KR102575309B1 - Optical Filters for Environmental Light Sensors - Google Patents

Abstract

An object of the present invention is to achieve both excellent visible light transmittance and near-infrared ray cutting performance even when the angle of incidence is increased as devices in which various environmental light sensors are provided are lowered in height, and also to reduce warpage or deformation and enable large-sized optics. It is to provide a filter. An optical filter for an environmental light sensor having a substrate that satisfies requirement (a) and also satisfying specific optical characteristics: (a) a compound (A) having an absorption maximum in a wavelength region of 650 nm or more and less than 800 nm, and A layer containing a compound (B) having an absorption maximum in a wavelength region of 800 nm or more and 1850 nm or less is provided.

Description

Optical Filters for Environmental Light Sensors

The present invention relates to an optical filter for an ambient light sensor. Specifically, it relates to an optical filter for an environmental light sensor that includes a compound having absorption in a specific wavelength region and has specific optical characteristics, an environmental light sensor using the optical filter, and an electronic device having the optical filter.

In recent years, development of environmental light sensors has been progressing as applications for information terminal devices such as smart phones and tablet terminals. An environmental light sensor in an information terminal device may be an illuminance sensor that detects the intensity of illumination of an environment where the information terminal device is placed and adjusts the brightness of the display, or a color sensor that detects the color tone of the environment where the information terminal device is placed and adjusts the color tone of the display. Used as a sensor, etc.

In order to match human visibility and luminance or color tone of a display in a natural form, it is important to allow only visible light to reach the ambient light sensor. For example, by providing an optical filter such as a near-infrared cut filter in an ambient light sensor, it is possible to bring the spectral sensitivity characteristic close to the visibility.

On the other hand, in view of the demand for emphasizing the design of information terminal devices, it is required to lower the transmittance of the transmission window through which light enters the environmental light sensor (to make the appearance darker), reduce the incident amount of visible light to infrared light, and achieve accurate illumination. However, there is a problem that color tone detection becomes difficult and malfunction occurs. Further, information terminal devices are being reduced in height, and the distance from the light incident window to the ambient light sensor is shortened. Therefore, the ratio of incident light from a high incident angle, such as an incident angle of 60°, increases, and it is required that the spectral characteristics of light reaching the environmental light sensor (particularly, the intensity of near-infrared rays) does not change even for incident light with a high incident angle. It is becoming.

As a means for matching the spectral characteristics of an environmental light sensor with human visibility, a device provided with a near-infrared cut filter having a metal multilayer film formed on a glass plate is disclosed (see Patent Document 1, for example). However, a near-infrared cut filter in which a metal multilayer thin film is formed on a glass plate has a problem in that the detection accuracy of the ambient light sensor is lowered because the optical characteristics vary greatly depending on the incident angle of incident light. In addition, when the metal multilayer film is formed by vapor deposition, warpage or deformation may occur when the optical filter is enlarged.

On the other hand, various near-infrared absorbing particles are known as materials that can cut near-infrared rays in a broadband regardless of the angle of incidence (eg, see Patent Document 2 and Patent Document 3). In order to achieve sufficient near-infrared ray cutting performance for environmental light sensors using such near-infrared absorbing particles, it is necessary to increase the addition amount of the near-infrared absorbing particles. However, in the near-infrared cut filter, when the amount of the near-infrared absorbing particles is increased, there is a problem that the visible light transmittance is lowered.

On the other hand, a near-infrared cut filter having a norbornene-based resin substrate, a near-infrared absorbing dye having an absorption maximum at a specific wavelength, and a near-infrared reflective film has a characteristic that the change in transmittance in the visible region is small when light rays are incident from an oblique direction ( See Patent Document 4). In order to use this near-infrared cut filter for environmental light sensor applications, it is considered desirable to further improve the infrared cut performance at a high incident angle of 60 degrees.

Japanese Unexamined Patent Publication No. 2011-060788 Specification International Publication No. 2005/037932 Japanese Unexamined Patent Publication No. 2011-118255 Japanese Unexamined Patent Publication No. 2011-100084

The present invention is an optical filter that can achieve both excellent visible light transmittance and near-infrared ray cutting performance even when the incident angle is increased, and can reduce warpage or deformation and can be enlarged as a device in which various environmental light sensors are provided is lowered in height. It aims to provide

An example of the aspect of the present invention is shown below.

[1] An optical filter for an environmental light sensor characterized in that it has a substrate that satisfies the following requirement (a) and also satisfies the following requirements (b), (c) and (d):

(a) has a layer containing a compound (A) having an absorption maximum in a wavelength region of 650 nm or more and less than 800 nm, and a compound (B) having an absorption maximum in a wavelength region of 800 nm or more and 1850 nm or less;

(b) In the wavelength range of 800 to 1000 nm, the average value Rf _a-5 of the reflectance of light incident from an oblique direction of 5 degrees with respect to the vertical direction on one surface of the optical filter and the vertical direction on the other surface the average value Rf _b-5 of reflectances of light incident from a direction obliquely 5 degrees relative to each other is 15% or less;

(c) In the wavelength range of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter and the average value T _a- 30 of the transmittance of light incident from an oblique direction of 30 degrees with respect to the vertical direction, , the average value T _{a -60} of the transmittance of light incident from a direction obliquely 60 degrees with respect to the vertical direction is all 20% or more and less than 75%;

(d) In the wavelength range of 800 nm to 1200 nm, the average value OD _a-0 of the optical density (OD value) for light incident from the vertical direction of the optical filter and the light incident from an oblique direction of 30 degrees with respect to the vertical direction The average value OD _a-30 of the optical density (OD value) for light and the average value OD _a-60 of the optical density (OD value) for light incident from an oblique direction of 60 degrees with respect to the vertical direction are both 1.5 or more.

[2] The optical filter for an environmental light sensor according to item [1], characterized by not having a dielectric multilayer film.

[3] The optical filter for an ambient light sensor according to item [1] or [2], wherein the layer containing the compound (A) is a transparent resin layer.

[4] The optical filter for an environmental light sensor according to item [3], wherein the transparent resin layer further contains a compound (B) having an absorption maximum in a wavelength range of 800 nm to 1850 nm.

[5] Any one of items [1] to [4], wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. An optical filter for an environmental light sensor described in .

[6] The compound (B) is near-infrared absorbing fine particles, squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, cyanine-based compounds, dimonium-based compounds, metal dithiolate-based compounds, and The optical filter for an ambient light sensor according to any one of items [1] to [5], characterized by being at least one compound selected from the group consisting of rolopyrrole compounds.

[7] The near-infrared absorbing fine particles are selected from the group consisting of first fine particles containing a compound represented by the following formula (P-1) and second fine particles containing a compound represented by the following formula (P-2) The optical filter for an environmental light sensor according to item [6], characterized in that it is at least one type of filter.

A _1/n CuPO ₄ ... (P-1)

In formula (P-1), A is at least one selected from the group consisting of alkali metals, alkaline earth metals and NH ₄ , n is 1 when A is an alkali metal or NH ₄ , and A is an alkaline earth metal In case of , it is 2.

M _x W _y O _z ... (P-2)

In formula (P-2), M is H, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, It is at least one element selected from Be, Hf, Os, Bi and I, and x, y and z satisfy the conditions of 0.001≤x/y≤1 and 2.2≤z/y≤3.0.

[8] The resin constituting the transparent resin layer is a cyclic polyolefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a fluorene polycarbonate-based resin, a fluorene polyester-based resin, or a polycarbonate-based resin. Resins, polyamide-based resins, aramid-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorinated aromatic polymer-based resins, (modified) acrylic-based resins Resins, epoxy-based resins, silsesquioxane-based UV curable resins, maleimide-based resins, alicyclic epoxy thermosetting resins, polyether ether ketone-based resins, polyarylate-based resins, allyl ester-based curable resins, acrylic UV-curable resins, vinyl The optical filter for an environmental light sensor according to item [3] or [4], characterized in that it is at least one resin selected from the group consisting of based ultraviolet curable resins and resins containing silica as a main component formed by a sol-gel method. .

[9] The ambient light sensor according to any one of items [1] to [8], wherein the substrate includes a fluorophosphate-based glass layer containing a copper component or a substrate made of phosphate-based glass. optical filter.

[10] In the optical filter for the ambient light sensor, when incident from a vertical direction, when incident from a direction of 30 ° to the vertical direction, and when incident from a direction of 60 ° to the vertical direction,

The change rate of the R (red) transmittance ratio derived from the following formula (1), the change ratio of the G (green) transmittance ratio derived from the following formula (2), and the B (blue) transmittance derived from the following formula (3) The optical filter for an ambient light sensor according to any one of items [1] to [9], characterized in that the rate of change of the ratio of is in the range of 0.6 to 1.1.

(Ratio of transmittance) = (R transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (1)

(G transmittance ratio) = (G transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (2)

(Ratio of B transmittance) = (B transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (3)

In Formulas (1) to (3), R transmittance is the average transmittance in the wavelength range of 580 to 650 nm, G transmittance is the average transmittance in the wavelength range of 500 to 580 nm, and B transmittance is the average transmittance in the wavelength range of 420 to 500 nm.

[11] An ambient light sensor comprising the optical filter for an ambient light sensor according to any one of items [1] to [10].

[12] An electronic device characterized by having the environmental light sensor according to item [11].

According to the present invention, it is possible to provide an optical filter for an environmental light sensor having high visible light transmittance and near-infrared ray cutting performance with respect to both incident light from the vertical direction and incident light from an oblique direction, and with reduced warpage or deformation. . An ambient light sensor using such an optical filter has a small incident angle dependence of incident light, and can measure illuminance and color temperature with high precision.

1 is a diagram explaining the configuration of an ambient light sensor according to an embodiment of the present invention.
2 is a diagram explaining the configuration of an ambient light sensor according to an embodiment of the present invention.
3 is a diagram for explaining an example of an electronic device including an ambient light sensor according to an embodiment of the present invention.
FIG. 4 is a diagram showing a configuration for measuring transmission spectra in the vertical direction, in the direction of an inclination of 30 degrees, and in the direction of an inclination of 60 degrees.
5 is a schematic diagram showing an example of a method for measuring the reflectance of light incident at an angle of 5° with respect to the vertical direction of the optical filter.
6 is a graph showing the spectral transmittance of the optical filter obtained in Example 1 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
7 is a graph showing the spectral transmittance of the optical filter obtained in Example 2 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
8 is a graph showing the spectral transmittance of the optical filter obtained in Example 3 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
9 is a graph showing the spectral transmittance of the optical filter obtained in Example 4 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
10 is a graph showing the spectral transmittance of the optical filter obtained in Example 5 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
11 is a graph showing the spectral transmittance of the optical filter obtained in Example 6 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
12 is a graph showing the spectral transmittance of the optical filter obtained in Example 7 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
13 is a graph showing the spectral transmittance of the optical filter obtained in Example 8 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
14 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 1 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
15 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 2 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
16 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 3 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.
17 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 4 measured in the vertical direction, at an angle of 30° from the vertical direction, and at an angle of 60° from the vertical direction.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described, referring drawings etc. as needed. However, the present invention can be implemented in many different modes, and is not construed as being limited to the description of the embodiments exemplified below. In order to make the description clearer, the drawings may be schematically displayed with respect to the width, thickness, shape, etc. of each part compared to the actual embodiment, but they are examples only and do not limit the interpretation of the present invention. In addition, in this specification and each drawing, the same elements as those described above with respect to previous drawings are given the same codes or similar codes (codes with only A, B, etc. attached after the numbers), so that the detailed description is properly explained. may be omitted.

In this specification, "image" refers to a relative position with respect to the main surface of the support substrate (the light-receiving surface of the sensor), and the direction away from the main surface of the support substrate is the "image". In the drawings of this application, the upper direction toward the ground is "upper". In addition, "on" includes the case of touching the object (ie, the case of "on") and the case of being located above the object (ie, the case of "over"). Conversely, “lower” refers to a relative position with respect to the main surface of the support substrate as a reference, and the direction approaching the main surface of the support substrate is “lower”. In the drawings of this application, the downward direction toward the ground is "lower".

[Optical filter]

The optical filter of the present invention is characterized in that it has a substrate (i) that satisfies the following requirement (a), and also satisfies the following requirements (b), (c) and (d).

Requirement (a): A layer containing a compound (A) having an absorption maximum in a wavelength region of 650 nm or more and less than 800 nm, and a compound (B) having an absorption maximum in a wavelength region of 800 nm or more and 1850 nm or less.

Requirement (b): In the wavelength range of 800 to 1000 nm, the average value Rf _a-5 of the reflectance of light incident from a direction obliquely 5 degrees with respect to the vertical direction on one side of the optical filter and the vertical direction on the other side The average value Rf _b-5 of the reflectance of light incident from a direction inclined at 5 degrees with respect to the direction is 15% or less, preferably 0.1 to 12%, and more preferably 1 to 10%.

As a method of satisfying the requirement (b), that is, a method of adjusting the average value of each reflectance, for example, since the reflectance is determined by the refractive index of the material through which light passes, the refractive index at which the average value of the reflectance in the prescribed range is obtained A method of selecting a substrate having the same, or a method of providing a layer for adjusting the refractive index to the substrate. In the case of imparting a dielectric multilayer film within a range not impairing the effect of the present invention, optical thin film design software (e.g., Essential Macleod, manufactured by Thin Film Center) is used so that an average value of reflectance within a prescribed range is obtained. There are also ways to design.

Satisfying the requirement (b) is preferable because multiple reflected light in the optical sensor module can be reduced, suppressing malfunction of the optical sensor, and obtaining a highly functional optical sensor.

Requirement (c): In the wavelength range of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter and the average value T _a- of the transmittance of light incident from an oblique direction of 30 degrees with respect to the vertical direction ₃₀ and the average value T _a-60 of transmittances of light incident from a direction obliquely 60 degrees with respect to the vertical direction are both 20% or more and less than 75%, preferably 25 to 70%.

As a method that satisfies the requirement (c), that is, a method for adjusting the average value of each transmittance, for example, the type of compound (A) and the compound (B) described later as necessary so that the average value of the transmittance within the prescribed range is obtained. and a method of appropriately selecting and adjusting the addition amount.

By satisfying requirement (c), it is possible to obtain an environmental light sensor with excellent sensor sensitivity. In the wavelength range of 430 to 580 nm, if the average value of the transmittance is too high, the intensity of the light incident on the light receiving portion of the optical sensor becomes excessively strong, causing saturation of the optical sensor, and may not function normally. In addition, if the average value of the transmittance is too low, the intensity of the light incident on the light receiving section of the optical sensor is weakened, and the intensity of the light passing through the optical filter may not be sufficiently secured.

Requirement (d): Average value OD _a-0 of the optical density (OD value) for light incident from the vertical direction of the optical filter in the wavelength range of 800 nm to 1200 nm, and incident from a direction inclined at 30 degrees with respect to the vertical direction The average value OD _a-30 of the optical density (OD value) for light and the average value OD _{a-60 of the optical density (OD value) for light incident from a direction inclined at 60} degrees with respect to the vertical direction are both 1.5 or more, preferably Preferably it is 2.0 to 6.0.

When an optical filter having values of OD _a-0 , OD _a-30 , and OD _a-60 of less than 1.5 in the wavelength range of 800 nm to 1200 nm is used in the environmental light sensor module, light in the wavelength range is not sufficiently cut. Enter the ambient light sensor. Since the ambient light sensor has sensitivity to light in the above wavelength range, when light in the above wavelength range enters the ambient light sensor, it becomes noise and causes malfunction of the color tone control or the like. When the values of OD _a-0 , OD _a-30 , and OD _a-60 exceed 6.0, it is necessary to increase the concentration of compound (B) or increase the number of layers of the dielectric multilayer film, and the visible light transmittance decreases. Problems such as deterioration or increased warpage may occur.

As a method that satisfies the requirement (d), that is, a method for adjusting the average value of the optical density, for example, the types and addition amounts of the compound (A) and the compound (B) are appropriately selected so that the average value of the transmittance within the prescribed range is obtained. and an adjustment method.

By satisfying requirement (d), the optical filter can sufficiently cut not only near-infrared rays transmitted in the vertical direction but also near-infrared rays transmitted at a high incident angle. When such an optical filter is used in an optical sensor of a mobile phone or tablet, malfunction of the luminance or color correction function of the screen can be prevented. In particular, in the optical sensor module, near-infrared light can be suitably cut even when a light-diffusion film is provided above the optical filter of the present invention.

The OD value is a common logarithmic value of transmittance and can be calculated by the following formula (4). If the average OD value of the specified wavelength range is high, the optical filter indicates that the light cutting characteristic of the wavelength range is high.

Average OD value in a certain wavelength range = -Log ₁₀ (Average transmittance (%)/100 in a certain wavelength range) ... Equation (4)

From the viewpoint of preventing malfunction of the ambient light sensor, the RGB balance of visible light when incident from the vertical direction of the optical filter, the RGB balance of visible light when incident from a direction of 30° with respect to the vertical direction of the optical filter, and the optical filter It is preferable that the change in RGB balance of visible light when incident from a direction of 60° with respect to the vertical direction is small. That is, the change rate of the R (red) transmittance ratio derived from the following formula (1), the change rate of the G (green) transmittance ratio derived from the following formula (2), and the B (blue) transmittance derived from the following formula (3) ) It is preferable that the rate of change of the transmittance ratio is in the range of 0.6 to 1.1. The closer the change rate is to 1.0, the smaller the incident angle dependent change of the RGB balance.

(Ratio of transmittance) = (R transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (1)

(G transmittance ratio) = (G transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (2)

(Ratio of B transmittance) = (B transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (3)

In Formulas (1) to (3), R transmittance is the average transmittance in the wavelength range of 580 to 650 nm, G transmittance is the average transmittance in the wavelength range of 500 to 580 nm, and B transmittance is the average transmittance in the wavelength range of 420 to 500 nm.

The value obtained by dividing the ratio of the R transmittance when measured at an angle of 30° to the vertical direction of the optical filter by the ratio of the R transmittance when measured in the vertical direction of the optical filter (R transmittance in the case of 0°→30° The rate of change of the ratio) can be derived from the following formula (5).

(Ratio of change of R transmittance ratio in the case of 0°→30°) = (Ratio of R transmittance when incident at an angle of 30° with respect to the vertical direction of the optical filter)/(In the case of incident from the vertical direction of the optical filter) Ratio of transmittance of R) ... Equation (5)

Further, the value obtained by dividing the ratio of the G transmittance when measured at an angle of 30° to the vertical direction of the optical filter by the ratio of the G transmittance when measured in the vertical direction of the optical filter (G when 0°→30° The rate of change of the transmittance ratio) can be derived from the following formula (6).

(rate of change of ratio of G transmittance in the case of 0°→30°) = (ratio of G transmittance when incident at an angle of 30° with respect to the vertical direction of the optical filter)/(when incident from the vertical direction of the optical filter) Ratio of G transmittance of) ... Equation (6)

In addition, the value obtained by dividing the ratio of transmittance of B when measured at an angle of 30° to the vertical direction of the optical filter by the ratio of transmittance of B when measured in the vertical direction of the optical filter (B in the case of 0°→30°) The rate of change of the transmittance ratio) can be derived from the following formula (7).

(Ratio of change in ratio of B transmittance in the case of 0°→30°) = (Ratio of B transmittance when incident at an angle of 30° to the vertical direction of the optical filter)/(In the case of incident from the vertical direction of the optical filter) Ratio of transmittance of B) ... Equation (7)

Similarly, the ratio of the R transmittance when measured at an angle of 60° to the vertical direction of the optical filter divided by the ratio of the R transmittance when measured in the vertical direction of the optical filter (0°→60° The rate of change of the R transmittance ratio) can be derived from the following formula (8).

(rate of change of R transmittance ratio in the case of 0°→60°) = (Ratio of R transmittance when incident at an angle of 60° with respect to the vertical direction of the optical filter)/(when incident from the vertical direction of the optical filter) Ratio of transmittance of R) ... Equation (8)

Further, the value obtained by dividing the ratio of the G transmittance when measured at an angle of 60° to the vertical direction of the optical filter by the ratio of the G transmittance when measured in the vertical direction of the optical filter (G when 0°→60°) The rate of change of the transmittance ratio) can be derived from the following formula (9).

(rate of change of ratio of G transmittance in the case of 0°→60°) = (ratio of G transmittance when incident at an angle of 60° to the vertical direction of the optical filter)/(when incident from the vertical direction of the optical filter) Ratio of G transmittance of ) ... Equation (9)

The change rate of the G transmittance ratio in the case of 0°→60° is preferably 0.4 or more and 2.0 or less, more preferably 0.5 or more and 1.8 or less, still more preferably 0.6 or more and 1.6 or less, and the closer the change rate is to 1.0, the better. , the incident angle dependent change of the RGB balance is small.

Further, the value obtained by dividing the ratio of transmittance of B when measured at an angle of 60° to the vertical direction of the optical filter by the ratio of transmittance of B when measured in the vertical direction of the optical filter (B in the case of 0°→60°) The rate of change of the transmittance ratio) can be derived from the following formula (10).

(Ratio of change in ratio of B transmittance in the case of 0°→60°) = (Ratio of B transmittance in the case of incident at an angle of 60° to the vertical direction of the optical filter)/(In the case of incident from the vertical direction of the optical filter) Ratio of transmittance of B) ... Equation (10)

When such an optical filter is used for the ambient light sensor of a mobile phone or tablet, it is easy to correct the luminance and color of the screen, so that in a bright environment, the luminance of the display is insufficient and it is difficult to see, or a specific color is not displayed on the screen. It is possible to solve the problem of being unable to display normally.

The optical filter of the present invention preferably does not have a dielectric multilayer film. In the case of an ambient light sensor of a type in which an optical filter is attached to a silicon wafer, when the silicon wafer is enlarged, deformation or warping resulting from deposition for forming a multilayer dielectric film may become a problem. By not having the dielectric multilayer film, warpage or deformation can be reduced compared to an optical filter having a dielectric multilayer film. As a result, it is possible to increase the size of the optical filter. Further, the optical filter of the present invention can exhibit optical characteristics equivalent to those of conventional environmental light sensors without having a dielectric multilayer film.

The thickness of the optical filter of the present invention is not particularly limited, but is preferably 40 to 1000 μm, more preferably 50 to 800 μm, still more preferably 80 to 500 μm, and particularly preferably 90 to 250 μm. When the thickness of the optical filter is within the above range, the optical filter can be reduced in size and weight.

<Description (i)>

The substrate (i) may be a single layer or a multilayer as long as it has a layer containing the compound (A) having an absorption maximum in a wavelength range of 650 nm to less than 800 nm. In addition, the base material (i) preferably contains a compound (B) having an absorption maximum in a wavelength range of 800 nm to 1850 nm, and even if the compound (B) is contained in the same layer as the compound (A), it is in a different layer. may be included. Hereinafter, a layer containing at least one compound selected from compounds (A) and (B) and a transparent resin is also referred to as a "transparent resin layer", and other resin layers are simply referred to as a "resin layer".

When the layer containing the compound (A) and the layer containing the compound (B) are the same, for example, a substrate containing a transparent resin substrate containing the compounds (A) and the compound (B), the compound (A) and Compound (A) on a base material on which a resin layer such as an overcoat layer containing a curable resin or a thermoplastic resin is laminated on a transparent resin substrate containing the compound (B), or a support such as a glass support or a base resin support. ) and a base material on which a transparent resin layer such as an overcoat layer containing a curable resin or a thermoplastic resin containing the compound (B) is laminated.

When the layer containing the compound (A) and the layer containing the compound (B) are different, for example, a curable resin or thermoplastic resin containing the compound (A) on a transparent resin substrate containing the compound (B) A base material on which a transparent resin layer such as an overcoat layer containing a layer is laminated, a transparent resin substrate containing a compound (A), a transparent resin such as an overcoat layer containing a curable resin or a thermoplastic resin containing the compound (B), or the like. A transparent resin layer, such as a curable resin containing the compound (A) or an overcoat layer containing a thermoplastic resin, and the like, and a compound (B) on a support such as a substrate on which a paper layer is laminated, a glass support, or a resin support as a base. An overcoat containing a curable resin or a thermoplastic resin containing a compound (A) on a substrate laminated with a transparent resin layer such as an overcoat layer containing a curable resin or a thermoplastic resin, etc., or a glass substrate containing the compound (B). and substrates in which transparent resin layers such as layers are laminated.

<Compound (A)>

The compound (A) is not particularly limited as long as it has an absorption maximum in a wavelength range of 650 nm or more and less than 800 nm, but in the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds and cyanine compounds It is preferable that it is at least 1 type of compound chosen, and a squarylium type compound, a phthalocyanine type compound, and a cyanine type compound are especially preferable. In addition, a compound (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

The absorption maximum wavelength of the compound (A) is preferably 660 nm or more and 795 nm or less, more preferably 680 nm or more and 790 nm or less.

The amount of the compound (A) used is appropriately selected depending on the desired properties, but the substrate includes, for example, a substrate comprising a substrate made of a transparent resin containing the compound (A) or a transparent resin containing the compound (A). In the case of using a base material on which a resin layer such as an overcoat layer containing a curable resin or a thermoplastic resin is laminated on a substrate, the amount is preferably 0.01 to 2.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, based on 100 parts by weight of the transparent resin. 0.03 to 1.5 parts by weight, more preferably 0.05 to 1.0 parts by weight, and as the base material, a base material in which a transparent resin layer containing the compound (A) is laminated on a support such as a glass support or a base resin support. When used, it is preferably 0.4 to 20.0 parts by weight, more preferably 0.6 to 15.0 parts by weight, still more preferably 0.8 to 12.5 parts by weight, based on 100 parts by weight of the resin forming the transparent resin layer.

≪Squallium-based compounds≫

The squarylium-based compound is not particularly limited, but at least one compound selected from the group consisting of a squarylium-based compound represented by the following formula (I) and a squarylium-based compound represented by the following formula (II) desirable. Hereinafter, they are also referred to as "compound (I)" and "compound (II)", respectively.

In formula (I), R ^a , R ^b and ^{Y a} satisfy the following condition (α) or (β).

Condition (α):

plural R ^a 's each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^e R ^f group;

plural R ^b 's each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^g R ^h group;

a plurality of Y ^a 's each independently represents a -NR ^j R ^k group;

L ¹ represents L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h ;

R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;

R ^g and R ^h are each independently a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or a -C(O)R ⁱ group (R ⁱ is -L ^a , -L ^b , -L ^c , -L ^d or -L ^e );

R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;

L ^a represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L;

L ^b represents a halogen-substituted alkyl group having 1 to 12 carbon atoms which may have a substituent L;

L ^c represents an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L;

L ^d represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L;

L ^e represents a heterocyclic group having 3 to 14 carbon atoms which may have a substituent L;

L ^f represents an alkoxy group having 1 to 9 carbon atoms which may have a substituent L;

L ^g represents an acyl group having 1 to 9 carbon atoms which may have a substituent L;

L ^h represents an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L;

L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, represents at least one substituent selected from the group consisting of a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, and an amino group.

Condition (β):

At least one of the two R ^a on one benzene ring bonds with Y on the same benzene ring to form a heterocycle containing at least one nitrogen atom and having 5 or 6 constituent atoms;

The heterocycle may have a substituent, and R ^b and R ^a not involved in formation of the heterocycle each independently have the same meaning as R ^b and R ^a in the above condition (α).

The total number of carbon atoms including the substituents of L ^a to L ^h is preferably 50 or less, more preferably 40 or less carbon atoms, and particularly preferably 30 or less carbon atoms. When the carbon number is more than this range, the synthesis of the compound may be difficult, and the light absorption intensity per unit weight tends to decrease.

Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms for ^La and L include a methyl group (Me), an ethyl group (Et), an n-propyl group (n-Pr), an isopropyl group (i-Pr), Alkyl groups such as n-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, decyl group and dodecyl group ; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl, hexenyl and octenyl; and alkynyl groups such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group and octynyl group.

Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms for L ^b and L include trichloromethyl, trifluoromethyl, 1,1-dichloroethyl, pentachloroethyl, pentafluoroethyl and heptachloropropyl. and a heptafluoropropyl group.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms for L ^c and L include cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; Polycyclic alicyclic groups, such as a norbornane group and an adamantane group, are mentioned.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms for L ^d and L include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, A phenanthryl group, acenaphthyl group, phenalenyl group, tetrahydronaphthyl group, indanyl group, and biphenylyl group are mentioned.

Examples of the heterocyclic group having 3 to 14 carbon atoms for L ^e and L include furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, Indole, indoline, indolenine, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, acridine, morpholine and phena and groups containing heterocyclic rings such as gin.

Examples of the alkoxy group having 1 to 9 carbon atoms in L ^f include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and an octyloxy group. can

Examples of the acyl group having 1 to 9 carbon atoms in L ^g include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

Examples of the alkoxycarbonyl group having 1 to 9 carbon atoms for L ^h include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group and an octyloxycarbonyl group. can be heard

As said L ^a , Preferable methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 4-phenylbutyl group , 2-cyclohexylethyl, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.

As said L ^b , Preferably they are a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, More preferably, They are a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

As said ^Lc , Preferably they are a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, 4-ethylcyclohexyl group, a cyclooctyl group, and 4-phenylcycloheptyl group, More preferably, a cyclopentyl group and a cyclohexyl group , 4-ethylcyclohexyl group.

As said L ^d , Preferably, a phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 3,5-di-tert-butylphenyl group, 4-cyclopentylphenyl group, 2,3,6-triphenylphenyl group and 2,3,4,5,6-pentaphenylphenyl group, more preferably phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,3,4, It is a 5,6-pentaphenylphenyl group.

As said L ^e , Preferably it is a group containing furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, and morpholine, More preferably, furan, thiophene, pyrrole, morpholine It is a group containing poline.

As said L ^f , Preferably, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a methoxymethyl group, a methoxyethyl group, a 2-phenylethoxy group, a 3-cyclohexylpropoxy group, a phen They are a tyloxy group, a hexyloxy group, and an octyloxy group, More preferably, they are a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

As said ^Lg , Preferably they are an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, 4-propylbenzoyl group, and a trifluoromethylcarbonyl group, More preferably, an acetyl group, a propionyl group, a benzo It's a diary.

As said L ^h , Preferably they are methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, 2-trifluoromethylethoxycarbonyl group, 2-phenylethoxycarbonyl group, More preferably is a methoxycarbonyl group or an ethoxycarbonyl group.

Said L ^a - L ^h may further have at least 1 type of atom or group selected from the group which consists of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, and an amino group. Examples thereof include 4-sulfobutyl group, 4-cyanobutyl group, 5-carboxypentyl group, 5-aminopentyl group, 3-hydroxypropyl group, 2-phosphorylethyl group, 6-amino-2,2-dichlorohexyl. Practical group, 2-chloro-4-hydroxybutyl group, 2-cyanocyclobutyl group, 3-hydroxycyclopentyl group, 3-carboxycyclopentyl group, 4-aminocyclohexyl group, 4-hydroxycyclohexyl group , 4-hydroxyphenyl group, pentafluorophenyl group, 2-hydroxynaphthyl group, 4-aminophenyl group, 4-nitrophenyl group, 3-methylpyrrole group, 2-hydroxyethoxy group, 3-cyanopropoxyl group , 4-fluorobenzoyl group, 2-hydroxyethoxycarbonyl group, and 4-cyanobutoxycarbonyl group.

As R ^a in the condition (α), 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 sec-butyl group, or a tert-butyl group. group, a cyclohexyl group, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, and a nitro group, and more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a hydroxyl group.

As R ^b in the condition (α), 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 sec-butyl group, and a tert-butyl group. group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t -Butanoylamino group or cyclohexanoylamino group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group, dimethylamino group, nitro group, acetylamino group, propionyl They are an amino group, a trifluoromethanoylamino group, a pentafluoroethanoylamino group, a t-butanoylamino group, and a cyclohexanoylamino group.

As said Ya, Preferably, an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-t-butylamino group, N-ethyl-N -Methylamino group, N-cyclohexyl-N-methylamino group, more preferably dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-t-butyl is an amino group.

The number of constituting atoms containing at least one nitrogen atom formed by bonding at least one of the two R ^a on one benzene ring to Y on the same benzene ring in the condition (β) of the formula (I) Examples of the 5- or 6-membered heterocycle include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine. Among these heterocycles, a heterocycle in which one atom adjacent to a carbon atom constituting the heterocycle and constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

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

As R ^c in the formula (II), preferably a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n -A hexyl group, a cyclohexyl group, a phenyl group, a trifluoromethyl group, and a pentafluoroethyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

As R ^d in the formula (II), 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 sec-butyl group, a tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group and 4-aminocyclohexyl group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, They are a methyl group, an ethyl group, n-propyl group, an isopropyl group, a trifluoromethyl group, and a pentafluoroethyl group.

The X is preferably O, S, Se, N-Me, N-Et, CH ₂ , C-Me ₂ , C-Et ₂ , more preferably S, C-Me ₂ , C-Et ₂ am.

In the formula (II), adjacent R ^ds may be connected to each other to form a ring. Examples of such a ring include a benzoindolenine ring, an α-naphthoimidazole ring, a β-naphthoimidazole ring, an α-naphthoxazole ring, a β-naphthoxazole ring, an α-naphthothiazole ring, and a β-nap Tothiazole ring, α-naphthoselenazole ring, and β-naphthoselenazole ring are exemplified.

Compound (I) and Compound (II) are represented by the following formula (I-2) and the following formula (II-2) in addition to the description method such as the following formula (I-1) and the following formula (II-1) The structure can also be represented by a description method that takes a resonance structure. That is, the difference between the following formula (I-1) and the following formula (I-2) and the difference between the following formula (II-1) and the following formula (II-2) is only the method of describing the structure, and both are the same represents a compound. In the present invention, the structure of the squarylium-based compound is shown by a description method such as the following formula (I-1) and the following formula (II-1) unless otherwise specified.

In addition, for example, a compound represented by the following formula (I-3) and a compound represented by the following formula (I-4) can be regarded as the same compound.

The structures of the compounds (I) and (II) are not particularly limited as long as they satisfy the requirements of the formulas (I) and (II), respectively. For example, in the case of the structures shown in the above formulas (I-1) and (II-1), the left and right substituents bonded to the central 4-membered ring may be the same or different, but the same is easier to synthesize. desirable because

As specific examples of the compounds (I) and (II), compounds (a-1) to (a-36) described in Tables 1 to 3 having basic skeletons represented by the following formulas (I-A) to (I-H) can be heard

The compounds (I) and (II) may be synthesized by a generally known method, for example, Japanese Patent Laid-Open No. 1-228960, Japanese Patent Laid-Open No. 2001-40234, and Japanese Patent No. 3196383 It can be synthesized with reference to the method described in the like.

«Phthalocyanine-based compounds»

Although the said phthalocyanine type compound is not specifically limited, It is preferable that it is a compound represented by the following formula (III) (henceforth "compound (III)").

In formula (III), M represents a substituted metal atom containing two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom, and a plurality of R _a , R _b , R _c and R _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , - SO ₂ -L ³ , -N=NL ⁴ , or a combination of at least one of R _a and R _b , R _b and R _c , and R _c and R _d , represented by the following formulas (A) to (H) represents at least one type of group selected from the group consisting of groups. However, 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 amino group, amide group, imide group and silyl group may have the substituent L defined in the formula (I),

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

L ² represents a hydrogen atom or any of La to ^{L e defined} in the formula (I);

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

L ⁴ represents any one of the above La to ^{L e .}

In formulas (A) to (H), R _x and R _y represent a carbon atom, and a plurality of R _A to R _L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, and an imide group. , cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , and the amino group, amide group, imide group and silyl group are represented by the above formula It may have the substituent L defined in (I), and L ¹ to L ⁴ have the same meaning as L ¹ to L ⁴ defined in the formula (III).

In the above R _a to R _d and R _A to R _L , examples of the amino group which may have a substituent L include an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group, and a diisopropylamino group.

Examples of the amide group which may have a substituent L in R _a to R _d and R _A to R _L include an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, and a diisopropylamide group. group, dibutylamide group, α-lactam group, β-lactam group, γ-lactam group, δ-lactam group and the like.

Examples of the imide group which may have a substituent L in R _a to R _d and R _A to R _L include an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, A diisopropylimide group, a dibutylimide group, etc. are mentioned.

Examples of the silyl group which may have a substituent L in the above R _a to R _d and R _A to R _L include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a triethylsilyl group. .

In the above R _a to R _d and R _A to R _L , as -SL ² , a thiol group, a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, an isobutyl sulfide group, sec -Butyl sulfide group, tert-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butylphenyl sulfide group, 2,6-diphenylphenyl sulfide group, 4-cumylphenyl sulfide group etc. can be mentioned.

In the above R _a to R _d and R _A to R _L , as -SS-L ² , a disulfide group, a methyl disulfide group, an ethyl disulfide group, a propyl disulfide group, a butyl disulfide group, isobutyl disulfide group, sec-butyl disulfide group, tert-butyl disulfide group, phenyl disulfide group, 2,6-di-tert-butylphenyl disulfide group, 2,6-diphenylphenyl disulfide group, 4-cumylphenyl A disulfide group etc. are mentioned.

Examples of -SO ₂ -L ³ in R _a to R _d and R _A to R _L include a sulfo group, a mesyl group, an ethylsulfonyl group, an n-butylsulfonyl group, and a p-toluenesulfonyl group.

Examples of -N=NL ⁴ in the above R _a to R _d and R _A to R _L include a methylazo group, a phenylazo group, a p-methylphenylazo group, and a p-dimethylaminophenylazo group.

In the above M, examples of the monovalent metal atom include Li, Na, K, Rb, and Cs.

In the above M, as the divalent metal atom, Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, Hg, Sn, Pb etc. can be mentioned.

In the above M, as the substituted metal atom containing a trivalent metal atom, Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga-I, In -F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH and the like.

In M, as the substituted metal atom containing a tetravalent metal atom, TiF ₂ , TiCl ₂ , TiBr ₂ , TiI 2 , ZrCl ₂ , HfCl ₂ , CrCl ₂ , SiF ₂ , _{SiCl 2 ,} SiBr ₂ , SiI ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , SnI ₂ , Zr(OH) ₂ , Hf(OH) ₂ , Mn(OH) ₂ , Si(OH) ₂ , Ge( OH) ₂ , Sn(OH) ₂ , TiR 2 , CrR ₂ , SiR ₂ , GeR ₂ , SnR ₂ , Ti(OR) ₂ , Cr(OR) ₂ , Si(OR) ₂ , Ge(OR) _{2 ,} Sn (OR) ₂ (R represents an aliphatic group or an aromatic group), TiO, VO, MnO, and the like.

As said M, it is preferable that it is a divalent transition metal, a trivalent or tetravalent metal halide, or a tetravalent metal oxide which belongs to group 5 - 11 of the periodic table, and also the 4th - 5th period, and among them, high visible light transmittance However, Cu, Ni, Co and VO are particularly preferred in terms of achieving stability.

Although a method for synthesizing the phthalocyanine-based compound by a cyclization reaction of a phthalonitrile derivative as shown in the following formula (V) is generally known, the obtained phthalocyanine-based compound has the following formulas (VI-1) to (VI-4) It is a mixture of the same 4 isomers. In the present invention, unless otherwise noted, only one isomer is exemplified for one phthalocyanine-based compound, but the other three isomers can also be used in the same way. In addition, these isomers can also be used separately as needed, but in the present invention, isomer mixtures are collectively handled.

Specific examples of the compound (III) include (b-1) to (b-61) described in Tables 4 to 7 below, which have basic skeletons represented by the following formulas (III-A) to (III-J), and the like. can be heard

Compound (III) may be synthesized by a generally known method, for example, referring to the method described in Japanese Patent No. 4081149 or "Phthalocyanine -Chemistry and Function-" (IPC, 1997). there is.

≪Cyanine-based compounds≫

The cyanine-based compound is not particularly limited, but is a compound represented by any of the following formulas (IV-1) to (IV-3) (hereinafter also referred to as "compounds (IV-1) to (IV-3)"). It is desirable to be

In formulas (IV-1) to (IV-3), X _a ^- represents a monovalent anion, a plurality of D's independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and a plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, Silyl group, -L ¹ , -SL ² , -SS-L ³ , -SO ₂ -L ³ , -N=NL ⁴ , or R _b and R _c , R _d and _Re , Re _and R _f , R represents at least one group selected from the group consisting of groups represented by the formulas (A) to (H) to which at least one combination of _f and R _g , R _g and R _h , and R _h and R _i is bonded; The amino group, amide group, imide group and silyl group may have the substituent L defined in the formula (I),

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

L ² represents a hydrogen atom or any of La to ^{L e defined} in the formula (I);

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

L ⁴ represents any one of the above La to ^{L e ;}

Z _a to Z _c and Y _a to Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ (L ¹ to L ⁴ have the same meaning as L ¹ to L ⁴ in R _a to R _i ), or any of these An aromatic hydrocarbon group having 6 to 14 carbon atoms, formed by bonding Z or Y groups selected from two adjacent ones; a 5- to 6-membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, oxygen atom or sulfur atom; or a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, and these aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic hydrocarbon groups are aliphatic hydrocarbon groups having 1 to 9 carbon atoms; You may have a halogen atom.

As the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z or Y to each other in Z _a to Z _c and Y _a to Y _d , for example, the aromatic hydrocarbon group in the substituent L The compounds exemplified by can be mentioned.

A 5- to 6-membered alicyclic hydrocarbon which may contain at least one nitrogen atom, oxygen atom or sulfur atom, formed by bonding of Zs or Ys in the above Z _a to Z _c and Y _a to Y _d Examples of the group include compounds (excluding heteroaromatic hydrocarbon groups) exemplified in the alicyclic hydrocarbon group and heterocyclic group in the substituent L described above.

As the heterocyclic aromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding Z or Y to each other in Z _a to Z _c and Y _a to Y _d , for example, the heterocyclic group in the substituent L exemplified as (excluding an alicyclic hydrocarbon group containing at least one nitrogen atom, oxygen atom or sulfur atom).

In the above formulas (IV-1) to (IV-3), -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , an amino group that may have a substituent L, an amide group, Examples of the imide group and the silyl group include the same groups as those exemplified in the formula (III).

X _a ^- is not particularly limited as long as it is a monovalent anion, but I ^- , Br ^- , PF ₆ ^- , N(SO ₂ CF ₃ ) ₂ ^- , B(C ₆ F ₅ ) ₄ ^- , a nickel dithiolate complex, A copper dithiolate type complex etc. are mentioned.

Specific examples of the compounds (IV-1) to (IV-3) include (c-1) to (c-24) shown in Table 8 below.

The compounds (IV-1) to (IV-3) may be synthesized by a generally known method, for example, by a method described in Japanese Unexamined Patent Publication No. 2009-108267.

<Compound (B)>

The compound (B) is not particularly limited as long as it has an absorption maximum in a wavelength range of 800 nm or more and 1850 nm or less. Near-infrared absorbing fine particles, squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, and cyanine-based compounds , It is preferably at least one compound selected from the group consisting of a dimonium-based compound, a metal dithiolate-based compound, and a pyrrolopyrrole-based compound. The ambient light sensor usually has a sensitivity up to around 1200 nm outside the visible light range, and when light with a wavelength other than the visible light range enters the ambient light sensor, it malfunctions or does not properly control the color tone according to the ambient light environment. there is Therefore, as the compound (B), it is preferable to use a compound having a wide absorption in the near-infrared region, and among the above compounds, near-infrared absorbing fine particles, cyanine-based compounds, dimonium-based compounds, and squarylium-based compounds are more preferable. , Cs _x W _y O _z is most preferred as the near-infrared absorbing fine particles. In addition, a compound (B) may be used individually by 1 type, and may be used in combination of 2 or more type. By using such a compound (B), absorption characteristics in a wide near-infrared wavelength region and excellent visible light transmittance can be achieved.

The absorption maximum wavelength of the compound (B) is 800 nm or more and 1850 nm or less, preferably 810 nm or more and 1800 nm or less, more preferably 820 nm or more and 1750 nm or less. When the absorption maximum wavelength of the compound (B) is in this range, while being able to efficiently cut unnecessary near-infrared rays, the incidence angle dependence of incident light can be lowered. The maximum absorption wavelength of the compound (B) other than the near-infrared absorbing fine particles is preferably 800 nm or more and 1200 nm or less, more preferably 810 nm or more and 1180 nm or less, particularly preferably 820 nm or more and 1150 nm or less. On the other hand, the maximum absorption wavelength of the near-infrared absorbing fine particles is preferably 800 nm or more and 1850 nm or less, more preferably 840 nm or more and 1800 nm or less, and particularly preferably 870 nm or more and 1750 nm or less.

The amount of the compound (B) (except for the near-infrared absorbing fine particles) used is appropriately selected depending on the desired properties, but as the substrate, for example, a transparent resin containing the compound (A) and the compound (B). In the case of using a substrate including a substrate, it is preferably 0.01 to 5.0 parts by weight, more preferably 0.02 to 3.0 parts by weight, particularly preferably 0.03 to 2.0 parts by weight, based on 100 parts by weight of the transparent resin. As the base material, a base material in which a transparent resin layer containing the compound (A) and the compound (B) is laminated on a support such as a glass support or a base resin support, or a transparent resin substrate containing the compound (A) In the case of using a base material on which a resin layer containing the compound (B) is laminated, the amount is preferably 0.1 to 30.0 parts by weight, more preferably 0.1 to 30.0 parts by weight, based on 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). It is preferably 1.0 to 28.0 parts by weight, particularly preferably 2.0 to 25.0 parts by weight. When the content of the compound (B) is within the above range, an optical filter having both good near-infrared absorption characteristics and high visible light transmittance can be obtained. In the case of using near-infrared absorbing fine particles as the compound (B), the amount of the fine particles used will be described later.

The compound (B) may be synthesized by a generally known method, for example, Japanese Patent No. 4168031, Japanese Patent No. 4252961, Japanese Patent Publication No. 2010-516823, Japanese Patent Laid-Open No. 63-165392 It can be synthesized with reference to the method described in the publication No.

≪Dimonium-based compound≫

Although the said dimonium type compound is not specifically limited, For example, the compound represented by the following formula (s1) is preferable.

In formula (s1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any of the following L ^a to L ^h , and R ^g and R ^h are each independently a hydrogen atom, a -C(O)R ⁱ group or the following L ^a to L ^e represents any of the following, R ⁱ represents any of the following L ^a to L ^e ,

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

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

(L ^c ) An alicyclic hydrocarbon group having 3 to 14 carbon atoms

(L ^d ) Aromatic hydrocarbon group having 6 to 14 carbon atoms

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

(L ^f ) An alkoxy group having 1 to 12 carbon atoms

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

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

The substituent L is a group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. It is at least one selected from, n is an integer of 0 to 4, X represents an anion required to neutralize the electric charge.

As said R ^<1> , Preferably they are a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, a cyclohexyl group, a phenyl group, and a benzyl group, More Preferred are isopropyl group, sec-butyl group, tert-butyl group and benzyl group.

As the R ² , preferably, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a hydroxyl group, Amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoro roethanoylamino group, t-butanoylamino group, cyclohexanoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, and n-butylthio group, more preferably a chlorine atom , fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group, pentafluoro They are ethanoylamino group, t-butanoylamino group, and cyclohexanoylamino group, and methyl group, ethyl group, n-propyl group, and isopropyl group are especially preferred. The number (n value) of R ² bonded to the same aromatic ring is not particularly limited as long as it is 0 to 4, but is preferably 0 or 1.

The above X is an anion required to neutralize electric charges. When the anion is divalent, one molecule is required, and when the anion is monovalent, two molecules are required. In the case of the latter, the two anions may be the same or different, but the same is preferable from the synthetic viewpoint. X is not particularly limited as long as it is such an anion, but examples thereof include those described in Table 9 below.

If X has high acidity when used as an acid, it tends to improve the heat resistance of the dimonium-based compound when used as an anion of the dimonium-based compound, and (X-10) and (X-16) in Table 9 above. ), (X-17), (X-21), (X-22), (X-24) and (X-28) are particularly preferred.

«Metal dithiolate compound»

Although the said metal dithiolate type compound is not specifically limited, For example, the compound represented by the following formula (s2) is preferable.

In formula (s2), R ³ has the same meaning as R ¹ and R ² in formula (s1), and adjacent R ³ may form a ring which may have a substituent L. Z represents D(R ⁱ ) ₄ , D represents a nitrogen atom, a phosphorus atom or a bismuth atom, and y represents 0 or 1.

As R ³ , preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl, n-pentyl, n-hexyl, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, phenylthio group, benzylthio group, , When adjacent R ³ groups form a ring, it is preferably a heterocycle containing at least one sulfur atom or nitrogen atom in the ring.

As said M, Preferably it is a transition metal, More preferably, it is Ni, Pd, and Pt.

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

≪Commercial product≫

Examples of commercially available products of the compound (B) (but excluding near-infrared absorbing fine particles) include S2058 (manufactured by DKSH), CIR-108x, CIR-96x, CIR-RL, CIR-1080 (manufactured by Nihon Kalit), T090821, and T091021. , T89021, T090721, T090122 (made by Tosco), B4360, D4773, D5013 (made by Tokyo Kasei Kogyo), S4253, S1426, S1445 (made by Spectrum Informatics), Excolor IR1, IR2, IR3, IR4 (made by Nippon Shokubai), etc. can be heard

≪Near-infrared absorbing fine particles≫

The near-infrared absorbing fine particles are not particularly limited as long as they have absorption in a wavelength range of 800 nm or more and 1850 nm or less. Examples of such near-infrared absorbing fine particles include transparent conductive oxides such as ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), and GZO (gallium-doped zinc oxide), and compounds represented by the following formula (P-1) and second microparticles containing a compound represented by the following formula (P-2), and the first microparticles and the second microparticles are particularly preferable from the viewpoint of absorption-transmission characteristics.

A _1/n CuPO ₄ ... (P-1)

In formula (P-1), A is at least one selected from the group consisting of alkali metals, alkaline earth metals and NH ₄ , n is 1 when A is an alkali metal or NH ₄ , and A is an alkaline earth metal In case of , it is 2.

M _x W _y O _z ... (P-2)

In formula (P-2), M is H, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, and when M is plural, they may be individual atoms, and x, y, and z satisfy the conditions of 0.001≤x/y≤1 and 2.2≤z/y≤3.0.

In the present invention, the alkali metals refer to Li, Na, K, Rb, and Cs, the alkaline earth metals refer to Ca, Sr, and Ba, and the rare earth elements refer to Sc, Y, La, Ce, Pr, Nd, Pm, and Sm. , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.

The average particle diameter of the near-infrared absorbing fine particles is 1 to 200 nm, that is, preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 100 nm or less. The particle diameter of the near-infrared absorbing fine particles was determined by a dynamic light scattering method using a dynamic light scattering photometer (model number DLS-8000HL/HH, manufactured by Otsuka Electronics Co., Ltd.) of a suspension in which the near-infrared absorbing fine particles were dispersed (hereinafter, simply referred to as "dispersion"). (He-Ne laser used, cell chamber temperature 25°C). When the average value of the particle diameter of the near-infrared absorbing fine particles is within this range, geometric scattering and micro-scattering that cause a decrease in visible light transmittance can be reduced, resulting in a Rayleigh scattering region. In the Rayleigh scattering region, since scattered light is reduced in inverse proportion to the sixth power of the particle diameter, scattering is reduced as the particle diameter is reduced, and the visible light transmittance is improved. For this reason, when the particle size is within the above range, it is preferable because scattered light becomes very small and good visible light transmittance can be achieved. From the viewpoint of scattered light, the particle diameter is preferably smaller, but considering industrial ease of manufacture and manufacturing cost, the lower limit of the average particle diameter is preferably 1 nm or more, particularly preferably 2 nm or more.

The content of the near-infrared absorbing fine particles is preferably 5 to 60 parts by weight based on 100 parts by weight of the resin component constituting the layer containing the near-infrared absorbing fine particles. The upper limit of the content is more preferably 55 parts by weight, particularly preferably 50 parts by weight. The lower limit of the content is more preferably 10 parts by weight, particularly preferably 15 parts by weight. If the content of the near-infrared absorbing fine particles is less than 5 parts by weight, sufficient near-infrared absorbing properties may not be obtained, and if it is greater than 60 parts by weight, the decrease in visible light transmittance and the increase in the haze value due to the aggregation of the near-infrared absorbing fine particles tend to tend to occur. there is

Examples of the dispersion medium for near-infrared absorbing fine particles include water, alcohols, ketones, ethers, esters, aldehydes, amines, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. A dispersion medium may be used individually by 1 type, and may mix and use 2 or more types. The amount of the dispersion medium is preferably 50 to 95 parts by weight with respect to 100 parts by weight of the dispersion from the viewpoint of maintaining the dispersibility of the near-infrared absorbing fine particles.

In the dispersion medium of the near-infrared absorbing fine particles, if necessary, a dispersing agent may be blended in order to improve the dispersion state of the near-infrared absorbing fine particles. As the dispersing agent, those exhibiting a modifying effect on the surface of the near-infrared absorbing fine particles, for example, surfactants, silane compounds, silicone resins, titanate-based coupling agents, aluminum-based coupling agents, zirco aluminate-based coupling agents, etc. are used. .

As the surfactant, anionic surfactants (special polycarboxylic acid type polymeric surfactants, alkyl phosphate esters, etc.), nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene carboxylic acid ester , sorbitan higher carboxylic acid esters, etc.), cationic surfactants (polyoxyethylene alkylamine carboxylic acid esters, alkylamines, alkylammonium salts, etc.), and amphoteric surfactants (higher alkyl betaines, etc.).

As a silane compound, a silane coupling agent, chlorosilane, an alkoxysilane, a silazane, etc. are mentioned. As a silane coupling agent, the alkoxysilane etc. which have a functional group (a glycidoxy group, a vinyl group, an amino group, an alkenyl group, an epoxy group, a mercapto group, a chloro group, an ammonium group, an acryloxy group, a methacryloxy group, etc.) are mentioned.

As silicone resin, methyl silicone resin, methylphenyl silicone resin, etc. are mentioned.

Examples of the titanate-based coupling agent include those having an acyloxy group, a phosphoroxy group, a pyrophosphoxy group, a sulfoxy group, an aryloxy group, and the like.

As an aluminum-type coupling agent, acetoalkoxy aluminum diisopropylate is mentioned.

Examples of the zirco aluminate coupling agent include those having an amino group, a mercapto group, an alkyl group, an alkenyl group, and the like.

The amount of the dispersant varies depending on the type of dispersant, but is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the dispersion. When the amount of the dispersant is within the range, the dispersibility of the near-infrared absorbing fine particles is improved, the transparency is not impaired, and sedimentation of the near-infrared absorbing fine particles over time is suppressed.

Examples of commercial products of the near-infrared absorbing fine particles include P-2 (ITO) manufactured by Mitsubishi Materials Co., Ltd., Fastolan (ITO) manufactured by Mitsui Kinzoku Co., Ltd., T-1 (ATO) manufactured by Mitsubishi Material Co., Ltd., and Ishihara Sangyo. Co., Ltd. SN-100P (ATO), Hakusuitec Co., Ltd. Paget GK (GZO), Sumitomo Kinzoku Kozan Co., Ltd. YMF-02A (secondary particle), etc. are mentioned.

≪First Particles≫

The first fine particles have a near-infrared absorption characteristic derived from the crystal structure (crystallite) of the compound represented by the formula (P-1).

Here, a "crystal" means a unit crystal that can be regarded as a single crystal, and a "particle" is composed of a plurality of crystallites. "Including the crystallites of the compound represented by Formula (1)" means that the crystal structure of A _1/n CuPO ₄ can be confirmed by, for example, X-ray diffraction, and substantially the crystallites of A _1/n CuPO ₄ It means that it is identified by X-ray diffraction, and "substantially contains crystallites of A _1/n CuPO ₄ " means that the crystallites can sufficiently maintain the crystal structure of A _1/n CuPO ₄ ( It means that impurities may be included within the range where the crystal structure of A _1/n CuPO ₄ can be confirmed by X-ray diffraction. In addition, X-ray diffraction is measured using an X-ray diffractometer for near-infrared absorbing fine particles in powder form.

As A in Formula (1), the reasons for adopting alkali metals (Li, Na, K, Rb, Cs), alkaline earth metals (Ca, Sr, Ba) or NH ₄ are as follows (i) to (iii) same.

(i) The crystal structure of the crystallites in the near-infrared absorbing fine particles is a network-like three-dimensional skeleton containing alternating bonds of PO ₄ ^3- and Cu ²⁺ , and has a space inside the skeleton. The size of the corresponding space is alkali metal ion (Li ⁺ : 0.090nm, Na ⁺ : 0.116nm, K ⁺ : 0.152nm, Rb ⁺ : 0.166nm, Cs ⁺ : 0.181nm), alkaline earth metal ion (Ca ²⁺ : 0.114 nm, Sr ²⁺ : ^0.132 nm, Ba ²⁺ : 0.149 nm) and NH ₄₊ (0.166 nm), the crystal structure can be sufficiently maintained.

(ii) Since alkali metal ions, alkaline earth metal ions, and NH ₄₊ can exist stably as monovalent or divalent cations in a solution, in the process of preparing ^near -infrared absorbing fine particles, when a precursor is produced, the crystal structure It is easy for cations to be introduced into

(iii) A cation having strong coordinative bonding with PO ₄ ^3- (for example, a transition metal ion) can give a crystal structure different from the crystal structure in the present embodiment, which exhibits sufficient near-infrared absorption characteristics. There is a possibility.

As A, K is particularly preferable in view of having the most suitable cation size as an ion introduced into the skeleton containing PO ₄ ^3- and Cu ²⁺ and having a thermodynamically stable structure.

The near-infrared absorbing fine particles can express sufficient near-infrared absorbing characteristics when the crystallites sufficiently maintain the crystal structure of A _1/n CuPO ₄ . Therefore, when water or hydroxyl groups are attached to the crystallite surface, the crystal structure of A _1/n CuPO ₄ cannot be maintained, and thus the difference in light transmittance between the visible light region and the near infrared wavelength region is reduced, making it suitable for use as an optical filter. cannot be used

Therefore, in the near-infrared absorbing fine particles, when the absorption intensity of the peak at approximately 1000 cm ^-1 attributed to a phosphoric acid group is taken as a standard (100%) in the brown rice IR spectrum, the absorption intensity of the peak at approximately 1600 cm ^-1 attributed to water is It is 8% or less, and it is preferable that the absorption intensity of the peak around 3750 cm ^-1 attributed to the hydroxyl group is 26% or less, and the absorption intensity of the peak around 1600 cm ^-1 attributed to water is 5% or less and is also attributed to the hydroxyl group. It is more preferable that the absorption intensity of the peak near 3750 cm ^-1 to be 15% or less. In addition, the microscopic IR spectrum is measured using a Fourier transform infrared spectrophotometer with respect to the powdery near-infrared absorbing fine particles. Specifically, using, for example, a Fourier transform infrared spectrophotometer Magna760 manufactured by Thermo Fisher Scientific, a piece of the first fine particle is placed on its diamond plate, flattened with a roller, and measured by the microscopic FT-IR method. Measure.

≪Second Particles≫

It is known that when the ratio of oxygen to tungsten in tungsten trioxide (WO ₃ ) is lower than 3 and set to a specific composition range, free electrons are generated in the tungsten oxide, and good properties as a near-infrared absorbing material can be achieved.

The composition range of the tungsten and oxygen is preferably 2.2≤z/y≤2.999 when the composition ratio of oxygen to tungsten is 3 or less and the tungsten oxide is described as W _y O _z . When the value of z/y is 2.2 or more, it is possible to avoid the appearance of crystal phases of WO ₂ other than the purpose in the tungsten oxide, and to obtain chemical stability as a material, so that it can be applied as an effective near-infrared absorbing material. . On the other hand, when the value of z/y is 2.999 or less, a necessary amount of free electrons are generated in the tungsten oxide, and the material becomes an efficient near-infrared absorbing material.

In addition, in the tungsten oxide fine particles in which the tungsten oxide is finely divided, the so-called "Magnelli phase" having a composition ratio expressed by 2.45≤z/y≤2.999 when the general formula W _y O _z is used is chemically stable, and is stable in the near infrared Since the absorption characteristics of the region are also good, it is preferable as a near-infrared ray absorbing material.

In addition, by adding element M to the tungsten oxide to form a composite tungsten oxide, free electrons are generated in the composite tungsten oxide, and absorption characteristics derived from free electrons are expressed in the near infrared region, and as a near infrared ray absorbing material at a wavelength of around 1000 nm, It is desirable because it becomes effective.

Here, the value of x/y representing the addition amount of element M will be described. When the value of x/y is larger than 0.001, a sufficient amount of free electrons are generated so that the desired infrared shielding effect can be obtained. Further, as the added amount of element M increases, the amount of free electrons supplied increases and the infrared shielding efficiency also increases, but the effect is also saturated when the value of x/y is about 1. In addition, when the value of x/y is less than 1, it is possible to avoid generation of an impurity phase in the infrared shielding material, so it is preferable, and 0.2 or more and 0.5 or less are more preferable. Element M is H, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, It is preferably one or more types selected from among Os, Bi, and I. Here, from the viewpoint of stability in the M _x W _y O _z to which the element M is added, the element M is an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh , Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te , Ti, Nb, V, Mo, Ta, and more preferably one or more elements selected from Re. From the viewpoint of improving the optical properties and weather resistance as a near-infrared absorbing material, the element M is an alkali metal or an alkaline earth. What belongs to a metal element, a transition metal element, a group 4 element, and a group 5 element is more preferable.

Next, the value of z/y indicating the control of the amount of oxygen will be described. Regarding the value of z/y, even in the near-infrared absorbing material represented by M _x W _y O _z , the same mechanism as that of the above-described near-infrared absorbing material represented by W _y O _z acts, and at z / y = 3.0 2.2 ≤ z/y ≤ 3.0 is preferable because free electrons are supplied by the addition amount of the element M described above.

<transparent resin>

The transparent resin is not particularly limited as long as the effects of the present invention are not impaired. For example, in order to secure thermal stability and moldability into a film, the glass transition temperature (Tg) is preferably 110 to 380 °C, more preferably from 110 to 370°C, and still more preferably from 120 to 360°C. Moreover, since it is suitable for a reflow process, it is preferable that the glass transition temperature of the said resin is 140 degreeC or more, and it is more preferable if it is 230 degreeC or more.

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

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

Examples of the transparent resin include cyclic polyolefin-based resins, aromatic polyether-based resins, polyimide-based resins, fluorene polycarbonate-based resins, fluorene polyester-based resins, polycarbonate-based resins, and polyamide-based resins. , aramid-based resin, polysulfone-based resin, polyethersulfone-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate-based resin, fluorinated aromatic polymer-based resin, (modified) acrylic-based resin, epoxy-based resin, Silsesquioxane-based UV-curable resins, maleimide-based resins, alicyclic epoxy thermosetting resins, polyether ether ketone-based resins, polyarylate-based resins, allyl ester-based curable resins, acrylic UV-curable resins, vinyl-based UV-curable resins, and and resins containing silica as a main component formed by the sol-gel method. Among these, it is preferable to use cyclic polyolefin-based resins, aromatic polyether-based resins, fluorene polycarbonate-based resins, fluorene polyester-based resins, polycarbonate-based resins, and polyarylate-based resins because of their high transparency (optical properties ), it is preferable in that an optical filter excellent in balance, such as heat resistance and reflowability, can be obtained.

≪Cyclic Polyolefin Resin≫

As the cyclic polyolefin resin, a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ), and a resin obtained by hydrogenating the resin Resin is preferred.

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

(i') hydrogen atom

(ii') halogen atom

(iii') trialkylsilyl group

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

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

(vi') a polar group (except for (iv'))

(vii') an alkylidene group formed by combining R ^x1 and R ^x2 or R ^x3 and R ^x4 (provided that R ^x1 to R ^x4 not involved in the bonding are each independently the above (i') to (vi) ') represents an atom or group selected from)

(viii') a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by combining R ^x1 and R ^x2 or R ^x3 and R ^x4 (provided that R ^x1 to R ^x4 not involved in the bonding are each independently the above ( represents an atom or group selected from i') to (vi').)

(ix') A monocyclic hydrocarbon ring or heterocyclic ring formed by combining R ^x2 and R ^x3 with each other (provided that R ^x1 and R ^x4 not involved in the bonding are each independently the above (i') to (vi') Represents an atom or group selected from.)

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

≪Aromatic polyether-based resin≫

It is preferable that the aromatic polyether-based resin has at least one structural unit selected from the group consisting of 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 of 0 to 4.

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

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

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

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

≪Polyimide-based resin≫

The polyimide-based resin is not particularly limited, as long as it is a high molecular compound containing an imide bond in a repeating unit. can be synthesized in this way.

<<Fluorene polycarbonate type resin>>

The fluorene polycarbonate-based resin is not particularly limited, as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in Japanese Unexamined Patent Publication No. there is.

<<Fluorene polyester type resin>>

The fluorene polyester resin is not particularly limited, as long as it is a polyester resin containing a fluorene moiety, and is described in, for example, Japanese Patent Laid-Open No. 2010-285505 and Japanese Unexamined Patent Publication No. 2011-197450 can be synthesized in any way.

≪Fluorinated aromatic polymer-based resin≫

The fluorinated aromatic polymer-based resin is not particularly limited, but at least one bond selected from the group consisting of an aromatic ring having at least one fluorine atom and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. It is preferable that it is a polymer containing the repeating unit containing, and it is compoundable by the method described in Unexamined-Japanese-Patent No. 2008-181121, for example.

≪Acrylic UV curable resin≫

Examples of the acrylic UV-curable resin include, but are not particularly limited to, those synthesized from a resin composition containing a compound having at least one acrylic or methacrylic group in a molecule and a compound decomposed by ultraviolet rays to generate active radicals. An acrylic ultraviolet curable resin is a substrate (i) in which a transparent resin layer (light absorption layer) containing a compound (A) and a curable resin is laminated on a glass support or on a resin support as a base, or a compound (A) ) When using a base material in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated on a transparent resin substrate containing a curable resin, it can be used particularly suitably as the curable resin.

<<resin containing silica as a main component formed by the sol-gel method>>

As a resin whose main component is silica obtained by the sol-gel method, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, and methoxytriethoxysilane, phenyltrimethoxysilane, and phenyl trie A compound obtained by a sol-gel reaction by hydrolysis of one or more silanes selected from phenylalkoxysilanes such as oxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane can be used as the resin.

≪Commercial product≫

Examples of commercially available transparent resins include the following commercially available products. As a commercial item of cyclic polyolefin resin, JSR Co., Ltd. Aton, Nippon Zeon Co., Ltd. Zeonoa, Mitsui Chemicals Co., Ltd. APEL, Polyplastics Co., Ltd. TOPAS, etc. are mentioned. As a commercial item of polyether sulfone type-resin, Sumitomo Chemical Co., Ltd. product Sumica Excel PES etc. are mentioned. As a commercial item of polyimide-type resin, Mitsubishi Gas Chemical Co., Ltd. neoplym L etc. are mentioned. As a commercial item of polycarbonate-type resin, Teijin Co., Ltd. pure ace etc. are mentioned. As a commercial item of a fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. product Uphizeta EP-5000 etc. are mentioned. As a commercial item of a fluorene polyester type resin, Osaka Gas Chemical Co., Ltd. OKP4HT etc. are mentioned. As a commercial item of acrylic resin, Ac reviewer by Nippon Shokubai Co., Ltd., etc. are mentioned. As a commercial item of a silsesquioxane type|system|group ultraviolet curable resin, Nippon-Steel-Chemical Co., Ltd. Silplus etc. are mentioned.

<Other ingredients>

The base material (i) may further contain additives such as antioxidants, near-ultraviolet absorbers, and fluorescence quenchers within a range not impairing the effects of the present invention. These other components may be used individually by 1 type, and may use 2 or more types together.

As said near-ultraviolet absorber, an azomethine type compound, an indole type compound, a benzotriazole type compound, a triazine type compound etc. are mentioned, for example.

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

In addition, when manufacturing the said transparent resin, these additives may be mixed with resin etc., or may be added when synthesize|combining resin. The addition amount is appropriately selected depending on the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the transparent resin.

<support>

≪Resin Support≫

The resin used for the transparent resin substrate or the resin support can be the same as that of the transparent resin layer.

≪Glass support≫

Although it does not specifically limit as said glass support body, For example, borosilicate-type glass, silicate-type glass, soda-lime glass, and near-infrared absorption glass etc. are mentioned. The near-infrared absorbing glass is preferable in terms of improving near-infrared cut characteristics and reducing incidence angle dependence, and specific examples thereof include fluorophosphate-based glass and phosphate-based glass containing a copper component. there is.

<Method for producing substrate (i)>

When the substrate (i) is a substrate comprising a transparent resin substrate containing the compound (A) or the like, the transparent resin substrate can be formed, for example, by melt molding or cast molding. As necessary, after molding, a substrate on which an overcoat layer is laminated can be produced by coating a coating agent such as an antireflection agent, a hard coating agent, and/or an antistatic agent.

When the base material (i) is a base material in which a transparent resin layer such as an overcoat layer containing a curable resin containing a compound (A) or the like or a thermoplastic resin is laminated on a glass support or a base resin support, Example For example, a resin solution containing compound (A) is melt-molded or cast-molded on a glass support or a resin-made support as a base, preferably by spin coating, slit coating, inkjet, etc. After coating, the solvent is dried By removing and further performing light irradiation or heating as necessary, a base material in which a transparent resin layer is formed on a glass support or a base resin support can be manufactured.

≪Melt molding≫

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

≪Cast molding≫

Examples of the cast molding include a method in which a resin composition containing a resin and a solvent, such as compound (A), is cast on a suitable support to remove the solvent; Alternatively, it may be produced by a method of casting a curable composition containing compound (A) and the like and a photocurable resin and/or thermosetting resin onto an appropriate support, removing the solvent, and then curing by an appropriate method such as ultraviolet irradiation or heating. there is.

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

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

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

The amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the above method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less with respect to the weight of the transparent resin layer (transparent resin substrate). When the amount of residual solvent is within the above range, a transparent resin layer (substrate made of transparent resin) that is hard to deform or change in characteristics and can easily exhibit desired functions is obtained.

<Dielectric multilayer film>

As described above, the optical filter of the present invention preferably does not have a dielectric multilayer film from the viewpoint of warpage reduction, but within a range not impairing the effect of the present invention, a dielectric multilayer film is provided on at least one side of the substrate (i). You can have it. The dielectric multilayer film in the present invention is a film having an ability to reflect near-infrared rays or a film having an antireflection effect in the visible region. In the present invention, the constitution of having about 1 to 9 layers of films having an antireflection effect in the visible region (antireflection film) on both sides of the substrate (i) prevents warping when high visible light transmittance of the optical filter is required. It is preferable from the viewpoint that the visible light transmittance can be improved without greatly deteriorating.

As the dielectric multilayer film, one in which high refractive index material layers and low refractive index material layers are alternately laminated is exemplified. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of 1.7 to 2.5 is usually selected. Examples of such a material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as a main component, and titanium oxide, tin oxide, and/or cerium oxide. What contained a small amount (for example, 0 to 10% by weight relative to the main component) is exemplified.

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

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

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

The total number of layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is preferably 1 to 20 layers, and more preferably 2 to 12 layers as a whole of the optical filter.

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

Here, in order to optimize the above conditions, for example, by using optical thin film design software (e.g., Essential Macleod, manufactured by Thin Film Center), the antireflection effect in the visible region and the ray cutting effect in the near infrared region must be compatible. You just need to set the parameters to be able to. In the case of the above software, for example, when designing the first optical layer, the target transmittance of wavelengths of 400 to 700 nm is set to 100% and the value of the target tolerance is set to 1, and then the target transmittance of wavelengths of 705 to 950 nm is set to 100%. 0%, a parameter setting method such as setting the value of the target tolerance to 0.5. These parameters may further finely divide the wavelength range according to various characteristics of the base material (i) and change the value of the target tolerance.

<Other Functional Films>

The optical filter of the present invention is provided between the substrate (i) and the dielectric multilayer film, on the surface opposite to the surface of the substrate (i) on which the dielectric multilayer film is provided, or on the substrate of the dielectric multilayer film (i) within a range not impairing the effects of the present invention. ), a functional film such as an antireflection film, a hard coating film, or an antistatic film is applied to the surface opposite to the surface provided with the base material (i) or the dielectric multilayer film for the purpose of improving surface hardness, improving chemical resistance, preventing static electricity, and removing scratches. can be properly provided.

The optical filter of the present invention may include one layer or two or more layers including the functional film. When the optical filter of the present invention includes two or more layers including the functional film, it may include two or more of the same layer or two or more of different layers.

The method for laminating the functional film is not particularly limited, but a method in which a coating agent such as an antireflection agent, a hard coating agent, and/or an antistatic agent is melt-molded or cast-molded to the substrate (i) or the dielectric multilayer film in the same manner as described above is mentioned. can

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

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins and thermosetting resins, and specifically, vinyl compounds, urethanes, urethane acrylates, acrylates, epoxies, and epoxy acrylates. A base resin etc. are mentioned. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy and epoxy acrylate curable compositions.

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

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

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

These solvents may be used individually by 1 type, and may use 2 or more types together.

The thickness of the functional film is preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm, and particularly preferably 0.7 to 5 μm.

In addition, for the purpose of enhancing the adhesion between the substrate (i) and the functional film and/or the dielectric multilayer film or the adhesion between the functional film and the dielectric multilayer film, corona treatment or plasma treatment is applied to the surface of the substrate (i), the functional film, or the dielectric multilayer film. Surface treatment may be performed.

[Usage of optical filter]

The optical filter of the present invention has excellent visible light transmittance and near-infrared ray cutting ability even when the incident angle is large. Therefore, it is useful for various environmental light sensors, such as an illuminance sensor and a sensor for color correction. In particular, it is useful for environmental light sensors mounted on digital still cameras, smart phones, tablet terminals, mobile phones, wearable devices, automobiles, televisions, game machines, and the like. Moreover, it is useful also as a hot wire cut filter etc. attached to the window glass plate of a car, a building, etc.

[Environmental light sensor]

A combination of the optical filter of the present invention described above and the photoelectric conversion element can be used as an environmental light sensor. Here, the environmental light sensor is a sensor capable of detecting ambient brightness or color tone (e.g. strong red color in the evening), such as an illuminance sensor or a sensor for color correction. It is possible to control the brightness and color tone of the displayed display.

1 shows an example of an ambient light sensor 200a that detects ambient brightness. The environmental light sensor 200a includes an optical filter 100 and a photoelectric conversion element 202 . The photoelectric conversion element 202 generates a current or voltage due to a photovoltaic effect when light is incident on the light receiving unit. The optical filter 100 is provided on the light-receiving surface side of the photoelectric conversion element 202 . By the optical filter 100, light incident on the light receiving surface of the photoelectric conversion element 202 becomes light in the visible light band, and light in the near infrared band (800 nm to 2500 nm) is blocked. The ambient light sensor 200a outputs a signal in response to visible light.

In the ambient light sensor 200a, another translucent layer may be interposed between the optical filter 100 and the photoelectric conversion element 202. For example, a light-transmitting resin layer may be provided between the optical filter 100 and the photoelectric conversion element 202 as a sealing material.

The photoelectric conversion element 202 has a first electrode 206 , a photoelectric conversion layer 208 , and a second electrode 210 . Further, a passivation film 216 is provided on the light-receiving surface side. The photoelectric conversion layer 208 is formed of a semiconductor exhibiting a photoelectric effect. For example, the photoelectric conversion layer 208 is formed using a silicon semiconductor. The photoelectric conversion layer 208 is a diode type element and develops photovoltaic power by a built-in electric field. Further, the photoelectric conversion element 202 is not limited to a diode type element, but may be a photoconductive element (also called a photoresistor, a light-dependent resistor, a photoconductor, or a photocell) or a phototransistor type element.

The photoelectric conversion layer 208 may use a germanium semiconductor or a silicon/germanium semiconductor other than a silicon semiconductor. Further, as the photoelectric conversion layer 208 , a compound semiconductor material such as GaP, GaAsP, CdS, CdTe, or CuInSe ₂ may be used. The photoelectric conversion element 202 formed of a semiconductor material has sensitivity to light in the visible ray band to the near infrared ray band. For example, when the photoelectric conversion layer 208 is formed of a silicon semiconductor, since the bandgap energy of the silicon semiconductor is 1.12 eV, light with a wavelength of 700 to 1100 nm, which is near infrared light, can be absorbed in principle. However, by providing the optical filter 100, the ambient light sensor 200a is not sensitive to near-infrared light and has sensitivity to light in the visible light region. Further, the photoelectric conversion element 202 is preferably surrounded by a light-blocking housing 204 so that light transmitted through the optical filter 100 is selectively irradiated. The ambient light sensor 200a includes the optical filter 100 to block near infrared light and detect ambient light. Accordingly, it is possible to solve the problem that the environmental light sensor 200a responds to near-infrared light and malfunctions.

Fig. 2 shows an example of an ambient light sensor 200b that detects color tone in addition to ambient brightness. The ambient light sensor 200b includes an optical filter 100, photoelectric conversion elements 202a to 202c, and color filters 212a to 212c. A color filter 212a transmitting red light band light is provided on the light receiving surface of the photoelectric conversion element 202a, and a color filter 212b transmitting green light band light is provided on the light receiving surface of the photoelectric conversion element 202b. On the light-receiving surface of the photoelectric conversion element 202c, a color filter 212c that transmits light in the blue light band is provided. The photoelectric conversion elements 202a to 202c have the same configuration as that shown in FIG. 1, except that they are insulated with an element isolation insulating layer 214. With this configuration, the photoelectric conversion elements 202a to 202c can independently detect the illuminance. In addition, a passivation film 216 may be provided between the color filters 212a to 212c and the photoelectric conversion elements 202a to 202c.

The photoelectric conversion elements 202a to 202c have a sensitivity over a wide range from the visible ray wavelength range to the near-infrared ray wavelength range. Therefore, in addition to the optical filter 100, by providing color filters 212a to 212c corresponding to the photoelectric conversion elements 202a to 202c, the ambient light sensor 200b blocks near-infrared light, preventing malfunction of the sensor. While preventing it, it is possible to detect light corresponding to each color. The environmental light sensor 200b is provided with the optical filter 100 that blocks light in the near infrared region and the color filters 212a to 212c, so that the ambient light can be separated into light in a plurality of wavelength bands for detection. In addition, the conventional color sensor can be applied even in a dark environment in which accurate detection cannot be performed due to the influence of near-infrared rays.

[Electronics]

The electronic device of the present invention includes the ambient light sensor of the present invention described above. EMBODIMENT OF THE INVENTION Hereinafter, the electronic apparatus of this invention is demonstrated, referring drawings.

3(A) to (C) show an example of an electronic device 300 having an ambient light sensor 200 according to an embodiment of the present invention. 3(A) is a front view, FIG. 3(B) is a top view, and FIG. 3(C) is a detailed view illustrating the configuration of the area D surrounded by dotted lines in FIG. 3(B). indicates The electronic device 300 includes a housing 302 , a display panel 304 , a microphone unit 306 , a speaker unit 308 , and an ambient light sensor 200 . The display panel 304 adopts a touch panel and has an input function in addition to a display function.

The environmental light sensor 200 is provided on the rear surface panel 310 provided on the housing 302 . That is, the ambient light sensor 200 does not appear on the exterior of the electronic device 300, and light enters through the translucent surface panel 310. Light in the near infrared region of the surface panel 310 is blocked by the optical filter 100 and light in the visible region is incident to the photoelectric conversion element 202 . The electronic device 300 can control the brightness or color tone of the display panel 304 by the ambient light sensor 200 .

According to the present embodiment, in the environmental light sensor 200, since the optical filter 100 is provided close to the light receiving surface of the photoelectric conversion element 202, the illuminance can be accurately adjusted even for light incident at a wide angle. can be measured

Example

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples at all. In addition, "part" means "part by weight" unless otherwise indicated. In addition, the measuring method of each physical property value and the evaluation method of a physical property are as follows.

<molecular weight>

The molecular weight of the resin was measured by the method of the following (a) or (b) in consideration of the solubility of each resin in a solvent.

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

(b) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a GPC device manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: THF).

<Glass transition temperature (Tg)>

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

<Spectral transmittance>

The transmittance in each wavelength region of the optical filter was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).

Here, in the case of transmittance measured in the vertical direction of the optical filter, as shown in FIG. In the case of transmittance measured at an angle of 30 degrees with respect to the vertical direction of , the light 1' transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. ), and the transmittance measured at an angle of 60 degrees with respect to the vertical direction of the optical filter, as shown in FIG. ") was measured with a spectrophotometer (3).

<Spectral reflectance>

The reflectance in each wavelength region of the optical filter was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).

Here, in the case of reflectance measured at an angle of 5 degrees with respect to the vertical direction of the optical filter, as shown in FIG. was measured.

<Optical density (OD value)>

The optical density (OD value) of the optical filter was determined by calculation from a transmittance value measured using a Nippon Bunko Co., Ltd. ultraviolet visible infrared spectrophotometer V-7300.

<Warpage evaluation>

An optical filter measuring 200 mm in length x 200 mm in width was placed on a flat glass plate, and the vertical height at which the corner of the optical filter was bent from the glass plate was defined as the deflection and measured using a regular ruler. For the four corners of the optical filter, the warpage was measured, and the average warpage value of the four corners was taken as the warpage amount. When the warpage amount was 10 mm or less, the warpage characteristic was evaluated as "○", and when it was 10 mm or more, the warpage characteristic was evaluated as "x".

<Evaluation of environmental light sensor performance (color correction performance)>

The near-infrared ray cut filter of the environmental light sensor module of Apple's "iPad (registered trademark) Pro 9.7 inch" was taken out, and the optical filters produced in the examples and comparative examples described later were assembled to the ambient light sensor module instead, Changes in the color tone of the screen were observed in outdoor light during the day, outdoor light in the evening, bright and dark rooms, and the environmental light sensor performance was evaluated by controlling the color tone according to the outdoor light environment (brightness and color tone). The case where color tone control could be appropriately performed according to the external light environment was rated as "○", the case where there was a problem with some color tone control was evaluated as "Δ", and the case where color tone control was poor was rated as "x".

The near-infrared absorbing dye used in the following examples was synthesized by a generally known method. As a general synthesis method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Unexamined Patent Publication No. 60-228448, Japanese Patent Laid-open Publication Publication No. 1-146846, Japanese Unexamined Patent Publication No. Hei 1-228960, Japanese Patent No. 4081149, Japanese Unexamined Patent Publication No. 63-124054, "Phthalocyanine -Chemistry and Function-" (IPC, 1997), Japanese Patent The method described in Unexamined-Japanese-Patent No. 2007-169315, Unexamined-Japanese-Patent No. 2009-108267, Unexamined-Japanese-Patent No. 2010-241873, Unexamined-Japanese-Patent No. 3699464, Unexamined-Japanese-Patent No. 4740631, etc. is mentioned. .

<Resin Synthesis Example 1>

In a 3L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g (0.300 mol) of potassium carbonate ), 443 g of N,N-dimethylacetamide (hereinafter also referred to as "DMAc") and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way coke with a nitrogen inlet pipe, a Dean Stark pipe, and a cooling pipe were installed in the four-necked flask. Next, after purging the inside of the flask with nitrogen, the obtained solution was reacted at 140°C for 3 hours, and the resulting water was removed from the Dean Stark tube at any time. When the production of water was not confirmed, the temperature was gradually raised to 160°C, and the mixture was reacted at the same temperature for 6 hours. After cooling to room temperature (25°C), the formed salt was removed with a filter paper, the filtrate was reprecipitated in methanol, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60°C overnight to obtain a white powder (hereinafter also referred to as "Resin A") (yield: 95%). The obtained Resin A 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 2>

8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^{2,5.1 7,10} ]dodec-3-ene represented by the following formula (8) (hereinafter also referred to as "DNM") 100 parts , 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (a solvent for ring-opening polymerization) were charged into a nitrogen-purged reaction vessel, and the solution was heated to 80°C. Next, to the solution in the reaction vessel, as a polymerization catalyst, 0.2 part of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.9 part of a methanol-modified toluene solution of tungsten hexachloride (concentration of 0.025 mol/liter) were added, The ring-opening polymerization reaction was carried out by heat-stirring the solution at 80 degreeC for 3 hours, and the ring-opening polymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opened polymer solution obtained in this way was put into an autoclave, and 0.12 part of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution, followed by a reaction under a hydrogen gas pressure of 100 kg/cm ² . A hydrogenation reaction was performed by heating and stirring for 3 hours under conditions of a temperature of 165°C. After the obtained reaction solution (hydrogenated polymer solution) was cooled, hydrogen gas was released from pressure. This reaction solution was poured into a large amount of methanol, the coagulated material was separated and recovered, and this was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin B"). The obtained Resin B 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.

[Example 1]

In Example 1, an optical filter having a substrate comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

In a container, 100 parts by weight of Resin A obtained in Resin Synthesis Example 1, as compound (A)

0.04 part of compound (a-1) represented by the following formula (a-1) (maximum absorption wavelength in dichloromethane: 713 nm);

0.08 part of compound (a-2) represented by the following formula (a-2) (maximum absorption wavelength in dichloromethane: 736 nm); and

0.10 part of compound (a-3) represented by the following formula (a-3) (maximum absorption wavelength in dichloromethane: 776 nm);

As compound (B), 1.50 parts of light absorber "CIR-RL" (maximum absorption wavelength; 1095 nm, also referred to as "compound (b-1)" hereinafter) manufactured by Nippon Kallit Co., Ltd.;

Then, N,N-dimethylacetamide was added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

On one side of the obtained transparent resin substrate, a resin composition (1) having the following composition was applied with a bar coater and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor type exposure machine, the resin composition (1) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (1) was formed on the other side of the transparent resin substrate to obtain a substrate having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Resin composition (1): 60 parts by weight of tricyclodecane dimethanol acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexylphenyl ketone, a near-infrared absorbing fine particle dispersion (Sumitomo Kinzoku Kozan Co., Ltd. YMF-02A, maximum absorption wavelength: 1715 nm, commercially available dispersion of second fine particles) 117 parts by weight (about 33 parts by weight in terms of solid content), methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 6 and Table 13.

[Example 2]

In Example 2, an optical filter having a base material comprising a transparent glass substrate was produced in the following procedure and conditions.

<Preparation of Resin Solution (D-1)>

In a container, 100 parts by weight of Resin B obtained in Resin Synthesis Example 2, as compound (A),

2.00 parts of compound (a-1);

4.00 parts of compound (a-2), and

5.00 parts of compound (a-3);

As compound (B), 15.00 parts of compound (b-1);

Then, dichloromethane was added to prepare a solution having a resin concentration of 10% by weight. Thereafter, it was filtered through a Millipore filter having a pore diameter of 5 μm to obtain a resin solution (D-1).

<Manufacture of base material>

Subsequently, the resin composition (1) was applied to one side of a near-infrared absorbing glass substrate "BS-11" (thickness: 120 µm) manufactured by Matsunami Glass Kogyo Co., Ltd., cut to a size of 200 mm in length and 200 mm in width, by a bar coater. , and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 4 μm. Then, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine, the resin composition (1) was cured, and a resin layer was formed on the glass substrate.

Next, the resin solution (D-1) was applied on the resin layer using a spin coater under the condition that the thickness after drying was 2 μm, heated on a hot plate at 80° C. for 5 minutes, and the solvent was evaporated off to make it transparent. A resin layer was formed, and then baked in an oven at 230° C. for 20 minutes to obtain a substrate having a length of 200 mm and a width of 200 mm.

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 7 and Table 13.

[Example 3]

In Example 3, an optical filter having a base material comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

To a container, 100 parts by weight of Resin B obtained in Resin Synthesis Example 2, 0.04 part of Compound (a-3) as Compound (A), 0.15 part of Compound (b-1) as Compound (B), and dichloromethane were added, and Resin A solution having a concentration of 20% by weight was prepared. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

The resin composition (1) was applied to one side of the obtained transparent resin substrate with a bar coater, and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 4 μm. Next, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor type exposure machine, the resin composition (1) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (1) was formed on the other side of the transparent resin substrate to obtain a substrate having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 8 and Table 13.

[Example 4]

In Example 4, an optical filter having a base material including a glass substrate was produced in the following procedure and conditions.

<Preparation of resin solution (D-2)>

To a container, 100 parts by weight of Resin A obtained in Resin Synthesis Example 1, 10.00 parts of Compound (a-3) as Compound (A), 22.50 parts of Compound (b-1) as Compound (B), and dichloromethane were added, and the resin A solution having a concentration of 10% by weight was prepared. Thereafter, it was filtered through a Millipore filter having a pore diameter of 5 μm to obtain a resin solution (D-2).

<Preparation of resin composition (2)>

Isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Chemical Co., Ltd.) 30 parts by weight, 1,9-nonanediol diacrylate 20 parts by weight, methacrylic acid 20 parts by weight part, 30 parts by weight of glycidyl methacrylate, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 After mixing parts by weight and 1 part by weight of Sun-Aid SI-110 main ingredient (manufactured by Sanshin Kagaku Kogyo Co., Ltd.), dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 50 wt%, a Millipore filter with a pore diameter of 0.2 μm and filtered to prepare a resin composition (2).

<Manufacture of base material>

Subsequently, resin composition (2) was applied by spin coating to one side of a near-infrared absorbing glass substrate "BS-11" (thickness: 120 µm), manufactured by Matsunami Glass Kogyo Co., Ltd., which had been cut to a size of 200 mm in length and 200 mm in width. After that, it was heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent, and a resin layer functioning as an adhesive layer with a transparent resin layer described later was formed. At this time, the coating conditions of the spin coater were adjusted so that the film thickness of the resin layer was about 0.8 μm. Next, the resin solution (D-2) was applied on the resin layer using a spin coater under the condition that the film thickness after drying was 2 μm, heated on a hot plate at 80° C. for 5 minutes, and the solvent was evaporated off to make it transparent. A resin layer was formed. Subsequently, it was exposed using a conveyor-type exposure machine from the glass surface side (exposure amount 1 J/cm ² , illumination intensity 200 mW), and then baked in an oven at 230° C. for 20 minutes to obtain a substrate having a length of 200 mm and a width of 200 mm.

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 9 and Table 13.

[Example 5]

In Example 5, an optical filter having a substrate comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

To a container, add 100 parts by weight of Resin B obtained in Resin Synthesis Example 2, 0.10 parts of Compound (a-3) as Compound (A), 1.50 parts of Compound (b-1) as Compound (B), and dichloromethane, and add Resin A solution having a concentration of 20% by weight was prepared. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

On one side of the obtained transparent resin substrate, a resin composition (3) having the following composition was applied with a bar coater and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Then, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine, the resin composition (3) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (3) was formed on the other side of the transparent resin substrate to obtain a base material having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Resin composition (3): 60 parts by weight of tricyclodecane dimethanol diacrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexylphenyl ketone, methyl ethyl ketone (solvent, solid content concentration ( TSC): 30%)

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 10 and Table 13.

[Example 6]

In Example 6, an optical filter having a substrate comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

Into a container, 100 parts by weight of Resin A obtained in Resin Synthesis Example 1, 0.02 part of Compound (a-1) and 0.04 part of Compound (a-2) as Compound (A), and N,N-dimethylacetamide were added to the resin. A solution having a concentration of 20% by weight was prepared. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

The resin composition (1) was applied to one side of the obtained transparent resin substrate with a bar coater, and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 6 μm. Subsequently, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor type exposure machine, the resin composition (1) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (1) was formed on the other side of the transparent resin substrate to obtain a base material having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 11 and Table 13.

[Example 7]

In Example 7, an optical filter having a base material comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

In a container, 100 parts by weight of Resin B obtained in Resin Synthesis Example 1, 0.03 part of Compound (a-1) and 0.06 part of Compound (a-2) as Compound (A), and 0.60 part of Compound (b-1) as Compound (B) part, and dichloromethane was added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

The resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Then, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine, the resin composition (3) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (3) was formed on the other side of the transparent resin substrate to obtain a base material having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 12 and Table 13.

[Example 8]

In Example 8, an optical filter having a substrate comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

In a container, 100 parts by weight of Resin B obtained in Resin Synthesis Example 1, as compound (A)

0.04 part of compound (a-1);

0.08 part of compound (a-2), and

0.10 part of compound (a-3);

1.50 parts of compound (b-1) as compound (B);

Then, dichloromethane was added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

The resin composition (1) was applied to one side of the obtained transparent resin substrate with a bar coater, and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor type exposure machine, the resin composition (1) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (1) was formed on the other side of the transparent resin substrate to obtain a substrate having a resin layer on both sides of the transparent resin substrate containing the compound (A).

<Manufacture of optical filter>

A dielectric multilayer film (I) was formed on one side of the obtained substrate as a first optical layer, and the same dielectric multilayer film (I) was formed on the other side of the substrate to obtain an optical filter having a thickness of about 0.104 mm.

The dielectric multilayer film (I) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 120° C. (four layers in total). The silica layer and titania layer of the dielectric multilayer film (I) were alternately laminated in the order of titania layer, silica layer, titania layer, and silica layer from the substrate side, and the outermost layer of the optical filter was the silica layer.

In Example 8, the dielectric multilayer film (I) was a multilayer deposited film having a thickness of 4, in which a silica layer having a thickness of 33 to 88 nm and a titania layer having a thickness of 13 to 111 nm were alternately laminated. An example of the membrane structure is shown in Table 10 below.

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in Figure 13 and Table 13.

[Example 9]

In Example 9, an optical filter having a substrate comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

In a container, 100 parts by weight of resin A obtained in Resin Synthesis Example 1, 0.10 part of compound (a-3) as compound (A), 1.00 part of compound (b-1) as compound (B) and the following formula (b-2) 0.30 part of the compound represented by (maximum absorption wavelength in dichloromethane: 850 nm) and dichloromethane were added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

The resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Then, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine, the resin composition (3) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (3) was formed on the other side of the transparent resin substrate to obtain a base material having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Table 13 shows the evaluation results.

[Example 10]

In Example 10, an optical filter having a substrate comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

In a container, 100 parts by weight of Resin B obtained in Resin Synthesis Example 2, 0.10 part of compound (a-3) as compound (A), 1.00 part of compound (b-1) as compound (B) and the following formula (b-3) 0.10 part of the compound represented by (maximum absorption wavelength in dichloromethane: 886 nm) and dichloromethane were added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

The resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Then, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine, the resin composition (3) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (3) was formed on the other side of the transparent resin substrate to obtain a base material having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Table 13 shows the evaluation results.

[Comparative Example 1]

In the same method as in Example 1, a dielectric multilayer film (II) is formed as a first optical layer on one side of the obtained substrate, and further a dielectric multilayer film (III) is formed as a second optical layer on the other side of the substrate, An optical filter with a thickness of about 0.109 mm was obtained.

The dielectric multilayer film (II) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 120° C. (26 layers in total). The dielectric multilayer film (III) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 120° C. (20 layers in total). In any of the dielectric multilayer films (II) and (III), the silica layer and the titania layer are alternately laminated in the order of titania layer, silica layer, titania layer, ...silica layer, titania layer, silica layer from the substrate side. and the outermost layer of the optical filter was a silica layer.

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

Regarding the thickness and number of layers of each layer, the wavelength dependence of the refractive index of the substrate or the applied compound (A) and compound (B) can achieve the antireflection effect in the visible region and the selective transmission/reflection performance in the near infrared region. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) according to the absorption characteristics. When performing optimization, in this embodiment, input parameters (target values) to the software were set as shown in Table 11 below.

As a result of optimizing the film configuration, in Comparative Example 1, the dielectric multilayer film (II) is a multilayer deposited film having a thickness of 26, in which silica layers with a film thickness of 31 to 155 nm and titania layers with a film thickness of 10 to 94 nm are alternately laminated. , The dielectric multilayer film (III) was a multilayer deposited film having a thickness of 20, in which a silica layer having a thickness of 38 to 189 nm and a titania layer having a thickness of 11 to 109 nm were alternately laminated. Table 12 shows an example of an optimized film configuration.

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 14 and Table 13.

The rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the ratio of change of the B transmittance ratio of the optical filter obtained in Comparative Example 1 were 0.6 or less, and did not show good RGB balance. In addition, the amount of warpage of the optical filter obtained in Comparative Example 1 was 17 mm, which did not show good warpage characteristics.

[Comparative Example 2]

In Comparative Example 2, an optical filter having a base material comprising a transparent resin substrate having resin layers on both sides was produced in the following procedure and conditions.

<Production of Transparent Resin Substrate>

In a container, 100 parts by weight of resin A obtained in Resin Synthesis Example 1, 0.04 part of compound (a-1) and 0.08 part of compound (a-2) as compound (A), and 0.15 part of compound (b-1) as compound (B) part, and N,N-dimethylacetamide was added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

The resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Then, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine, the resin composition (3) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (3) was formed on the other side of the transparent resin substrate to obtain a base material having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 15 and Table 13.

The optical density of the optical filter obtained in Comparative Example 2 at 800 nm to 1200 nm was 1.5 or less in all cases of 0 degrees, 30 degrees, and 60 degrees, and did not exhibit good near-infrared ray cut characteristics, and the environmental light sensor performance also depended on the external light environment. Tonal control was poor.

[Comparative Example 3]

In Comparative Example 3, an optical filter having a substrate comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

<Production of Transparent Resin Substrate>

To a container, 100 parts by weight of Resin B obtained in Resin Synthesis Example 2, 0.04 parts of compounds (a-1) and 0.08 parts of (a-2) as compound (A), and dichloromethane were added to a resin concentration of 20% by weight. A solution was prepared. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

<Manufacture of base material>

The resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Then, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine, the resin composition (3) was cured, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (3) was formed on the other side of the transparent resin substrate to obtain a base material having a resin layer on both sides of the transparent resin substrate containing the compound (A).

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. Results are shown in Figure 16 and Table 13.

The optical density of the optical filter obtained in Comparative Example 3 at 800 nm to 1200 nm was 1.5 or less in all cases of 0 degrees, 30 degrees, and 60 degrees, and did not exhibit good near-infrared ray cut characteristics, and the environmental light sensor performance also depended on the external light environment. Tonal control was poor.

[Comparative Example 4]

In Comparative Example 4, an optical filter having a base material including a glass substrate was produced in the following procedure and conditions.

<Preparation of resin solution (D-3)>

To a container, 100 parts by weight of Resin B obtained in Resin Synthesis Example 2, 0.8 parts of Compound (a-1) and 1.6 parts of Compound (a-2) as Compound (A), and dichloromethane were added to obtain a resin concentration of 10% by weight. A phosphorus solution was prepared. Thereafter, it was filtered through a Millipore filter having a pore diameter of 5 μm to obtain a resin solution (D-3).

<Manufacture of base material>

Subsequently, the resin composition (2) was spin-coated on one side of a near-infrared absorbing glass substrate "BS-11" (thickness: 120 µm), manufactured by Matsunami Glass Kogyo Co., Ltd., cut to a size of 200 mm in length and 200 mm in width. After coating, it was heated on a hot plate at 80°C for 2 minutes to volatilize off the solvent, and a resin layer functioning as an adhesive layer with a transparent resin layer described later was formed. At this time, the coating conditions of the spin coater were adjusted so that the film thickness of the resin layer was about 0.8 μm. Next, the resin solution (D-3) was applied on the resin layer using a spin coater under conditions such that the film thickness after drying was 5 μm, heated on a hot plate at 80° C. for 5 minutes, and the solvent was evaporated off to make it transparent. A resin layer was formed. Subsequently, it was exposed using a conveyor-type exposure machine from the glass surface side (exposure amount 1 J/cm ² , illumination intensity 200 mW), and then baked in an oven at 230° C. for 20 minutes to obtain a substrate having a length of 200 mm and a width of 200 mm.

Using the obtained substrate as an optical filter, the spectral transmittance in the vertical direction of the optical filter and at angles of 30 ° and 60 ° with respect to the vertical direction, the spectral reflectance at an angle of 5 ° with respect to the vertical direction of the optical filter, and the other The spectral reflectance was measured from an angle of 5° with respect to the vertical direction on the plane, and the optical characteristics and the rate of change of the ratio of R transmittance, the rate of change of the ratio of G transmittance, and the rate of change of the ratio of B transmittance in each wavelength region were determined. evaluated. In addition, the bending characteristics and environmental light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in Figure 17 and Table 13.

The optical density of the optical filter obtained in Comparative Example 4 at 800 nm to 1200 nm was 1.5 or less in all cases of 0 degrees, 30 degrees, and 60 degrees, and did not exhibit good near-infrared ray cut characteristics, and the environmental light sensor performance also depended on the external light environment. Tonal control was poor.

100... optical filter
200... environmental light sensor
202, 202a, 202b, 202c... photoelectric conversion element
204... Housing
206... first electrode
208... photoelectric conversion layer
210... second electrode
212a, 212b, 212c... color filters
214... element isolation insulating layer
216... passivation film
300... electronic devices
302... housing
304... display panel
306... microphone section
308... speaker section
310... surface panel

Claims (12)

An optical filter for an environmental light sensor having a substrate that satisfies the following requirement (a) and also satisfying the following requirements (b), (c) and (d),
A dielectric multilayer film is provided on at least one surface of the substrate, and the dielectric multilayer film is obtained by alternately laminating high refractive index material layers and low refractive index material layers, and the sum of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is An optical filter for an environmental light sensor, characterized in that the number of layers is 1 to 20 as a whole of the optical filter:
(a) has a layer containing a compound (A) having an absorption maximum in a wavelength region of 650 nm or more and less than 800 nm, and a compound (B) having an absorption maximum in a wavelength region of 800 nm or more and 1850 nm or less;
(b) In the wavelength range of 800 to 1000 nm, the average value Rf _a-5 of the reflectance of light incident from an oblique direction of 5 degrees with respect to the vertical direction on one surface of the optical filter and the vertical direction on the other surface the average value Rf _b-5 of reflectances of light incident from a direction obliquely 5 degrees relative to each other is 15% or less;
(c) In the wavelength range of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter and the average value T _a- 30 of the transmittance of light incident from an oblique direction of 30 degrees with respect to the vertical direction, , the average value T _{a -60} of the transmittance of light incident from a direction obliquely 60 degrees with respect to the vertical direction is all 20% or more and less than 75%;
(d) In the wavelength range of 800 nm to 1200 nm, the average value OD _a-0 of the optical density (OD value) for light incident from the vertical direction of the optical filter and the light incident from an oblique direction of 30 degrees with respect to the vertical direction The average value OD _a-30 of the optical density (OD value) for light and the average value OD _a-60 of the optical density (OD value) for light incident from an oblique direction of 60 degrees with respect to the vertical direction are both 1.5 or more. The optical filter for an environmental light sensor according to claim 1, wherein the layer containing the compound (A) is a transparent resin layer. The optical filter for an environmental light sensor according to claim 2, wherein the transparent resin layer further comprises the compound (B). The environmental light according to any one of claims 1 to 3, wherein the compound (A) is at least one compound selected from the group consisting of squarylium-based compounds, phthalocyanine-based compounds, and cyanine-based compounds. Optical filter for sensor. The compound (B) according to any one of claims 1 to 3, wherein the compound (B) is a near-infrared absorbing particle, a squarylium-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, a croconium-based compound, a cyanine-based compound, or a dimonium-based compound. An optical filter for an environmental light sensor, characterized in that it is at least one compound selected from the group consisting of compounds, metal dithiolate compounds and pyrrolopyrrole compounds. The method according to claim 5, wherein the near-infrared absorbing fine particles are composed of first fine particles containing a compound represented by the following formula (P-1) and second fine particles containing a compound represented by the following formula (P-2) An optical filter for an environmental light sensor, characterized in that it is at least one selected from the group
A _1/n CuPO ₄ ... (P-1)
[In formula (P-1), A is at least one selected from the group consisting of alkali metals, alkaline earth metals, and NH ₄ , n is 1 when A is an alkali metal or NH ₄ , and A is alkaline earth For metal, it is 2.]
M _x W _y O _z ... (P-2)
[In Formula (P-2), M is H, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, at least one element selected from Bi and I, and x, y and z satisfy the conditions of 0.001 ≤ x / y ≤ 1 and 2.2 ≤ z / y ≤ 3.0.] The resin of claim 2 or 3, wherein the resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, or a fluorene polyester resin. Resins, polycarbonate-based resins, polyamide-based resins, aramid-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorinated aromatic polymers based resins, (modified) acrylic resins, epoxy resins, silsesquioxane based ultraviolet curable resins, maleimide based resins, alicyclic epoxy thermosetting resins, polyether ether ketone based resins, polyarylate based resins, allyl ester based curable resins An optical filter for an environmental light sensor, characterized in that it is at least one resin selected from the group consisting of an acrylic ultraviolet curable resin, a vinyl ultraviolet curable resin, and a silica-containing resin formed by a sol-gel method. The optical filter for an environmental light sensor according to any one of claims 1 to 3, wherein the substrate includes a fluorophosphate-based glass layer containing a copper component or a substrate made of phosphate-based glass. The method according to any one of claims 1 to 3, wherein the optical filter for the environmental light sensor is incident from a vertical direction, incident from a direction of 30° to the vertical direction, and incident from a direction of 60° from the vertical direction. In the case of incident from the direction of
The change rate of the R (red) transmittance ratio derived from the following formula (1), the change ratio of the G (green) transmittance ratio derived from the following formula (2), and the B (blue) transmittance derived from the following formula (3) An optical filter for an environmental light sensor, characterized in that the rate of change of the ratio of is all in the range of 0.6 to 1.1.
(Ratio of transmittance) = (R transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (1)
(G transmittance ratio) = (G transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (2)
(Ratio of B transmittance) = (B transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) Equation (3)
[In formulas (1) to (3), R transmittance is the average transmittance in the wavelength range of 580 to 650 nm, G transmittance is the average transmittance in the wavelength range of 500 to 580 nm, and B transmittance is the average transmittance in the wavelength range of 420 to 500 nm. .] An ambient light sensor comprising the optical filter for an ambient light sensor according to any one of claims 1 to 3. An electronic device comprising the ambient light sensor according to claim 10. delete

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