vi ′) represents an atom or group selected from.
(Viii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring (provided that R ^x1 to R which are not involved in the bond) ^x4 each independently represents an atom or group selected from (i ′) to (vi ′).
(Ix ′) A monocyclic hydrocarbon ring or heterocycle formed by bonding R ^x2 and R ^x3 to each other (provided that R ^x1 and R ^x4 not involved in the bonding are each independently the above (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 the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i ′) to (vi ′), or R ^y1 and R ^y2 are bonded to each other formed monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or heterocyclic, k ^y and p ^y are each independently, represent 0 or a positive integer.

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

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

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

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

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

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

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

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

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

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

≪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, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. The polymer preferably contains 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 or methacrylic groups in the molecule and a compound that decomposes by ultraviolet rays to generate active radicals. Can be mentioned. The acrylic ultraviolet curable resin is a base material in which a transparent resin layer containing a compound (S) and a curable resin is laminated on a glass support or a base resin support as the base (i) In the case of using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on the transparent resin substrate (ii) containing the compound (S), it is particularly preferably used as the curable resin. be able to.

≪Commercial product≫
The following commercial products etc. can be mentioned as a commercial item of transparent resin. Examples of commercially available cyclic (poly) olefin-based resins include Arton manufactured by JSR Co., Ltd., ZEONOR manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. . Examples of commercially available polyethersulfone resins include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polycarbonate resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include NIPPON CATALYST ACRYVIEWER. Examples of commercially available silsesquioxane-based ultraviolet curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Other ingredients>
The base material (i) may further contain additives such as an antioxidant, a near-ultraviolet absorber, and a fluorescence quencher as long as the effects of the present invention are not impaired. These other components may be used alone or in combination of two or more.

Examples of the near ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, and triazine compounds.
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (2,4-di-t-butylphenyl) phosphite and the like.

Note that these additives may be mixed with a resin or the like when the base material (i) is produced, or may be added when a resin is synthesized. The addition amount is appropriately selected according to the desired properties, 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. Part.

<Method for producing substrate (i)>
When the base material (i) is a base material containing the transparent resin substrates (ii) to (iv), the transparent resin substrates (ii) to (iv) are obtained by, for example, melt molding or cast molding. Furthermore, if necessary, after forming, a coating material such as an antireflection agent, a hard coating agent and / or an antistatic agent is coated to produce a substrate on which an overcoat layer is laminated. Can do.

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 glass substrate or a resin substrate as a base. For example, by spin-molding or slit-molding a resin solution containing the compound (A) and the compound (S) on a glass support or a base resin support, for example, a glass support or a base. After coating by a method such as coating or inkjet, the solvent is dried and removed, and if necessary, light irradiation or heating is performed to form a transparent resin layer on the glass support or the base resin support. The manufactured base material can be manufactured.

≪Melt molding≫
Specifically, as the melt molding, a method of melt-molding pellets obtained by melt-kneading resin, compound (A), compound (S) and the like; resin, compound (A) and compound (S Or a resin composition containing a compound (A), a compound (S), a resin and a solvent, a pellet obtained by removing the solvent from the resin composition, and the like. Is mentioned. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫
As the cast molding, a method of removing a solvent by casting a resin composition containing the compound (A), the compound (S), a resin and a solvent on an appropriate support; or the compound (A) and the compound (S ), A method in which a curable composition containing a photocurable resin and / or a thermosetting resin is cast on an appropriate support to remove the solvent, and then cured by an appropriate method such as ultraviolet irradiation or heating. It can also be manufactured by, for example.

When the base material (i) is a base material made of a transparent resin substrate (ii) containing the compound (A) and the compound (S), the base material (i) is supported after casting. The substrate (i) can be obtained by peeling the coating film from the body, and the substrate (i) is a compound (A) and compound (A) on a support such as a glass support or a resin support as a base. In the case of a base material on which a transparent resin layer such as an overcoat layer made of a curable resin containing S) is laminated, the base material (i) is obtained by not peeling the coating film after cast molding. Obtainable.

Examples of the support include a glass plate, a steel belt, a steel drum, and a support made of a transparent resin (for example, a polyester film and a cyclic olefin resin film).

Further, the optical component such as glass plate, quartz or transparent plastic is coated with the resin composition and the solvent is dried, or the curable composition is coated and 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 (ii)) 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, and still more preferably 0.8% by weight with respect to the weight of the transparent resin layer (transparent resin substrate (ii)). 5% by weight or less. When the amount of residual solvent is in the above range, a transparent resin layer (transparent resin substrate (ii)) that can easily exhibit a desired function is obtained, in which deformation and characteristics are hardly changed.

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

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

The method for laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a high-refractive index material layer and a low-refractive index material layer are alternately laminated directly on the substrate (i) by CVD, sputtering, vacuum deposition, ion-assisted deposition, or ion plating. A dielectric 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 from 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 within this range, the optical thickness obtained by multiplying the refractive index (n) by the thickness (d) (n × d) by λ / 4, the high refractive index material layer, and the low refractive index. The thicknesses of the respective layers of the refractive index material layer are almost the same value, and there is a tendency that the blocking / transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection / refraction.

The total number of high refractive index material layers and low refractive index material layers in the dielectric multilayer film is preferably 16 to 70 layers, more preferably 20 to 60 layers, as a whole. 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 the warpage of the optical filter and cracks in the dielectric multilayer film can be reduced. can do.

In the present invention, the material types 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 material layer according to the absorption characteristics of the compound (A) and the compound (S). Appropriate selection of thickness, stacking order, and number of stacks ensures sufficient transmittance in the visible range and sufficient light cut characteristics in the near-infrared wavelength range, and is close to the oblique direction. The reflectance when infrared rays are incident can be reduced.

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

[Other functional membranes]
As long as the optical filter of the present invention does not impair the effects of the present invention, the optical filter between the substrate (i) and the dielectric multilayer film is on the side opposite to the surface on which the dielectric multilayer film of the substrate (i) is provided. On the surface or the surface opposite to the surface on which the substrate (i) of the dielectric multilayer film is provided, the surface hardness of the substrate (i) or the dielectric multilayer film is improved, the chemical resistance is improved, the antistatic A functional film such as an antireflection film, a hard coat film, or an antistatic film can be appropriately provided for the purpose of scratch removal.

The optical filter of the present invention may include one layer made of the functional film or two or more layers. When the optical filter of the present invention includes two or more layers made of the functional film, it may include 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 melted in the base material (i) or the dielectric multilayer film as described above. Examples of the method include molding or cast molding.

Further, it can also be produced by applying a curable composition containing the coating agent or the like on the substrate (i) or the dielectric multilayer film with a bar coater or the like and then curing it by ultraviolet irradiation or the like.

Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethanes, urethane acrylates, acrylates, epoxy And epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.

Moreover, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

The blending ratio 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 antireflective film, a hard coat film or an antistatic film having excellent curing characteristics and handleability of the curable composition and having a desired hardness. it can.

Furthermore, an organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Examples 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 (i) and the functional film and / or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, the base material (i), the functional film or the dielectric Surface treatment such as corona treatment or plasma treatment may be applied to the surface of the multilayer film.

[Use of optical filter]
The optical filter of the present invention has a wide viewing angle and has excellent near-infrared cutting ability and the like. Therefore, it is useful for correcting the visibility of a solid-state imaging device 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, automotive cameras, TVs, car navigation systems, personal digital assistants, video game machines, and portable game machines It is useful for fingerprint authentication system, digital music player, etc. Furthermore, it is also useful as a heat ray cut filter attached to a glass plate of an automobile or a building.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device is an image sensor including a solid-state imaging device such as a CCD or a CMOS image sensor. Specifically, a digital still camera, a camera for a smartphone, a camera for a mobile phone, a camera for a wearable device, a digital camera It can be used for applications such as video cameras. For example, the camera module of the present invention includes the optical filter of the present invention.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. “Parts” means “parts by weight” unless otherwise specified. Moreover, the measurement method of each physical property value and the evaluation method of 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.
(A) Weight average molecular weight in terms of standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS (Mw) and number average molecular weight (Mn) were measured.
(B) Standard polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a GPC apparatus (HLC-8220 type, column: TSKgelα-M, developing solvent: THF) manufactured by Tosoh Corporation.

In addition, about the resin synthesize | combined in the resin synthesis example 3 mentioned later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the said method.
(C) A part of the polyimide resin solution was added to anhydrous methanol to precipitate the polyimide resin, and filtered to separate from the unreacted monomer. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. Asked.
_{μ = {ln (t s /} t 0)} / C
t ₀ : Flowing time of solvent t _s : Flowing time of dilute polymer solution C: 0.5 g / dL

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

<Spectral transmittance>
The base material (Ta), (Xc), and (Tb), and the transmittance in each wavelength region of the optical filter, (Xa) and (Xb), are spectrophotometers (U- 4100).

Here, with respect to the transmittance when measured from the vertical direction of the optical filter, the light transmitted perpendicular to the filter is measured as shown in FIG. 2A, and the angle is 30 ° with respect to the vertical direction of the optical filter. As for the transmittance when measured from the above, the light transmitted at an angle of 30 ° with respect to the vertical direction of the filter as shown in FIG. 2B was measured. In addition, the reflectance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter is measured by setting the optical filter on a jig attached to the apparatus as shown in FIG. The reflectance when measured from an angle of 5 ° with respect to the vertical direction of the glass was measured by setting an optical filter in a jig attached to the apparatus as shown in FIG.

Note that this transmittance is measured using the spectrophotometer under the condition that light is perpendicularly incident on the substrate and the filter, except when measuring (Xb). In the case of measuring (Xb), it is measured using the spectrophotometer under the condition that light is incident at an angle of 30 ° with respect to the vertical direction of the filter.

[Synthesis example]
Compound (A) and compound (S) used in the following examples were synthesized by a generally known method. Examples of the general synthesis method include, for example, Japanese Patent No. 336697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open No. 1-146846, JP-A-1-228960, JP-A-4081149, JP-A-63-124054, “Phthalocyanine—Chemistry and Function” (IPC, 1997), JP-A-2007-169315, JP2009. -108267, JP2010-241873, JP3699464, JP4740631, and the like.

<Resin synthesis example 1>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodec-3-ene (hereinafter also referred to as “DNM”) 100 parts, 1-hexene (molecular weight regulator) 18 parts, and toluene (ring-opening polymerization solvent) 300 parts nitrogen-substituted reaction The vessel was charged and the solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel. 9 parts was added and this 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１，０００部をオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．１２部添加し、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 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed 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), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin A”). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

<Resin synthesis example 2>
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask. Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that 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 overnight at 60 ° C. to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

<Resin synthesis example 3>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean-Stark tube and condenser tube, 1,4-bis (4-amino-α, α -Dimethylbenzyl) benzene (27.66 g, 0.08 mol) and 4,4′-bis (4-aminophenoxy) biphenyl (7.38 g, 0.02 mol) were added, and γ-butyrolactone (68.65 g) and N, It was dissolved in 17.16 g of N-dimethylacetamide. The obtained solution was cooled to 5 ° C. using an ice-water bath, and while maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an imidization catalyst As a result, 0.50 g (0.005 mol) of triethylamine was added all at once. After completion of the addition, the temperature was raised to 180 ° C. and refluxed for 6 hours while distilling off the distillate as needed. After completion of the reaction, the reaction solution was air-cooled until the internal temperature reached 100 ° C., diluted by adding 143.6 g of N, N-dimethylacetamide, cooled with stirring, and 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 dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). The IR spectrum of the obtained resin C was measured, 1704 cm ^-1 characteristic of imido group, absorption of 1770 cm ^-1 were observed. Resin C had a glass transition temperature (Tg) of 310 ° C. and a logarithmic viscosity of 0.87.

[Example 1]
In Example 1, an optical filter having a base material made of a transparent resin substrate was prepared according to the following procedure and conditions.

In a container, 100 parts of the resin A obtained in Resin Synthesis Example 1, 0.02 part of the compound (s-11) described in Table 1 above as the compound (S) (absorption maximum wavelength 776 nm in dichloromethane), compound (S A) 0.03 parts of the compound (a-1) represented by the following formula (a-1) (absorption maximum wavelength 698 nm in dichloromethane) and the compound (a-2) represented by the following formula (a-2) 0.03 part (absorption maximum wavelength in dichloromethane) of 733 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 at 100 ° C. under reduced pressure for 8 hours to obtain a base material composed 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 (Ta), (Tb) and (Xc) were determined. The results are shown in FIG.

Subsequently, a dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained base material, and a dielectric multilayer film (II) is formed as a second optical layer on the other side of the base material. Thus, an optical filter having a thickness of about 0.104 mm was obtained.

The dielectric multilayer film (I) is formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a 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 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 in 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 outermost layer of the optical filter was a silica layer.

The dielectric multilayer films (I) and (II) were designed as follows.
Regarding the thickness and the number of layers of each layer, the wavelength-dependent characteristics of the base material refractive index and the applied compound (S) and compound (in order to achieve the antireflection effect in the visible range and the selective transmission / reflection performance in the near infrared range, Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) according to the absorption characteristics of A). When performing optimization, in this example, the input parameters (Target values) to the software are as shown in Table 3 below.

As a result of the optimization of the film configuration, in Example 1, the dielectric multilayer film (I) is formed by alternately stacking a silica layer having a film thickness of 31 to 157 nm and a titania layer having a film thickness of 10 to 95 nm. The dielectric multi-layer film (II) is a multi-layer vapor-deposited film having 20 layers, in which a silica layer having a thickness of 38 to 199 nm and a titania layer having a thickness of 12 to 117 nm are alternately stacked. It was. An example of the optimized film configuration is shown in Table 4, and the spectral reflectance spectrum measured from an angle of 5 ° from the vertical direction of the glass substrate for the vapor deposition monitor in which each dielectric multilayer film is formed on one side as a single figure is shown. As shown in FIG. When measuring the reflectivity of the glass for vapor deposition monitoring, the surface on which the dielectric multilayer film is not formed is painted with black acrylic paint to prevent the influence of back reflection, and after applying antireflection treatment, The surface on which the body multilayer film was formed was used as the incident surface for the measurement light.

The spectral transmittance measured from the vertical direction of the obtained optical filter and 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. Moreover, when the spectral reflectance measured from the angle of 30 ° with respect to the vertical direction of each surface of the obtained optical filter was measured, the incident surface of the light beam was set to the dielectric multilayer film (II) side (second optical layer side). As a result, it was confirmed that the minimum reflectance value at a wavelength of 815 to 935 nm was small. FIG. 7 shows a spectral reflectance spectrum measured from an angle of 30 ° from the vertical direction of the optical filter when the light incident surface is on the dielectric multilayer film (II) side. The average value of the transmittance at a wavelength of 430 to 580 nm is 88%, the average value of the transmittance at a wavelength of 800 to 1000 nm is 1% or less, and at least when measured from an angle of 30 ° with respect to the vertical direction at a wavelength of 815 to 935 nm The minimum reflectance measured from one surface was 61%, and the absolute value | Xa−Xb | was 3 nm.

[Example 2]
In Example 1, instead of 0.02 part of compound (s-11), 0.005 part of compound (s-27) (absorption maximum wavelength 868 nm in dichloromethane) described in Table 1 was used, and As compound (A), 0.03 part of compound (a-3) represented by the following formula (a-3) (maximum absorption wavelength 703 nm in dichloromethane) and a compound represented by the following formula (a-4) ( a-4) Transparent resin substrate containing compound (S) and compound (A) under the same procedure and conditions as in Example 1 except that 0.07 part (absorption maximum wavelength in dichloromethane 736 nm) was used A substrate consisting of The spectral transmittance of this substrate was measured, and (Ta), (Tb) and (Xc) were determined. The results are shown in FIG.

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). The multilayer film (III) is formed, and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as the 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 0.104 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the base material refractive index. The spectral transmittance of the obtained optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. Moreover, when the spectral reflectance measured from the angle of 30 ° with respect to the vertical direction of each surface of the obtained optical filter was measured, the incident surface of the light beam was set to the dielectric multilayer film (IV) side (second optical layer side). As a result, it was confirmed that the minimum reflectance value at a wavelength of 815 to 935 nm was small. FIG. 10 shows a spectral reflectance spectrum measured from an angle of 30 ° from the vertical direction of the optical filter when the light incident surface is on the dielectric multilayer film (IV) side.

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

In Example 1, 0.02 part of the compound (s-25) shown in Table 1 (maximum absorption wavelength 781 nm in dichloromethane) was used instead of 0.02 part of the compound (s-11), and Example 1 except that 0.03 part of compound (a-1), 0.01 part of compound (a-3) and 0.08 part of compound (a-4) were used as compound (A). A transparent resin substrate containing the compound (S) and the compound (A) was obtained under the same procedure and conditions.

A 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, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. 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 formed on both surfaces of the transparent resin substrate containing the compound (S) and the compound (A). A substrate was obtained. The spectral transmittance of this substrate was measured to determine (Ta), (Tb), and (Xc). The results are shown in Table 5.

Resin composition (1): 60 parts by weight of tricyclodecane dimethanol acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). And a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as the second optical layer on the other surface of the substrate (20 layers in total). A dielectric multilayer film (VI) was formed to obtain an optical filter having a thickness of about 0.108 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance and spectral reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 5.

[Example 4]
In Example 4, an optical filter having a base material composed of a resin substrate having a transparent resin layer containing the compound (S) and the compound (A) on both surfaces was prepared according to the following procedure and conditions.

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

A resin layer made of the resin composition (2) having the following composition is formed on both surfaces of the resin substrate obtained in the same manner as in Example 3, and a transparent resin layer containing the compound (S) and the compound (A) is formed on both surfaces. A base material made of a resin substrate was obtained. The spectral transmittance of this substrate was measured, and (Ta), (Tb) and (Xc) were determined. The results are shown in Table 5.

Resin composition (2): 100 parts by weight of tricyclodecane dimethanol acrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.50 part by weight of compound (s-11), 0.75 part by weight of compound (a-1) , 0.75 parts by weight of compound (a-2), methyl ethyl ketone (solvent, TSC: 25%)

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). And a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as the second optical layer on the other surface of the base material (total 20 layers). A dielectric multilayer film (VIII) was formed to obtain an optical filter having a thickness of about 0.108 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance and spectral reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 5.

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

On a transparent glass substrate “OA-10G (thickness: 200 μm)” (manufactured by Nippon Electric Glass Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width, a resin composition (3) having the following composition was applied by a spin coater. The solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes. Under the present circumstances, the application | coating conditions of the spin coater were adjusted so that the thickness after drying might be set to 2 micrometers. Next, it exposes (exposure amount 500mJ / cm < ² >, 200mW) using a conveyor type exposure machine, hardens the resin composition (3), and has a transparent resin layer containing the compound (S) and the compound (A). A base material made of a transparent glass substrate was obtained. The spectral transmittance of this substrate was measured, and (Ta), (Tb) and (Xc) were determined. The results are shown in Table 5.

Resin composition (3): 20 parts by weight of tricyclodecane dimethanol acrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 1.0 part by weight of compound (s-11), compound ( a-1) 1.5 parts by weight, compound (a-2) 1.5 parts by weight, methyl ethyl ketone (solvent, TSC: 35%)

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). A multilayer film (IX) is formed, and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the base material (20 layers in total) A dielectric multilayer film (X) was formed to obtain an optical filter having a thickness of about 0.108 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance of this optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 5.

[Examples 6 to 15]
A base material and an optical filter were prepared in the same manner as in Example 3 except that the resin, the solvent, the drying conditions for the resin substrate, the compound (S), and the compound (A) were changed as shown in Table 5. Table 5 shows the optical properties of the obtained substrate and optical filter.

[Comparative Example 1]
In Example 1, a substrate 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. Table 5 shows the optical properties of the obtained substrate and optical filter.

[Comparative Example 2]
The same as Example 3 except that the compound (S) was not used and 0.03 part of the compound (a-1) and 0.03 part of the compound (a-2) were used as the compound (A). Thus, a base material and an optical filter were prepared. Table 5 shows the optical properties of the obtained substrate and optical filter.

[Comparative Example 3]
An optical filter was prepared in the same manner as in Example 1 except that a transparent glass substrate “OA-10G (thickness: 200 μm)” (manufactured by Nippon Electric Glass Co., Ltd.) was used as the substrate. Table 5 shows the optical characteristics of the base material and the obtained optical filter.

The configurations of the base materials and various compounds applied in the examples and comparative examples are as follows.
<Form of substrate>
Form (1): Transparent resin substrate containing compound (S) and compound (A) Form (2): Transparent resin substrate containing compound (S) and compound (A) has resin layers on both sides Form (3 ): A transparent resin layer containing the compound (S) and the compound (A) is provided on both surfaces of the resin substrate. Form (4): A transparent resin layer containing the compound (S) and the compound (A) on one surface of the glass substrate. Form (5): A transparent resin substrate containing no compound (S) or compound (A) (Comparative Example)
Form (6): having resin layers on both surfaces of a transparent resin substrate containing the compound (A) (Comparative Example)
Form (7): Glass substrate (comparative example)

<Transparent resin>
Resin A: Cyclic olefin resin (resin synthesis example 1)
Resin B: Aromatic polyether resin (resin synthesis example 2)
Resin C: Polyimide resin (resin synthesis example 3)
Resin D: Cyclic olefin resin “Zeonor 1420R” (manufactured by Nippon Zeon Co., Ltd.)

<Glass substrate>
Glass substrate (1): Transparent glass substrate “OA-10G (thickness: 200 μm)” cut to 60 mm length and 60 mm width (manufactured by Nippon Electric Glass Co., Ltd.)

<Near-infrared absorbing dye>
<Compound (A)>
Compound (a-1): Compound (a-1) above (absorption maximum wavelength in dichloromethane 698 nm)
Compound (a-2): Compound (a-2) above (absorption maximum wavelength in dichloromethane: 733 nm)
Compound (a-3): Compound (a-3) described above (maximum absorption wavelength 703 nm in dichloromethane)
Compound (a-4): Compound (a-4) above (absorption maximum wavelength in dichloromethane 736 nm)
Compound (a-5): a cyanine compound represented by the following formula (a-5) (absorption maximum wavelength in dichloromethane: 681 nm)

　化合物（ａ－６）：下記式（ａ－６）で表されるスクアリリウム系化合物（ジクロロメタン中での吸収極大波長７１３ｎｍ）

Compound (a-6): A squarylium compound represented by the following formula (a-6) (absorption maximum wavelength in dichloromethane: 713 nm)

<Solvent>
Solvent (1): Methylene chloride Solvent (2): N, N-dimethylacetamide Solvent (3): Cyclohexane / xylene (weight ratio: 7/3)

In Table 5, the drying conditions of the (transparent) resin substrates of Examples and Comparative Examples are as follows. In addition, the coating film was peeled from the glass plate before drying under reduced pressure.
<Film drying conditions>
Condition (1): 20 ° C./8 hr → under reduced pressure 100 ° C./8 hr
Condition (2): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 140 ° C./8 hr
Condition (3): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 100 ° C./24 hr

The optical filter of the present invention is a digital still camera, a mobile phone camera, a digital video camera, a personal computer camera, a surveillance camera, an automobile camera, a television, an in-vehicle device for a car navigation system, a portable information terminal, a video game machine, a mobile phone. It can be suitably used for game machines, fingerprint authentication system devices, digital music players, and the like. Furthermore, it can be suitably used as a heat ray cut filter or the like attached to glass or the like of automobiles and buildings.

1: Optical filter 2: Spectrophotometer 3: Light 4: Lens 5: Solid-state imaging device 6: Multiple reflection light 7: Reflection mirror 8: Dielectric multilayer film 9: Glass for vapor deposition monitor (back surface is treated with antireflection film)
10: Substrate (i)
11: First optical layer 12: Second optical layer 13: Third optical layer 14: Fourth optical layer

Claims (11)

A dielectric multilayer film on at least one surface of the substrate and the substrate;
The substrate has a transparent resin layer containing a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm and a compound (S) having an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less, or the compound ( A transparent resin layer containing A) and a transparent resin layer containing the compound (S),
An optical filter characterized by satisfying the following requirement (a):
(A) In the wavelength region of 800 to 1000 nm, the average transmittance when measured from the vertical direction of the optical filter is 5% or less. The optical filter according to claim 1, further satisfying the following requirement (b):
(B) In the wavelength range of 430 to 580 nm, the average transmittance when measured from the vertical direction of the optical filter is 75% or more. The optical system according to claim 1 or 2, wherein the compound (S) is at least one selected from the group consisting of squarylium compounds, cyanine compounds, pyrrolopyrrole compounds, and metal dithiolate compounds. filter. The optical filter according to any one of claims 1 to 3, wherein the compound (S) is a squarylium compound represented by the following formula (Z).

[In the formula (Z), the substitution units A and B each independently represent any of the substitution units represented by the following formulas (I) and (II). ]

[In formulas (I) and (II), the portion represented by the wavy line represents the binding site with the central four-membered ring,
X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or —NR ⁸ —;
R ¹ to R ⁸ are each independently a 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 ⁱ group, —OSO ₂ R ⁱ group or any of the following L ^a to L ^h , wherein R ^g and R ^h are each independently a hydrogen atom, —C (O) R ⁱ group or the following L ^a to L ^e It represents either, R ⁱ represents any of the following L ^a ~ L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon C ^6-14 aromatic hydrocarbon group (L ^e ) C ^3-14 heterocyclic group (L ^f ) C ^1-12 alkoxy group (L ^g ) carbon number optionally having substituent L 1 to 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, 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. ] The optical filter according to any one of claims 1 to 4, further comprising a dielectric multilayer film on both surfaces of the substrate. The optical filter according to any one of claims 1 to 5, wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. . The transparent resin is a cyclic (poly) olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, polysulfone resin. , Polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins 7. The resin according to claim 1, wherein the resin is at least one selected from the group consisting of silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins. The optical filter according to item 1. The optical filter according to any one of claims 1 to 7, wherein the substrate 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 used for a solid-state imaging device. A solid-state imaging device comprising the optical filter according to any one of claims 1 to 8. A camera module comprising the optical filter according to any one of claims 1 to 8.

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