TWI812631B - Near-infrared cut filter, manufacturing method thereof, solid-state imaging device, and camera module - Google Patents

Abstract

An object of the present invention is to provide a near-infrared cutoff filter that is excellent in near-infrared cutoff characteristics, has little dependence on incident angle, and is excellent in transmittance characteristics in the visible wavelength range and in reducing multiple reflected light in the near-infrared wavelength range. The near-infrared cut filter of the present invention includes a base material having a transparent resin layer containing a near-infrared absorber, and a dielectric multilayer film formed on at least one side of the base material, and satisfies the following necessary condition (a): (a) In the wavelength range of 600 nm to 800 nm, the transmittance when measured in the vertical direction of the base material becomes 50% of the shortest wavelength value (Xa), and in the wavelength range of 700 nm to 1200 nm from the base material The absolute value of the difference |

Description

Near-infrared cut filter and manufacturing method thereof, solid-state imaging Devices and camera modules

The present invention relates to a near-infrared cutoff filter and a device using the near-infrared cutoff filter. Specifically, the present invention relates to a near-infrared cut filter containing a pigment compound that absorbs in a specific wavelength range, and a solid-state imaging device and camera module using the near-infrared cut filter.

In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, charge-coupled device (CCD) image sensors or complementary metal oxide semiconductors are used as solid-state imaging elements for color images. (Complementary Metal Oxide Semiconductor, CMOS) image sensor. These solid-state imaging elements use silicon photodiodes that are sensitive to near-infrared rays that are imperceptible to the human eye in their light receiving parts. These solid-state imaging devices require correction of visual sensitivity to produce a natural color tone when viewed by the human eye, and many use near-infrared cut filters that selectively transmit or block light in a specific wavelength range.

As this type of near-infrared cut filter, various methods have been used to manufacture it. For example, a near-infrared cut filter is known which uses a transparent resin as a base material and contains a near-infrared absorbing dye in the transparent resin (for example, see Patent Document 1).

However, the near-infrared cut filter described in Patent Document 1 cannot expand the absorption range width of the base material while maintaining a high level of visible light transmittance. In order to sufficiently reduce the transmittance near 700 nm to 800 nm, the dielectric needs to be The cutoff wavelength of the multilayer film is on the shorter wavelength side.

The near-infrared cut filter built into the camera module is configured with a dielectric multilayer film (near-infrared reflective film) on the lens side and an anti-reflection film on the image sensor side. However, the dielectric multilayer film The reflected light between the film and the lens sometimes causes multiple reflections. As a result, the multiple reflected light in the vicinity of 700nm to 800nm, where the sensor sensitivity is high, may be incident on the imaging element and the camera image may be degraded.

However, the near-infrared cutoff filter described in Patent Document 1 does not have a sufficient light absorption range in the near-infrared region. To sufficiently cut off the near-infrared light incident on the sensor, it is necessary to increase the near-infrared cutoff filter's near-infrared rays. Reflectivity.

Furthermore, with the miniaturization of camera modules in mobile devices, there is a tendency that the incident angle of light, especially at the edge of the screen, becomes larger than before. In the conventional near-infrared cutoff filter, there is a problem caused by the near-infrared cutoff filter. Ghost images caused by multiple reflections between the detector and the lens become a problem. Specifically, as shown in FIG. 1 , visible light among the incident lights passing through the lens 4 passes through the near-infrared cut filter 1 and the near-infrared light is reflected (reflected light 3A). The reflected near-infrared light is reflected again on the surface of the lens 4 (reflected light 3B), causing multiple reflections. There are cases where the multiple reflected light (transmitted light 3C) between the near-infrared cut filter and the lens is incident on the sensor 5, resulting in deterioration of the camera image.

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 6-200113

In recent years, the image quality level required for camera images in mobile devices and the like has also become very high. According to research by the present inventors, in order to meet the requirements for high image quality, in addition to a wide viewing angle and high visible light transmittance, a near-infrared cutoff filter also needs high light cutoff characteristics in the long wavelength region. However, in the conventional near-infrared cut filter, ghost images caused by multiple reflections sometimes become a problem as described above.

An object of the present invention is to provide a near-infrared cutoff filter that is excellent in near-infrared cutoff characteristics, has little dependence on incident angle, and has excellent transmittance characteristics in the visible wavelength range and a reduction effect of multiple reflected light in the near-infrared wavelength range.

The present applicant has conducted diligent research to solve the above-mentioned problems and found that by expanding the absorption range width of the base material to the near-infrared region, even when the incident angle changes, the optical characteristics can be obtained with little change due to multiple reflections. The present invention was completed by developing a near-infrared cut filter with less image degradation. Examples of aspects of the present invention are shown below.

[1] A near-infrared cut filter, which includes a base material having a transparent resin layer containing a near-infrared absorber, and a dielectric multilayer film formed on at least one side of the base material, and satisfies the following necessary conditions ( a): (a) In the wavelength region of 600 nm to 800 nm, the value (Xa) of the shortest wavelength at which the transmittance when measured from the vertical direction of the substrate becomes 50% is the same as the value (Xa) of the base material in the wavelength region of 700 nm to 1200 nm. When measured in the vertical direction of the material, the absolute value of the difference |

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

[3] The near-infrared cutoff filter according to item [1] or item [2], which further satisfies the following necessary condition (b): (b) in the wavelength range of 560 nm to 800 nm, since The value of the shortest wavelength (Ya) at which the transmittance of the near-infrared cutoff filter when measured in the vertical direction is 50%, and the transmittance when measured at an angle of 30° from the vertical direction of the near-infrared cutoff filter. The absolute value of the difference between the shortest wavelength value (Yb) with a rate of 50% | Ya-Yb | is less than 15 nm.

[4] The near-infrared cut filter according to any one of items [1] to [3], wherein the near-infrared absorber is selected from a squarylium compound. , at least one of the group consisting of phthalocyanine compounds, naphthalocyanine compounds, croconium compounds and cyanine compounds.

[5] Near-infrared cutoff filter as described in any one of items [1] to [4] The device is characterized in that the transparent resin layer contains two or more types of near-infrared absorbers.

[6] The near-infrared cut filter according to any one of items [1] to [5], wherein the near-infrared absorber is contained in squaraine having maximum absorption in a wavelength range of 650 nm to 750 nm. Onium salt compound (A) and compound (B) having maximum absorption at a wavelength of 660 nm to 850 nm (excluding the compound (A)).

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

[8] The near-infrared cut filter according to item [7], wherein the dielectric multilayer films formed on both sides of the base material include a near-infrared reflective film and a visible light anti-reflective film.

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

[10] The near-infrared cut filter according to any one of items [1] to [9], wherein the transparent resin is selected from the group consisting of cyclic (poly)olefin-based resin and aromatic polyether. Polyamide resin, polyimide resin, polycarbonate resin, polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, polyether resin, polyether resin Resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, olefin Propyl-based hardening resin, silsesquioxane-based At least one resin from the group consisting of ultraviolet curable resin, acrylic ultraviolet curable resin, and vinyl ultraviolet curable resin.

[11] The near-infrared cut filter according to any one of items [1] to [10], wherein the base material includes at least one selected from the group consisting of a transparent resin support and a glass support. One kind.

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

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

[14] A camera module equipped with the near-infrared cutoff filter as described in any one of items [1] to [12].

[15] A method of manufacturing a near infrared cut filter, which includes the step of forming a dielectric multilayer film on at least one side of a base material having a transparent resin layer containing a near infrared absorber, the near infrared cut filter having a transparent resin layer containing a near infrared absorber. The manufacturing method is characterized in that the near-infrared cutoff filter satisfies the following necessary conditions (a): (a) in the wavelength range of 600 nm to 800 nm, the transmittance when measured from the vertical direction of the substrate becomes 50% The absolute value of the difference between the value of the shortest wavelength (Xa) and the value (Xb) of the longest wavelength at which the transmittance becomes 50% when measured in the vertical direction of the substrate in the wavelength range of 700 nm to 1200 nm | Xa -Xb| is above 120nm.

According to the present invention, it is possible to provide an incident light with excellent near-infrared cutoff characteristics A near-infrared cut filter with small angular dependence and excellent transmittance characteristics in the visible wavelength range and multiple reflection light reduction effects in the near-infrared wavelength range.

1: Near infrared cut filter

2: Spectrophotometer

3:Light

3A: Reflected light

3B: Reflected light

3C: Transmitted light (multiple reflected light)

4: Lens

5: Sensor (solid-state imaging element)

7: Reflector

10:Glass support

11:Transparent resin layer

12: First optical layer

13: Second optical layer

14:Substrate(i)

15:Third optical layer

16: The fourth optical layer

111:Camera image

112:White board

113: Example of the center part of the white board

114: Example of the end of the white plate

FIG. 1 is a schematic diagram illustrating the light rays that have undergone multiple reflections between the near-infrared cut filter and the lens and enter the solid-state imaging element.

FIG. 2( a ) is a schematic diagram showing a method of measuring transmittance when measuring from a perpendicular direction of a near-infrared cut filter. FIG. 2( b ) is a schematic diagram showing a method of measuring the transmittance when measured at 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 the reflectance when measuring at 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 an example of a preferred structure of the near-infrared cut filter of the present invention.

FIG. 4 is a spectral transmission spectrum of the base material obtained in Example 1.

FIG. 5(a) is a spectral reflection spectrum measured at 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 a spectrum from the vertical direction of the dielectric multilayer film (I) formed in Example 1. Spectroscopic reflection spectrum when the vertical direction of the dielectric multilayer film (II) formed in 1 was measured at an angle of 5°.

FIG. 6 is a spectral transmission spectrum of the near-infrared cutoff filter obtained in Example 1.

Figure 7 shows the near-infrared cutoff filter obtained in Example 1. Spectroscopic reflection spectrum measured at an angle of 30° with respect to the vertical direction of the near-infrared cut filter when the incident surface of the ray is on the side of the dielectric multilayer film (II) (second optical layer).

FIG. 8 is a spectral transmission spectrum of the base material obtained in Example 2.

FIG. 9 is a spectral transmission spectrum of the near-infrared cut filter obtained in Example 2.

FIG. 10 shows the near-infrared cutoff filter obtained in Example 2, when the incident surface of light is set to the side of the dielectric multilayer film (IV) (second optical layer). Spectroscopic reflectance spectrum measured at an angle of 30° in the vertical direction.

FIG. 11 is a schematic diagram for explaining color evaluation of camera images performed in Examples and Comparative Examples.

Hereinafter, the present invention will be specifically described.

[Near infrared cut filter]

The near-infrared cut filter of the present invention is characterized by including a base material (i) having a transparent resin layer containing a near-infrared absorber, and a dielectric multilayer film formed on at least one side of the base material (i). , and satisfy the following necessary condition (a).

Necessary condition (a): In the wavelength range of 600 nm to 800 nm, the transmittance of the shortest wavelength (Xa) when measured from the vertical direction of the substrate (i) is 50%, and the value (Xa) at the wavelength of 700 nm to The value of the longest wavelength at which the transmittance becomes 50% when measured in the direction perpendicular to the base material (i) in the 1200 nm region The absolute value of the difference (Xb) (absorption half-value width) |Xa-Xb| is 120 nm or more.

The near-infrared cutoff filter of the present invention has excellent near-infrared cutoff characteristics, little dependence on incident angle, transmittance characteristics in the visible wavelength range, and an effect of reducing multiple reflected light in the near-infrared wavelength range.

Furthermore, it is a near-infrared cut filter that has an excellent multiple reflection reduction effect in the near-infrared region when the transmittance value in the wavelength range Xa to Xb is large.

When the near-infrared cut filter of the present invention is used for a solid-state imaging device, it is preferable that the transmittance in the near-infrared wavelength region is low. In particular, it is known that the light reception sensitivity of solid-state imaging elements is high in the wavelength range of 700nm to 1000nm. By reducing the transmittance in this wavelength range, the camera image and the visual sensitivity of the human eye can be effectively corrected, achieving excellent Color reproduction.

The near-infrared cutoff filter of the present invention has an average transmittance of 5% or less, preferably 4% or less, and even more preferably 3% or less when measured in the vertical direction of the filter in the wavelength range of 700 nm to 1000 nm. The best value is less than 2%. If the average transmittance at a wavelength of 700nm to 1000nm is within this range, it is preferable because near-infrared rays can be sufficiently cut off and excellent color reproducibility can be achieved.

When the near-infrared cut filter of the present invention is used in a solid-state imaging device or the like, it is preferable that the visible light transmittance is high. Specifically, in the wavelength range of 430 nm 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, and still more preferably 83% or more. The best is above 85%. If the average transmittance in this wavelength region is within this range, the near-infrared cut filter of the present invention can be used as a solid-state imaging device. , excellent imaging sensitivity can be achieved.

The near-infrared cut filter of the present invention preferably further satisfies the following necessary condition (b).

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

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

In such a near-infrared cut filter, the L* value, the a* value, and the b* value in the L*a*b* color system are preferred values. Here, the so-called "L*a*b* color system" is planned and formulated by the International Commission on Illumination (CIE). "L*" is called the "lightness index" and represents brightness, and "a*" and "b*" are called "chromaticness index" and represents the position corresponding to hue and chroma. Regarding the hue and saturation, if the value of a* is negative, the color becomes a green color, and if the value of a* is positive, the color becomes a red color. In addition, if the value of b* is negative, the color becomes a blue-based color, and if the value of b* is positive, the color becomes a yellow-based color. When the "a* value", "b* value" and "L* value" of the L*a*b* color system of the near-infrared cut filter are used in a camera module, It affects the brightness and color of camera images, so it is ideal to be within a certain value range.

In the present invention, the "value of L*", "the value of a*", and "the value of b*" in the L*a*b* color system are set to adopt the following values: using Hitachi High-Technology (Hitachi High-Technology) Technologies) Co., Ltd., a value obtained by measuring the transmittance of 380nm to 780nm from the vertical direction of the near-infrared cut filter (incident angle 0°).

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

The value of a* in the L*a*b* color system is preferably from -31 to 5, more preferably from -25 to -2, further preferably from -21 to -5. In addition, the value of b* in the L*a*b* color system is preferably -5 or more and 10 or less. If the values of a* and b* in the L*a*b* color system are within this range, visual evaluation of the color reproducibility of the obtained image will show good results.

The L*a*b* color system can also be used as an indicator of the color difference of an image. From an angle of 30° with respect to the vertical direction of the near-infrared cut filter (incident angle of 30°), measure the transmittance from 380nm to 780nm in the same manner as described above and obtain the value in the L*a*b* color system , let the value of L*, the value of a* and the value of b* at this time be respectively "the value of L* (30°)", "the value of a* (30°)" and "the value of b* ( 30°)”, the absolute values of the differences |△L*|, |△a*| and |△b*| from the values when the incident angle is 0° can be calculated using the following formulas.

｜△L*｜=｜(value of L*(30°))-(value of L*)｜

|△a*|=|(value of a*(30°))-(value of a*)|

|△b*|=|(value of b*(30°))-(value of b*)|

|Δa*| calculated by the above formula is preferably 9 or less, more preferably 3 or less, and |Δb*| calculated by the above formula is preferably 9 or less, more preferably 3 or less. When a near-infrared cut filter with |△a*| and |△b*| within the above range is used as a solid-state imaging device, the visual evaluation of the color reproducibility of the obtained image shows good results. .

The near-infrared cutoff filter of the present invention has a low reflectivity in the wavelength region of 700 nm to 800nm on the lens-side surface of the base material (i), so the reflection of light between the near-infrared cutoff filter and the lens can be reduced.

In the wavelength range of 700 nm to 800 nm, the minimum value of the reflectivity when measured at an angle of 30° from the vertical direction to at least one surface of the near-infrared cut filter is preferably 80% or less, and more preferably 50% or less. , the best is less than 10%. If the reflectance is in this range, it is preferable because it tends to reduce various ghost images due to multiple reflected light, especially when used in a solid-state imaging device.

Here, ghost intensity due to multiple reflections will be described with reference to FIG. 1 . The light that passes through the lens 4 is reflected on a part of the near-infrared cut filter 1 (reflected light 3A), is further reflected on the lens surface (reflected light 3B), passes through the near-infrared cut filter 1 (transmitted light 3C), and reaches the sensor. on the surface of device 5. Therefore, regarding the ghost intensity due to multiple reflections between the near-infrared cut filter and the lens, when Let the average reflectance measured from a direction of 30° perpendicular to the near-infrared cut filter in 700nm to 850nm be (a)%, and the average reflectance of the lens in 700nm to 850nm be (b) %. When the average transmittance of the near-infrared cutoff filter measured from a direction of 30° with respect to the vertical direction in 700nm to 850nm is (c)%, it can be calculated using the following formula.

[Ghosting intensity]=(a)×(b)×(c)

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

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

The thickness of the near-infrared cutoff filter of the present invention may be appropriately selected depending on the intended use. In view of recent trends such as thinning and lightweighting of solid-state imaging devices, the thickness of the near-infrared cutoff filter of the present invention is preferably It's also thin. Since the near-infrared cut filter of the present invention includes the base material (i), it can be reduced in thickness.

The thickness of the near-infrared cut filter of the present invention is preferably, for example, 200 μm or less, more preferably 180 μm or less, further preferably 150 μm or less, particularly preferably 120 μm or less. The lower limit is not particularly limited, but is preferably, for example, 20 μm. .

If the thickness of the resin substrate is within the above range, a near-infrared cut filter using the substrate can be miniaturized and lightweight, and can be preferably used for solid-state imaging. devices and other uses. In particular, when the resin substrate is used for a lens unit of a camera module or the like, it is preferable because the lens unit can be made low-profile.

[Substrate (i)]

The base material (i) has a transparent resin layer containing a near-infrared absorber. Examples of the near-infrared absorber include: a squarylium-based compound (A) (hereinafter also referred to as "compound (A)") having maximum absorption at a wavelength of 650 nm to 750 nm; and a squarylium compound (A) having a maximum absorption at a wavelength of 660 nm to 850 nm. Compound (B) with maximum absorption (except the above-mentioned compound (A). Hereinafter also referred to as "compound (B)"), etc.

The substrate (i) may be a single layer or multiple layers. When the base material (i) is a single layer, for example, a base material including a transparent resin substrate (ii) containing the compound (A) and the compound (B), and the transparent resin substrate (ii) becomes the above-mentioned Transparent resin layer. When the base material (i) is a multi-layer structure, for example, a curable resin containing the compound (A) and the compound (B) is laminated on a support body such as a glass support body or a resin support body serving as a base. A base material made of a transparent resin layer such as an overcoat or the like, and a resin layer such as an overcoat or the like containing a curable resin containing the compound (A) is laminated on a transparent resin substrate (iii) containing the compound (B). A base material formed by laminating a resin layer such as an overcoat layer containing a curable resin containing compound (B) on a transparent resin substrate (iv) containing compound (A), and a base material containing compound (A) ) and a transparent resin substrate (ii) of the compound (B), a base material, etc., in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated. In terms of manufacturing cost and ease of adjustment of optical properties, it is possible to achieve a resin support or a transparent tree. In terms of the damage-removing effect of the lipid substrate (ii) or the improvement of the damage resistance of the base material (i), it is particularly preferable to use the transparent resin substrate (ii) containing the compound (A) and the compound (B). A base material in which resin layers such as an overcoat layer containing a curable resin are laminated.

Hereinafter, the layer containing at least one near-infrared absorber and a transparent resin will also be called a "transparent resin layer", and the other resin layers will also be simply called a "resin layer."

The absolute value | If the | Multiple reflections of light in the described area. Particularly when used in solid-state imaging devices, various ghost images due to multiple reflected lights tend to be reduced.

In the region of wavelengths Xa to % or less, the best is less than 20%. If (Ta) of the base material (i) is in this range, when a dielectric multilayer film is formed on the base material (i), the reflectivity in the vicinity of 700 nm to 800 nm can be more optimally reduced. Particularly when used in solid-state imaging devices, various ghost images due to multiple reflected lights tend to be reduced.

<Near-infrared absorber>

The near-infrared absorber is not particularly limited as long as it is a compound having maximum absorption at a wavelength of 650 nm or more and 850 nm or less. From the viewpoint of suppressing aggregation in the resin, a solvent-soluble dye compound is preferred. As such near red Examples of the external ray absorber include squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, ketonium-based compounds, cyanine-based compounds, and the like. 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 maximum absorption at a wavelength of 650 nm to 750 nm. The squarylium salt-based compound has excellent visible light transmittance, steep absorption characteristics, and high molar absorption coefficient. However, when it absorbs light, it sometimes generates fluorescence that causes scattered light. In this case, by using compound (A) and compound (B) in combination, a near-infrared cut filter with less scattered light and better camera image quality can be obtained.

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

Specific examples of compound (A) are preferably selected from the group consisting of squarylium compounds represented by formula (A-I) and squarylium compounds represented by formula (A-II) of at least one. Hereinafter, they are also referred to as "compound (A-I)" and "compound (A-II)" respectively.

[Chemical 1]

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 carboxyl group, a phosphate group, a -L ¹ or -NR ^e R ^f group. Re ^and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e .

A plurality of R ^b each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -L ¹ or -NR ^g R ^h group. R ^g and R ^h respectively independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C(O)R ⁱ group (R ⁱ represents -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ).

Multiple Ys independently represent -NR ^j R ^k groups. 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 La, L ^b , L ^c , L ^d , ^Le , L ^f , Lg ^or L ^h .

The above-mentioned L ^a to L ^h represent (L ^a ) an aliphatic hydrocarbon group having 1 to 9 carbon atoms which may have a substituent L, and (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 ) may have a substituent L is a heterocyclic group having 3 to 14 carbon atoms, (L ^f ) is an alkoxy group having 1 to 9 carbon atoms which may have a substituent L, (L ^g ) is a hydroxyl group having 1 to 9 carbon atoms which may have a substituent L. , or (L ^h ) is an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L.

The substituent L is selected from an aliphatic hydrocarbon group with 1 to 9 carbon atoms, a halogen-substituted alkyl group with 1 to 9 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, and At least one of the group consisting of heterocyclic groups having 3 to 14 carbon atoms.

The L ^a ~ L ^h may further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group and an amine group.

The total number of carbon atoms of L ^a to L ^h including substituents is preferably 50 or less, more preferably 40 or less carbon atoms, particularly preferably 30 or less carbon atoms. If the number of carbon atoms exceeds this range, synthesis of the pigment may become difficult, and the absorption strength per unit weight tends to decrease.

Condition (A-ii)

At least one of the two R ^a on a benzene ring is bonded to Y on the same benzene ring to form a heterocyclic ring containing at least one nitrogen atom and a constituent number of atoms of 5 or 6. The heterocyclic ring may also have substitution The radicals, R ^b and R ^a which do not participate in the formation of the heterocycle, respectively and independently have the same meanings as R ^b and R ^a of the (Ai).

[Chemicalization 2]

^{In formula ( A - II ) ,} or -L ^e ; multiple R ^d independently represent hydrogen atom, halogen atom, sulfo group, hydroxyl, cyano group, nitro group, carboxyl group, phosphate group, -L ¹ or -NR ^e R ^f group, and adjacent R ^d can be connected to each other to form a ring that may have a substituent; La ^~ L ^e , L ¹ , Re and ^{R f are} the same as La ^~ L ^e , L ¹ , R ^e defined in the formula (AI) and R ^f have the same meaning.

Compound (A-I) and compound (A-II) can also be described using the following formula (A-I-1) and the following formula (A-II-1), as well as the following formula (A-I-2) and the following formula: Formula (A-II-2) generally uses the resonance structure recording method to express the structure. That is, the difference between the following formula (A-I-1) and the following formula (A-I-2), and the difference between the following formula (A-II-1) and the following formula (A-II-2) Only in the description of the structure, the compounds are represented by the same one. In the present invention, unless otherwise specified, the structure of the squarylium salt-based compound is represented by a description method similar to the following formula (A-I-1) and the following formula (A-II-1).

[Chemical 3]

The structures of compound (A-I) and compound (A-II) are not particularly limited as long as they meet the necessary conditions of formula (A-I) and formula (A-II) respectively. For example, in formula (A-I-1) When the formula (A-II-1) generally represents a structure, the left and right substituents bonded to the central four-membered ring may be the same or different. The same is preferred because it is easy to synthesize. 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.

[Chemical 4]

Regarding the content of the compound (A), for example, a base material including a transparent resin substrate (ii) containing the compound (A) and a compound (B) is used, or a transparent resin substrate (iv) containing the compound (A) is used. When the base material (i) is laminated with a resin layer such as an overcoat layer including a curable resin containing compound (B), the amount is preferably 0.01 parts by weight relative to 100 parts by weight of the transparent resin. ~2.0 parts by weight, more preferably 0.015 parts by weight~1.50 parts by weight, particularly preferably 0.02 parts by weight~1.00 parts by weight. In addition, a base material in which a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) and the compound (B) is laminated on a resin support used as a base or a glass support, or a base material formed on a resin support used as a base. When the base material (i) is a base material in which a transparent resin layer such as an overcoat layer containing a curable resin or the like containing the compound (A) is laminated on a transparent resin substrate (iii) containing the compound (B) , relative to 100 parts by weight of the resin forming the transparent resin layer containing compound (A), preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.5 parts by weight, particularly preferably 0.3 to 4.0 parts by weight share.

"Compound (B)"

The compound (B) is not particularly limited as long as it has maximum absorption at a wavelength of 660 nm to 850 nm. It is preferably a solvent-soluble pigment compound, and more preferably is selected from the group consisting of squarium ylide compounds, phthalocyanine compounds, At least one kind from the group consisting of a cyanine-based compound, a naphthalocyanine-based compound, and a ketonium-based compound, and more preferably a squarylium-based compound and a phthalocyanine-based compound. By using such a compound (B), high near-infrared cutoff characteristics near the maximum absorption and good visible light transmittance can be achieved simultaneously.

The maximum absorption wavelength of compound (B) is preferably 680nm~830nm, more preferably 700nm~820nm, and particularly preferably 720nm~800nm. If the maximum absorption wavelength of the compound (B) is within this range, unnecessary near-infrared rays that cause various ghost images can be efficiently cut off.

The structure of the phthalocyanine-based compound is not particularly limited, and examples thereof include compounds represented by the following formula (III).

In the formula (III), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom or a substituted metal atom including a trivalent or tetravalent metal atom, and a plurality of R _a , R _b , R _c and R _d respectively independently represent a group selected from the group consisting of hydrogen atom, halogen atom, hydroxyl group, carboxyl group, nitro group, amine group, amide group, amide group, cyano group, silane group, -L ¹ , -SL ² , - The following formula is formed by bonding 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 , or R _c and R _d (A) ~ At least one group in the group consisting of groups represented by formula (H), at least one of R _a , R _b , R _c and R _d bonded to the same aromatic ring is not a hydrogen atom .

The amine group, amide group, amide group and silane group may have the substituent L defined in the formula (AI), and L ¹ has the same meaning as L ¹ defined in the formula (AI). , L ² represents a hydrogen atom or any one of La ^to L ^e defined in the formula (AI), L ³ represents a hydroxyl group or any one of the La ^to L ^e , and L ⁴ represents the L Any one of ^a ~L ^e .

[Chemical 6]

In Formula (A) ~ Formula (H), the combination of R _x and R _y is the combination of R _a and R _b , R _b and R _c or R _c and R _d , and multiple R _A ~ R _L are independently represented. Hydrogen atom, halogen atom, hydroxyl group, nitro group, amine group, amide group, amide group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , the amino group, amide group, amide group and silane group may have the substituent L, L ¹ to L ⁴ and L ¹ to L defined in the formula (III) ⁴ has the same meaning.

The structure of the naphthalocyanine-based compound is not particularly limited, and examples thereof include compounds represented by the following formula (IV).

[Chemical 7]

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

The structure of the cyanine-based compound is not particularly limited, and examples thereof include compounds represented by the following formulas (V-1) to (V-3).

[Chemical 8]

In formulas (V-1) to formula (V-3), X _a ^- represents a monovalent anion, multiple Ds independently represent carbon atoms, nitrogen atoms, oxygen atoms or sulfur atoms, and multiple R _a , R _b , R _c , R _d , Re , R _f , R _g , _Rh and R _i each independently represent a hydrogen atom, a halogen atom, a hydroxyl _group , a carboxyl group, a nitro group, an amine group, an amide group, and an amide 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 _e and A group consisting of groups represented by the following formulas (A) to (H) in which at least one of R _f , R _f and R _g , R _g and R _h , or R _h and R _i is bonded. At least one group in the group, the amino group, amide group, amide group and silane group may also have the substituent L defined in the formula (AI), L ¹ and the substituent L in the formula (AI) L ¹ as defined has the same meaning, L ² represents a hydrogen atom or any one of La ^~ L ^e defined in the formula (AI), and L ³ represents a hydrogen atom or any one of La ^~ L ^e defined in the formula (AI). One, L ⁴ represents any one of the above-mentioned La ^~ L ^e , Za _~ Z _d and _Ya ~ Y _d each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amine group, or a hydroxyl group. Amino group, amide group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ (L ¹ ~ L ⁴ are the same as the R L ¹ to L ⁴ in _a to R _i have the same meaning), or at least one selected from the group consisting of two adjacent ones in which Z or Y are bonded to each other and may contain a nitrogen atom, an oxygen atom or a sulfur atom. The 5-membered ring or 6-membered ring alicyclic hydrocarbon group is selected from the aromatic hydrocarbon group with 6 to 14 carbon atoms formed by bonding Z to each other or Y to each other, or selected from the two adjacent ones. Z in Z or Y are bonded to each other to form a heteroaromatic hydrocarbon group with a carbon number of 3 to 14 containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom, and these alicyclic hydrocarbon groups, aromatic hydrocarbon groups and heteroaromatic hydrocarbon groups are The aromatic hydrocarbon group may also have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

[Chemical 9]

In formulas (A) to (H), the combinations of R _x and R _y are 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 The combination of _h and R _i , multiple _RA ~ R _L independently represent hydrogen atom, halogen atom, hydroxyl group, carboxyl group, nitro group, amino group, amide group, amide imine group, cyano group, silane group, - L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ or -N=NL ⁴ (L ¹ ~L ⁴ are as defined in the above formulas (V-1) ~ formula (V-3) L ¹ to L ⁴ have the same meaning), and the amine group, amide group, amide group and silane group may have the substituent L.

Examples of the squarylium dye include compounds represented by the following formula (VI).

In ^the formula ( ^VI ) ^, Nitro group, carboxyl group, phosphate group, -NR ^g R ^h group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any one of the following L ^a ~ L ^h , R ^g and R ^h represent independently A hydrogen atom, a -C(O)R ⁱ group or any one of the following La ^to L ^e , and R ⁱ represents any one of the following La ^to L ^e .

(L ^a )aliphatic hydrocarbon group with 1 to 12 carbon atoms

(L ^b ) Halogen-substituted alkyl group having 1 to 12 carbon atoms

(L ^c ) Alicyclic hydrocarbon group with 3 to 14 carbon atoms

(L ^d )aromatic hydrocarbon group with 6 to 14 carbon atoms

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

(L ^f )Alkoxy group with 1 to 12 carbon atoms

(L ^g ) A hydroxyl group having 1 to 12 carbon atoms which may have a substituent L

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

The substituent L is selected from an aliphatic hydrocarbon group with 1 to 12 carbon atoms, a halogen-substituted alkyl group with 1 to 12 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, and At least one of the group consisting of heterocyclic groups having 3 to 14 carbon atoms.

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, an n-butyl group, a second butyl group, a third butyl group, a cyclohexyl group, a phenyl group, hydroxyl group, amine group, dimethylamino group, nitro group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group and hydroxyl group.

The R ² to R ⁷ are preferably each independently a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, or a third butyl group. , cyclohexyl, phenyl, hydroxyl, amino, dimethylamino, cyano, nitro, acetylamino, propylamino, N-methylacetylamino, trifluoromethane hydroxylamino group, pentafluoroacetylamino group, tert-butylamine group, cyclohexylamine group, n-butylsulfonylamine group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, n-propyl, isopropyl, tert-butyl, hydroxyl, dimethylamino, nitro, acetylamino, propylamino, trifluoroacetylamino, pentafluoroacetylamino base, tert-butylamine group, cyclohexylamine group.

The R ⁸ is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, cyclohexyl, phenyl, more preferably a hydrogen atom, Methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl.

The X is preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.

In addition to the description method of the following formula (VI-1), the structure of the compound (VI) can also be expressed by the description method using the resonance structure like the following formula (VI-2). That is, the following formula (VI-1) and the following formula (VI-2) differ only in the description method of the structure, and they both represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium salt-based compound is represented by a description method such as the following formula (VI-1).

[Chemical 11]

Furthermore, 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.

As long as the compound (VI) satisfies the necessary conditions of the formula (VI-1), the structure There are no special restrictions. The left and right substituents bonded to the central four-membered ring may be the same or different, but being the same is preferred because it is easier to synthesize.

Compound (B) may be used individually by 1 type, or may use 2 or more types together. In addition, regarding the content of compound (B), for example, when using a base material including a transparent resin substrate (ii) containing compound (A) and compound (B), or when using a transparent resin substrate (iii) containing compound (B), ) is laminated with a resin layer such as an overcoat layer including a curable resin containing compound (A) as the base material (i), preferably 0.003 parts by weight based on 100 parts by weight of the transparent resin Parts by weight ~ 2.0 parts by weight, more preferably 0.0005 parts by weight ~ 1.8 parts by weight, particularly preferably 0.008 parts by weight ~ 1.5 parts by weight. In addition, a base material in which a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) and the compound (B) is laminated on a resin support used as a base or a glass support, or a base material formed on a resin support used as a base. When the base material (i) is a base material in which a resin layer such as an overcoat layer including a curable resin or the like containing the compound (B) is laminated on a transparent resin substrate (iv) containing the compound (A), 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 relative to 100 parts by weight of the resin forming the transparent resin layer containing compound (A). . If the content of the compound (B) is within the above range, a near-infrared cut filter that has both good near-infrared absorption characteristics and high visible light transmittance can be obtained.

<Other pigments (X)>

The base material (i) may further contain other pigments (X) that are incompatible with compound (A) and compound (B).

The other dye (X) is not particularly limited as long as the maximum absorption wavelength is less than 650 nm or exceeds 850 nm. Examples thereof include those selected from the group consisting of squarium ylide-based compounds, phthalocyanine-based compounds, cyanine-based compounds, and naphthalene-based compounds. At least one compound from the group consisting of phthalocyanine-based compounds, ketonium-based compounds, eight-membered porphyrin-based compounds, diimmonium-based compounds, perylene-based compounds, and metal dithiolate-based compounds. By using such other pigments (X), a wider range of near-infrared light can be absorbed and the transmittance in the near-infrared region can be reduced.

<Transparent resin>

The transparent resin layer and the transparent resin substrate (ii) to the transparent resin substrate (iv) laminated on a resin support, a glass support, etc. can be formed using a transparent resin. The transparent resin used in the base material (i) may be a single type or two or more types.

The transparent resin is not particularly limited as long as the effect of the present invention is not impaired. For example, in order to ensure thermal stability and formability of the film, and to form a transparent resin, it can be made by high-temperature vapor deposition at a vapor deposition temperature of 100° C. or higher. Films used to form dielectric multilayer films include resins whose glass transition temperature (Tg) is preferably 110°C to 380°C, more preferably 110°C to 370°C, and further preferably 120°C to 360°C. In addition, it is particularly preferable if the glass transition temperature of the resin is 140° C. or higher because a film that can be evaporated at a higher temperature to form a dielectric multilayer film can be obtained.

Regarding the transparent resin, when forming a resin plate with a thickness of 0.1 mm including the resin, the total light transmittance (Japanese Industrial Standards (JIS) K7105) of the resin plate can be preferably 75%~ 95%, preferably 78%~95%, particularly preferably 80%~95% resin. If using total When a resin has a light transmittance within this range, the obtained substrate exhibits good transparency as an optical film.

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

Examples of the transparent resin include: cyclic (poly)olefin-based resin, aromatic polyether-based resin, polyimide-based resin, fluoropolycarbonate-based resin, fluoropolyester-based resin, polycarbonate-based resin, Polyamide (aromatic polyamide) resin, polyarylate resin, polyethylene resin, polyether resin, polyparaphenylene resin, polyamide imine resin, polyethylene naphthalate Diester (Polyethylene Naphthalate, PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester curable resin, silsesquioxane ultraviolet curable resin Resin, acrylic ultraviolet curable resin and vinyl ultraviolet curable resin.

《Cyclic (poly)olefin resin》

The cyclic (poly)olefin-based resin is preferably at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ). The resin obtained in bulk and the resin obtained by hydrogenating the resin.

[Chemical 13]

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

(i')Hydrogen atom

(ii') Halogen atoms

(iii')trialkylsilyl

(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') Substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms

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

( ^{vii ' ) An} alkylene group ^formed by ^bonding R ')~(vi') atoms or radicals.)

(viii') A ^{monocyclic or polycyclic} hydrocarbon ring ^{or heterocyclic} ring formed by ^the mutual bonding of R represents an atom or group selected from (i')~(vi').)

(ix') A ^monocyclic hydrocarbon ^ring or ^heterocyclic ring formed by the mutual bonding ^of R ~(vi') atoms or radicals.)

In the formula (Y ₀ ), R ^y1 and R ^y2 independently represent atoms or groups selected from (i') to (vi'), or represent a single ring formed by R ^y1 and R ^y2 bonded to each other. or a polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or ^heterocyclic ring, ky and ^py respectively independently represent 0 or a positive integer.

"Aromatic polyether resin"

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

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 from 0 to 4.

In the formula (2), R ¹ ~ R ⁴ and a ~ d are independently the same as R ¹ ~ R ⁴ and a ~ d in the formula (1), and Y represents a single bond, -SO ₂ - or >C=O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group with 1 to 12 carbon atoms or a nitro group, g and h each independently represent an integer from 0 to 4, and m represents 0 or 1. Among them, when m is 0, R ⁷ is not cyano group.

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

[Chemical 17]

In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group with 1 to 12 carbon atoms, and Z represents a single bond, -O-, -S-, -SO ₂ -, >C=O, - CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, e and f 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 independently the same as R ⁷ , R ⁸ , Y, m, g and h in formula (2), and R ⁵ , R ⁶ , Z, n, e and f are independently the same as R ⁵ , R ⁶ , Z, n, e and f in the formula (3).

"Polyimide Resin"

The polyimide-based resin is not particularly limited as long as it is a polymer compound containing an imine bond in the repeating unit. For example, it can be obtained by Japanese Patent Application Laid-Open No. 2006-199945 or Japanese Patent Application Laid-Open No. 2008 -163107.

"Polycarbonate Resin"

The polycarbonate-based resin is not particularly limited as long as it contains a polycarbonate moiety. For example, it can be synthesized by the method described in Japanese Patent Application Laid-Open No. 2008-163194.

"Polyester Resin"

There is no particular limitation on the polyester resin as long as it contains a polyester moiety. For example, the polyester resin described in Japanese Patent Laid-Open No. 2010-285505 or Japanese Patent Laid-Open No. 2011-197450 can be used. method to synthesize.

"Fluorinated aromatic polymer resin"

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

"Acrylic UV-curable resin"

The acrylic ultraviolet curable resin is not particularly limited, and examples thereof include resin compositions containing compounds having one or more acrylic groups or methacrylic groups in the molecule, and compounds that are decomposed by ultraviolet rays to generate active radicals. The synthesizer of things. A base material in which a transparent resin layer containing compound (B) and a curable resin is laminated on a resin support used as a glass support or as a base, or a transparent resin substrate containing compound (B) (ii ) is used as the base material (i) on which a resin layer such as an overcoat layer including a curable resin or the like is laminated, an acrylic ultraviolet curable resin is particularly preferably used as the curable resin.

"Commercially Available Products"

Examples of commercially available transparent resins include the following commercially available products. Commercially available products of cyclic (poly)olefin resins include: Arton manufactured by Japan Synthetic Rubber (JSR) Co., Ltd., and Zeon Noa manufactured by Japan Zeon Co., Ltd. Zeonor), APEL manufactured by Mitsui Chemicals Co., Ltd., TOPAS manufactured by Polyplastics Co., Ltd., etc. Examples of commercially available polyether resins include Sumikaexcel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide-based resins include Neopulim L manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polycarbonate resins include PURE-ACE manufactured by Teijin Co., Ltd. Examples of commercially available polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polyester-based resins include OKP4HT manufactured by Osaka Gas Chemicals Co., Ltd. Examples of commercially available acrylic resins include Acryviewa manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available silsesquioxane-based ultraviolet curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Other ingredients>

The base material (i) may further contain additives such as antioxidants, near-ultraviolet absorbers, fluorescent matting agents, and metal complex compounds within the scope that does not impair the effects of the present invention. These other components may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of the near-ultraviolet absorber include: imine compounds compounds, indole compounds, benzotriazole compounds, triazine compounds, etc.

Examples of the antioxidant include: 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxo-3,3'-di-tert-butyl-5,5 '-Dimethyldiphenylmethane, and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, etc.

In addition, these additives may be mixed with resin etc. when manufacturing base material (i), or may be added when synthesizing resin. In addition, the addition amount can be appropriately selected according to the desired characteristics, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the resin.

<Manufacturing method of base material (i)>

When the base material (i) is a base material including the transparent resin substrate (ii) to the transparent resin substrate (iv), the transparent resin substrate (ii) to the transparent resin substrate (iv) For example, it can be formed by melt molding or casting, and if necessary, a coating agent such as an antireflective agent, a hard coat agent, and/or an antistatic agent can be applied after the molding, thereby producing a base material laminated with an outer coating layer. .

The base material (i) is a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) and the compound (B), which is laminated on a glass support body or a resin support body serving as a base. In the case of the base material, for example, a resin solution containing the compound (A) and the compound (B) is melt-molded or cast-molded on a glass support or a resin support serving as the base, preferably by spin coating or slit. After applying by coating, inkjet, or other methods, the solvent is dried and removed, and if necessary, light irradiation or heating is performed to produce a base material in which a transparent resin layer is formed on a glass support or a resin support that serves as the base. .

"Melt Forming"

Specific examples of the melt molding include: a method of melt molding pellets obtained by melt-kneading a resin, a compound (A), a compound (B), etc.; A method of melt-molding a resin composition; or a method of melt-molding particles obtained by removing a solvent from a resin composition containing compound (A), compound (B), a resin, and a solvent, etc. Examples of melt molding methods include injection molding, melt extrusion molding, blow molding, and the like.

"Casting Forming"

The casting molding can also be produced by the following methods: casting a resin composition including compound (A), compound (B), resin, and a solvent onto an appropriate support and removing the solvent; or After the curable composition including compound (A), compound (B), photocurable resin and/or thermosetting resin is cast on an appropriate support and the solvent is removed, it is irradiated with ultraviolet rays or heated by an appropriate method such as to harden it.

In the case where the base material (i) is a base material including a transparent resin substrate (ii) containing the compound (A) and the compound (B), the base material (i) can be formed by casting. The support is obtained by peeling off the coating film, and the base material (i) is a support such as a glass support or a resin support serving as a base, and a cured resin containing the compound (A) and the compound (B) is laminated on the support. In the case of a base material made of a transparent resin layer such as an overcoat layer of a flexible resin or the like, the base material (i) can be obtained by not peeling off the coating film after casting.

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

Furthermore, a transparent resin layer can also be formed on an optical component by the following method: coating the resin composition on an optical component made of glass, quartz, or transparent plastic and drying the solvent; or applying the hardened resin composition. Methods for hardening and drying the sexual composition.

The amount of residual solvent in the transparent resin layer (transparent resin substrate (ii)) obtained by the 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 or less based on the weight of the transparent resin layer (transparent resin substrate (ii)). When the residual solvent amount is within the above range, a transparent resin layer (transparent resin substrate (ii)) that is difficult to deform or change in characteristics and can easily exhibit a desired function can be obtained.

[Dielectric multilayer film]

The near-infrared cut filter of the present invention has a dielectric multilayer film on at least one side of the substrate (i). The dielectric multilayer film of the present invention is a film capable of reflecting near-infrared rays. In the present invention, the near-infrared reflective film can be provided on one side of the substrate (i) or on both sides. When the filter is disposed on one side, the manufacturing cost and ease of production are excellent. When the filter is disposed on both sides, a near-infrared cut filter that has high strength and is difficult to warp or twist can be obtained. When a near-infrared cutoff filter is used for a solid-state imaging device, it is preferable that the near-infrared cutoff filter has small warpage or distortion, so it is preferable to provide a dielectric multilayer film. on both sides of substrate (i).

The dielectric multilayer film preferably has reflective properties over the entire wavelength range of 700 nm to 1100 nm, further preferably has reflective properties over the entire wavelength range of 700 nm to 1150 nm, and particularly preferably has reflective properties over the entire wavelength range of 700 nm to 1200 nm. . An example of a form in which a dielectric multilayer film is provided on both sides of the base material (i) is: a near-infrared cut filter having a near-infrared cutoff filter on one side of the base material (i) having a glass support. When measured at an angle of 30°, the first optical layer mainly has reflective properties around the wavelength of 700nm to 1150nm, and the second optical layer has anti-reflective properties in the visible area on the other side (see Figure 3(a) ), or a third optical layer having reflective properties mainly in the vicinity of wavelengths of 700 nm to 950 nm when measured at an angle of 30° from the vertical direction to the near-infrared cut filter on one side of the base material (i), and The other surface of the base material (i) has a fourth optical layer having reflective characteristics mainly in the vicinity of 900 nm to 1150 nm when measured at an angle of 30° from the vertical direction to the near-infrared cut filter (see Figure 3 (b)) etc.

The near-infrared cutoff filter of the present invention is preferably such that the substrate (i) has a glass support and includes dielectric multilayer films on both sides of the substrate (i), and more preferably these dielectric multilayer films It is a near-infrared reflective film and a visible light anti-reflective film, and it is particularly preferred to have a near-infrared reflective film on one side of the substrate (i) and a visible light anti-reflective film on the other side.

Examples of dielectric multilayer films include those in which high refractive index material layers and low refractive index material layers are alternately laminated. As a material constituting the high refractive index material layer, it can be Use materials with a refractive index of 1.7 or above, and choose materials with a refractive index of usually 1.7 to 2.5. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, etc. as a main component and containing a small amount (for example, relative to the main component). The composition is 0% to 10% by weight) titanium oxide, tin oxide and/or cerium oxide, etc.

As the material constituting the low refractive index material layer, a material with a refractive index of 1.6 or less can be used, and a material with a refractive index of generally 1.2 to 1.6 is selected. Examples of such materials include silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

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

Generally, if the near-infrared wavelength to be blocked is λ (nm), the thickness of each layer of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ~0.5λ. The value of λ (nm) is, for example, 700nm~1400nm, preferably 750nm~1300nm. If the thickness is within this range, the product (n×d) of the refractive index (n) and the film thickness (d) is calculated using λ/4, and the optical film thickness is calculated from the relationship between the high refractive index material layer and the low refractive index material layer. The thickness of each layer has approximately the same value, and the blocking and transmission of a specific wavelength tend to be easily controllable based on the relationship between the optical properties of reflection and refraction.

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

In the present invention, the types of materials constituting the high refractive index material layer and the low refractive index material layer, and the composition of the high refractive index material layer and the low refractive index material layer are appropriately selected in conjunction with the absorption characteristics of the compound (A) or the compound (B). The thickness of each layer, the order of lamination, and the number of laminations can ensure sufficient transmittance in the visible region, sufficient light-cutting characteristics in the near-infrared wavelength region, and can reduce the reflection of near-infrared rays when incident from an oblique direction. Rate.

Here, in order to optimize the conditions, for example, optical film design software (for example, Essential Macleod, manufactured by Thin Film Center) can be used to take into account the anti-reflection in the visible area. Just set the parameters according to the effect and the light cutoff effect in the near-infrared region. In the case of the software, for example, when designing the first optical layer, setting the target transmittance at wavelengths of 400 nm to 700 nm to 100% and setting the value of the target tolerance (Target Tolerance) to 1, This is a parameter setting method that sets the target transmittance for wavelengths 705nm to 950nm to 0%, and sets the target tolerance value to 0.5. These parameters can also be combined with various characteristics of the substrate (i) to further divide the wavelength range to change the value of the target tolerance.

[Other functional films]

The near-infrared cut filter of the present invention is used for improving the surface hardness of the base material (i) or the dielectric multilayer film, improving chemical resistance, antistatic, and eliminating damage, etc. within the scope that does not impair the effects of the present invention. For this purpose, it can be provided between the substrate (i) and the dielectric multilayer film, the surface opposite to the surface of the substrate (i) on which the dielectric multilayer film is provided, or the surface of the substrate (i) on which the dielectric multilayer film is provided. The opposite surface of the base material (i) is suitably provided with a functional film such as an antireflection film, a hard coat film, or an antistatic film.

The near-infrared cut filter of the present invention may include one layer containing 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, it may include two or more identical layers, or may include two or more different layers.

The method of laminating the functional film is not particularly limited, and examples thereof include coating an antireflective agent, a hard coat agent, and/or an antistatic agent on the base material (i) or the dielectric multilayer film in the same manner as described above. Methods such as melt molding or casting molding of cloth agents, etc.

In addition, it can also be produced by applying a curable composition containing the coating agent or the like on the base material (i) or the dielectric multilayer film using a bar coater or the like, and then irradiating it with ultraviolet rays. Wait for hardening.

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curing resins or thermosetting resins, and specific examples include vinyl compounds or urethanes. series, acrylic urethane series, acrylate series, epoxy series and epoxy acrylate series resins, etc. Examples of the curable composition containing these coating agents include vinyl-based and urethane-based coating agents. Ester-based, acrylic urethane-based, acrylate-based, epoxy-based and epoxy acrylate-based curable compositions, etc.

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

In the curable composition, when the total amount of the curable composition is 100% by weight, the proportion of the polymerization initiator is preferably 0.1% to 10% by weight, more preferably 0.5% by weight. ~10% by weight, preferably 1% by weight~5% by weight. When the blending ratio of the polymerization initiator is within the above range, a functional film such as an antireflective film, a hard coat film, or an antistatic film having a desired hardness can be obtained.

Furthermore, an organic solvent may be added to the curable composition as a solvent. As the organic solvent, a known organic solvent may be used. Specific examples of organic solvents include: alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetic acid Esters such as ethyl ester, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc. Ethers; aromatic hydrocarbons such as benzene, toluene, and xylene; amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. One type of these solvents may be used alone, or two or more types may be used in combination.

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

In addition, for the purpose of improving 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, the base material (i) and the functional film may be Or the surface of the dielectric multilayer film is subjected to surface treatment such as corona treatment or plasma treatment.

[Method for manufacturing near-infrared cut filter]

The method of manufacturing a near-infrared cut filter of the present invention is characterized by including the step of forming a dielectric multilayer film on at least one side of the base material (i). The method of forming a dielectric multilayer film is as described above. In addition, if necessary, the step of forming a functional film on the substrate (i) may also be included.

Furthermore, in the case where warping occurs in the near-infrared cutoff filter during the formation of the dielectric multilayer film, in order to eliminate the problem, the following method may be used: forming dielectric multilayers on both sides of the near-infrared cutoff filter film, or the surface of the near-infrared cut filter on which the dielectric multilayer film is formed is irradiated with electromagnetic waves such as ultraviolet rays. Furthermore, when irradiating electromagnetic waves, the irradiation may be performed during the formation process of the dielectric multilayer film, or may be irradiated separately after formation.

[Use of near-infrared cut filter]

The near-infrared cutoff filter of the present invention has a wide viewing angle, excellent near-infrared cutoff ability, and the like. Therefore, it is effectively used for visual sensitivity correction of solid-state imaging elements such as CCD image sensors or CMOS image sensors of camera modules. In particular, it is effectively used in digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, personal computer (PC) cameras, surveillance cameras, automotive cameras, televisions, and automobiles. Navigation, portable information Terminals, video game consoles, portable game consoles, fingerprint authentication systems, digital music players, etc. Furthermore, it is also effectively used as an infrared cut filter installed on glass plates of automobiles, buildings, etc.

[Solid-state camera device]

The solid-state imaging device of the present invention includes the near-infrared cut filter of the present invention. Here, the so-called solid-state imaging device refers to an image sensor including a solid-state imaging element such as a CCD image sensor or a CMOS image sensor. Specifically, it can be used in digital still cameras, smartphone cameras, mobile phone cameras, and Wearable device cameras, digital cameras, etc. For example, the camera module of the present invention is equipped with 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 in any way. In addition, unless otherwise specified, "part" means "part by weight". In addition, the measurement method of each physical property value and the evaluation method of the physical property are as follows.

<Molecular weight>

The molecular weight of the resin is measured by the method (a) or (b) below, taking into consideration the solubility of each resin in a solvent.

(a) Use a gel permeation chromatography (GPC) device manufactured by WATERS (Type 150C, column: H-type column manufactured by Tosoh, developing solvent: o-dichlorobenzene) , measure the weight average molecular weight (Mw) and number average molecular weight (Mn) converted to standard polystyrene.

(b) Using a GPC device manufactured by Tosoh Corporation (model HLC-8220, column: TSKgel α-M, developing solvent: tetrahydrofuran (THF)), measure the weight average molecular weight (Mw) converted to standard polystyrene and Number average molecular weight (Mn).

In addition, regarding the resin synthesized in Resin Synthesis Example 3 described later, the logarithmic viscosity was measured using the following method (c) instead of the molecular weight using the method described above.

(c) Put a part of the polyimide resin solution into anhydrous methanol to precipitate the polyimide resin, filter it, and then separate it 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-pyrrolidinone, and a Cannon-Fenske viscometer was used. The logarithmic viscosity (μ) at 30°C is calculated using the following formula.

μ={ln(t _s /t ₀ )}/C

t ₀ : The flowing time of the solvent

t _s : The flowing time of the thin polymer solution

C：0.5g/dL

<Glass transition temperature (Tg)>

A differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies Co., Ltd. was used, and the temperature was measured at a heating rate of 20°C per minute and nitrogen flow.

<Spectral transmittance>

The transmittance of the base material, and the transmittance and reflectance of the near-infrared cut filter It was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-technologies Co., Ltd.

Here, if the transmittance is measured from the perpendicular direction of the near-infrared cut filter, the light transmitted perpendicularly to the filter is measured as shown in Figure 2(a). When measuring the transmittance at an angle of 30° to the vertical direction of the filter, measure the light transmitted at an angle of 30° to the vertical direction of the filter as shown in Figure 2(b). In addition, if the reflectance is measured at an angle of 30° from the vertical direction to the near-infrared cut filter, the near-infrared cut filter is mounted on the jig attached to the device as shown in Figure 2(c) and measured. . Furthermore, the ghost intensity due to multiple reflections between the near-infrared cutoff filter and the lens is the average reflectance measured from a direction of 30° perpendicular to the near-infrared cutoff filter at 700nm to 850nm. Calculated by the product of (a) (%) and the average transmittance (c) (%) of the near-infrared cut filter measured at 700 nm to 850 nm from a direction of 30° with respect to the vertical direction.

In addition, "the value of a*", "the value of b*", "the value of L*", "the value of a* (30°)", and "the value of b*" in the L*a*b* color system (30°)" and "L* value (30°)" are values obtained by measuring the transmittance from 380nm to 780nm in the vertical direction (incident angle 0°) of the near-infrared cut filter, And the value obtained by measuring the transmittance of 380nm to 780nm from an angle of 30° with respect to the vertical direction of the near-infrared cut filter (incident angle of 30°).

<Warp>

Near-infrared cut filter with 5mm square tip cut It was placed on the observation stage of "Digital Microscope VHX-600" manufactured by KEYENCE Co., Ltd., and the height of the warpage of the tip portion was observed and measured laterally, and evaluated based on the following standards.

○○○: Warp height <20μm

○○：20μm≦warp height<40μm

○: 40μm≦ warpage height <60μm

△: 60μm≦ warpage height <80μm

×: 80μm≦ height of warpage

<Color evaluation of camera images>

The color evaluation when a near-infrared cut filter is incorporated into a camera module is performed using the following method. A camera module was produced using the same method as in Japanese Patent Application Laid-Open No. 2016-110067, and the produced camera module was used in a D65 light source (standard light source device "Macbeth Judge II" manufactured by X-Rite) ”), a white plate of 300mm×400mm size was photographed, and the color in the camera image was evaluated according to the following criteria.

The acceptable level that has no problem at all is judged as ○, the acceptable level that can confirm some difference in color tone but has no problem in practical use as a high-definition camera module is judged as △, and the color and luster have problems and it is judged as a high-quality camera module. The level of image quality that is not acceptable for use as a camera module is judged as ×, and the level of color that is obviously different and is not acceptable for general camera module use is judged as ××.

Furthermore, as shown in FIG. 11 , when shooting, the white plate 112 and the camera module are adjusted in such a way that the white plate 112 occupies more than 90% of the area in the camera image 111 positional relationship.

[Synthesis example]

Compound (A) and compound (B) used in the following examples were synthesized by generally known methods. Examples of general synthesis methods include: Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. Sho 60-228448, Japan Japanese Patent Application Publication No. 1-146846, Japanese Patent Application Publication No. 1-228960, Japanese Patent Application Publication No. 4081149, Japanese Patent Application Publication No. 63-124054, "Phthalocyanine-Chemistry and Function-" (IPC, 1997 Year), Japanese Patent Laid-Open No. 2007-169315, Japanese Patent Laid-Open No. 2009-108267, Japanese Patent Laid-Open No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, etc. Methods.

<Resin synthesis example 1>

8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene (hereinafter also referred to as "DNM") represented by the following formula (a) ), 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were put into a nitrogen-substituted reaction vessel, and the solution was heated to 80°C. Then, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol/liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol/liter) were added to the solution in the reaction vessel. )0.9 part, the solution was heated and stirred at 80° C. for 3 hours, thereby performing a ring-opening polymerization reaction 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 obtained in the above manner was put into an autoclave, and 0.12 parts of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution. The hydrogenation reaction was performed by heating and stirring for 3 hours at a hydrogen pressure of 100 kg/cm ² and a reaction temperature of 165°C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. The reaction solution is poured into a large amount of methanol, and the coagulated product is separated, recovered, 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>

To a 3L four-necked flask, add 35.12g (0.253mol) of 2,6-difluorobenzonitrile, 87.60g (0.250mol) of 9,9-bis(4-hydroxyphenyl)quinone, and 41.46g (0.300mol) of potassium carbonate. ), 443g of N,N-dimethylacetamide (hereinafter also referred to as "DMAc") and 111g of toluene. Then, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were installed in the four-necked flask. Then, after replacing the inside of the flask with nitrogen, the obtained solution was reacted at 140° C. for 3 hours. time, and remove the generated water from the Dean-Stark tube at any time. At the time when water production was no longer visible, the temperature was gradually raised to 160° C., and the reaction was carried out at this temperature for 6 hours. After cooling to room temperature (25° C.), the generated salt was removed using filter paper, the filtrate was poured into methanol to reprecipitate, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum dried at 60° C. overnight to obtain a white powder (hereinafter also referred to as "resin B") (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285°C.

<Resin synthesis example 3>

Under nitrogen flow, put 1,4-double (4 -Amino-α,α-dimethylbenzyl)benzene 27.66g (0.08 mol) and 4,4'-bis(4-aminophenoxy)biphenyl 7.38g (0.02 mol), and dissolved In 68.65g of γ-butyrolactone and 17.16g of N,N-dimethylacetamide. The obtained solution was cooled to 5°C using an ice-water bath, and while maintaining the temperature, 22.62g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride were added in one go Amination catalyst triethylamine 0.50g (0.005 mol). After the addition, the temperature was raised to 180°C, and the distillate was distilled away at any time while refluxing for 6 hours. After the reaction was completed, the mixture was air-cooled until the internal temperature reached 100°C, and then 143.6 g of N,N-dimethylacetamide was added to dilute it and cooled while stirring to obtain a polyimide resin with a solid content concentration of 20% by weight. Solution 264.16g. A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. After washing the polyimide separated by filtration with methanol, it was dried in a vacuum dryer at 100°C for 24 hours to obtain a white powder (hereinafter also referred to as "resin C"). The infrared (IR) spectrum of the obtained resin C was measured, and as a result, absorption at 1704 cm ^-1 and 1770 cm ^-1 unique to the acyl imine group was observed. The glass transition temperature (Tg) of resin C was 310°C, and the logarithmic viscosity was measured to be 0.87.

[Example 1]

In Example 1, a near-infrared cut filter having a base material including a transparent glass substrate having a compound (A) and a compound ( B) transparent resin layer.

100 parts of the resin A obtained in Resin Synthesis Example 1 and a squarylium salt-based compound (a-1) represented by the following formula (a-1) as the compound (A) (in dichloro The maximum absorption wavelength in methane (dichloromethane is 698 nm) 0.03 part, as compound (B), a squarylium salt-based compound (b-1) represented by the following formula (b-1) (in dichloromethane 0.02 part of the phthalocyanine compound (b-2) represented by the following formula (b-2) (the maximum absorption wavelength in dichloromethane is 733 nm), and 0.03 part of dichloro Methane (methylene chloride) was used to prepare a solution with a resin concentration of 20% by weight. The obtained solution was cast onto a transparent glass substrate "OA-10G (thickness 100 μm)" (manufactured by Nippon Electric Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width, dried at 20° C. for 8 hours, and then Dry under reduced pressure at 100°C for 8 hours. Thereby, a base material having a thickness of 190 μm, a length of 60 mm, and a width of 60 mm having a transparent resin layer on one side of the glass substrate was obtained. The spectral transmittance of the base material is measured, and the average transmittance, Xa, Xb, and absolute value |Xa-Xb| And the average transmittance in the wavelength range Xa~Xb. The results are shown in Figure 4 and Table 4.

Then, a dielectric multilayer film (I) as a first optical layer is formed on one side of the obtained base material, and a dielectric multilayer film (II) as a second optical layer is formed on the other side of the base material. ), thereby obtaining a near-infrared cutoff filter with a thickness of approximately 0.194mm.

The dielectric multilayer film (I) is formed by alternately stacking silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers at a vapor deposition temperature of 100° C. (26 layers in total). The dielectric multilayer film (II) is formed by alternately stacking silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers at a vapor deposition temperature of 100° C. (20 layers in total). In either of the dielectric multilayer film (I) and the dielectric multilayer film (II), the silicon dioxide layer and the titanium dioxide layer are arranged from the substrate side to the titanium dioxide layer, the silicon dioxide layer, the titanium dioxide layer,. ..A silicon dioxide layer, a titanium dioxide layer, and a silicon dioxide layer are stacked alternately in this order, and the outermost layer of the near-infrared cut filter is made into a silicon dioxide layer.

The dielectric multilayer film (I) and the dielectric multilayer film (II) are designed in the following manner.

The thickness and number of layers of each layer should be combined with the wavelength-dependent characteristics of the refractive index of the base material or the applied compound (B) in such a way that the anti-reflection effect in the visible region and the selective transmission and reflection performance in the near-infrared region can be achieved. and the absorption characteristics of compound (A) were optimized using optical film design software (Essential Macleod, manufactured by Thin Film Center). When performing optimization, in this embodiment, the input parameters (target values) for the software are set as shown in Table 1 below.

As a result of the optimization of the film composition, in Example 1, the dielectric multilayer film (I) became a laminate in which silicon dioxide layers with a film thickness of 31 nm to 157 nm and titanium dioxide layers with a film thickness of 10 nm to 95 nm were alternately laminated. A multilayer vapor-deposited film with a layer number of 26. The dielectric multilayer film (II) is a multilayer vapor-deposited film with a layer number of 20, in which silicon dioxide layers with a film thickness of 36 nm to 194 nm and titanium dioxide layers with a film thickness of 11 nm to 114 nm are alternately laminated. . An example of the optimized film structure is shown in Table 2, and the spectral reflectance spectrum measured at an angle of 5° with respect to the vertical direction of the evaporated monitor glass substrate is shown in Figure 5(b), In FIG. 5(b) , the glass substrate for a vapor-deposited monitor is a film in which each dielectric multilayer film is formed as a single body on one side. Furthermore, when measuring the reflectance of evaporated monitor glass, in order to eliminate the influence of back reflection, the surface without the dielectric multilayer film was coated with black acrylic paint to perform anti-reflection treatment, and then the dielectric multilayer film was The surface of the electrical multilayer film is the incident surface of the measurement light.

The spectral transmittance measured from the vertical direction and an angle of 30° with respect to the vertical direction of the obtained near-infrared cut filter was measured, and the optical characteristics were evaluated. The results are shown in Figure 6 and Table 4. In addition, the spectral reflectance measured from an angle of 30° with respect to the vertical direction of each surface of the obtained near-infrared cut filter was confirmed. As a result, it was confirmed that the light incident surface was a dielectric multilayer film ( II) side (second optical layer side), the value of the lowest reflectance in the wavelength range of 700 nm to 800 nm becomes smaller. The results are shown in Table 4. Figure 7 shows the spectral reflection measured at 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. rate spectrum. Furthermore, the transmittance of 380 nm to 780 nm was measured from the vertical direction (incident angle 0°) of the obtained near-infrared cut filter and from an angle of 30° with respect to the vertical direction (incident angle 30°), and L*a was calculated "The value of a*", "the value of b*", "the value of L*", "the value of a* (30°)", "the value of b* (30°)" in the *b* color system and "value of L* (30°)", and calculate the absolute values of the differences from each value when the incident angle is 0°, |△a*|, |△b*|, and |△L*|. These results and various other evaluation results are shown in Table 4.

[Example 2]

In Example 1, as the compound (A), a squarylium salt compound (a-2) represented by the following formula (a-2) (maximum absorption wavelength in methylene chloride: 703 nm) 0.033 was used parts instead of 0.03 parts of compound (a-1), and as compound (B), use a phthalocyanine compound (b-3) represented by the following formula (b-3) (in dichloromethane The maximum absorption wavelength is 770nm) 0.077 parts instead of 0.02 parts of compound (b-1) and 0.03 parts of compound (b-2). Except for this, the same procedures and conditions as in Example 1 were used to obtain a single layer on the glass substrate. The surface has a base material including a transparent resin layer containing compound (A) and compound (B). The spectral transmittance of the base material was measured, and the optical properties were evaluated. The results are shown in Figure 8 and Table 4.

Then, in the same manner as in Example 1, a silicon dioxide (SiO ₂ ) layer and a titanium dioxide (TiO ₂ ) layer were alternately laminated as a first optical layer on one side of the obtained base material (a total of 26 layer) of the dielectric multilayer film (III), and further formed as a second optical layer on the other side of the substrate by alternately laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers (total 20 layers) of dielectric multilayer film (IV) to obtain a near-infrared cut filter with a thickness of approximately 0.194mm. The design of the dielectric multilayer film was performed using the same design parameters as in Example 1, taking into account the wavelength dependence of the refractive index of the substrate. The spectral transmittance and spectral reflectance of the obtained near-infrared cut filter were measured, and the optical characteristics were evaluated. The results are shown in Figure 9 and Table 5. In addition, the spectral reflectance measured from an angle of 30° with respect to the vertical direction of each surface of the obtained near-infrared cut filter was confirmed. As a result, it was confirmed that the light incident surface was a dielectric multilayer film ( IV) side (second optical layer side), the value of the average reflectance in the wavelength range of 700 nm to 800 nm becomes smaller. The results are shown in Table 4. Figure 10 shows the spectral reflection measured at 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) side. rate spectrum. Furthermore, "the value of a*", "the value of b*", "the value of L*", and "the value of a*" in the L*a*b* color system of the obtained near-infrared cut filter are determined (30°)", "b* value (30°)" and "L* value (30°)", and calculate the absolute value of the difference from each value when the incident angle is 0°｜△a*| , |△b*| and |△L*|. These results and various other evaluation results are also shown in Table 4.

[Example 3]

In Example 3, a near-infrared cutoff filter having a base material including a transparent resin substrate having resin layers on both sides was produced by the following procedures and conditions.

100 parts of resin A obtained in Resin Synthesis Example 1, 0.03 parts of compound (a-1) and 0.01 part of compound (a-2) as compound (A), and compound ((B)) were added to the container. b-3) 0.08 parts and 0.02 parts of compound (b-4) represented by the following formula (b-4) (maximum absorption wavelength in methylene chloride is 781 nm), and methylene chloride to prepare a resin with a concentration of 20% by weight solution. The obtained solution was cast onto a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried under reduced pressure at 100° C. for 8 hours to obtain a transparent resin substrate with a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

The resin composition (1) of the following composition was coated on one side of the obtained transparent resin substrate using a bar coater, and heated at 70° C. for 2 minutes in an oven to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying would become 2 μm. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (1), thereby forming a resin layer on the transparent resin substrate. Similarly, a resin layer including the resin composition (1) is also formed on the other side of the transparent resin substrate, and a base having resin layers on both sides of the transparent resin substrate including the compound (A) and the compound (B) is obtained. material. The spectral transmittance of the base material was measured, and the optical properties were evaluated. The results are shown in Table 4.

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

Then, in the same manner as in Example 1, a dielectric multilayer in which silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers were alternately laminated (26 layers in total) was formed on one side of the obtained base material. Film (V) is used as the first optical layer, and a dielectric multilayer film in which silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers are alternately laminated (20 layers in total) is formed on the other side of the substrate. (VI) As the second optical layer, a near-infrared cut filter with a thickness of about 0.108 mm is obtained. The design of the dielectric multilayer film was performed by taking into consideration the wavelength dependence of the refractive index of the base material and the like in the same manner as in Example 1, and using the same design parameters as in Example 1. This near-infrared cut filter was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[Example 4]

In Example 4, the following procedures and conditions were used to produce a near-infrared cutoff filter having a base material including a resin substrate having a film containing Transparent resin layer of compound (A) and compound (B).

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

In the same manner as in Example 3, a resin layer containing the resin composition (2) having the following composition was formed on both sides of the obtained resin substrate, thereby obtaining a layer containing the compound (A) and the compound on both sides of the resin substrate. The base material of the transparent resin layer of (B). The spectral transmittance of the base material was measured, and the optical properties were evaluated. The results are shown in Table 4.

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

Then, in the same manner as in Example 1, a dielectric multilayer in which silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers were alternately laminated (26 layers in total) was formed on one side of the obtained base material. Film (VII) is used as the first optical layer, and a dielectric multilayer film in which silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers are alternately laminated (20 layers in total) is formed on the other side of the substrate. (VIII) As the second optical layer, a near-infrared cut filter with a thickness of about 0.108 mm is obtained. The design of the dielectric multilayer film was performed by taking into consideration the wavelength dependence of the refractive index of the base material and the like in the same manner as in Example 1, and using the same design parameters as in Example 1. This near-infrared cut filter was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[Example 5~Example 12]

A substrate and a substrate were prepared 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. Near-infrared cutoff filter and evaluation. The results are shown in Table 4.

[Example 13~Example 15]

A base material and a near-infrared cut filter were prepared 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. Evaluation. The results are shown in Table 4.

[Example 16~Example 17]

Except for changing the drying conditions of the resin, compound (A), compound (B), solvent, and resin substrate as shown in Table 4, the substrate and near-infrared cut filter were prepared in the same manner as in Example 3, and performed. Evaluation. The results are shown in Table 4.

[Example 18~Example 19]

A base material and a near-infrared cut filter were prepared 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. Evaluation. The results are shown in Table 4.

[Comparative example 1]

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

[Comparative example 2]

Except using 0.01 part of compound (a-1) and 0.01 part of compound (a-2) as compound (A), a base material and a near-infrared cut filter were produced and evaluated in the same manner as in Example 3. The results are shown in Table 5.

[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 (thickness: 100 μm)" (manufactured by Nippon Electric Glass Co., Ltd.) was used as a base material. The results are shown in Table 5.

[Comparative example 4]

In Comparative Example 4, a near-infrared cutoff filter having a base material including a transparent resin substrate having resin layers on both sides was produced by the following procedures and conditions.

100 parts of resin A obtained in Resin Synthesis Example 1 and 0.135 parts of compound (b-3) as compound (B) were added to a container to prepare a solution with a resin concentration of 20% by weight. The obtained solution was cast onto a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried under reduced pressure at 100° C. for 8 hours to obtain a transparent resin substrate with a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

In the same manner as in Example 3, a resin layer containing a resin composition (3) having the following composition was formed on both sides of the obtained resin substrate, thereby obtaining a transparent resin layer containing an absorbent material on both sides of the resin substrate. base material, and near-infrared cutoff filter. The base material and the near-infrared cut filter were evaluated in the same manner as in Example 1. The results are shown in Table 5.

Resin composition (3): 100 parts by weight of tricyclodecane dimethanol acrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, YMF-02 [manufactured by Sumitomo Metal Mining Co., Ltd., cesium tungsten oxide (Cs _0.33 WO) ₃ (18.5% by mass dispersion of 3 (average dispersed particle diameter 800nm or less; maximum absorption wavelength (λmax) = 1550nm~1650nm (film))) 30 parts by weight, methyl ethyl ketone (solvent, TSC: 25%)

[Comparative example 5]

Except for changing the drying conditions of the resin, compound (A), compound (B), solvent, and resin substrate as shown in Table 5, the substrate and near-infrared cut filter were prepared in the same manner as in Example 3, and were carried out. Evaluation. The results are shown in Table 5.

[Comparative example 6]

It was produced in the same manner as in Example 3 except that a thermoplastic polyimide film (manufactured by ASONE Co., Ltd., 0.5 mm thick) was used as the base material, and neither an absorbent material nor a composition for forming a transparent resin layer was used. into a near-infrared cutoff filter and evaluated. The results are shown in Table 5.

[Comparative Example 7]

A transparent glass substrate "OA-10G (thickness: 100 μm)" (manufactured by Nippon Electric Glass Co., Ltd.) was used as the base material, and a dielectric multilayer film as shown in Table 3 was laminated. The process was carried out in the same manner as in Example 1 except that the Infrared cut filter and evaluation. The results are shown in Table 5.

[Comparative example 8]

The drying conditions of the resin, compound (A), compound (B), solvent and resin substrate were changed as shown in Table 5, and the dielectric multilayer film (I), dielectric multilayer film (II), base The dielectric multilayer film (I) and the dielectric multilayer film (II) were formed on one side of the obtained substrate in a sequential manner. The substrate and near-infrared rays were prepared in the same manner as in Example 3 except that cutoff filter and evaluate it. The results are shown in Table 5.

[Table 4]

[table 5]

The contents of the base materials, various compounds, etc. in Tables 4 to 5 are as follows.

<Form of base material>

Form (1): A form in which a transparent resin layer containing compound (A) and compound (B) is provided on a single surface of a glass substrate

Form (2): A form in which a transparent resin substrate containing compound (A) and compound (B) has resin layers on both sides.

Form (3): A form in which a transparent resin layer containing compound (A) and compound (B) is provided on both sides of a resin substrate.

Form (4): Transparent resin substrate not containing compound (A) and compound (B)

Form (5): A form in which a transparent resin substrate containing compound (A) has resin layers on both sides.

Form (6): glass substrate

Form (7): Resin substrate

<Transparent resin>

Resin A: cyclic olefin resin (resin synthesis example 1)

Resin B: aromatic polyether resin (resin synthesis example 2)

Resin C: polyimide-based resin (resin synthesis example 3)

Resin D: Cyclic olefin resin "Zeonor 1420R" (manufactured by Zeon Corporation, Japan)

<Glass substrate>

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

<Near-infrared absorbing pigment>

"Compound (A)"

Compound (a-1): squarylium salt compound (a-1) represented by the formula (a-1) (maximum absorption wavelength in dichloromethane is 698 nm)

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

Compound (a-3): squarylium 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): squarylium compound (a-5) represented by the following formula (a-5) (maximum absorption wavelength in dichloromethane: 713 nm)

[Chemistry 24]

"Compound (B)"

Compound (b-1): squarylium salt compound (b-1) represented by the formula (b-1) (maximum absorption wavelength in dichloromethane is 776 nm)

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

Compound (b-3): phthalocyanine compound (b-3) represented by the formula (b-3) (The maximum absorption wavelength in dichloromethane is 770nm)

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

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

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

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

Compound (b-8): Cyanine 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)

[Chemical 27]

[Chemical 30]

<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

Furthermore, peel the coating film from the glass plate before drying under reduced pressure (except for form (1))

[Industrial availability]

The near-infrared cutoff filter of the present invention can be preferably used in digital still cameras, mobile phone cameras, digital video cameras, personal computer cameras, surveillance cameras, automotive cameras, televisions, and in-vehicle devices for car navigation systems. Portable information terminals, video game consoles, portable game consoles, devices for fingerprint authentication systems, digital music players, etc. Furthermore, it can also be suitably used as an infrared cut filter etc. installed on the glass of a car, a building, etc.

1: Near infrared cut filter

3:Light

3A: Reflected light

3B: Reflected light

3C:Through light

4: Lens

5: Sensor

Claims (16)

A near-infrared cut filter, which includes a base material having a transparent resin layer containing a near-infrared absorber, and a dielectric multilayer film formed on at least one side of the base material, and satisfies the following necessary condition (a) , the base material includes a glass support: (a) in the wavelength range of 600 nm to 800 nm, the value (Xa) of the shortest wavelength at which the transmittance when measured from the vertical direction of the base material becomes 50%, The absolute value of the difference | The near-infrared cutoff filter as described in claim 1, wherein in the wavelength range Xa~Xb, the average transmittance (Ta) measured from the vertical direction of the substrate is 35 %the following. For example, the near-infrared cut-off filter described in item 1 or 2 of the patent scope further satisfies the following necessary condition (b): (b) in the wavelength range of 560nm~800nm, from the near-infrared cut-off filter The shortest wavelength value (Ya) at which the transmittance becomes 50% when measured in the vertical direction of the filter, and the transmittance of 50% when measured at an angle of 30° from the vertical direction to the near-infrared cut filter The absolute value of the difference between the shortest wavelength value (Yb) | Ya-Yb | is less than 15 nm. The near-infrared cutoff filter described in item 1 or 2 of the patent application, wherein the near-infrared absorber is selected from the group consisting of squarium ylide compounds, At least one kind from the group consisting of phthalocyanine-based compounds, naphthalocyanine-based compounds, ketonium-based compounds, and cyanine-based compounds. In the near-infrared cut-off filter described in item 1 or 2 of the patent application, the transparent resin layer contains two or more types of near-infrared absorbers. The near-infrared cut-off filter as described in item 1 or 2 of the patent application, wherein the near-infrared absorber includes a squarylium salt compound (A) with maximum absorption at a wavelength of 650 nm to 750 nm and a Compound (B) having maximum absorption in the wavelength range of 660 nm to 850 nm, said compound (B) being a compound other than said compound (A). In the near-infrared cutoff filter described in Item 1 or 2 of the patent application, the dielectric multilayer film is formed on both sides of the base material. In the near-infrared cut filter described in claim 7, the dielectric multilayer films formed on both sides of the substrate include a near-infrared reflective film and a visible light anti-reflective film. The near-infrared cutoff filter as described in Item 1 or 2 of the patent application, wherein in the wavelength range of 600nm to 900nm, an angle of 30° is performed from the vertical direction to any surface of the near-infrared cutoff filter. The value (Xr) of the shortest wavelength at which the reflectance becomes 50% during measurement is 620 nm or more. The near-infrared cut-off filter as described in item 1 or 2 of the patent application, wherein the transparent resin is selected from the group consisting of cyclic (poly)olefin-based resin, aromatic polyether-based resin, and polyimide-based resin. , polycarbonate resin, polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, polyurethane Polyether resin, polyether resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin , at least one resin in the group consisting of epoxy resin, allyl ester curable resin, silsesquioxane ultraviolet curable resin, acrylic ultraviolet curable resin and vinyl ultraviolet curable resin. The near-infrared cutoff filter described in Item 1 or 2 of the patent application is used in a solid-state imaging device. The near-infrared cutoff filter described in Item 1 or 2 of the patent application, wherein the absolute value |Xa-Xb| in the necessary condition (a) is 160 nm or more. A solid-state imaging device including a near-infrared cut filter as described in any one of items 1 to 12 of the patent application. A camera module including a near-infrared cut filter as described in any one of items 1 to 12 of the patent application scope. A method of manufacturing a near-infrared cut filter, which includes the step of forming a dielectric multilayer film on at least one side of a base material having a transparent resin layer containing a near-infrared absorber, the method of manufacturing a near-infrared cut filter having It is characterized in that the near-infrared cutoff filter satisfies the following necessary condition (a), and the base material includes a glass support: (a) in the wavelength range of 600 nm to 800 nm, from the vertical direction of the base material The value (Xa) at the shortest wavelength at which the transmittance becomes 50% during measurement is the same as the value when measured in the vertical direction of the substrate in the wavelength range of 700 nm to 1200 nm. The absolute value of the difference | The method for manufacturing a near-infrared cutoff filter as described in Item 15 of the patent application, wherein the absolute value |Xa-Xb| in the necessary condition (a) is 160 nm or more.