KR20200028956A - Devices using near infrared cut filters and corresponding near infrared cut filters - Google Patents

Abstract

An object of the present invention is to provide a near-infrared cut filter having excellent near-infrared cut characteristics, low incidence of angle of incidence, excellent transmittance characteristics in the visible wavelength region, and a reduction effect of multiple reflected light in the near-infrared wavelength region. The near-infrared cut filter of the present invention includes a substrate having a transparent resin layer containing a near-infrared absorbent, and a dielectric multilayer film formed on at least one side of the substrate, and also satisfies the following requirement (a): (a) Wavelength 600 In the region of 800 nm, the shortest wavelength value (Xa) in which the transmittance is 50% when measured from the vertical direction of the substrate, and in the region of the wavelength of 700 to 1200 nm, is measured from the vertical direction of the substrate. In one case, the absolute value | Xa-Xb | of the difference from the value (Xb) of the longest wavelength at which the transmittance is 50% is 120 nm or more.

Description

Devices using near infrared cut filters and corresponding near infrared cut filters

The present invention relates to an apparatus using a near infrared cut filter and a near infrared cut filter. More specifically, the present invention relates to a near infrared cut filter comprising a dye compound having absorption in a specific wavelength region, and a solid-state imaging device and camera module using the near infrared cut filter.

A solid-state imaging device such as a video camera, a digital still camera, or a mobile phone equipped with a camera function uses a CCD or CMOS image sensor, which is a solid-state imaging device for color images, but these solid-state imaging devices are used by human eyes in their light-receiving units. A silicon photodiode is used which has sensitivity to near-infrared rays that cannot be detected. In these solid-state imaging devices, it is necessary to correct the visibility to make natural tones visible to the human eye, and in many cases, a near-infrared cut filter that selectively transmits or cuts light in a specific wavelength range is used.

As such a near-infrared cut filter, conventionally manufactured by various methods are used. For example, a near-infrared cut filter using a transparent resin as a base material and containing a near-infrared absorbing dye in a transparent resin is known (for example, see Patent Document 1).

However, the near-infrared cut filter described in Patent Document 1 cannot extend the absorption bandwidth of the substrate while keeping the visible light transmittance high, and in order to sufficiently lower the transmittance around 700 to 800 nm, cut the wavelength of the dielectric multilayer film to a relatively short wavelength side. Needs to be.

The near-infrared cut filter incorporated in the camera module is used in an arrangement called a dielectric multilayer film (near-infrared reflective film) on the lens side and an anti-reflection film on the image sensor side, but the reflected light between the dielectric multilayer film and the lens may cause multiple reflections. As a result, there have been cases in which multiple reflected light having a relatively high sensor sensitivity of 700 to 800 nm enters the imaging element and deteriorates the camera image.

However, the near-infrared cut filter described in Patent Document 1 does not have a sufficient light absorption band in the near-infrared region, and it is necessary to increase the near-infrared reflectance of the near-infrared cut filter in order to sufficiently cut the incident light of the near-infrared light to the sensor. have.

Further, with the miniaturization of the camera module in a mobile device, the incident angle of light rays tends to be larger than in the prior art, especially at the edge of the screen, but in the conventional near-infrared cut filter, due to multiple reflections between the near-infrared cut filter and the lens Ghost was a problem in some cases. Specifically, as shown in FIG. 1, among the incident light transmitted through the lens 4, visible light passes through the near-infrared cut filter 1, but near-infrared light is reflected (reflected light 3A). The reflected near-infrared light is reflected back from the surface of the lens 4 (reflected light 3B), causing multiple reflections. In some cases, multiple reflected light (transmitted light 3C) between the near-infrared cut filter and the lens enters the sensor 5, and the camera image is deteriorated.

Japanese Patent Publication No. Hei 6-200113

In recent years, the image quality level required for a camera image has been very high even in mobile devices. According to the studies of the present inventors, in order to meet the demand for high image quality, in addition to a wide viewing angle and a high visible light transmittance in the near-infrared cut filter, high light cut characteristics are required even in a long wavelength region. However, in the conventional near-infrared cut filter, as described above, ghost caused by multiple reflections has been a problem in some cases.

An object of the present invention is to provide a near-infrared cut filter having excellent near-infrared cut characteristics, low incidence of angle of incidence, excellent transmittance characteristics in the visible wavelength region and a reduction effect of multiple reflected light in the near-infrared wavelength region.

As a result of earnest examination to solve the above problems, the present applicant has broadened the absorption bandwidth of the substrate to the near-infrared region, so that even if the angle of incidence is changed, the change in optical properties is small, and the near-infrared cut filter with less image degradation due to multiple reflections is obtained. It has been discovered, and the present invention has been completed. Examples of aspects of the present invention are shown below.

[1] A near-infrared cut filter comprising a base material having a transparent resin layer containing a near-infrared absorbent and a dielectric multilayer film formed on at least one side of the base material and satisfying the following requirement (a):

(a) In the region of a wavelength of 600 to 800 nm, in the region of a wavelength of 700 to 1200 nm and the value of the shortest wavelength (Xa) in which the transmittance is 50% when measured from the vertical direction of the substrate, The absolute value | Xa-Xb | of the difference from the value (Xb) of the longest wavelength at which the transmittance is 50% when measured from the vertical direction of is 120 nm or more.

[2] The near-infrared cut filter according to item [1], wherein in the region of the wavelengths Xa to Xb, an average value (Ta) of transmittance when measured from the vertical direction of the substrate is 35% or less.

[3] The near-infrared cut filter according to item [1] or [2], further comprising:

(b) In the range of wavelengths 560 to 800 nm, the shortest wavelength value (Ya) in which the transmittance is 50% when measured from the vertical direction of the near-infrared cut filter and 30 with respect to the vertical direction of the near-infrared cut filter When measured from an angle of °, the absolute value | Ya-Yb | of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% is less than 15 nm.

[4] The anti-infrared absorbent is at least one member selected from the group consisting of squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, and cyanine-based compounds. ] Near infrared cut filter as described in any one of.

[5] The near-infrared cut filter according to any one of items [1] to [4], wherein the transparent resin layer contains two or more kinds of the near-infrared absorbent.

[6] The near-infrared absorbent is a squarylium compound (A) having an absorption maximum at a wavelength of 650 to 750 nm and a compound (B) having an absorption maximum at a wavelength of 660 to 850 nm (excluding the compound (A)) The near-infrared cut filter according to any one of items [1] to [5], comprising a.

[7] The near-infrared cut filter according to any one of [1] to [6], wherein the dielectric multilayer film is formed on both surfaces of the substrate.

[8] The near-infrared cut filter according to item [7], wherein the dielectric multilayer film formed on both surfaces of the substrate includes a near-infrared reflective film and a visible light antireflection film.

[9] In the region of 600 to 900 nm in wavelength, the shortest wavelength value (Xr) at which the reflectance is 50% when measured from an angle of 30 ° with respect to the vertical direction of either side of the near infrared cut filter is 620 The near-infrared cut filter according to any one of items [1] to [8], characterized in that it is nm or more.

[10] The transparent resin is a cyclic (poly) olefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, Polyamide resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyparaphenylene resin, polyamide imide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin Item 1, characterized in that it is at least one resin selected from the group consisting of epoxy resins, allyl ester-based curable resins, silsesquioxane-based ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins. The near-infrared cut filter according to any one of [9] to [9].

[11] The near-infrared cut filter according to any one of [1] to [10], wherein the substrate contains at least one selected from a transparent resin support and a glass support.

[12] The near-infrared cut filter according to any one of [1] to [11], which is for a solid-state imaging device.

[13] A solid-state imaging device comprising the near infrared cut filter according to any one of [1] to [12].

[14] A camera module comprising the near infrared cut filter according to any one of [1] to [12].

[15] A method for producing a near-infrared cut filter comprising a step of forming a dielectric multilayer film on at least one side of a substrate having a transparent resin layer containing a near-infrared absorbent, wherein the near-infrared cut filter satisfies the following requirement (a) Characterized by a method for manufacturing a near infrared cut filter:

(a) In the region of a wavelength of 600 to 800 nm, in the region of a wavelength of 700 to 1200 nm and the value of the shortest wavelength (Xa) in which the transmittance is 50% when measured from the vertical direction of the substrate, The absolute value | Xa-Xb | of the difference from the value (Xb) of the longest wavelength at which the transmittance is 50% when measured from the vertical direction of is 120 nm or more.

According to the present invention, it is possible to provide a near-infrared cut filter having excellent near-infrared cut characteristics, low incidence of angle of incidence, excellent transmittance characteristics in the visible wavelength region and a reduction effect of multiple reflections in the near-infrared wavelength region.

1 is a schematic diagram showing that light reflected multiple times between a near-infrared cut filter and a lens enters a solid-state imaging device.
Fig. 2A is a schematic diagram showing a method of measuring transmittance when measured from the vertical direction of a near infrared cut filter. 2B is a schematic diagram showing a method of measuring transmittance when measured from an angle of 30 ° with respect to the vertical direction of the near infrared cut filter. Fig. 2 (c) is a schematic diagram showing a method of measuring reflectance when measured from an angle of 30 ° with respect to the vertical direction of the near infrared cut filter.
3 (a) and 3 (b) are schematic diagrams showing examples of preferred configurations of the near-infrared cut filter of the present invention.
4 is a spectral transmission spectrum of the substrate obtained in Example 1.
5 (a) is a spectroscopic reflection spectrum when measured from an angle of 5 ° with respect to the vertical direction of the dielectric multilayer film (I) formed in Example 1, and FIG. 5 (b) is formed in Example 1 Spectral reflection spectrum when measured from an angle of 5 ° with respect to the vertical direction of the dielectric multilayer film (II).
6 is a spectral transmission spectrum of the near infrared cut filter obtained in Example 1.
FIG. 7 shows the near-infrared cut filter obtained in Example 1, measured from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter when the light incident surface is the dielectric multilayer film (II) (second optical layer) side. Spectral reflection spectrum.
8 is a spectral transmission spectrum of the substrate obtained in Example 2.
9 is a spectral transmission spectrum of the near infrared cut filter obtained in Example 2.
FIG. 10 shows the near-infrared cut filter obtained in Example 2, measured from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter when the light incident surface is the dielectric multilayer film (IV) (second optical layer) side. Spectral reflection spectrum.
11 is a schematic view for explaining the evaluation of color sense of camera images performed in Examples and Comparative Examples.

Hereinafter, the present invention will be described in detail.

[Near infrared cut filter]

The near-infrared cut filter according to the present invention includes a base material (i) having a transparent resin layer containing a near-infrared absorbent, and a dielectric multilayer film formed on at least one side of the base material (i), and further complies with the following requirement (a). It is characterized by meeting.

Requirements (a); In the region of the wavelength of 600 to 800 nm, in the region of the shortest wavelength (Xa) where the transmittance is 50% when measured from the vertical direction of the substrate (i), and in the region of the wavelength of 700 to 1200 nm, the When measured from the vertical direction of the substrate (i), the absolute value (absorption half value width) | Xa-Xb | of the difference from the value (Xb) of the longest wavelength at which the transmittance is 50% is 120 nm or more.

The near-infrared cut filter of the present invention is excellent in near-infrared cut characteristics, has less dependence on incident angle, and has excellent transmittance characteristics in the visible wavelength region and a reduction effect of multiple reflections in the near-infrared wavelength region.

Moreover, the transmittance | permeability in the area | region of wavelength Xa-Xb is a near-infrared cut filter excellent in the multiple reflection reduction effect of a near-infrared area, when the value is large.

When the near-infrared cut filter of the present invention is used for a solid-state imaging element, it is preferable that the transmittance of the near-infrared wavelength region is low. Particularly, it is known that a region having a wavelength of 700 to 1000 nm has a relatively high light-receiving sensitivity of a solid-state imaging element, and by reducing the transmittance of this wavelength region, it is possible to effectively correct the visibility of a camera image and a human eye, and to achieve excellent color reproduction. Can achieve.

The near-infrared cut filter of the present invention has an average transmittance of 5% or less, preferably 4% or less, more preferably 3% or less, when measured from the vertical direction of the filter in a region having a wavelength of 700 to 1000 nm, Especially preferably, it is 2% or less. When the average transmittance of a wavelength of 700 to 1000 nm is in this range, near-infrared rays can be sufficiently cut and excellent color reproducibility can be achieved, which is preferable.

When the near-infrared cut filter of the present invention is used for a solid-state imaging element or the like, it is preferable that the visible light transmittance is high. Specifically, in the region of the wavelength of 430 to 580 nm, the average transmittance when measured from the vertical direction of the near infrared cut 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 in this wavelength range is within this range, excellent imaging sensitivity can be achieved when the near-infrared cut filter of the present invention is used as a solid-state imaging device.

It is preferable that the near-infrared cut filter of this invention further satisfies the following requirement (b).

Requirement (b); In the range of wavelengths 560 to 800 nm, the shortest wavelength value (Ya) in which the transmittance when measured from the vertical direction of the near-infrared cut filter is 50%, and from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter When measured, the absolute value | Ya-Yb | of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% is less than 15 nm.

The absolute value | Ya-Yb | is more preferably less than 10 nm, particularly preferably less than 5 nm. When a near-infrared cut filter that satisfies requirement (b) is used as a solid-state imaging element, the change in transmittance depending on the angle of incidence becomes small, so that the color shading of the image becomes good. Such a near-infrared cut filter is obtained by forming a dielectric multilayer film on the substrate (i).

In the near-infrared cut filter as described above, the value of L ^*, the value of a ^{* and} the value of b ^{* in} the L ^* a ^* b ^* colorimetric system are preferred values. Here, the "L ^* a ^* b ^* colorimetric system" is established by the International Lighting Commission (CIE). "L ^* " is called "brightness index" and represents brightness, and "a ^* " and "b ^* " are called "chromaticness index" and indicate positions corresponding to color and saturation. For the color and saturation, if the value of a ^* is negative, it becomes a green color, and if the value of a ^* is positive, it becomes a red color. In addition, if the value of b ^* is negative, it becomes a blue color, and when the value of b ^* is positive, it becomes a yellow color. The L ^* a ^* b ^* colorimeter "a ^* value", "b ^* value" and "L ^* value" of the near infrared cut filter, when used in the camera module, affect the brightness and color of the camera image. Therefore, it is preferable that it is in the range of a certain value.

In the present invention, the "L ^* value", "a ^* value", and "b ^* value" in the L ^* a ^* b ^* colorimetric system refer to a spectrophotometer "U-4100" manufactured by Hitachi High-Technologies Corporation. It is assumed that a value obtained by measuring transmittance of 380 to 780 nm from the vertical direction (incident angle 0 °) of the near-infrared cut filter is employed.

The value of L ^{* in} the L ^* a ^* b ^* colorimetric system is preferably 70 or more, and more preferably 80 or more. When a near-infrared cut filter in which the value of L ^* is in this range is used as a solid-state imaging element, visual evaluation of color reproducibility of the resulting image shows good results.

The value of a ^{* in} the L ^* a ^* b ^* colorimetric system is preferably -31 or more and 5 or less, more preferably -25 or more and -2 or less, and even more preferably -21 or more and -5 or less. In addition, the value of b ^{* in} the L ^* a ^* b ^* colorimetric system is preferably -5 or more and 10 or less. When the values of a ^* and b ^{* in} the L ^* a ^* b ^* colorimetric system are within this range, visual evaluation of the color reproducibility of the resulting image shows good results.

The L ^* a ^* b ^* colorimetric system can also be used as an index for color shading of an image. The value of L ^* when the transmittance of 380 to 780 nm was measured from the angle of 30 ° (incident angle 30 °) in the vertical direction of the near-infrared cut filter to obtain a value in the L ^* a ^* b ^* colorimetric system, as described above, The value of a ^{* and} the value of b ^* are set to "L ^* value (30 °)", "a ^* value (30 °)" and "b ^* value (30 °)", respectively, and the incident angle is 0 °. The absolute value of the difference from each value in | ΔL ^* |, | Δa ^* | And | Δb ^* | are calculated from the following equation.

| ΔL ^* | = | (Value of L ^* (30 °))-(Value of L ^* ) |

| Δa ^* | = | (value of a ^* (30 °))-(value of a ^* ) |

| Δb ^* | = | (value of b ^* (30 °))-(value of b ^* ) |

| Δa ^* | calculated in the above formula is preferably 9 or less, more preferably 3 or less, and | Δb ^* | calculated in the above formula is preferably 9 or less, more preferably 3 or less. | Δa ^* | And when a near-infrared cut filter in which | Δb ^* | is within the above range is used as a solid-state imaging device, visual evaluation of color reproducibility of the resulting image shows good results.

The near-infrared cut filter of the present invention relates to the lens-side surface of the substrate (i), and since the reflectance in the region of 700 to 800 nm in wavelength is low, reflection of light between the near-infrared cut filter and the lens can be reduced.

In the region of 700 to 800 nm in wavelength, the lowest value of reflectance when measured from an angle of 30 ° with respect to the vertical direction of at least one side of the near infrared cut filter is preferably 80% or less, more preferably 50% or less , Particularly preferably 10% or less. When the reflectance is in this range, it is preferable because it tends to reduce various ghosts originating from multiple reflected light, especially when used in a solid-state imaging element.

Here, the ghost intensity by multiple reflections will be described with reference to FIG. 1. The light transmitted through the lens 4 is partially reflected (reflected light 3A) on the near-infrared cut filter 1, further reflected from the lens surface (reflected light 3B), and the near-infrared cut filter 1 is applied. Transmitted (transmitted light 3C) reaches the surface of the sensor 5. Therefore, the ghost intensity due to multiple reflections between the near-infrared cut filter and the lens is (a)% of the average reflectance measured from the direction of 30 ° in the vertical direction of the near-infrared cut filter at 700 to 850 nm (a)%, 700 to 850 nm. When the average reflectance of the lens in (b)% and the average transmittance of the near-infrared cut filter measured from the direction of 30 ° in the vertical direction at 700 to 850 nm are (c)%, it can be calculated by the following equation.

[Ghost strength] = (a) × (b) × (c)

In the present invention, the average reflectance (b) of the lens at 700 to 850 nm is calculated as 1%.

The ghost intensity by multiple reflections calculated in the above formula is preferably 0.300 or less, more preferably 0.100 or less, and even more preferably 0.060 or less. When such a ghost-intensity near-infrared cut filter is used in a camera, visual evaluation of the color reproducibility of the obtained image shows good results.

The thickness of the near-infrared cut filter of the present invention may be appropriately selected depending on the intended use, but according to the flow of thinning and lightening of the solid-state imaging device of recent years, it is preferable that the thickness of the near-infrared cut filter of the present invention is also thin. Since the near-infrared cut filter of this invention contains the said base material (i), thickness reduction is possible.

The thickness of the near-infrared cut filter of the present invention is, for example, preferably 200 μm or less, more preferably 180 μm or less, still more preferably 150 μm or less, particularly preferably 120 μm or less, and the lower limit is particularly Although not limited, it is preferred to be, for example, 20 μm.

If the thickness of the resinous substrate is within the above range, the near-infrared cut filter using the substrate can be downsized and light-weighted, and can be suitably used for various applications such as a solid-state imaging device. Particularly, when the above-mentioned resinous substrate is used for a lens unit such as a camera module, it is preferable because reduction of the lens unit can be realized.

[Substrate (i)]

The said base material (i) has a transparent resin layer containing a near infrared absorber. Examples of the near-infrared absorbing agent include, for example, a squarylium-based compound (A) having an absorption maximum at a wavelength of 650 to 750 nm (hereinafter also referred to as "compound (A)") and a compound having an absorption maximum at a wavelength of 660 to 850 nm ( B) (except the said compound (A). It is also called "compound (B)" below.) Etc. are mentioned.

The base material (i) may be a single layer or multiple layers. When the base material (i) is a single layer, for example, a base material comprising a transparent resin substrate (ii) containing the compound (A) and the compound (B) is mentioned, and the transparent resin substrate (ii) is the above. It becomes a transparent resin layer. When the base material (i) is a multi-layer, for example, a transparent support such as an overcoat layer containing a curable resin containing compound (A) and compound (B) on a support such as a glass support or a resin support serving as a base A substrate on which a resin layer is laminated, a substrate on which a resin layer such as an overcoat layer containing a curable resin containing compound (A), etc. is laminated on a substrate (iii) made of a transparent resin containing a compound (B), a compound (A) ), A base material on which a resin layer such as an overcoat layer containing a curable resin containing compound (B) or the like is laminated on a substrate (iv) made of a transparent resin containing compound, transparent containing compound (A) and compound (B) And a substrate on which a resin layer such as an overcoat layer containing a curable resin or the like is laminated on a resin substrate (ii). Compound (A) in view of the ease of adjusting the manufacturing cost and the optical properties, further improving the scratch-removal effect of the resin support or the transparent resin substrate (ii), and improving the scratch resistance of the substrate (i) Particularly preferred is a substrate in which a resin layer such as an overcoat layer containing a curable resin is laminated on a transparent resin substrate (ii) containing a compound (B).

Hereinafter, a layer containing at least one near-infrared absorbent and a transparent resin is also referred to as a “transparent resin layer”, and other resin layers are simply referred to as a “resin layer”.

The absolute value | Xa-Xb | in the above-mentioned requirement (a) is preferably 120 nm or more, more preferably 160 nm or more, particularly preferably 180 nm or more. When | Xa-Xb | of the substrate (i) is in this range, when a dielectric multilayer film is formed on the substrate (i), the reflectance around 700 to 800 nm can be reduced. Reflection can be reduced. In particular, when used for a solid-state imaging element, there is a tendency to reduce various ghosts originating from multiple reflected light.

In the region of the wavelengths Xa to Xb, the average value (Ta) of transmittance when measured from the vertical direction of the substrate (i) is preferably 35% or less, more preferably 30% or less, still more preferably 25 % Or less, particularly preferably 20% or less. When (Ta) of the base material (i) is in such a range, when a dielectric multilayer film is formed on the base material (i), the reflectance around 700 to 800 nm can be more suitably reduced. In particular, when used for a solid-state imaging device, there is a tendency to reduce various ghosts derived from multiple reflected light.

<Near infrared absorbent>

The near-infrared absorbent is not particularly limited as long as it is a compound having a maximum absorption at a wavelength of 650 nm or more and 850 nm or less, but is preferably a solvent-soluble dye compound from the viewpoint of suppressing aggregation in the resin. Examples of such near infrared absorbers include squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds. In the present invention, it is preferable to include the compound (A) and the compound (B) as a near infrared absorber.

≪Compound (A) ≫

The compound (A) is not particularly limited as long as it is a squarylium compound having an absorption maximum at a wavelength of 650 to 750 nm. The squarylium-based compound has excellent visible light transmittance, steep absorption characteristics, and high molar absorption coefficient, but may generate fluorescence that causes scattered light when absorbing light. In such a case, by using the compound (A) and the compound (B) in combination, a near-infrared cut filter with less scattered light and better camera quality can be obtained.

The maximum absorption wavelength of the compound (A) is preferably 650 to 748 nm, more preferably 655 to 745 nm, particularly preferably 660 to 740 nm.

As a specific example of compound (A), it is preferable to contain at least 1 sort (s) selected from the group which consists of the squarylium-type compound represented by Formula (A-I) and the squarylium-type compound represented by Formula (A-II). Hereinafter, it is also called "compound (A-I)" and "compound (A-II)", respectively.

In formula (AI), R ^a , R ^b and Y satisfy the following conditions (Ai) or (A-ii).

Condition (A-i)

A plurality of R ^a each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, or a -L ¹ or -NR ^e R ^f group. R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e .

The plural R ^bs each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, or a -L ¹ or -NR ^g R ^h group. R ^g and R ^h are each independently a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C (O) R ⁱ group (R ⁱ is -L ^a ,- L ^b , -L ^c , -L ^d or -L ^e .).

The plural Ys each independently represent a -NR ^j R ^k group. R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e .

L ¹ is L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h .

The L ^a to L ^h is,

(L ^a ) an aliphatic hydrocarbon group having 1 to 9 carbon atoms which may have ^a substituent L,

(L ^b ) a halogen-substituted alkyl group having 1 to 9 carbon atoms which may have a substituent L,

(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L,

(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L,

(L ^e ) a heterocyclic group having 3 to 14 carbon atoms which may have a substituent L,

(L ^f ) an alkoxy group having 1 to 9 carbon atoms which may have a substituent L,

(L ^g ) an acyl group having 1 to 9 carbon atoms which may have a substituent L or

(L ^h ) An alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L

Indicates.

The substituent L is a group consisting of an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen substituted alkyl group having 1 to 9 carbon atoms, 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. It is at least one selected from.

The L ^a to L ^h may further have at least one atom or group selected from the group consisting of halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphoric acid group and amino group.

As for L ^a to L ^h , the total number of carbon atoms including a substituent is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the number of carbon atoms is more than this range, the synthesis of the dye may be difficult, and the absorption strength per unit weight tends to decrease.

Condition (A-ii)

At least one of two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a heterocycle having 5 or 6 constituent atoms containing at least one nitrogen atom, and the heterocycle is a substituent. which may have been, it is not involved in the formation of the R ^b and R ^a is a heterocyclic ring, are each independently the same meaning as R ^b, and R ^a of the (Ai).

In formula (A-II), X represents O, S, Se, NR ^c or CR ^d R ^d ; A plurality of R ^c each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ; A plurality of R ^d each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a -L ¹ or -NR ^e R ^f group, and adjacent R ^d groups are linked to each other to be a substituent. You may form a ring which may have; L ^a to L ^e , L ¹ , R ^e and R ^f have the same meanings as L ^a to L ^e , L ¹ , R ^e and R ^f defined in the formula (AI).

Compound (AI) and compound (A-II) are in addition to the following formulas (AI-1) and formulas (A-II-1) and the following formula (AI-2) and formula (A-) The structure can also be represented by a description method taking a resonance structure as in II-2). That is, the difference between the following formula (AI-1) and the following formula (AI-2), and the difference between the following formula (A-II-1) and the following formula (A-II-2) are only methods for describing the structure, As a compound, any of them shows the same thing. In the present invention, unless otherwise specified, the structure of the squarylium-based compound is represented by the following description methods (A-I-1) and (A-II-1).

The structure of the compound (I) and the compound (A-II) is not particularly limited as long as the requirements of the formula (AI) and the formula (A-II) are satisfied, respectively. For example, the formula (AI-1) and When the structure is represented as in the formula (A-II-1), the left and right substituents bonded by the central four-membered ring may be the same or different, but the same is preferable because it is easy for synthesis. In addition, for example, the compound represented by the following formula (A-I-3) and the compound represented by the following formula (A-I-4) can be regarded as the same compound.

The content of the compound (A) is as the base (i), for example, a base containing a transparent resin substrate (ii) containing the compound (A) and the compound (B), or the compound (A) containing the When using a base material on which a resin layer such as an overcoat layer containing a curable resin containing compound (B) or the like is laminated on a transparent resin substrate (iv), preferably 0.01 parts by weight with respect to 100 parts by weight of the transparent resin. To 2.0 parts by weight, more preferably 0.015 to 1.50 parts by weight, particularly preferably 0.02 to 1.00 parts by weight. Further, as the base material (i), a base material in which a transparent resin layer such as an overcoat layer containing a curable resin containing a compound (A) and a compound (B) is laminated on a glass support or a base resin-made support, or When using a base material on which a transparent resin layer such as an overcoat layer containing a curable resin containing compound (A) or the like is laminated on a substrate (iii) made of transparent resin containing compound (B), compound (A) It is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.5 parts by weight, and particularly preferably 0.3 to 4.0 parts by weight with respect to 100 parts by weight of the resin forming the transparent resin layer comprising a.

≪Compound (B) ≫

The compound (B) is not particularly limited as long as it has an absorption maximum at a wavelength of 660 to 850 nm, but is preferably a solvent-soluble dye compound, a squarylium compound, a phthalocyanine compound, a cyanine compound, a naphthalocyanine compound, and It is more preferable that it is at least 1 sort (s) selected from the group which consists of a croconium type compound, and it is still more preferable that it is a squarylium type compound and a phthalocyanine type compound. By using such a compound (B), it is possible to simultaneously achieve high near-infrared cut characteristics and good visible light transmittance near the absorption maximum.

The maximum absorption wavelength of the compound (B) is preferably 680 to 830 nm, more preferably 700 to 820 nm, particularly preferably 720 to 800 nm. When the absorption maximum wavelength of the compound (B) is in this range, unnecessary near-infrared rays that cause various ghosts can be efficiently cut.

Although the structure is not specifically limited as said phthalocyanine type compound, For example, the compound represented by following formula (III) is mentioned.

In formula (III), M represents a substituted metal atom containing two hydrogen atoms, two monovalent metal atoms, a bivalent metal atom, or a trivalent or tetravalent metal atom,

A plurality of R _a , R _b , R _c and R _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ ,- SL ² , -SS-L ² , -SO ₂ -L ³ , -N = NL ⁴ , or _a combination of at least one of R _a and R _b , R _b and R _c and R _c and R _d , At least one group selected from the group consisting of groups represented by (A) to (H), and at least one of R _a , R _b , R _c and R _d bonded in the same aromatic ring is not a hydrogen atom.

The amino group, amide group, imide group and silyl group may have a substituent L defined in the formula (A-I),

L ¹ has the same meaning as L ¹ defined in the formula (I),

L ² represents a hydrogen atom or any of L ^a to L ^e defined in the formula (AI),

L ³ represents a hydroxyl group or any of the above L ^a to L ^e ,

L ⁴ represents any of the above L ^a to L ^e .

In formulas (A) to (H), the combination of R _x and R _y is a combination of R _a and R _b , R _b and R _c or R _c and R _d ,

A plurality of R _A to R _L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = NL ⁴ ,

The amino group, amide group, imide group and silyl group may have the substituent L, and L ¹ to L ⁴ have the same meanings as L ¹ to L ⁴ defined in the formula (III).

Although the structure is not specifically limited as said naphthalocyanine type compound, For example, the compound represented by following formula (IV) is mentioned.

In formula (IV), M has the same meaning as M in formula (7), and R _a , R _b , R _c , R _d , R _e and R _f are each independently a hydrogen atom, a halogen atom, a hydroxyl group, Carboxyl group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = NL ⁴ .

Although the structure is not specifically limited as said cyanine type compound, For example, the compound represented by following formula (V-1)-(V-3) is mentioned.

In formulas (V-1) to (V-3), X _a ^- represents a monovalent anion,

A plurality of D's independently represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom,

A plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, Imide group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = NL ⁴ , or R _b and R _c , R _d and R _e , R at least 1 selected from the group consisting of groups represented by the following formulas (A) to (H), wherein a combination of at least one of _e and R _f , R _f and R _g , R _g and R _h and R _h and R _i is combined, Represents the species group,

The amino group, amide group, imide group and silyl group may have a substituent L defined in the formula (A-I),

L ¹ has the same meaning as L ¹ defined in the formula (AI),

L ² represents a hydrogen atom or any of L ^a to L ^e defined in the formula (AI),

L ³ represents a hydrogen atom or any of the above L ^a to L ^e ,

L ⁴ represents any of the above L ^a to L ^e ,

Z _a to Z _d and Y _a to Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = NL ⁴ (L ¹ to L ⁴ have the same meanings as L ¹ to L ⁴ in R _a to R _i above), or,

A 5-6 membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, oxygen atom, or sulfur atom formed by bonding between Z or Y selected from two adjacent groups,

An aromatic hydrocarbon group having 6 to 14 carbon atoms, formed by bonding between Z or Y selected from two adjacent groups, or

Z or Y selected from two adjacent groups is formed by bonding to each other, and represents a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms, which contains at least one nitrogen atom, oxygen atom, or sulfur atom, and these alicyclic hydrocarbon groups, The aromatic hydrocarbon group and the heteroaromatic hydrocarbon group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

In the formulas (A) to (H), the combination of R _x and R _y is R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h and R is a combination of _h and R _i ,

A plurality of R _A to R _L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS- L ² , -SO ₂ -L ³ or -N = NL ⁴ (L ¹ to L ⁴ have the same meaning as L ¹ to L ⁴ defined in the above formulas (V-1) to (V-3).) It represents, and said amino group, amide group, imide group, and silyl group may have the said substituent L.

As said squarylium dye, the compound represented by following formula (VI) is mentioned, for example.

In formula (VI), 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, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -NR ^g R ^h group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ Group or any of the following L ^a to L ^h , R ^g and R ^h each independently represent a hydrogen atom, -C (O) R ⁱ group or any of the following L ^a to L ^e , and R ⁱ L ^a to L ^e are shown.

(L ^a ) C1-C12 aliphatic hydrocarbon group

(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 ) Aromatic hydrocarbon group having 6 to 14 carbon atoms

(L ^e ) Heterocyclic group having 3 to 14 carbon atoms

(L ^f ) C1-C12 alkoxy group

(L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L,

(L ^h ) An alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L

The substituent L is composed of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. It is at least 1 sort (s) selected from a group.

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

As R ² to R ⁷ , preferably, each independently hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group , Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t- Butanoylamino group, cyclohexanoylamino group, n-butylsulfonyl group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, It is a dimethylamino group, a nitro group, an acetylamino group, a propionylamino group, a trifluoromethanoylamino group, a pentafluoroethanoylamino group, a t-butanoylamino group, and a cyclohexinoylamino group.

The R ⁸ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, or a phenyl group, more preferably Hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group.

As said X, Preferably it is an oxygen atom and a sulfur atom, Especially preferably, it is an oxygen atom.

The compound (VI) can also exhibit a structure in addition to a description method as in the following formula (VI-1), in a description method taking a resonance structure as in the following formula (VI-2). That is, the difference between the following formula (VI-1) and the following formula (VI-2) is only a method for describing the structure, and both represent the same compound. In the present invention, unless specifically stated, the structure of the squarylium-based compound is represented by the following method described in formula (VI-1).

In addition, for example, the compound represented by the following formula (VI-1) and the compound represented by the following formula (VI-3) can be regarded as the same compound.

The structure of the compound (VI) is not particularly limited as long as the requirements of the formula (VI-1) are satisfied. The left and right substituents bonded to the central four-membered ring may be the same or different, but the same is preferable because it is easy for synthesis.

The compound (B) may be used alone or in combination of two or more. In addition, the content of the compound (B) is, as the base (i), for example, a base comprising a transparent resin substrate (ii) containing the compound (A) and the compound (B), or the compound (B) When using a base material in which a resin layer such as an overcoat layer containing a curable resin containing the compound (A) or the like is laminated on the containing transparent resin substrate (iii), preferably 100 parts by weight of the transparent resin Is 0.003 to 2.0 parts by weight, more preferably 0.0005 to 1.8 parts by weight, particularly preferably 0.008 to 1.5 parts by weight. Further, as the base material (i), a base material in which a transparent resin layer such as an overcoat layer containing a curable resin containing a compound (A) and a compound (B) is laminated on a glass support or a base resin-made support, or When using a substrate on which a resin layer such as an overcoat layer containing a curable resin containing compound (B) or the like is laminated on a substrate (iv) made of transparent resin containing compound (A), compound (A) is used. It is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.0 parts by weight, and particularly preferably 0.3 to 3.0 parts by weight with respect to 100 parts by weight of the resin forming the containing transparent resin layer. When the content of the compound (B) is within the above range, a near-infrared cut filter having both good near-infrared absorption properties and high visible light transmittance can be obtained.

<Other pigments (X)>

The said base material (i) may further contain other pigment | dye (X) which does not correspond to a compound (A) and a compound (B).

The other dye (X) is not particularly limited as long as the absorption maximum wavelength is less than 650 nm or more than 850 nm, for example, a squarylium compound, a phthalocyanine compound, a cyanine compound, a naphthalocyanine compound, and a croconium system. And at least one compound selected from the group consisting of a compound, an octapyrine-based compound, a dimonium-based compound, a perylene-based compound, and a metal dithiolate-based compound. By using such other dye (X), it is possible to absorb a wider range of near infrared light and lower the transmittance of the near infrared region.

<Transparent resin>

The transparent resin layer and the transparent resin substrates (ii) to (iv) laminated on a resin support or a glass support can be formed using a transparent resin. As the transparent resin used for the base material (i), one type may be used alone, or two or more types may be used.

The transparent resin is not particularly limited as long as it does not impair the effects of the present invention, but, for example, ensures thermal stability and formability to a film, and also applies a dielectric multilayer film by high-temperature deposition performed at a deposition temperature of 100 ° C or higher. In order to form a film that can be formed, a resin having a glass transition temperature (Tg) of preferably 110 to 380 ° C, more preferably 110 to 370 ° C, and even more preferably 120 to 360 ° C can be mentioned. Further, the glass transition temperature of the resin is 140 ° C or higher, which is particularly preferable because a film capable of vapor-depositing a dielectric multilayer film at a higher temperature is obtained.

As a transparent resin, in the case of forming a resin plate having a thickness of 0.1 mm containing the resin, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95%. , Particularly preferably, it can be used a resin of 80 to 95%. When a resin having a total light transmittance in this range is used, the resulting substrate exhibits good transparency as an optical film.

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

As transparent resin, for example, cyclic (poly) olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, poly Amide (aramid) resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamide imide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (Modified) acrylic resin, epoxy resin, allyl ester-based curable resin, silsesquioxane-based ultraviolet curable resin, acrylic ultraviolet curable resin and vinyl-based ultraviolet curable resin.

≪Channel (poly) olefin resin≫

As the cyclic (poly) olefin-based resin, hydrogen obtained from a resin obtained from at least one monomer selected from the group consisting of monomers represented by the following formula (X ₀ ) and monomers represented by the following formula (Y ₀ ) and hydrogenation of the resin The resin obtained by doing so is preferable.

In the formula (X ₀ ), R ^x1 to R ^x4 each independently represent an atom or group selected from the following (i ') to (ix'), and k ^x , m ^x and p ^x are each independently 0 or Represents a positive integer.

(i ') hydrogen atom

(ii ') halogen atom

(iii ') trialkylsilyl group

(iv ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom

(ｖ ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms

(vi ') Polar group (except (iv'))

(vii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are alkylidene groups formed by bonding to each other (however, R ^x1 to R ^{x4 which} are not involved in the bonding are independently the above (i') to ( vi ') represents an atom or group.)

(viii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are a monocyclic or polycyclic hydrocarbon ring or heterocycle formed by bonding to each other (however, R ^x1 to R ^{x4 which} are not involved in the bond are independently independently It represents an atom or group selected from (i ') to (vi').)

(ix ') R ^x2 and R ^x3 are a monocyclic hydrocarbon ring or a heterocycle formed by bonding to each other (however, R ^x1 and R ^{x4 which} are not involved in the bond are independently the above (i') to (vi ') ) Represents an atom or group.)

In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from (i ') to (vi'), or R ^y1 and R ^y2 are monocyclic or formed by bonding to each other. The ring represents an alicyclic hydrocarbon, an aromatic hydrocarbon or a heterocycle, and k ^y and p ^y each independently represent 0 or a positive integer.

≪Aromatic polyether-based resin≫

It is preferable that the aromatic polyether-based resin has at least one structural unit selected from the group consisting of structural units represented by the following formula (1) and structural units represented by the following formula (2).

In Formula (1), R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represent an integer of 0 to 4.

In Formula (2), R ¹ to R ⁴ and a to d are each independently the same meaning as R ¹ to R ⁴ and a to d in Formula (1), and Y is a single bond, -SO ₂ -or > C = O, 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 an integer of 0 to 4, m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

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

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

In Formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently the same meaning as 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 the same as R ⁵ , R ⁶ , Z, n, e and f in the formula (3).

≪Polyimide-based resin≫

The polyimide-based resin is not particularly limited, and may be a polymer compound containing an imide bond in a repeating unit. For example, it is described in JP-A-2006-199945 or JP-A-2008-163107 It can be synthesized in any way.

≪Fluene polycarbonate-based resin≫

The fluorene polycarbonate-based resin is not particularly limited and may be a polycarbonate resin containing a fluorene moiety, and can be synthesized by, for example, the method described in Japanese Patent Laid-Open No. 2008-163194. have.

≪Fluene polyester-based resin≫

The fluorene polyester-based resin is not particularly limited and may be a polyester resin containing a fluorene moiety, for example, described in Japanese Patent Laid-Open No. 2010-285505 or Japanese Patent Laid-Open No. 2011-197450 It can be synthesized in any way.

≪Fluorinated aromatic polymer-based resin≫

The fluorinated aromatic polymer-based resin is not particularly limited, but an aromatic ring having at least one fluorine atom and at least one bond selected from the group consisting of ether bonds, ketone bonds, sulfone bonds, amide bonds, imide bonds, and ester bonds are used. It is preferably a polymer containing a repeating unit, and can be synthesized by, for example, the method described in Japanese Patent Laid-Open No. 2008-181121.

≪Acrylic UV Curable Resin≫

Although it does not specifically limit as an acryl-type ultraviolet curable resin, What synthesize | combines from the resin composition containing the compound which has one or more acryl group or methacryl group in a molecule | numerator, and a compound which decompose | disassembles with ultraviolet rays to generate an active radical is mentioned. The acrylic ultraviolet-curable resin contains, as the base material (i), a base material on which a transparent resin layer containing a compound (B) and a curable resin is laminated, or a compound (B) on a glass support or a base made of a resin. When using a base material in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated on a transparent resin substrate (ii), it can be particularly suitably used as the curable resin.

≪Commercial product≫

The following commercially available products etc. are mentioned as a commercial item of transparent resin. As a commercial item of a cyclic (poly) olefin resin, Atone manufactured by JSR Co., Ltd., Zeonoa manufactured by Nippon Xeon Co., Ltd., APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Co., Ltd. are listed. As a commercial item of polyethersulfone-based resin, Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. may be mentioned. As a commercial item of a polyimide-type resin, Mitsubishi Gas Chemical Co., Ltd. Neoprene L etc. are mentioned. As a commercial product of the polycarbonate-based resin, Teijin Co., Ltd. pure ace, etc. may be mentioned. Examples of commercially available products of the fluorene polycarbonate-based resin include Mitsubishi Gas Chemical Co., Ltd. Yupi Zeta EP-5000 and the like. As a commercial item of a fluorene-polyester resin, OKP4HT by Osaka Gas Chemical Co., Ltd. is mentioned. As a commercial item of an acrylic resin, Nippon Shokubai Corporation's Arc Reviewer etc. are mentioned. As a commercial item of silsesquioxane-type ultraviolet curable resin, Shin Plus, Inc., Silplus, etc. are mentioned.

<Other ingredients>

The base material (i) may further contain additives such as an antioxidant, a near-ultraviolet absorber, a fluorescent matting agent, and a metal complexing system compound within a range not impairing the effects of the present invention. These other components may be used alone or in combination of two or more.

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

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenyl And methane and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

In addition, these additives may be mixed with a resin or the like when manufacturing the substrate (i), or may be added when synthesizing the resin. The amount of addition is appropriately selected depending on 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.

<Manufacturing method of substrate (i)>

When the substrate (i) is a substrate comprising the transparent resin substrates (ii) to (iv), the transparent resin substrates (ii) to (iv) are, for example, by melt molding or cast molding. It can be formed, and further, if necessary, after molding, by coating a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent, a substrate on which an overcoat layer is laminated can be produced.

When the base material (i) is a base material on which a transparent resin layer such as an overcoat layer containing a curable resin containing a compound (A) and a compound (B) is laminated on a glass support or a resin base material serving as a base, For example, the resin solution containing the compound (A) and the compound (B) is melt-cast or cast-formed on a glass support or a resin support serving as a base, and is preferably coated by a method such as spin coat, slit coat, inkjet or the like. After that, the solvent is dried and removed, and if necessary, light irradiation or heating is further performed, whereby a substrate having a transparent resin layer formed on a glass support or a resin support serving as a base can be produced.

≪Melting molding≫

As said melt-molding, specifically, the method of melt-molding the pellet obtained by melt-kneading resin, compound (A), compound (B), etc .; A method of melt-molding a resin composition containing a resin and a compound (A) and a compound (B); Or the method of melt-molding the pellet obtained by removing a solvent from the resin composition containing a compound (A), a compound (B), a resin, and a solvent etc. are mentioned. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫

As said cast molding, the method of casting a resin composition containing a compound (A), a compound (B), a resin, and a solvent on a suitable support body to remove a solvent; Or a method in which a curable composition comprising a compound (A), a compound (B), a photocurable resin and / or a thermosetting resin is cast on a suitable support to remove a solvent, and then cured by an appropriate method such as ultraviolet irradiation or heating. It can also be manufactured by.

When the said base material (i) is a base material containing the transparent resin substrate (ii) containing a compound (A) and a compound (B), the said base material (i) peels a coating film from a support body after cast molding. It can be obtained by, and the base material (i), such as an overcoat layer containing a curable resin containing a compound (A) and a compound (B) on a support such as a glass support or a resin support serving as a base. In the case where the transparent resin layer is a laminated base material, the base material (i) can be obtained by not casting the coating film after cast molding.

As said support body, the support body made from a glass plate, a steel belt, a steel drum, and a transparent resin (for example, polyester film, cyclic olefin resin film) is mentioned.

In addition, a transparent resin layer on the optical component, such as a method of drying the solvent by coating the resin composition on an optical component such as a glass plate, quartz or transparent plastic, or a method of coating and curing and drying the curable composition, etc. It can also form.

The amount of residual solvent in the transparent resin layer (transparent resin substrate (ii)) obtained by the above method is preferably as small as possible. Specifically, the residual solvent amount is preferably 3% by weight or less, more preferably 1% by weight or less, and even more preferably 0.5% by weight with respect to the weight of the transparent resin layer (transparent resin substrate (ii)). % Or less. When the residual solvent amount is in the above range, deformation and characteristics are hardly changed, and a transparent resin layer (transparent resin substrate (ii)) capable of easily exerting desired functions is obtained.

[Dielectric multilayer film]

The near-infrared cut 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 on both sides. When provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when provided on both sides, a near-infrared cut filter having high strength and difficult to bend or twist can be obtained. When the near-infrared cut filter is applied to the use of a solid-state imaging device, it is preferable to provide a dielectric multilayer film on both sides of the substrate (i), since it is preferable that the near-infrared cut filter has a small warp or twist.

It is preferable that the dielectric multilayer film has reflective properties over the entire range of 700 to 1100 nm in wavelength, more preferably having reflective properties over the entire range of 700 to 1150 nm in wavelength, particularly preferably 700 to 1200 nm. It is preferred. In the form of having a dielectric multilayer film on both sides of the substrate (i), a first optical layer having a reflection property mainly around 700 to 1150 nm in wavelength when measured from an angle of 30 ° with respect to the vertical direction of the near infrared cut filter is glass. A form having a second optical layer on one side of the substrate (i) having a support and having anti-reflective properties in the visible region on the other side (see Fig. 3 (a)), or the vertical direction of the near infrared cut filter When measured from an angle of 30 ° with respect to a wavelength of 700 to 950 nm, a third optical layer having mainly reflective properties is provided on one side of the substrate (i), and near infrared cut on the other side of the substrate (i) When measured from an angle of 30 ° with respect to the vertical direction of the filter, a form having a fourth optical layer mainly having reflection properties around 900 nm to 1150 nm (see Fig. 3 (b)) and the like can be mentioned.

In the near-infrared cut filter of the present invention, it is preferable that the substrate (i) has a glass support, and a dielectric multilayer film is preferably provided on both sides of the substrate (i), and these dielectric multilayer films are a near-infrared reflective film and a visible light antireflection film. It is more preferable, and it is particularly preferable to have a near-infrared reflective film on one surface of the substrate (i) and a visible light antireflection film on the other surface.

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. As such materials, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium oxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide or indium oxide, etc. are mainly used, and titanium oxide, tin oxide, and / or cerium oxide, etc. What contained a small amount (for example, 0-10 weight% with respect to a main component) is mentioned.

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

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

The thickness of each layer of the high-refractive-index material layer and the low-refractive-index material layer is usually 0.1 to 0.5λ when the near-infrared wavelength to be blocked is set to λ (nm). 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 film thickness at which the product (n × d) of the refractive index (n) and the film thickness (d) is calculated as λ / 4, and the thickness of each layer of the high refractive index material layer and the low refractive index material layer It becomes 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 properties of reflection and refraction.

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

In the present invention, according to the absorption characteristics of compound (A) or compound (B), the material species constituting the high-refractive-index material layer and the low-refractive-index material layer, the thickness of each layer of the high-refractive-index material layer and the low-refractive-index material layer, the stacking By appropriately selecting the order and the number of layers, it is possible to ensure sufficient transmittance in the visible region and then have sufficient light cut characteristics in the near-infrared wavelength region, and reduce reflectance when near-infrared rays enter from the oblique direction.

Here, in order to optimize the above conditions, for example, by using an optical thin film design software (eg, Essential Macleod, manufactured by Thin Film Center), the anti-reflection effect in the visible region and the light cut effect in the near-infrared region are compatible. Parameter. In the case of the above software, for example, in the design of the first optical layer, the target transmittance of the wavelength of 400 to 700 nm is set to 100%, the value of the target tolerance is set to 1, and then the target of the wavelength of 705 to 950 nm. And a parameter setting method such as 0% transmittance and 0.5% target tolerance. These parameters may be further divided into finer wavelength ranges in accordance with various characteristics of the substrate (i) to change the target tolerance value.

[Other functional films]

The near-infrared cut filter of the present invention, between the substrate (i) and the dielectric multilayer film, the surface opposite to the surface on which the dielectric multilayer film is provided or the dielectric multilayer film substrate (i) between the substrate (i) and the dielectric multilayer film (i) ) On the surface opposite to the surface on which the substrate is provided, functions such as an antireflection film, a hard coat film or an antistatic film for the purpose of improving the surface hardness of the base material (i) or the dielectric multilayer film, improving chemical resistance, preventing anti-static and removing scratches A membrane can be appropriately provided.

The near-infrared cut filter of the present invention may include one layer including the functional film, or may include two or more layers. When the near-infrared cut filter of the present invention includes two or more layers including the functional film, two or more layers of the same layer may be included, or two or more layers of other layers may be included.

The method of laminating the functional film is not particularly limited, and a coating agent such as an antireflection agent, a hard coat agent, and / or an antistatic agent is applied to a base material (i) or a dielectric multilayer film, such as melt molding or cast molding. You can.

In addition, it can also be produced by applying a curable composition containing the coating agent or the like onto a substrate (i) or a dielectric multilayer film with a bar coater or the like, followed by curing by ultraviolet irradiation or the like.

Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins, and specifically, vinyl compounds, urethane, urethane acrylate, acrylate, epoxy and epoxy acrylics. And rate-based resins. As said curable composition containing these coating agents, vinyl type, urethane type, urethane acrylate type, acrylate type, epoxy type, and epoxy acrylate type curable composition etc. are mentioned.

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

In the curable composition, the blending ratio of the polymerization initiator is, when the total amount of the curable composition is 100% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, even more preferably 1 to 5 Weight percent. When the blending ratio of the polymerization initiator is in the above range, it is possible to obtain a functional film such as an antireflection film, a hard coat film or an antistatic film having excellent curing properties and handling properties of the curable composition and having a desired hardness.

Moreover, you may add an organic solvent as a solvent to the said curable composition, and a well-known thing can be used as an organic solvent. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene 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; And amides such as dimethylformamide, dimethylacetamide and N-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, particularly preferably 0.7 to 5 μm.

Further, for the purpose of enhancing the adhesion between the base material (i) and the functional film and / or the dielectric multilayer film, or the adhesion between the functional film and the dielectric multilayer film, corona treatment or plasma treatment is performed on the surface of the base material (i), the functional film or the dielectric multilayer film. You may perform surface treatment, such as.

[Method of manufacturing near infrared cut filter]

The manufacturing method of the near-infrared cut filter of this invention is characterized by including the process of forming a dielectric multilayer film on at least one surface of the said base material (i). The method of forming the dielectric multilayer film is as described above. Moreover, you may include the process of forming a functional film on the said base material (i) as needed.

In addition, when warpage occurs in the near-infrared cut filter when the dielectric multi-layer film is formed, in order to solve this, a dielectric multi-layer film is formed on both sides of the near-infrared cut filter, or ultraviolet rays or the like are formed on the surface on which the dielectric multi-layer film of the near-infrared cut filter is formed. And a method of irradiating electromagnetic waves. Moreover, when irradiating electromagnetic waves, you may irradiate during formation of a dielectric multilayer film, or you may irradiate separately after formation.

[Use of near infrared cut filter]

The near-infrared cut filter of the present invention has a wide viewing angle, and has excellent near-infrared cut 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 in 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, televisions, car navigation systems, portable information terminals, video game machines, mobile game machines, fingerprints Useful for authentication systems, digital music players, etc. It is also useful as a hot wire cut filter mounted on a glass plate such as a car or a building.

[Solid imaging device]

The solid-state imaging device of the present invention includes the near-infrared cut filter of the present invention. Here, the solid-state imaging device is an image sensor provided with a solid-state imaging element such as a CCD or CMOS image sensor, specifically, a digital still camera, a smartphone camera, a mobile phone camera, a wearable device camera, a digital video camera, and the like. Can be used for applications. For example, the camera module of the present invention includes the near infrared cut filter of the present invention.

Example

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples at all. In addition, "parts" means "parts by weight" unless otherwise specified. In addition, the measurement method of each physical property value and the evaluation method of 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 solubility in the solvent of each resin.

(a) Using a gel permeation chromatography (GPC) apparatus manufactured by Waters (WATERS) (type 150C, column: H-type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene), the weight average molecular weight (Mw) in terms of standard polystyrene ) And number average molecular weight (Mn) were measured.

(b) The weight average molecular weight (Mw) and number average molecular weight (Mn) of standard polystyrene conversion were measured using the Tosoh Corporation GPC apparatus (HLC-8220 type, column: TSKgelα-M, developing solvent: THF).

The resin synthesized in Resin Synthesis Example 3 described later was not measured for molecular weight by the above method, but was measured for logarithmic viscosity by the following method (c).

(c) A portion of the polyimide resin solution was added to anhydrous methanol to precipitate a polyimide resin, filtered and separated from unreacted monomers. 0.1 g of the polyimide obtained by vacuum drying at 80 ° C. for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. using a Canon-Penske viscometer was as follows. Asked by.

μ = {ln (t _s / t ₀ )} / C

t ₀ : time for flowing the solvent

t _s : Flow time of lean polymer solution

C: 0.5 g / dL

<Glass transition temperature (Tg)>

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

<Spectral transmittance>

The transmittance of the substrate and the transmittance and reflectance of the near-infrared cut filter were measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

Here, as a transmittance when measured from the vertical direction of the near-infrared cut filter, as shown in Fig. 2 (a), light transmitted perpendicularly to the filter is measured, and from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter. As a transmittance in the case of measurement, as shown in Fig. 2B, light transmitted at an angle of 30 ° with respect to the vertical direction of the filter was measured. In addition, as a reflectance when measured from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter, measurement was performed by setting a near-infrared cut filter on a jig attached to the apparatus as shown in Fig. 2 (c). In addition, the ghost intensity by multiple reflections between the near-infrared cut filter and the lens has an average reflectance (a) (%) measured from the direction of 30 ° in the vertical direction of the near-infrared cut filter at 700 to 850 nm, and 700 to 850 It was calculated as the product of the average transmittance (c) (%) of the near-infrared cut filter measured from the direction of 30 ° in the vertical direction in nm.

In addition, in the L ^* a ^* b ^* colorimetric system, "a ^* value", "b ^* value", "L ^* value", "a ^* value (30 °)", "b ^* value ( 30 °) ”and“ L ^* value (30 °) ”are values obtained by measuring the transmittance of 380 to 780 nm from the vertical direction (incident angle 0 °) of the near-infrared cut filter and 30 from the vertical direction of the near-infrared cut filter. The value obtained by measuring the transmittance of 380 to 780 nm from the angle of ° (incident angle 30 °) was adopted.

<Bending>

The near-infrared cut filter, which was chip-cut with a square of 5 mm on one side, was placed on the observation stage of "Digital Microscope VHX-600" manufactured by Keyence Co., Ltd., and observed from the side to measure the bending height of the end of the chip. It was evaluated as.

○○○: Bending height <20㎛

○○: 20㎛ ≤ height of warpage <40㎛

○: 40 µm ≤ bending height <60 µm

Δ: 60 μm ≤ height of warpage <80 μm

×: 80 μm ≤ height of warpage

<Evaluation of the color of the camera image>

Color evaluation when the optical filter was incorporated in the camera module was performed by the following method. A camera module was manufactured in the same manner as in Japanese Patent Laid-Open No. 2016-110067, and a 300 mm × 400 mm white plate was manufactured using the produced camera module using a D65 light source (X-Rite's standard light source device `` Macbeth Jersey II ”), And evaluated the color in the camera image based on the following criteria.

There is no problem at all, and the acceptable level is ○, and a slight difference in color tone is recognized. As a high-definition camera module, however, there is no practical problem, and the acceptable level is △. Due to this difference, it was judged that the level which was not allowable for general camera module use was ××.

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

[Synthesis example]

Compounds (A) and (B) used in the following examples were synthesized by a generally known method. As a general synthesis method, for example, Japanese Patent Publication No. 3366697, Japanese Patent Publication No. 2846091, Japanese Patent Publication No. 2864475, Japanese Patent Publication No. 3738696, Japanese Patent Publication No. 60-228448, Japanese Patent Publication Japanese Patent Publication No. 1-46846, Japanese Patent Publication No. Hei 1-228960, Japanese Patent Publication No. 4011149, Japanese Patent Publication No. 63-124054, "Pthalocyanine-Chemistry and Function" (IPC, 1997), Japanese Patent The method described in Japanese Unexamined Patent Publication No. 2007-169315, Japanese Patent Publication No. 2009-108267, Japanese Patent Publication No. 2010-241873, Japanese Patent Publication No. 3699464, Japanese Patent Publication No. 4740631, etc. may be mentioned. .

<Resin Synthesis Example 1>

(Hereinafter also referred to "DNM") the following formula (a) 8- methyl-8-methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodec-3-ene represented by 100 parts , 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel, and the solution was heated to 80 ° C. Subsequently, 0.2 parts of triethylaluminum toluene solution (0.6 mol / liter) and 0.9 parts of toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel as a polymerization catalyst. The ring-opening polymerization reaction was performed by heating and stirring the solution at 80 ° C for 3 hours to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opened polymer solution thus obtained was put into an autoclave, 0.12 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution, and hydrogen gas pressure was 100 kg / cm 2 and reaction temperature. Under the conditions of 165 ° C, the mixture was heated and stirred for 3 hours to carry out hydrogenation reaction. After the obtained reaction solution (hydrogenated polymer solution) was cooled, hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and collect 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 3L 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, and 41.46 g (0.300 mol) of potassium carbonate ), N, N-dimethylacetamide (hereinafter also referred to as "DMAc") 443 g and toluene 111 g were added. Subsequently, a three-way coke having a thermometer, a stirrer, and a nitrogen introduction tube, a Dean Stark tube, and a cooling tube were installed in the four-necked flask. Subsequently, after nitrogen substitution in the flask, the resulting solution was reacted at 140 ° C. for 3 hours, and the resulting water was often removed from the Dean Stark tube. When the formation of water was not confirmed, the temperature was gradually raised to 160 ° C and reacted at the same temperature for 6 hours. After cooling to room temperature (25 ° C), the resulting salt was removed with a filter paper, and the filtrate was reprecipitated in methanol to isolate the filtrate (residue) by filtration separation. The obtained filtrate was dried under vacuum at 60 ° C. overnight to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

<Resin Synthesis Example 3>

1,4-bis (4-amino-α, α-dimethylbenzyl) in a 500 mL 5-neck flask equipped with a thermometer, stirrer, nitrogen introduction tube, dropping funnel with side tubes, Dean Stark tube and cooling tube, under nitrogen flow ) 27.66 g (0.08 mol) of benzene and 7.38 g (0.02 mol) of 4,4'-bis (4-aminophenoxy) biphenyl, 68.65 g of γ-butyrolactone and 17.16 g of N, N-dimethylacetamide Dissolved in. The obtained solution was cooled to 5 ° C using an ice-water bath, and maintained at the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.5 ethyl triethylamine as an imidization catalyst. g (0.005 mol) was added in batch. After completion of the addition, the temperature was raised to 180 ° C, and reflux was performed for 6 hours while distilling off the effluent from time to time. After completion of the reaction, after cooling to an internal temperature of 100 ° C., 143.6 g of N, N-dimethylacetamide was added, diluted, cooled with stirring, and 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight was obtained. . A portion of this polyimide resin solution was poured into 1 L of methanol to precipitate polyimide. The filtered polyimide was washed with methanol, and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). Hanba measuring the IR spectrum of the obtained resin C, it showed a distinctive 1704㎝ ^-1, absorption of 1770㎝ ^-1 imide groups. Resin C had a glass transition temperature (Tg) of 310 ° C and a logarithmic viscosity of 0.87.

[Example 1]

In Example 1, a near-infrared cut filter having a substrate comprising a transparent glass substrate having a transparent resin layer containing compound (A) and compound (B) on one side was produced in the following procedure and conditions.

In a container, 100 parts of Resin A obtained in Resin Synthesis Example 1, squarylium compound (a-1) represented by the following formula (a-1) as compound (A) (maximum absorption wavelength in dichloromethane: 698 nm) 0.03 Part, 0.02 parts of squarylium compound (b-1) (maximum absorption wavelength in dichloromethane 776 nm) represented by the following formula (b-1) as compound (B) and represented by the following formula (b-2) A solution having a resin concentration of 20% by weight was prepared by adding 0.03 parts of phthalocyanine compound (b-2) (maximum absorption wavelength in dichloromethane: 733 nm) and methylene chloride. The obtained solution was cast on a transparent glass substrate “OA-10G (100 μm thick)” (manufactured by Nippon Denki Glass Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width, and dried at 20 ° C. for 8 hours. Then, it was further dried under reduced pressure at 100 ° C for 8 hours. Thus, a substrate having a thickness of 190 µm, a height of 60 mm, and a width of 60 mm with a transparent resin layer on one side of the glass substrate was obtained. The spectral transmittance of this substrate was measured, and the average value of transmittance in the region of wavelengths 430 to 580 nm, Xa, Xb, and absolute value | Xa-Xb | And the average transmittance values in the ranges of the wavelengths Xa to Xb. The results are shown in Fig. 4 and Table 4.

Subsequently, a dielectric multilayer film (I) was formed as a first optical layer on one side of the obtained substrate, and a dielectric multilayer film (II) was formed as a second optical layer on the other side of the substrate, and a near infrared cut of about 0.194 mm in thickness was formed. Filters were obtained.

The dielectric multilayer film (I) is formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer at a deposition temperature of 100 ° C. (26 layers in total). The dielectric multilayer film (II) is formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer at a deposition temperature of 100 ° C. (20 layers in total). In any of the dielectric multilayer films (I) and (II), the silica layer and the titania layer are titania layers, silica layers, titania layers, ... Silica layers, titania layers, and silica layers were alternately stacked in this order, and the outermost layer of the near infrared cut filter was used as the silica layer.

The dielectric multilayer films (I) and (II) were designed as follows.

For the thickness and number of layers of each layer, the wavelength-dependent characteristic of the refractive index of the substrate or the applied compound (B) and compound (A) to achieve the anti-reflection effect in the visible region and the selective transmission / reflection performance in the near-infrared region Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) in accordance with absorption characteristics. When performing optimization, the input parameters (target values) to the software in this example were as shown in Table 1 below.

As a result of optimizing the film structure, in Example 1, the dielectric multilayer film (I) was formed by alternately laminating 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. As a result, the dielectric multilayer film (II) was a multilayer deposition film having a stacking number of 20, in which a silica layer having a thickness of 36 to 194 nm and a titania layer having a thickness of 11 to 114 nm were alternately stacked. Table 2 shows an example of the structure of the optimized film, and Fig. 5 shows a spectral reflectance spectrum measured from an angle of 5 ° with respect to the vertical direction of the glass substrate for a vapor deposition monitor in which each dielectric multilayer film is formed on a single surface. When measuring the reflectance of the glass for evaporation monitors, the surface on which the dielectric multilayer film is not formed is completely painted with a black acrylic paint to prevent reflection, so that the dielectric multilayer film is formed. Was taken as the incident surface of the measurement light.

The spectral transmittance measured from the angle of 30 degrees with respect to the vertical direction and the vertical direction of the obtained near-infrared cut filter was measured, and optical properties were evaluated. The results are shown in Fig. 6 and Table 4. Further, the obtained near-infrared cut filter was measured for a spectral reflectance measured from an angle of 30 ° in the vertical direction of each surface. When the incident surface of the light was taken as the dielectric multilayer film (II) side (second optical layer side), the wavelength was 700. It was confirmed that the value of the lowest reflectance at -800 nm became small. The results are shown in Table 4, and FIG. 7 shows a spectrum of spectral reflectance measured from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter when the light incident surface is the dielectric multilayer film (II) side. Further, the obtained from the vertical direction of the near-infrared cut filter (incident angle 0 °) and an angle (incident angle 30 °) of 30 ° from the vertical measurement of the transmittance of 380 to 780㎚, L ^* a ^* b ^* color system 'a in ^* The value of "b ^* value", "L ^* value", "a ^* value (30 °)""b ^* value (30 °)" and "L ^* value (30 °)" In addition, the absolute value of the difference from each value at 0 ° incident angle | Δa ^* |, | Δb ^* | And | ΔL ^* |. Table 4 shows the results of these results and various other evaluations.

[Example 2]

In Example 1, as the compound (A), instead of 0.03 parts of the compound (a-1), the squarylium compound (a-2) represented by the following formula (a-2) (maximum absorption wavelength in dichloromethane: 703 nm) ) 0.033 parts, and 0.02 parts of compound (b-1) and 0.03 parts of compound (b-2) as compound (B), phthalocyanine-based compound (b-3) represented by the following formula (b-3) ( A substrate having a transparent resin layer containing compound (A) and compound (B) on one side of the glass substrate was obtained in the same procedure and conditions as in Example 1, except that 0.077 parts of the maximum absorption wavelength in dichloromethane (770 nm) was used. . The spectral transmittance of this substrate was measured to evaluate the optical properties. The results are shown in Fig. 8 and Table 4.

Subsequently, as in Example 1, a dielectric multi-layer film (III) formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a first optical layer on one surface of the obtained substrate (total 26 layers) was formed. In addition, on the other side of the substrate, a dielectric multi-layer film (IV) formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a second optical layer (total 20 layers) was formed to have a thickness of about 0.194. A near-infrared cut filter of mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the substrate refractive index. Spectral transmittance and spectral reflectance of the obtained near-infrared cut filter were measured, and optical properties were evaluated. The results are shown in Fig. 9 and Table 5. In addition, the obtained near-infrared cut filter was measured for a spectral reflectance measured from an angle of 30 ° with respect to the vertical direction of each surface. When the incident surface of the light was taken as the dielectric multilayer film (IV) side (second optical layer side), the wavelength It was confirmed that the value of the average reflectance at 700 to 800 nm became small. The results are shown in Table 4, and Fig. 10 shows a spectral reflectance spectrum measured from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter when the incident surface of the light beam is the dielectric multilayer film (IV) side. In addition, in the L ^* a ^* b ^* colorimetric system of the obtained near infrared cut filter, "a ^* value", "b ^* value", "L ^* value", "a ^* value (30 °)", "b ^* Value (30 °) ”and“ L ^* value (30 °) ”, and the absolute value of the difference from each value at 0 ° incident angle | Δa ^* |, | Δb ^* | And | ΔL ^* |. Table 4 also shows the results of these results and various other evaluations.

[Example 3]

In Example 3, a near-infrared cut filter having a substrate comprising a transparent resin substrate having a resin layer on both sides was produced under the following procedure and conditions.

In a container, 100 parts of resin A obtained in resin synthesis example 1, 0.03 parts of compound (a-1) as compound (A) and 0.01 parts of compound (a-2), and compound (b-3) 0.08 as compound (B) A solution having a resin concentration of 20% by weight was prepared by adding 0.02 parts of compound (b-4) represented by the following formula (b-4) (maximum absorption wavelength in dichloromethane: 781 nm) and methylene chloride. The obtained solution was cast on a smooth glass plate, dried at 20 ° C for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

On one side of the obtained transparent resin substrate, the resin composition (1) having the following composition was applied with a bar coater, heated at 70 ° C. for 2 minutes in an oven, and the solvent was volatilized off. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 2 µm. Subsequently, exposure (exposure amount 500 mJ / cm 2, 200 MPa) was performed using a conveyor-type exposure machine to cure the resin composition (1) to form a resin layer on a transparent resin substrate. Similarly, a resin layer containing the resin composition (1) is also formed on the other side of the transparent resin substrate, and a substrate having a resin layer on both sides of the transparent resin substrate containing the compound (A) and the compound (B) is provided. Got. The spectral transmittance of this substrate was measured, and the optical properties were evaluated. Table 4 shows the results.

Resin composition (1): tricyclodecane dimethanol acrylate 60 parts by weight, dipentaerythritol hexaacrylate 40 parts by weight, 1-hydroxycyclohexylphenyl ketone 5 parts by weight, methyl ethyl ketone (solvent, solids concentration (TSC ): 30%)

Subsequently, as in Example 1, a dielectric multi-layer film (V) formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a first optical layer on one surface of the obtained substrate (total 26 layers) is formed. In addition, on the other side of the substrate, a dielectric multi-layer film (VI) formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a second optical layer (total 20 layers) was formed to have a thickness of about 0.108. A near-infrared cut filter of mm was obtained. The dielectric multilayer film was designed in the same manner as in Example 1 by considering the wavelength dependence of the substrate refractive index and the like, and then using the same design parameters as in Example 1. This near-infrared cut filter was evaluated in the same manner as in Example 1. Table 4 shows the results.

[Example 4]

In Example 4, a near-infrared cut filter having a substrate comprising a resin-made substrate having a transparent resin layer containing compound (A) and compound (B) on both sides was produced under the following procedure and conditions.

Resin A and methylene chloride obtained in Resin Synthesis Example 1 were added to the container to prepare a solution having a resin concentration of 20% by weight, and a resin substrate was prepared in the same manner as in Example 3 except that the obtained solution was used.

On both sides of the obtained resin substrate, a resin layer containing the resin composition (2) having the following composition was formed in the same manner as in Example 3, and transparent water containing the compound (A) and the compound (B) was formed on both sides of the resin substrate. A substrate having a strata was obtained. The spectral transmittance of this substrate was measured, and the optical properties were evaluated. Table 4 shows the results.

Resin composition (2): tricyclodecane dimethanol acrylate 100 parts by weight, 1-hydroxycyclohexylphenyl ketone 4 parts by weight, compound (a-1) 0.75 parts by weight, compound (b-2) 0.75 parts by weight, methyl Ethyl ketone (solvent, TSC: 25%)

Subsequently, as in Example 1, a dielectric multi-layer film (VII) formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a first optical layer on one surface of the obtained substrate (26 layers in total) is formed. Then, on the other side of the substrate, a second dielectric layer, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer were alternately stacked (20 layers in total) to form a dielectric multilayer film (VIII), and a thickness of about A near infrared cut filter of 0.108 mm was obtained. The dielectric multilayer film was designed in the same manner as in Example 1 by considering the wavelength dependence of the substrate refractive index and the like, and then using the same design parameters as in Example 1. This near-infrared cut filter was evaluated in the same manner as in Example 1. Table 4 shows the results.

[Examples 5 to 12]

A substrate and a near-infrared cut filter were produced and evaluated in the same manner as in Example 3, except that the drying conditions of the resin, compound (A), compound (B), solvent, and resin substrate were changed as shown in Table 4. Table 4 shows the results.

[Examples 13 to 15]

A substrate and a near-infrared cut filter were produced and evaluated in the same manner as in Example 1, except that the drying conditions of the resin, compound (A), compound (B), solvent, and resin substrate were changed as shown in Table 4. Table 4 shows the results.

[Examples 16 to 17]

A substrate and a near-infrared cut filter were produced and evaluated in the same manner as in Example 3, except that the drying conditions of the resin, compound (A), compound (B), solvent, and resin substrate were changed as shown in Table 4. Table 4 shows the results.

[Examples 18 to 19]

A substrate and a near-infrared cut filter were produced and evaluated in the same manner as in Example 4, except that the drying conditions of the resin, compound (A), compound (B), solvent, and resin substrate were changed as shown in Table 4. Table 4 shows the results.

[Comparative Example 1]

In Example 1, a base material and a near-infrared cut filter were produced and evaluated in the same manner as in Example 1 except that Compound (A) and Compound (B) were not used. Table 5 shows the results.

[Comparative Example 2]

A substrate and a near-infrared cut filter were produced and evaluated in the same manner as in Example 3 except that 0.01 parts of the compound (a-1) and 0.01 parts of the compound (a-2) were used as the compound (A). Table 5 shows the results.

[Comparative Example 3]

A near-infrared cut filter was produced and evaluated in the same manner as in Example 1 except that a transparent glass substrate "OA-10G (100 mu m thick)" (manufactured by Nippon Denki Glass Co., Ltd.) was used as the substrate. Table 5 shows the results.

[Comparative Example 4]

In Comparative Example 4, a near-infrared cut filter having a substrate comprising a transparent resin substrate having a resin layer on both sides was produced under the following procedure and conditions.

To the container, 100 parts of the resin A obtained in the resin synthesis example 1 and 0.135 parts of the compound (b-3) as the compound (B) 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 from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

On both sides of the obtained resin substrate, a resin layer containing the resin composition (3) having the following composition was formed in the same manner as in Example 3, and a substrate having a transparent resin layer containing an absorbent on both sides of the resin substrate and near infrared rays A cut filter was obtained. This substrate and the near-infrared cut filter were evaluated in the same manner as in Example 1. Table 5 shows the results.

Resin composition (3): 100 parts by weight of tricyclodecane dimethanol acrylate, 4 parts by weight of 1-hydroxycyclohexylphenylketone, YMF-02 [Sumitomo Kinzoku Kozan Co., Ltd., cesium tungsten oxide (Cs _0.33 WO) ₃ (average dispersion particle size 800 nm or less; 18.5 mass% dispersion of maximum absorption wavelength (λmax) = 1550 to 1650 nm (membrane))] 30 parts by weight, methyl ethyl ketone (solvent, TSC: 25%)

[Comparative Example 5]

A substrate and a near-infrared cut filter were produced and evaluated in the same manner as in Example 3, except that the drying conditions of the resin, compound (A), compound (B), solvent, and resin substrate were changed as shown in Table 5. Table 5 shows the results.

[Comparative Example 6]

A near-infrared cut filter was produced and evaluated in the same manner as in Example 3, except that a thermoplastic polyimide film (manufactured by As Yarn, thickness of 0.5 mm) was used as the substrate, and that neither the absorber nor the composition for forming a transparent resin layer was used. Table 5 shows the results.

[Comparative Example 7]

A near-infrared cut filter in the same manner as in Example 1 except that a dielectric multilayer film as shown in Table 3 was laminated using a transparent glass substrate "OA-10G (100 mu m thick)" (manufactured by Nippon Denki Glass Co., Ltd.) as the base material. Was produced and evaluated. Table 5 shows the results.

[Comparative Example 8]

While changing the drying conditions of the resin, the compound (A), the compound (B), the solvent, and the resin substrate as shown in Table 5, in order of the dielectric multilayer film (I), the dielectric multilayer film (II), and the substrate, A substrate and a near-infrared cut filter were produced and evaluated in the same manner as in Example 3 except that the dielectric multilayer film (I) and the dielectric multilayer film (II) were formed on one surface of the obtained substrate. Table 5 shows the results.

The structure of the base material in Tables 4 to 5, contents of various compounds, and the like are as follows.

<Type of equipment>

Form (1): Form having a transparent resin layer containing compound (A) and compound (B) on one side of a glass substrate

Form (2): Form having a resin layer on both sides of a transparent resin substrate comprising compound (A) and compound (B)

Form (3): Form having a transparent resin layer containing compound (A) and compound (B) on both sides of a resin substrate

Form (4): Substrate made of transparent resin not containing compound (A) and compound (B)

Form (5): Form having a resin layer on both sides of a transparent resin substrate containing compound (A)

Form (6): Glass substrate

Form (7): Resin substrate

<Transparent resin>

Resin A: Cyclic olefin resin (Resin Synthesis Example 1)

Resin B: aromatic polyether-based resin (Resin Synthesis Example 2)

Resin C: Polyimide resin (Resin Synthesis Example 3)

Resin D: Cyclic olefin-based resin "Zeonoa 1420R" (made by Nippon Xeon Co., Ltd.)

<Glass substrate>

Glass substrate (1): Transparent glass substrate "OA-10G (thickness 100 µm)" cut to a size of 60 mm in length and 60 mm in width (manufactured by Nippon Denki Glass Co., Ltd.)

<Near infrared absorbing pigment>

≪Compound (A) ≫

Compound (a-1): Squalarylium compound (a-1) represented by formula (a-1) (maximum absorption wavelength in dichloromethane: 698 nm)

Compound (a-2): Squalarylium compound (a-2) represented by the formula (a-2) (maximum absorption wavelength in dichloromethane: 703 nm)

Compound (a-3): Squalarylium compound (a-3) represented by the following formula (a-3) (maximum absorption wavelength in dichloromethane: 710 nm)

Compound (a-4): squarylium compound (a-4) represented by the following formula (a-4) (maximum absorption wavelength in dichloromethane: 733 nm)

Compound (a-5): Squalarylium-based compound (a-5) represented by the following formula (a-5) (maximum absorption wavelength in dichloromethane: 713 nm)

≪Compound (B) ≫

Compound (b-1): Squalarylium compound (b-1) represented by the formula (b-1) (maximum absorption in dichloromethane, wavelength 776 nm)

Compound (b-2): Phthalocyanine-based compound (b-2) represented by the formula (b-2) (maximum absorption wavelength in dichloromethane: 733 nm)

Compound (b-3): Phthalocyanine-based compound (b-3) represented by formula (b-3) (maximum absorption wavelength in dichloromethane: 770 nm)

Compound (b-4): Squalarylium compound (b-4) represented by the formula (b-4) (maximum absorption wavelength in dichloromethane: 781 nm)

Compound (b-5): Cyanine-based compound (b-5) represented by the following formula (b-5) (maximum absorption wavelength in dichloromethane: 681 nm)

Compound (b-6): Cyanine-based compound (b-6) represented by the following formula (b-6) (maximum absorption wavelength in dichloromethane: 791 nm)

Compound (b-7): Cyanine-based compound (b-7) represented by the following formula (b-7) (maximum absorption wavelength in dichloromethane: 812 nm)

Compound (b-8): Cyanine-based compound (b-8) represented by the following formula (b-8) (maximum absorption wavelength in dichloromethane: 760 nm)

Compound (b-9): Phthalocyanine compound (b-9) represented by the following formula (b-9) (maximum absorption wavelength in dichloromethane: 752 nm)

<Solvent>

Solvent (1): methylene chloride

Solvent (2): N, N-dimethylacetamide

Solvent (3): cyclohexane / xylene (weight ratio: 7/3)

<Film drying conditions>

Condition (1): 20 ℃ / 8hr → 100 ℃ / 8hr under reduced pressure

Condition (2): 60 ℃ / 8hr → 80 ℃ / 8hr → 140 ℃ / 8hr under reduced pressure

Condition (3): 60 ℃ / 8hr → 80 ℃ / 8hr → 100 ℃ / 24hr under reduced pressure

Moreover, before drying under reduced pressure, the coating film was peeled from the glass plate (except the form (1)).

The near-infrared cut filter of the present invention includes a digital still camera, a mobile phone camera, a digital video camera, a personal computer camera, a surveillance camera, a car camera, a television, a vehicle-mounted device for a car navigation system, a mobile information terminal, a video game machine, It can be suitably used for portable game machines, devices for fingerprint authentication systems, and digital music players. Moreover, it can also be suitably used as a heating wire cut filter mounted in glass, such as a car or a building.

1: Near infrared cut filter
2: Spectrophotometer
3: Optical
3A: reflected light
3B: reflected light
3C: transmitted light (multi-reflected light)
4: Lens
5: sensor (solid-state imaging element)
7: reflective mirror
10: glass support
11: transparent resin layer
12: first optical layer
13: second optical layer
14: description (i)
15: third optical layer
16: 4th optical layer
111: camera image
112: white board
113: Example of the central portion of the white plate
114: Example of the end of the white plate

Claims (15)

A near-infrared cut filter comprising a base material having a transparent resin layer containing a near-infrared absorbent and a dielectric multilayer film formed on at least one side of the base material and satisfying the following requirement (a):
(a) In the region with a wavelength of 600 to 800 nm, in the region with a wavelength of shortest wavelength (Xa) at which the transmittance is 50% when measured from the vertical direction of the substrate, and in the region with a wavelength of 700 to 1200 nm, the substrate When measured from the vertical direction of, the absolute value | Xa-Xb | of the difference from the value (Xb) of the longest wavelength at which the transmittance is 50% is 120 nm or more. The near-infrared cut filter according to claim 1, wherein in the region of the wavelengths Xa to Xb, an average value (Ta) of transmittance when measured from the vertical direction of the substrate is 35% or less. The near-infrared cut filter according to claim 1 or 2, further comprising:
(b) In the range of wavelengths 560 to 800 nm, the shortest wavelength value (Ya) in which the transmittance is 50% when measured from the vertical direction of the near-infrared cut filter and 30 with respect to the vertical direction of the near-infrared cut filter When measured from an angle of °, the absolute value | Ya-Yb | of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% is less than 15 nm. The said near infrared absorber is at least 1 sort (s) selected from the group which consists of a squarylium type compound, a phthalocyanine type compound, a naphthalocyanine type compound, a croconium type compound, and a cyanine type compound of any one of Claims 1-3. A near-infrared cut filter, characterized in that. The near-infrared cut filter according to any one of claims 1 to 4, wherein the transparent resin layer contains two or more of the near-infrared absorbents. The squarylium-based compound (A) according to any one of claims 1 to 5, wherein the near infrared absorber has an absorption maximum at a wavelength of 650 to 750 nm, and a compound (B) having an absorption maximum at a wavelength of 660 to 850 nm. ) (Excluding the compound (A)) is a near infrared cut filter. The near-infrared cut filter according to any one of claims 1 to 6, wherein the dielectric multilayer film is formed on both surfaces of the substrate. The near infrared cut filter according to claim 7, wherein the dielectric multilayer films formed on both surfaces of the substrate include a near infrared reflecting film and a visible light antireflection film. The reflectance of any one of claims 1 to 8, when measured from an angle of 30 ° with respect to the vertical direction of either side of the near-infrared cut filter in the region of wavelength 600 to 900 nm, is 50%. The near-infrared cut filter, characterized in that the shortest wavelength value (Xr) becomes 620 nm or more. The transparent resin is a cyclic (poly) olefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a fluorene polycarbonate-based resin, or a fluorene poly according to any one of claims 1 to 9. Ester resin, polycarbonate resin, polyamide resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyparaphenylene resin, polyamide imide resin, polyethylene naphthalate resin, At least one member selected from the group consisting of fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester-based curable resins, silsesquioxane-based ultraviolet curable resins, acrylic ultraviolet curable resins and vinyl-based ultraviolet curable resins A near-infrared cut filter, characterized in that it is a resin. The near-infrared cut filter according to any one of claims 1 to 10, wherein the substrate includes at least one selected from a transparent resin support and a glass support. The near-infrared cut filter according to any one of claims 1 to 11, which is for a solid-state imaging device. A solid-state imaging device comprising the near-infrared cut filter according to any one of claims 1 to 12. A camera module comprising the near-infrared cut filter according to any one of claims 1 to 12. A method of manufacturing a near-infrared cut filter comprising a step of forming a dielectric multilayer film on at least one side of a substrate having a transparent resin layer containing a near-infrared absorbent, wherein the near-infrared cut filter satisfies the following requirement (a) Manufacturing method of near infrared cut filter:
(a) In the region of a wavelength of 600 to 800 nm, in the region of a wavelength of 700 to 1200 nm and the value of the shortest wavelength (Xa) in which the transmittance is 50% when measured from the vertical direction of the substrate, The absolute value | Xa-Xb | of the difference from the value (Xb) of the longest wavelength at which the transmittance is 50% when measured from the vertical direction of is 120 nm or more.

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