JP2019032371A - Optical filters and their applications - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical filter which is thin, has excellent near-infrared shielding property and has low reflection characteristics, and an apparatus using the optical filter, by improving the drawbacks of a conventional optical filter such as a near-infrared cut filter. thing. An optical filter having a base material satisfying the requirement (a) and an antireflection layer formed on at least one surface of the base material, and satisfying specific optical characteristics: (A) It has a layer containing the compound (A) having an absorption maximum in a region having a wavelength of 650 nm or more and less than 950 nm. [Selection diagram] None

Description

  The present invention relates to an optical filter and its use. Specifically, the present invention relates to an optical filter (for example, a near-infrared cut filter) containing a compound having absorption in a specific wavelength region and having specific optical characteristics, and a solid-state imaging device and a camera module using the optical filter.

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

  As such a near-infrared cut filter, what was conventionally manufactured by various methods is used. For example, an absorption glass type optical filter in which copper oxide is dispersed in phosphate glass (for example, see Patent Document 1) is known.

  In recent years, thinning of solid-state imaging devices has been demanded, and thinning of optical filters to be used is also demanded. The absorption principle of the absorption glass type optical filter often uses absorption derived from the d orbit of copper ions. However, since the absorption intensity is weak, it is difficult to express sufficient cutting performance when the thickness is reduced.

  In such a thin absorption glass type optical filter, a dielectric multilayer film having near infrared reflection performance is often provided on the surface of the substrate in order to supplement the absorption strength (see, for example, Patent Document 2). By providing a dielectric multilayer film having near-infrared reflecting performance on the surface of the base material, both thinning and near-infrared shielding can be achieved.

  Such an optical filter having a dielectric multilayer film having near-infrared reflection performance is not limited to an absorption glass type, and for example, a transparent resin is used as a base material, and an absorption maximum is obtained in a region of 650 to 800 nm in the transparent resin. An optical filter using a dielectric multilayer film having near-infrared reflective performance on both sides of the substrate (Patent Document 3), an optical filter coated with copper phosphate salt or cesium tungsten oxide particles on glass (patent) Document 4), various optical filters (Patent Document 5) in which a glass substrate is coated with a resin layer containing a dye having absorption in the vicinity of 700 to 750 nm are known.

  However, optical filters having near-infrared reflecting performance on the surface of the base material, such as the above-described absorption glass type, resin type, and glass substrate coating type optical filter, light reflected by the surface of the optical filter is incident on the sensor again. Phenomenon, that is, ghosting may occur, causing an image defect of the obtained solid-state imaging device.

  It has been known for a long time that a ghost is suppressed by providing an antireflection layer on an optical filter (Patent Document 6), but an antireflection layer in a conventional optical filter has a wavelength in the visible light region of 420 nm to 780 nm. Because of this antireflection layer, a ghost was generated by light having a wavelength in the near infrared region of 781 nm to 1000 nm. In addition, when the near-infrared reflecting performance is not imparted to a thin base material, the optical density (Optical Density, OD) in the near-infrared region having a wavelength of 800 nm or more and 1200 nm or less is not sufficient, and both thinning and near-infrared shielding performance are compatible. could not. That is, an optical filter that is thin and excellent in near-infrared shielding performance and low in reflectance from visible light to wavelengths in the near-infrared region has not been obtained.

International Publication No. 2011/071157 Pamphlet International Publication No. 2011/158635 Pamphlet JP-A-6-200113 JP 2014-054822 A JP 2014-063144 A International Publication No. 2016/174754

  An object of the present invention is to improve the shortcomings of conventional optical filters such as near-infrared cut filters, thin, excellent near-infrared shielding properties and low reflection characteristics, and an apparatus using the optical filter Is to provide.

Examples of embodiments of the present invention are shown below.
[1] It has a base material that satisfies the following requirement (a) and an antireflection layer formed on at least one surface of the base material, and the following requirements (b), (c), and (d) Optical filter characterized by filling:
(A) having a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and less than 950 nm;
(B) In the region of wavelength 420 nm or more and 1000 nm or less, the average value Rfa _-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 And the average value Rf _b-5 of the reflectance of light incident from an oblique direction with respect to 5 degrees is 6% or less;
(C) In the region of wavelength 430 nm or more and 580 nm or less, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter and the light of non-polarized light incident from an oblique direction of 30 degrees with respect to the vertical direction The average value T _a-30 of the transmittance and the average value T _a-60 of the transmittance of the non-polarized light incident from an oblique direction of 60 degrees with respect to the vertical direction are both 20% or more;
(D) In the region of wavelength 800 nm or more and 1200 nm or less, the average value OD _a-0 of the optical density (OD value) with respect to the 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) with respect to the light and the average value OD _a-60 of the optical density (OD value) with respect to light incident from an oblique direction of 60 degrees with respect to the vertical direction are 1. 5 or more.

  [2] The optical filter according to item [1], which has antireflection layers on both surfaces of the substrate.

  [3] The optical filter according to item [1] or [2], wherein the thickness is 100 μm or less.

  [4] The optical filter according to any one of items [1] to [3], wherein the layer containing the compound (A) is a transparent resin layer.

  [5] Any of [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. The optical filter according to item 1.

  [6] The optical filter according to any one of items [1] to [5], wherein the base material contains a compound (B) having an absorption maximum in a wavelength range of 950 nm to 1800 nm. .

  [7] The compound (B) is composed of near-infrared absorbing fine particles, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, cyanine compounds, diimonium compounds, metal dithiolate compounds, and pyrrolopyrrole compounds. The optical filter according to item [6], wherein the optical filter is at least one compound selected from the group consisting of:

  [8] The optical filter according to any one of items [1] to [7], wherein the compound (A) includes a compound having an absorption maximum in a wavelength region of 650 nm or more and less than 800 nm.

  [9] The optical filter according to any one of items [1] to [8], wherein the compound (A) includes a compound having an absorption maximum in a wavelength region of 800 nm or more and less than 950 nm.

  [10] The item [1], wherein the compound (A) includes a compound having an absorption maximum in a region of a wavelength of 650 nm or more and less than 800 nm and a compound having an absorption maximum in a region of a wavelength of 800 nm or more and less than 950 nm. The optical filter according to any one of to [7].

[11] A group in which the near-infrared absorbing fine particles are composed of first fine particles made of a compound represented by the following formula (P-1) and second fine particles made of a compound represented by the following formula (P-2). The optical filter according to item [7], wherein the optical filter is at least one selected from the group consisting of:
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 , and n is 1 when A is an alkali metal or NH ₄ . , A is 2 when alkaline earth metal. ]
M _x W _y O _z (P-2)
[In the formula (P-2), M is H, alkali metal, alkaline earth metal, 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 and I, x, y and z are 0.001 ≦ x / y ≦ 1 and 2.2 ≦ z / y ≦ 3. Satisfy the condition of 0. ]

  [12] The resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or an aramid resin. , Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesqui Oxan UV curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin Mold resin and Sorge The optical filter according to claim [4], wherein the silica formed by law is at least one resin selected from the group consisting of a resin whose main component.

  [13] The item [1] to [12], wherein the base material includes a substrate made of a fluorophosphate glass layer or a phosphate glass layer containing a copper component. The optical filter described in 1.

[14] In the case where the optical filter is incident from the vertical direction, when incident from the direction of 30 ° with respect to the vertical direction, and when incident from the direction of 60 ° with respect to the vertical direction,
Change rate of ratio of R (red) transmittance derived from the following formula (1), change rate of ratio of G (green) transmittance derived from the following formula (2), and B derived from the following formula (3) (Blue) The optical filter according to any one of items [1] to [13], wherein a change rate of a transmittance ratio is in a range of 0.6 to 1.1.
(R transmittance ratio) = (R transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (1)
(G transmittance ratio) = (G transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (2)
(B transmittance ratio) = (B transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (3)
In the formulas (1) to (3), the R transmittance is an average transmittance at a wavelength of 580 to 650 nm, the G transmittance is an average transmittance at a wavelength of 500 to 580 nm, and the B transmittance is an average transmittance at a wavelength of 420 to 500 nm. .

  [15] An optical filter substrate used for the optical filter according to any one of items [1] to [14].

  [16] An imaging device comprising the optical filter according to any one of items [1] to [14].

  [17] A camera module comprising the optical filter according to any one of items [1] to [14].

  ADVANTAGE OF THE INVENTION According to this invention, although it is thin, while being excellent in near-infrared shielding, it can provide the optical filter which has a low reflective characteristic, and the apparatus using this optical filter.

It is the figure which showed the structure which measures a transmission spectrum from the perpendicular direction, the direction of diagonal 30 degree | times, and the direction of diagonal 60 degree | times. It is the schematic which shows the example of the method of measuring the reflectance of the light which injected from the angle of 5 degrees with respect to the orthogonal | vertical direction of an optical filter. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 1, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 2, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 3, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 4, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 5, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 6, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 7, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 8, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained in Example 9, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral reflectance measured from the angle of 5 degrees from the perpendicular direction of the optical filter obtained in Example 9. FIG. 4 is a graph showing the spectral transmittance measured from the vertical direction of the optical filter obtained in Comparative Example 1, an angle of 30 ° from the vertical direction, and an angle of 60 ° from the vertical direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained by the comparative example 2, the angle of 30 degrees from the perpendicular direction, and the angle of 60 degrees from the perpendicular direction. It is a graph which shows the spectral transmission factor measured from the perpendicular direction of the optical filter obtained by the comparative example 3, the angle of 30 degrees from a perpendicular direction, and the angle of 60 degrees from a perpendicular direction. It is a graph which shows the spectral reflectance measured from the angle of 5 degrees from the perpendicular direction in the near-infrared cut layer surface and antireflection layer surface of the optical filter obtained in the comparative example 3.

Hereinafter, embodiments of the present invention will be described in detail.
[Optical filter]
The optical filter of the present invention has a base material (i) satisfying the following requirement (a) and an antireflection layer formed on at least one surface of the base material (i), and the following requirement (b ), (C) and (d) are satisfied.

Requirement (a): It has a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and less than 950 nm.
Requirement (b): In the region of wavelength 420 nm or more and 1000 nm or less, the average value Rf _a-5 of the reflectance of light incident from an angle of 5 degrees with respect to the vertical direction on one surface of the optical filter, and the other surface The average reflectance Rf _{b-5 of} light incident from an angle of 5 degrees with respect to the vertical direction is 6% or less, preferably 0.1 to 4%, more preferably 0.1 to 2%. It is.

  As a method of satisfying the requirement (b), that is, a method of adjusting the average value of each reflectance, for example, a large number of conical structures having a size less than the wavelength of light are provided, and the refractive index is continuously changed from the incident medium to the substrate. Examples thereof include a method of forming a layer to be changed and a method of forming an antireflection layer using a multilayer dielectric film.

  By satisfying the requirement (b), the reflectance of light having a wavelength of 420 nm or more and 1000 nm or less, in which the silicon photodiode is strongly sensitive, can be reduced on either side of the optical filter. When used as a solid-state imaging device or as a camera module, a good image can be obtained.

Requirement (c): In the region of wavelength 430 nm or more and 580 nm or less, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter and the non-polarized light incident from a direction oblique to the vertical direction by 30 degrees The average value T _a-30 of the light transmittance of the light and the average value T _a-60 of the light transmittance of the non-polarized light incident from the oblique direction of 60 degrees with respect to the vertical direction are both 20% or more, Preferably it is 22-95%, More preferably, it is 28-90%, Most preferably, it is 46-85%.

As a method of satisfying the requirement (c), that is, a method of adjusting the average value of each transmittance, for example, the concentration of the compound added to the substrate is adjusted, and the average absorbance in the region of 430 nm to 580 nm is preferably 0.6. Hereinafter, a method of setting the average absorbance to 0.3 or less is more preferable.
By satisfying the requirement (c), a good image can be obtained when the optical filter of the present invention is used for a solid-state imaging device.

Requirement (d): In the region of wavelength 800 nm or more and 1200 nm or less, the average value OD _a-0 of the optical density (OD value) with respect to the 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) with respect to the light to be emitted and the average value OD _a-60 of the optical density (OD value) with respect to the light incident from an oblique direction of 60 degrees with respect to the vertical direction are both It is 1.5 or more, preferably 1.9 or more and 5.0 or less, more preferably 2.5 or more and 5.0 or less, and particularly preferably 2.9 or more and 5.0 or less.

  As a method of satisfying the requirement (d), that is, a method of adjusting the average value of each transmittance, for example, the concentration of the compound contained in the substrate is adjusted, and the average absorbance in the region of 800 nm or more and 1200 nm or less is 1.5 or more. The method of doing is mentioned.

By satisfying the 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.
As a method of satisfying both requirements (c) and (d), that is, a method for adjusting the average value of each transmittance, for example, there is little absorption in the region of wavelength 430 nm or more and 580 nm or less and maximum in the region of wavelength 800 nm to 950 nm There is a method of providing a layer containing a compound having absorption and a compound having little absorption in a wavelength region of 430 nm to 580 nm and having maximum absorption in a wavelength region of 950 nm to 1800 nm. As preferable conditions of the compound to be contained in the layer provided in order to satisfy both the requirements (c) and (d),
<1> From the viewpoint of obtaining excellent near-infrared shielding performance even at a film thickness of 100 μm or less, the weight extinction coefficient at the maximum absorption wavelength is preferably 1.0 × 10 ² L · cm ⁻¹ · g ⁻¹ or more. Preferably it is 2.0 × 10 ² L · cm ⁻¹ · g ⁻¹ or more, more preferably 3.0 × 10 ² L · cm ⁻¹ · g ⁻¹ or more, and particularly preferably 4.0 × 10 ² L · g ^−1. cm ^-1 · g ^-1 or more
<2> The maximum weight extinction coefficient in the region of 430 nm or more and 580 nm or less is preferably 15 L · cm ⁻¹ · g ⁻¹ or less, more preferably 12 L, from the viewpoint of achieving both near-infrared shielding performance and transmission characteristics in the visible light region. ^-Cm <^-1> * g <^-1> or less, More preferably, it is 10 L * cm <^-1> * g <^-1> or less. Among the compounds to be contained in the layer, compounds satisfying the above conditions <1> and <2> are preferably 1 or more, more preferably 2 or more, further preferably 3 or more, particularly preferably 4 or more. It is desirable to be.

  The OD value is a common logarithm of transmittance, and can be calculated by the following formula (4). When the average OD value in the specified wavelength range is high, it indicates that the optical filter has high light cut characteristics in the wavelength region.

Average OD value in a certain wavelength region = −Log ₁₀ (Average transmittance in a certain wavelength region (%) / 100) Equation (4)
From the viewpoint of the in-plane distribution of color in the image obtained by the imaging device or camera module, RGB balance of visible light when incident from the vertical direction of the optical filter, incident from a direction of 30 ° with respect to the vertical direction of the optical filter In this case, it is desirable that the change in the RGB balance of visible light and the change in the RGB balance of visible light when incident from a direction of 60 ° with respect to the vertical direction of the optical filter are small. That is, the rate of change of the R (red) transmittance ratio derived from the following equation (1), the rate of change of the G (green) transmittance ratio derived from the following equation (2), and the following equation (3): It is preferable that the rate of change in the ratio of B (blue) transmittance 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 RGB balance.

(R transmittance ratio) = (R transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (1)
(G transmittance ratio) = (G transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (2)
(B transmittance ratio) = (B transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (3)
In the formulas (1) to (3), the R transmittance is an average transmittance at a wavelength of 580 to 650 nm, the G transmittance is an average transmittance at a wavelength of 500 to 580 nm, and the B transmittance is an average transmittance at a wavelength of 420 to 500 nm. .

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

(Change rate of R transmittance ratio when 0 ° → 30 °) = (R transmittance ratio when incident at an angle of 30 ° with respect to the vertical direction of the optical filter) / (Vertical direction of the optical filter) Ratio of R transmittance when incident from the light source) (5)
Further, a value (0 ° → 30) obtained by dividing the ratio of G transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter by the ratio of G transmittance when measured from the vertical direction of the optical filter. The rate of change of the ratio of G transmittance in the case of ° can be derived from the following formula (6).

(Change rate of G transmittance ratio when 0 ° → 30 °) = (G transmittance ratio when incident from an angle of 30 ° with respect to the vertical direction of the optical filter) / (Vertical direction of the optical filter) Ratio of the G transmittance when the light is incident from the light source) (6)
Further, the ratio of the B transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter is divided by the ratio of the B transmittance when measured from the vertical direction of the optical filter (0 ° → 30). The change rate of the ratio of the B transmittance in the case of ° can be derived from the following formula (7).

(Change rate of ratio of B transmittance when 0 ° → 30 °) = (B transmittance ratio when incident at an angle of 30 ° with respect to the vertical direction of the optical filter) / (Vertical direction of the optical filter) Ratio of B transmittance when incident from the light source) (7)
Similarly, the ratio of the R transmittance when measured from an angle of 60 ° with respect to the vertical direction of the optical filter is divided by the ratio of the R transmittance when measured from the vertical direction of the optical filter (0 ° → The rate of change in the ratio of R transmittance at 60 ° can be derived from the following equation (8).

(Change rate of R transmittance ratio when 0 ° → 60 °) = (R transmittance ratio when incident at an angle of 60 ° with respect to the vertical direction of the optical filter) / (Vertical direction of the optical filter) Ratio of R transmittance when incident from the light source) (8)
Also, a value (0 ° → 60) obtained by dividing the ratio of G transmittance when measured from an angle of 60 ° with respect to the vertical direction of the optical filter by the ratio of G transmittance when measured from the vertical direction of the optical filter. The rate of change in the ratio of G transmittance in the case of ° can be derived from the following equation (9).

(Change rate of G transmittance ratio in the case of 0 ° → 60 °) = (G transmittance ratio when incident at an angle of 60 ° with respect to the vertical direction of the optical filter) / (Vertical direction of the optical filter) Ratio of the G transmittance when the light is incident from the light source) (9)
The rate of change in the ratio of G transmittance in the case of 0 ° to 60 ° is preferably 0.4 or more and 2.0 or less, more preferably 0.5 or more and 1.8 or less, and further preferably 0.6 or more and 1. It is 6 or less, and the closer the change rate is to 1.0, the smaller the incident angle dependent change of RGB balance.

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

(Change rate of ratio of B transmittance when 0 ° → 60 °) = (B transmittance ratio when incident at an angle of 60 ° with respect to the vertical direction of the optical filter) / (Vertical direction of the optical filter) Ratio of B transmittance when incident from the light source) (10)
When such an optical filter is used in an image pickup apparatus or a camera module, it becomes easy to correct the luminance and color of an image, so that it is easy to correct the visibility so that a natural color can be seen with human eyes.

  The optical filter of the present invention preferably has an antireflection layer on both sides of the substrate (i). By having an antireflection layer on both surfaces of the base material (i), stray light reflected by various components such as a cover glass, a lens, a microlens, a sensor, and a housing incorporated in an imaging device or a camera module, The phenomenon of reflecting the optical filter and entering the sensor can be reduced, and the occurrence of ghost can be reduced.

  The thickness of the optical filter of the present invention is not particularly limited, but is preferably 100 μm or less, more preferably 10 to 90 μm, still more preferably 10 to 80 μm, and particularly preferably 20 to 60 μm. When the thickness of the optical filter is within the above range, the optical filter can be reduced in thickness, size, and weight. A thickness of 20 μm or more is preferable because the warpage can be easily controlled.

<Base material (i)>
The substrate (i) may be a single layer or multiple layers as long as it has a layer containing the compound (A) having an absorption maximum in a region of a wavelength of 650 nm or more and less than 950 nm. Moreover, it is preferable that the said base material (i) contains the compound (B) which has an absorption maximum in the area | region of wavelength 950 nm or more and 1800 nm or less, and the compound (B) is contained in the same layer as the compound (A). May also be included in different layers. Hereinafter, a layer containing at least one compound (A) and a transparent resin is also referred to as “transparent resin layer”, and the other resin layers are also simply referred to as “resin layers”.

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

  When the layer containing the compound (A) is different from the layer containing the compound (B), for example, an overcoat layer made of a curable resin containing the compound (A) on a transparent resin substrate containing the compound (B), etc. Base material on which a resin layer is laminated, base material on which a resin layer such as an overcoat layer made of a curable resin containing compound (B) is laminated on a transparent resin substrate containing compound (A), glass support An overcoat layer made of a curable resin containing the compound (A) and an overcoat layer made of a curable resin containing the compound (B) are laminated on a support such as a resin support as a body or a base. And a base material in which a resin layer such as an overcoat layer made of a curable resin containing the compound (A) is laminated on a glass substrate containing the compound (B).

<Compound (A)>
The compound (A) is not particularly limited as long as it has an absorption maximum in a wavelength region of 650 nm or more and less than 950 nm, but is selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds. It is preferable that the compound is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. In addition, a compound (A) may be used individually by 1 type, and may be used in combination of 2 or more type. A compound having an absorption maximum at a wavelength of 649 nm or less tends to have a high weight extinction coefficient at 420 nm to 580 nm due to absorption caused by the peak of the maximum absorption wavelength.

  The absorption maximum wavelength of the compound (A) is preferably 670 nm or more and less than 950 nm, more preferably 690 nm or more and less than 950 nm, still more preferably 700 nm or more and less than 950 nm.

  The base material (i) preferably contains, as the compound (A), at least one compound having an absorption maximum in a wavelength region of 650 nm or more and less than 800 nm, more preferably 700 nm or more and less than 800 nm. When the optical filter thus obtained is used in an imaging apparatus or a camera module, red visibility correction is good.

  Moreover, it is preferable that the said base material (i) contains 1 or more types of compounds which have an absorption maximum in the area | region of wavelength 800nm or more and less than 950nm as a compound (A). When the optical filter obtained by this is used for an imaging device or a camera module, the sensitivity of the silicon photodiode is high, and the light in the region of 800 nm or more and less than 1000 nm where the sensitivity of the human eye is low can be efficiently shielded. Visibility correction of flames that emit near infrared rays strongly, halogen lamps, and black body radiation light sources is improved.

  Furthermore, the base material (i) includes, as the compound (A), a compound having an absorption maximum in a region having a wavelength of 650 nm or more and less than 800 nm and a compound having an absorption maximum in a region having a wavelength of 800 nm or more and less than 950 nm, respectively. It is preferable to contain above. When the optical filter thus obtained is used in an imaging apparatus or a camera module, red visibility correction and light shielding performance in a region of 800 nm or more and less than 1000 nm are both compatible, and the obtained image is good.

The weight extinction coefficient of the compound (A) at the absorption maximum wavelength is preferably 1.0 × 10 ² L · cm ⁻¹ · g ⁻¹ or more. If it is 1.0 × 10 ² L · cm ⁻¹ · g ⁻¹ or more, it is possible to efficiently shield near infrared rays even in a thin optical filter provided with an antireflection layer.

  Although the usage-amount of a compound (A) is suitably selected according to a desired characteristic, as the said base material, the base material which consists of a transparent resin board | substrate containing a compound (A), a compound ( When using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing A), it is preferably 0.01 with respect to 100 parts by weight of the transparent resin. -2.0 parts by weight, more preferably 0.03-1.5 parts by weight, and still more preferably 0.05-1.0 parts by weight. As the substrate, a glass support or a resin support serving as a base When using a base material in which a transparent resin layer containing the compound (A) is laminated on a support such as a body, it is preferably 0.4 to 20 with respect to 100 parts by weight of the resin forming the transparent resin layer. 0.0 part by weight, more preferably 0.6-15.0 parts by weight , More preferably from 0.8 to 12.5 parts by weight.

≪Squaryllium compound≫
Although it does not specifically limit as said squarylium type compound, It represents with the squarylium type compound (henceforth "compound (I)") represented by the following formula (I), and the following formula (II). A squarylium compound (hereinafter also referred to as “compound (II)”), and a squarylium compound represented by the following formulas (III-J), (III-K) and (III-L) (hereinafter referred to as “compounds”). III-J) ”,“ compound (III-K) ”and (compound (III-L)), which are also collectively referred to as“ compound (III) ”). Are preferred.

  ・ Formula (I)

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

Condition (α):
A plurality of R ^a each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L ¹ or —NR ^e R ^f group;
A plurality of R ^{b s} 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 Yas 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 represents 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 -C (O) R ⁱ group (R ⁱ is -L ^a , . which -L ^b, -L ^c, represents a -L ^d or -L ^e) represents;
R ^j and R ^k each independently represents a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d, or -L ^e ;
L ^a represents an aliphatic hydrocarbon group of good 1 to 12 carbon atoms have a substituent L;
L ^b represents a C1-C12 halogen-substituted alkyl group 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 carbon atoms of 3 to 14 which may have a substituent group L;
L ^f represents a C 1-9 alkoxy group 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, and an aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents at least one substituent selected from the group consisting of a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group and an amino group.

Condition (β):
At least one of two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a heterocycle having 5 or 6 member atoms containing at least one nitrogen atom;
The heterocyclic ring may have a substituent, and R ^b and R ^{a that} is not involved in the formation of the heterocyclic ring are independently synonymous with R ^b and R ^{a in} the condition (α).

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

The aliphatic hydrocarbon group having 1 to 12 carbon atoms in the L ^a and L, for example, a methyl group (Me), ethyl (Et), n-propyl group (n-Pr), isopropyl (i-Pr ), 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, dodecyl group, etc. Alkyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group and octenyl group 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 in L ^b and L include, for example, trichloromethyl group, trifluoromethyl group, 1,1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group, heptachloro Mention may be made of propyl and heptafluoropropyl groups.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in 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; a norbornane group and an adamantane group And polycyclic alicyclic groups such as

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L ^d and L include, for example, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, Mention may be made of phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl and biphenylyl groups.

Wherein L Examples of the heterocyclic group having 3 to 14 carbon atoms in the ^e and L, for example, 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 phenazine.

Examples of the alkoxy group having 1 to 12 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. it 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 in L ^h include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, and an octyl group. An oxycarbonyl group can be mentioned.

As the L ^a, preferably a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- butyl group, a pentyl group, a hexyl group, an octyl group, 4-phenylbutyl Group, 2-cyclohexylethyl, more preferably 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.

L ^b is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, or a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, and more preferably a trichloromethyl group. A methyl group, a pentachloroethyl group, a trifluoromethyl group, and a pentafluoroethyl group;

L ^c is preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group, or a 4-phenylcycloheptyl group, and more preferably a cyclopentyl group, a cyclohexyl group, or a 4-ethylcyclohexyl group. It is.

The L ^d is 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, 2,3,4,5,6-pentaphenylphenyl group, more preferably phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,3 , 4,5,6-pentaphenylphenyl group.

As the L ^e, preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, consisting morpholine group, more preferably furan, thiophene, pyrrole, consisting morpholine group.

The L ^f is preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, methoxymethyl group, methoxyethyl group, 2-phenylethoxy group, 3-cyclohexylpropoxy group, pentyloxy group, hexyloxy Group, octyloxy group, more preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group.

L ^g is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, or a trifluoromethylcarbonyl group, and more preferably an acetyl group, a propionyl group, or a benzoyl group. .

The L ^h is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group, more preferably A methoxycarbonyl group and an ethoxycarbonyl group;

The L ^{a to} L ^h further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, and an amino group. May be. Examples include 4-sulfobutyl, 4-cyanobutyl, 5-carboxypentyl, 5-aminopentyl, 3-hydroxypropyl, 2-phosphorylethyl, 6-amino-2,2-dichloro. Hexyl 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, group consisting of 3-methylpyrrole, 2-hydroxyethoxy group, 3-cyanopropoxy group, 4-fluorobenzoyl group, 2 -Hydroxyethoxycarbonyl group, 4-cyanobutoxy It can be mentioned carbonyl group.

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

R ^b in the condition (α) is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group. Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group , T-butanoylamino group, cyclohexinoylamino 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, propionylamino group, trifluoromethanoylamino group, These are an ntafluoroethanoylamino group, a t-butanoylamino group, and a cyclohexinoylamino group.

  The Ya is preferably an amino group, methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, 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 , A di-t-butylamino group.

In the condition (β) of the formula (I), at least one of two R ^a on one benzene ring is bonded to Y on the same benzene ring, and at least 1 nitrogen atom is formed. Examples of the heterocyclic ring containing 5 or 6 atoms include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine. Among these heterocyclic rings, a heterocyclic ring that constitutes the heterocyclic ring and in which one atom adjacent to the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

  Formula (II)

Wherein (II), X is independently, O, S, Se, represents N-R ^c or C (R ^d R ^d); in each plurality of R ^c independently represents a hydrogen atom, L ^a, L ^b, L ^c, represents L ^d or L ^e; each independently plurality of R ^d, 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 may be linked to form an optionally substituted ring; L ^{a to} L ^e , L ¹ , R ^e and R ^f are the same meanings as defined ^{L a ~L e, L 1,} R e and R ^f in formula (I).

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

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

X is preferably O, S, Se, N-Me, N-Et, CH ₂ , C-Me ₂ , C-Et ₂ , and more preferably S, C-Me ₂ , C-Et _2. It is.
In the formula (II), adjacent R ^ds may be linked to form a ring. Examples of such rings include benzoindolenin ring, α-naphthimidazole ring, β-naphthimidazole ring, α-naphthoxazole ring, β-naphthoxazole ring, α-naphthothiazole ring, β-naphthothiazole ring. , Α-naphthoselenazole ring and β-naphthoselenazole ring.

  Formulas (III-J) to (III-L)

Wherein (III-J) ~ (III -L), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ - represents,
R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a —NR ^g R ^h group, a —SO ₂ R ⁱ group, or —OSO. It represents either ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h each independently represents a hydrogen atom, one of the -C (O) R ⁱ groups or the following L ^a ~L ^e , R ⁱ represents any of the following L ^a ~L ^e.
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon the number 6 to 14 aromatic hydrocarbon group (L ^e) carbon atoms, which may have a number Hajime Tamaki 3 to 14 (L ^f) an alkoxy group having 1 to 12 carbon atoms (L ^g) substituents L carbon 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L

  The substituent L includes 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, and an aromatic carbon group having 6 to 14 carbon atoms. It is at least one selected from the group consisting of a hydrogen group and a heterocyclic group having 3 to 14 carbon atoms.

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

R ^{2 to} R ⁷ are preferably each independently a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl. Group, cyclohexyl group phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group , T-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert- Butyl group, hydroxyl group, dimethylamino group, nitro group, acetylamino group, propioni Amino group, trifluoromethyl meth alkanoylamino group, pentafluoro ethanoyl group, t-butanoyl group, a cyclohexylene Sino-yl-amino group.

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

X is preferably an oxygen atom, a sulfur atom and —NR ⁸ —, particularly preferably an oxygen atom and a sulfur atom in compound (III-J), and —NR in compound (III-K). ⁸ - and a sulfur atom in a compound (III-L). When X has —NR ⁸ —, it may form a salt with a counter anion.

  Compound (I), Compound (II) and Compound (III-J) are added to the description methods such as Formula (I-1), Formula (II-1) and Formula (III-J-1) below. The structure can also be represented by a description method that takes a resonance structure such as the following formula (I-2), the following formula (II-2), and the following formula (III-2) (compound (III-K) and The same applies to (III-L)). That is, the difference between the following formula (I-1) and the following formula (I-2), the difference between the following formula (II-1) and the following formula (II-2), and the following formula (III-J-1 ) And (III-J-2) differ only in the structure description method, and both represent the same compound. Unless otherwise specified, in the present invention, the structure of the squarylium compound is represented by a description method such as the following formula (I-1), the following formula (II-1) and the following formula (III-J-1). And

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

The structures of the compounds (I), (II) and (III) are not particularly limited as long as they satisfy the requirements of the respective formulas. For example, when the structures are represented as in the formulas (I-1), (II-1) and (III-J-1), the left and right substituents bonded to the central four-membered ring are the same. May be different, but it is preferable that they are the same because synthesis is easy.

  Specific examples of the compounds (I), (II) and (III) include the following formulas (IA) to (IF), the following formulas (II-G) to (II to H), and the following formulas: The compounds (a-1) to (a-94) shown in the following Tables 1 to 7 having basic skeletons represented by (III to J) to (III-L) can be mentioned.

  The compounds (I), (II), and (III) may be synthesized by a generally known method. For example, JP-A-1-228960, JP-A-2001-40234, and JP-A-3196383. It can be synthesized with reference to the method described in the publication.

≪Phthalocyanine compounds≫
The phthalocyanine compound is not particularly limited, but is preferably a compound represented by the following formula (IV) (hereinafter also referred to as “compound (IV)”).

In the formula (IV), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing 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, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -S ^{-L 2, -SS-L 2,} -SO 2 -L 3, -N = N-L 4 , or at least one combination of R _a and R _b, R _b and R _c and R _c and R _d Represents at least one group selected from the group consisting of groups represented by the following formulas (A) to (H). 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 Formula (I),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydroxyl group or the L ^a ~L ^e,
L ⁴ represents represents any of the L ^a ~L ^e.

In formulas (A) to (H), R _x and R _y each 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, Represents an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , and the amino group, amide group, imide groups and silyl groups may have a substituent group L as defined in formula (I), L ¹ ~L ⁴ has the same meaning as L ¹ ~L ⁴ as defined in formula (IV).

In R _{a to} R _d and R _{A to} R _L , the amino group which may have a substituent L is an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group, diisopropylamino. Group and the like.

In R _{a to} R _d and R _{A to} R _L , as an amide group which may have a substituent L, an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, a diisopropylamide group, Examples thereof include a dibutylamide group, an α-lactam group, a β-lactam group, a γ-lactam group, and a δ-lactam group.

In R _{a to} R _d and R _{A to} R _L , the imide group that may have a substituent L is an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, a diisopropylimide group, A dibutylimide group etc. are mentioned.

In R _{a to} R _d and R _{A to} R _L , examples of the silyl group which may have a substituent 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 , -SL ² includes thiol group, methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, 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, and the like.

In the above R _{a to} R _d and R _{A to} R _L , -SS-L ² includes disulfide group, methyl disulfide group, ethyl disulfide group, propyl disulfide group, 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 disulfide group and the like.

In R _{a to} R _d and R _{A to} R _L , examples of —SO ₂ —L ³ include a sulfo group, a mesyl group, an ethylsulfonyl group, an n-butylsulfonyl group, and a p-toluenesulfonyl group.

In the above R _{a to} R _d and R _{A to} R _L , examples of —N═N—L ⁴ include a methylazo group, a phenylazo group, a p-methylphenylazo group, and a p-dimethylaminophenylazo group.

In M, examples of the monovalent metal atom include Li, Na, K, Rb, and Cs.
In M, the divalent metal atoms include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, Hg, Sn, Pb etc. are mentioned.

  In M, the substituted metal atom containing a trivalent metal atom includes 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 can be mentioned.

In M, the substituted metal atom containing a tetravalent metal atom includes 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.

  The M is a divalent transition metal, trivalent or tetravalent metal halide or tetravalent metal oxide belonging to Groups 5 to 11 of the periodic table and belonging to the 4th to 5th periods. Among them, Cu, Ni, Co, and VO are particularly preferable because high visible light transmittance and stability can be achieved.

  A method of synthesizing the phthalocyanine compound by a cyclization reaction of a phthalonitrile derivative such as the following formula (V) is generally known, but the obtained phthalocyanine compounds are represented by the following formulas (VI-1) to ( It is a mixture of four isomers such as VI-4). In the present invention, unless otherwise specified, only one isomer is illustrated for one phthalocyanine compound, but the other three isomers can be used similarly. These isomers can be separated and used as necessary, but in the present invention, the isomer mixture is collectively handled.

Specific examples of the compound (IV) include (b-1) to (b-61) shown in the following Tables 8 to 11 having basic skeletons represented by the following formulas (IV-A) to (IV-J). ) And the like.

Compound (IV) may be synthesized by a generally known method. For example, a method described in Japanese Patent No. 4081149 or “phthalocyanine-chemistry and function” (IPC, 1997) is used. It can be synthesized by reference.

≪Cyanine compounds≫
The cyanine compound is not particularly limited, but is a compound represented by any one of the following formulas (VII-1) to (VII-3) (hereinafter referred to as “compounds (VII-1) to (VII-3). ) ").) Is preferred.

Wherein (VII-1) ~ (VII -3), X a - represents a monovalent anion, a plurality of D are independently represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, are 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, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, Imido group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ³ , -SO ₂ -L ³ , -N = N-L ⁴ , or R _b and R _c , R _d And R _e , R _e and R _f , R _f and R _g , R _g and R _h, and R _h and R _i are represented by the above formulas (A) to (H). Represents at least one group selected from the group consisting of groups, and the amino group, amide group, imide group and silyl group are defined in the formula (I). It may have a substituent L,
L ¹ has the same meaning as L ¹ defined in Formula (I),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydrogen atom or the L ^a ~L ^e,
L ⁴ are, represents any of the L ^a ~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 ,- ^{S-L 2, -SS-L} 2, -SO 2 -L 3, -N = N-L 4 (L 1 ~L 4 has the same meaning as L ¹ ~L ⁴ in the R _a to R _i. ), Or an aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z or Y selected from adjacent two of these; a nitrogen atom, an oxygen atom or a sulfur atom. A 5- to 6-membered alicyclic hydrocarbon group which may contain at least one; or a C3-C14 heteroaromatic hydrocarbon group containing at least one nitrogen atom, oxygen atom or sulfur atom, These aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic carbons The hydrogenation group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z or Y in Z _{a to} Z _c and Y _{a to} Y _d include, for example, the substituent L The compound illustrated by the aromatic hydrocarbon group is mentioned.

A 5- to 6-membered ring which may contain at least one nitrogen atom, oxygen atom or sulfur atom, formed by bonding Z or Y to each other in Z _{a to} Z _c and Y _{a to} Y _d Examples of the alicyclic hydrocarbon group include compounds exemplified by the alicyclic hydrocarbon group and the heterocyclic ring in the substituent L (excluding the heteroaromatic hydrocarbon group).

Examples of the heteroaromatic 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 include, for example, the substituent L And the compounds exemplified as the heterocyclic group (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom or sulfur atom).

In the formula (VII-1) ~ (VII -3), -S-L 2, -SS-L 2, -SO 2 -L 3, -N = N-L 4, which may have a substituent L Examples of the good amino group, amide group, imide group and silyl group include the same groups as those exemplified in the formula (IV).

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 ⁻ , nickel dithiolate. And the like, and copper dithiolate complex.

  Specific examples of the compounds (VII-1) to (VII-3) include (c-1) to (c-24) described in Table 12 below.

The compounds (VII-1) to (VII-3) may be synthesized by a generally known method, for example, by the method described in JP-A-2009-108267.

<Compound (B)>
The compound (B) is not particularly limited as long as it has an absorption maximum in a wavelength range of 950 nm to 1800 nm. It is preferable that the compound is at least one compound selected from the group consisting of a compound based on a compound, a diimonium compound, a metal dithiolate compound and a pyrrolopyrrole compound. 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 preferably from 1020 nm to 1750 nm, more preferably from 1020 nm to 1720 nm. When the absorption maximum wavelength of the compound (B) is in such a range, unnecessary near-infrared rays can be efficiently cut and the incident angle dependency of incident light can be reduced.

The weight extinction coefficient at the absorption maximum wavelength of the compound (B) is preferably 8 × 10 L · cm ⁻¹ · g ⁻¹ or more, more preferably 9.5 × 10 L · cm ⁻¹ · g ⁻¹ or more. If it is 8 × 10 L · cm ⁻¹ · g ⁻¹ or more, it is possible to efficiently shield near infrared rays even in a thin optical filter provided with an antireflection layer, and it is possible to reduce the thickness and provide high near infrared shielding properties. It is possible to achieve both low reflection characteristics.

  The amount of the compound (B) (excluding near-infrared-absorbing fine particles) is appropriately selected according to the desired properties. Examples of the substrate include the compound (A) and the compound (B). When using the base material which consists of a transparent resin board | substrate to contain, Preferably it is 0.01-5.0 weight part with respect to 100 weight part of transparent resin, More preferably, 0.02-3.0 weight part, Particularly preferably, it is 0.03 to 2.0 parts by weight, and as the substrate, a transparent material containing the compound (A) and the compound (B) on a support such as a glass support or a resin support as a base. When using the base material on which the resin layer is laminated or the base material on which the resin layer containing the compound (B) is laminated on the transparent resin substrate containing the compound (A), the compound (A) is included. Preferred for 100 parts by weight of resin forming the transparent resin layer Ku is 0.1 to 40.0 parts by weight, more preferably 0.2 to 30.0 parts by weight, particularly preferably 0.3 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 addition, the usage-amount of this microparticles | fine-particles at the time of using near-infrared absorptive microparticles | fine-particles as said compound (B) is mentioned later.

  The compound (B) may be synthesized by a generally known method. For example, Japanese Patent No. 4168031, Japanese Patent No. 4225296, Japanese Translation of PCT International Publication No. 2010-516823, Japanese Patent Laid-Open No. 63-165392. It can be synthesized with reference to the method described in the publication.

≪Diimonium compounds≫
Although the said diimonium type compound is not specifically limited, For example, the compound represented by a following formula (s1) is preferable.

In the 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 phosphate group, a —NR ^g R ^h group, —SR ^i. group, -SO ₂ R ⁱ group, or an -OSO ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or represents one of the following L ^a ~L ^e, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon the number 6 to 14 aromatic hydrocarbon group (L ^e) carbon atoms, which may have a number Hajime Tamaki 3 to 14 (L ^f) an alkoxy group having 1 to 12 carbon atoms (L ^g) substituents L carbon 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms that may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms, and n is 0 to 0. An integer of 4, X represents an anion necessary for neutralizing the charge.

R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, or a benzyl group. And more preferably an isopropyl group, a sec-butyl group, a tert-butyl group, or a benzyl group.

R ² is preferably a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, 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 , Pentafluoroethanoylamino group, t-butanoylamino group, cyclohexylinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, more preferably a chlorine atom , Fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, ert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexinoylamino And particularly preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group. The number of R ² (value of n) bonded to the same aromatic ring is not particularly limited as long as it is 0 to 4, but is preferably 0 or 1.

  X is an anion necessary for neutralizing the electric charge, and one molecule is required when the anion is divalent, and two molecules are required when the anion is monovalent. In the latter case, the two anions may be the same or different, but are preferably the same from the viewpoint of synthesis. Although X will not be restrict | limited especially if it is such an anion, As an example, the thing of following Table 13 can be mentioned.

X has a tendency to improve the heat resistance of the diimonium compound when it is used as an anion of the diimonium compound as long as it has high acidity when converted to an acid. (X-10) and (X) in Table 13 above X-16), (X-17), (X-21), (X-22), (X-24), and (X-28) are particularly preferable.

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

In the formula (s2), R ³ has the same meaning as R ¹ and R ² in the 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.

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

The M is preferably a transition metal, more preferably Ni, Pd, or Pt.
The D is preferably a nitrogen atom or a phosphorus atom, and the ^Ri is preferably an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl. Group, n-hexyl group, n-heptyl group and phenyl group.

≪Near-infrared absorbing fine particles≫
The near-infrared absorbing fine particles are not particularly limited as long as they have absorption in a wavelength region of 950 nm to 1800 nm. 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 the following formula (P-1) And the second fine particles composed of the compound represented by the following formula (P-2). From the viewpoint of absorption-transmission characteristics, the first fine particles and the second fine particles are particularly preferable. Fine particles are preferred.

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 , and n is 1 when A is an alkali metal or NH ₄ , 2 when A is an alkaline earth metal.

MxWyOz (P-2)
In the formula (P-2), M is H, alkali metal, alkaline earth metal, 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 there are a plurality of M, they may be separate atoms, and x, y, and z are 0.001 ≦ x / y ≦ 1 and 2.2 ≦ z / y The condition of ≦ 3.0 is satisfied.

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

  The average value of the particle diameter of the near-infrared absorbing fine particles is preferably 1 to 200 nm, that is, 200 nm or less, more preferably 150 nm or less, particularly preferably 100 nm or less, and most preferably 20 nm or less. The diameter of the near-infrared absorbing fine particles is a dynamic light scattering photometer (model number DLS-8000HL / HH, manufactured by Otsuka Electronics Co., Ltd.), which is a suspension in which the near-infrared absorbing fine particles are dispersed (hereinafter simply referred to as “dispersion liquid”). ) Using a dynamic light scattering method (using a He—Ne laser, a cell chamber temperature of 25 ° C.). If the average value of the particle diameter of the near-infrared absorbing fine particles is within this range, geometric scattering and Mie scattering that cause a decrease in visible light transmittance can be reduced, and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, the scattered light decreases in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the visible light transmittance is improved as the particle diameter decreases. For this reason, it is preferable if the particle diameter is in the above-mentioned range since the scattered light is extremely reduced and a good visible light transmittance can be achieved. From the viewpoint of scattered light, it is preferable that the particle diameter is small, but considering the ease of industrial production, production cost, etc., the lower limit of the average value of the 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 with respect to 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, and 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 absorption characteristics may not be obtained. If the content is more than 60 parts by weight, the visible transmittance decreases and the haze due to aggregation of the near-infrared absorbing fine particles The value tends to increase.

  Examples of the dispersion medium for the near-infrared absorbing fine particles include water, alcohol, ketone, ether, ester, aldehyde, amine, aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic hydrocarbon. A dispersion medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. 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, a dispersant can be blended as needed to improve the dispersion state of the near-infrared absorbing fine particles. Dispersing agents that have a modifying effect on the surface of near-infrared absorbing fine particles, such as surfactants, silane compounds, silicone resins, titanate coupling agents, aluminum coupling agents, zircoaluminate cups A ring agent or the like is used.

  Surfactants include anionic surfactants (special polycarboxylic acid type polymer surfactants, alkyl phosphate esters, etc.), nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxy Ethylene carboxylic acid esters, sorbitan higher carboxylic acid esters, etc.), cationic surfactants (polyoxyethylene alkylamine carboxylic acid esters, alkylamines, alkylammonium salts, etc.), and amphoteric surfactants (higher alkylbetaines, etc.). .

  Examples of the silane compound include a silane coupling agent, chlorosilane, alkoxysilane, and silazane. Examples of the silane coupling agent include alkoxysilanes having a functional group (glycidoxy group, vinyl group, amino group, alkenyl group, epoxy group, mercapto group, chloro group, ammonium group, acryloxy group, methacryloxy group, etc.).

Examples of the silicone resin include methyl silicone resin and methylphenyl silicone resin.
Examples of titanate coupling agents include those having an acyloxy group, phosphoxy group, pyrophosphoxy group, sulfoxy group, aryloxy group, and the like.

Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.
Examples of the zircoaluminate 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 is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the dispersion, although it depends on the type of the dispersant. If the amount of the dispersant is within the above range, the dispersibility of the near-infrared absorbing fine particles becomes good, the transparency is not impaired, and the sedimentation of the near-infrared absorbing fine particles over time can be suppressed.

  Commercially available products of near-infrared absorbing fine particles include P-2 (ITO) manufactured by Mitsubishi Materials Corporation, Pastoran (ITO) manufactured by Mitsui Metals Co., Ltd., T-1 (ATO) manufactured by Mitsubishi Materials Corporation, Ishihara Sangyo ( SN-100P (ATO) manufactured by Co., Ltd., Passet GK (GZO) manufactured by Hakusuitec Co., Ltd., YMF-02A (second fine particles) manufactured by Sumitomo Metal Mining Co., Ltd. and the like can be mentioned.

-1st microparticles | fine-particles 1st microparticles | fine-particles have the near-infrared absorption characteristic resulting from the crystal structure (crystallite) of the compound represented by the said Formula (P-1).

Here, “crystallite” means a unit crystal that can be regarded as a single crystal, and “particle” is composed of a plurality of crystallites. The "consisting crystallites of the compound represented by formula (1)", for example, can confirm the crystal structure of A _{1 / n} CuPO ₄ by X-ray diffraction, the crystallite substantially A _{1 / n} CuPO ₄ made it means that have been identified by X-ray diffraction, the term "consists crystallites substantially a _{1 / n} CuPO _4", crystallite sufficiently the crystal structure of a _{1 / n} CuPO ₄ It means that impurities may be contained within a range that can be maintained (the crystal structure of A _{1 / n} CuPO ₄ can be confirmed by X-ray diffraction). X-ray diffraction is measured using a X-ray diffractometer for near-infrared absorbing fine particles in a powder state.

The reason for employing alkali metal (Li, Na, K, Rb, Cs), alkaline earth metal (Ca, Sr, Ba), or NH ₄ as A in formula (1) is as follows. It is as (iii).

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

(Ii) Alkali metal ions, alkaline earth metal ions, and NH ₄ ⁺ can stably exist as monovalent or divalent cations in the solution, so that a precursor is generated in the process of producing near-infrared absorbing fine particles. At this time, cations are easily incorporated into the crystal structure.

(Iii) A cation having strong coordination bond with PO ₄ ^3- (for example, a transition metal ion or the like) may give a crystal structure different from the crystal structure in the present embodiment that exhibits sufficient near-infrared absorption characteristics. is there.

As A, K is particularly preferable because it has the most suitable cation size as an ion taken into the skeleton composed of PO ₄ ^3- and Cu ²⁺ and takes a thermodynamically stable structure.
The near-infrared absorbing fine particles can exhibit sufficient near-infrared absorption characteristics when the crystallites sufficiently maintain the crystal structure of A _{1 / n} CuPO ₄ . Therefore, when water or a hydroxyl group adheres to the surface of the crystallite, the crystal structure of A _{1 / n} CuPO ₄ cannot be maintained, so that the difference in light transmittance between the visible light region and the near infrared wavelength region is reduced. It cannot be suitably used as an optical filter.

Therefore, the near-infrared absorbing fine particles have a wavelength of around 1600 cm ⁻¹ attributed to water when the absorption intensity of the peak near 1000 cm ⁻¹ attributed to the phosphate group is used as a reference (100%) in the microscopic IR spectrum. The peak absorption intensity is preferably 8% or less, and the peak absorption intensity near 3750 cm ⁻¹ attributed to hydroxyl groups is preferably 26% or less. The peak absorption intensity near 1600 cm ⁻¹ attributed to water is preferred. Is 5% or less, and the absorption intensity of a peak near 3750 cm ⁻¹ attributed to a hydroxyl group is more preferably 15% or less. The microscopic IR spectrum is measured using a Fourier transform infrared spectrophotometer for powdered near-infrared absorbing fine particles. Specifically, for example, a Fourier transform infrared spectrophotometer Magna 760 manufactured by Thermo Fisher Scientific is used, and a piece of the first fine particles is placed on the diamond plate, flattened with a roller, and a microscopic FT-IR method. Measure with

・ The second fine particles Tungsten trioxide (WO ₃ ) has a ratio of oxygen to tungsten that is less than 3 and has a specific composition range, so free electrons are generated in the tungsten oxide, making it a good near-infrared absorbing material. It is known that a variety of properties can be achieved.

The composition range of the tungsten and oxygen is such that the composition ratio of oxygen to tungsten is 3 or less. Furthermore, when the tungsten oxide is described as W _y O _z , 2.2 ≦ z / y ≦ 2.999. It is preferable that If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a WO ₂ crystal phase other than the target in the tungsten oxide, and to improve the chemical stability as a material. Therefore, it can be applied as an effective near-infrared absorbing material. On the other hand, if the value of z / y is 2.999 or less, the required amount of free electrons is generated in the tungsten oxide, and an efficient near-infrared absorbing material is obtained.

Further, in the tungsten oxide fine particles obtained by making the tungsten oxide into fine particles, a so-called “Magneli phase” having a composition ratio represented by 2.45 ≦ z / y ≦ 2.999 when the general formula is W _y O _z. Is chemically stable and has good absorption characteristics in the near-infrared region, and is therefore preferable as a near-infrared absorbing material.

  Furthermore, by adding the element M to the tungsten oxide to form a composite tungsten oxide, free electrons are generated in the composite tungsten oxide, and free electron-derived absorption characteristics are expressed in the near infrared region, This is preferable because it is effective as a near-infrared absorbing material having a wavelength of around 1000 nm.

  Here, the value of x / y indicating the addition amount of the element M will be described. If the value of x / y is larger than 0.001, a sufficient amount of free electrons is generated and the intended infrared shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the infrared shielding efficiency also increases. However, when the value of x / y is about 1, the effect is saturated. Moreover, if the value of x / y is smaller than 1, it is preferable since an impurity phase can be prevented from being generated in the infrared shielding material, and more preferably 0.2 or more and 0.5 or less. The element M is H, alkali metal, alkaline earth metal, 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 are preferably at least one selected from the group. Here, from the viewpoint of stability in the MxWyOz 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, More preferably, the element is one or more elements selected from Ti, Nb, V, Mo, Ta, and Re. From the viewpoint of improving optical properties and weather resistance as a near-infrared absorbing material, More preferably, the element M belongs to an alkali metal, alkaline earth metal element, transition metal element, group 4 element, or group 5 element.

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

≪Commercially available compounds (A) and (B) ≫
Examples of commercially available compounds (A) include T090821, T091021, T089021, T090721, T090122 (manufactured by Tosco), B4360, D4773, D5013 (manufactured by Tokyo Chemical Industry), S4253, S1426 (manufactured by Spectrum Info), Excolor IR12, ExcolorIR14. ExcolorIR10A, ExcolorIR28, ExcolorTX-EX720, ExcolorTX-EX820, ExcolorTX-EX906 (manufactured by Nippon Shokubai Co., Ltd.) and the like.

  Commercially available products of the compound (B) (excluding near-infrared absorbing fine particles) include CIR-108x, CIR-96x, CIR-RL, CIR-1080 (manufactured by Nippon Carlit), S1445 (manufactured by Spectrum Info), Excolor IR915, ExcolorIR906 (made by Nippon Shokubai), S2058, S2007 (made by FEW Chemicals), etc. can be mentioned.

<Transparent resin>
The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, the transparent resin ensures thermal stability and moldability to a film, and is performed by high-temperature deposition performed at a deposition temperature of 100 ° C. or higher. In order to obtain a film capable of forming a dielectric multilayer film, a resin having a glass transition temperature (Tg) of preferably 110 to 380 ° C, more preferably 110 to 370 ° C, and still more preferably 120 to 360 ° C. Further, when the glass transition temperature of the resin is 150 ° C. or higher, even when a compound is added to the resin at a high concentration and the glass transition temperature is lowered, the glass transition temperature at which the dielectric multilayer film can be deposited at a high temperature is reduced. It is particularly preferable because a film having the same can be obtained.

  As a transparent resin, when a 0.05 mm thick resin plate made of the resin is formed, the total light transmittance (JIS K7105) of this resin plate is preferably 75 to 95%, more preferably 78 to 95. %, Particularly preferably 80 to 95% of the resin can be used. If a resin having a total light transmittance in such a range is used, the resulting substrate exhibits good transparency as an optical film.

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

  Transparent resins include, for example, cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, poly Ether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane UV curable Resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin and sol-gel method Formed Silica may be mentioned a resin as a main component. Of these, cyclic polyolefin resins, aromatic polyether resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polyarylate resins can be used for transparency (optical properties), heat resistance, and reflow resistance. It is preferable at the point from which the optical filter excellent in the balance of these etc. can be obtained.

≪Cyclic polyolefin resin≫
The cyclic polyolefin-based resin is obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ). A resin and a resin obtained by hydrogenating the resin are preferable.

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

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

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

In formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.

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

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

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

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

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

≪Fluorene polycarbonate resin≫
The fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety. For example, the fluorene polycarbonate resin can be synthesized by a method described in JP-A-2008-163194.

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

≪Fluorinated aromatic polymer resin≫
The fluorinated aromatic polymer resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. The polymer preferably contains a repeating unit containing at least one bond, and can be synthesized, for example, by the method described in JP-A-2008-181121.

≪Acrylic UV curable resin≫
The acrylic ultraviolet curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic or methacrylic groups in the molecule and a compound that decomposes by ultraviolet rays to generate active radicals. Can be mentioned. In the acrylic ultraviolet curable resin, a transparent resin layer (light absorption layer) containing a compound (A) and a curable resin is laminated on a glass support or a resin support as a base as the base (i). When using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing the prepared base material or compound (A), it is particularly suitable as the curable resin. Can be used.

≪Resin mainly composed of silica formed by sol-gel process≫
Examples of resins based on silica by the sol-gel method include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxylane, and methoxytriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, A compound obtained by a sol-gel reaction by hydrolysis of one or more silanes selected from phenylalkoxysilanes such as diphenyldiethoxysilane can be used as the resin.

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

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

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

  These additives may be mixed with the resin or the like when the transparent resin is produced, or may be added when the resin is synthesized. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2. parts by weight with respect to 100 parts by weight of the transparent resin. 0 parts by weight.

<Support>
≪Resin support≫
As the resin used for the transparent resin substrate or resin support, the same resin as the transparent resin layer can be used.

≪Glass support≫
The glass support is not particularly limited, and examples thereof include borosilicate glass, silicate glass, soda lime glass, and near infrared absorbing glass. The near-infrared absorbing glass is preferable in that the near-infrared cut characteristics can be improved and the incident angle dependency can be reduced. Specific examples thereof include a fluorophosphate glass and a phosphate system containing a copper component. Glass etc. are mentioned.

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

  The base material (i) is a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing the compound (A) is laminated on a glass support or a base resin support. In this case, for example, a resin solution containing the compound (A) is melt-molded or cast-molded on a glass support or a base resin support, and preferably applied by a method such as spin coating, slit coating, or inkjet. After that, the solvent is dried and removed, and if necessary, further irradiation with light or heating can be performed to produce a substrate on which a transparent resin layer is formed on a glass support or a resin support as a base. .

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

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

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

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

  Further, the optical component such as glass plate, quartz or transparent plastic is coated with the resin composition and the solvent is dried, or the curable composition is coated and cured and dried. A transparent resin layer can also be formed on the component.

  The amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the above method should be as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight with respect to the weight of the transparent resin layer (transparent resin substrate). It is as follows. When the amount of residual solvent is in the above range, a transparent resin layer (transparent resin substrate) that can easily exhibit a desired function, in which deformation and characteristics hardly change can be obtained.

<Antireflection layer>
The optical filter of the present invention has an antireflection layer on at least one surface of the substrate (i). The antireflection layer in the present invention means that the average reflectance after forming the antireflection layer on at least one surface of the base material (i) is only the base material (i) in the wavelength region of 420 nm to 1000 nm. It is a layer having an effect equivalent to or smaller than the average reflectance.

  The antireflection layer preferably has antireflection properties over the entire wavelength range of 420 to 1050 nm, more preferably 420 to 1100 nm, and even more preferably 420 to 1150 nm.

  As the antireflection layer, a large number of conical structures with a size smaller than the wavelength of light are provided, and a layer having a structure in which the refractive index is continuously changed from the incident medium to the substrate, a high refractive index material layer, and a low refractive index For example, a dielectric multilayer film in which an index material layer is alternately laminated. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of 1.8 to 3.6 is usually selected. Such materials include, for example, titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, barium titanate, silicon, etc. One containing a small amount of titanium, niobium oxide, tin oxide and / or cerium oxide (for example, 0 to 10% by weight based on the main component); cyclic polyolefin resin, aromatic polyether resin, polyimide resin, Fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, Fluorinated aromatic polymer Resin, (modified) acrylic resin, epoxy resin, silsesquioxane UV curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester resin Examples thereof include a curable resin, an acrylic ultraviolet curable resin, a vinyl ultraviolet curable resin, and a transparent resin such as a resin mainly composed of silica formed by a sol-gel method in which the main component is dispersed.

  As a material constituting the low refractive index material layer, a material having a refractive index of 1.7 or less can be used, and a material having a refractive index of 1.2 to 1.7 is usually selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride; cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, and fluorene polyester. Resin, polycarbonate resin, polyamide resin, aramid resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin , (Modified) acrylic resins, epoxy resins, silsesquioxane UV curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyether ether ketone resins, polyarylate resins, allyl esters Transparent resin such as curable resin, acrylic ultraviolet curable resin, vinyl ultraviolet curable resin and resin mainly composed of silica formed by sol-gel method; or silica, alumina, lanthanum fluoride, magnesium fluoride or six Examples include sodium aluminum fluoride dispersed in the transparent resin.

  The dielectric multilayer film may have a metal layer and / or a semiconductor layer of about 1 to 100 nm. As a material constituting the metal layer, a material having a refractive index of 0.1 to 5.0 can be used. Examples of such a material include gold, silver, copper, zinc, aluminum, tungsten, titanium, magnesium, nickel, silicon, and germanium. These metal layers and semiconductor layers tend to have high extinction coefficients of wavelengths in the visible light region, and are preferably thin layers of about 1 to 20 nm.

  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 high-refractive index material layer and a low-refractive index material layer are alternately laminated directly on the substrate (i) by CVD, sputtering, vacuum deposition, ion-assisted deposition, or ion plating. A dielectric multilayer film can be formed. When laminating a layer containing a transparent resin, it is preferably formed by melt molding or cast molding, coating and forming in the same manner as the base material (i), preferably by spin coating, dip coating, slit coating, gravure coating, etc. Can be formed.

  In the present invention, the material type constituting the high refractive index material layer and the low refractive index material layer, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, the order of lamination, and the number of laminations are appropriately selected. Thus, the reflectance of light having a wavelength of 420 nm or more and 1000 nm or less is suppressed.

In the present invention, in order to suppress the reflectance of light having a wavelength of 420 nm or more and 1000 nm or less, the material types constituting the high refractive index material layer and the low refractive index material layer, the high refractive index material layer, and the low refractive index material layer. The equivalent admittance Y _E of the antireflection layer including the substrate (i) is set to an air refractive index of 1.0 at a wavelength of 420 nm to 1000 nm. Appropriately selected to approach.

The equivalent admittance Y _E of the antireflection layer composed of the L layer provided on the side incident on the optical filter is expressed by the following equation.

In the above formula, M _j is the first film on which light is incident as the first, the characteristic matrix of the layer located j-th towards the substrate (i) side, n _m is the base material of (i) Refractive index. M _j is represented by the following equation.

In the above formula, n _j is the refractive index of the j-th layer, d _j is the physical film thickness of the j-th layer, λ is the wavelength of light, and i represents a complex number.

Similar to the equivalent admittance on the incident side, the equivalent admittance Y ′ _E of the antireflection layer composed of the q layer provided on the emission side from the optical filter is expressed by the following equation.

In the above formula, M _j ′ is a characteristic matrix of a layer located at the j-th layer toward the base material (i) side, with the last layer (outgoing side outermost layer) from which light is emitted first. n _m is the refractive index of the substrate (i). M _j ′ is represented by the following equation.

In the above formula, n _j is the refractive index of the j-th layer, d _j is the physical film thickness of the j-th layer, λ is the wavelength of light, and i represents a complex number.

  In order to optimize the conditions, for example, an optical thin film design software (for example, manufactured by Essential Macleod, Thin Film Center) is used, and the equivalent admittance in the visible light region to the near infrared region is set for the physical film thickness and the number of film layers. The parameters should be set so that they can be obtained low. Here, regarding the design of the dielectric multilayer film on the light incident surface side and the light exit surface side of the optical filter, the equivalent admittance and air of the dielectric multilayer film including the base material (i) represented by the following formula: The absolute value (Δn) of the difference from the refractive index is preferably 0.4 or less, more preferably 0.3 or less, and even more preferably 0.2 or less at the wavelength at which the antireflection function is desired.

Here, the dielectric multilayer film and the reflectance R have a relationship represented by the following formula.

In the above formula, n ₀ represents the refractive index of the incident medium, and () ^* represents the complex conjugate in ().

  From the above formula, the equivalent admittance of the dielectric multilayer film including the base material (i) of the optical filter can be obtained by measuring the reflectance R in the air of the optical filter. The obtained equivalent admittance is a conjugate solution, but in the case of a preferable dielectric multilayer film design, the smaller the absolute value (Δn) of the difference between the equivalent admittance and the refractive index of the air, the two conjugate solutions, Meets the preferred range.

  When the light emission side has a dielectric multilayer film and the equivalent admittance of the dielectric multilayer film including the base material (i) excluding the influence of the reflectance on the light emission side is obtained, You may measure using the sample except the dielectric multilayer film, or the sample which apply | coated the black material which has the characteristic to absorb from a visible light area to a near-infrared area | region to the light emission side.

The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 3 nm to 115 nm. In the case of designing a layer having a thickness of less than 3 nm, it is not preferable because a sufficient manufacturing margin cannot be ensured, for example, the difficulty of manufacturing is improved and a uniform film is difficult to obtain. The layer having a physical film thickness of 115 nm to 900 nm is 5 layers or less, more preferably 3 layers or less, and particularly preferably 1 layer or less for each surface of the substrate. As the number of layers having a physical thickness of 115 nm to 900 nm increases, the equivalent admittance Y _E or Y ′ _E in which the dielectric multilayer film and the substrate are combined tends to move away from 1.0 in any wavelength region of 420 nm to 1000 nm. And tends to form a reflective layer. When a layer exceeding 900 nm is provided, the optical interference action is weak, and the influence on the equivalent admittance is small.

  The total number of layers of the high refractive index material layer and the low refractive index material layer in the antireflection layer is preferably 8 to 30 layers, and more preferably 10 to 22 layers as a whole. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and the warpage of the optical filter and cracks in the dielectric multilayer film can be reduced. can do.

<Other functional membranes>
The optical filter of the present invention has a surface provided with the antireflection layer of the base material (i) between the base material (i) and the antireflection layer (dielectric multilayer film) within a range not impairing the effects of the present invention. On the surface opposite to the surface on which the substrate (i) of the antireflection layer is provided or on the surface opposite to the surface on which the substrate (i) is provided, the surface hardness of the substrate (i) or the antireflection layer is improved, the chemical resistance is improved, charging For the purpose of prevention and scratch removal, a functional film such as an antireflection layer hard coat film or an antistatic film can be appropriately provided.

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

  The method of laminating the functional film is not particularly limited, and a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded on the substrate (i) or the antireflection layer in the same manner as described above. Or the method of cast molding etc. can be mentioned.

  Moreover, after apply | coating the curable composition containing the said coating agent etc. on a base material (i) or an antireflection layer with a bar coater etc., it can manufacture also by hardening | curing by ultraviolet irradiation etc.

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

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

  In the curable composition, the blending ratio of the polymerization initiator is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, when the total amount of the curable composition is 100% by weight. More preferably, it is 1 to 5% by weight. When the blending ratio of the polymerization initiator is in the above range, the curing characteristics and handleability of the curable composition are excellent, and a functional film such as an antireflection layer hard coat film or an antistatic film having a desired hardness can be obtained. .

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

These solvents may be used alone or in combination of two or more.
The thickness of the functional film is preferably 0.9 to 30 μm, more preferably 0.9 to 20 μm, and particularly preferably 0.9 to 5 μm. In the case of 0.9 μm or less, as described above, the influence of optical interference becomes strong and tends to inhibit the effect of the antireflection layer.

  Further, for the purpose of improving the adhesion between the base material (i) and the functional film and / or the antireflection layer, and the adhesion between the functional film and the antireflection layer, the base material (i), the functional film or the antireflection layer Surface treatment such as corona treatment or plasma treatment may be applied to the surface.

[Use of optical filter]
The optical filter of the present invention has a wide viewing angle, high red sensitivity, and improved ghost characteristics. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS of a camera module. In particular, digital still cameras, mobile phone cameras, smartphone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, TVs, car navigation systems, personal digital assistants, personal computers, video games, portable game machines, fingerprint authentication systems, It is useful for ambient light sensors, distance measurement sensors, iris authentication systems, face authentication systems, distance measurement cameras, digital music players, and the like.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device is an image sensor including a solid-state imaging device such as a CCD or a CMOS. As a member constituting the solid-state imaging element, a photoelectric conversion element that converts light of a specific wavelength, such as a silicon photodiode or an organic semiconductor, into an electric charge is used.

<Camera module>
The camera module of the present invention includes the optical filter of the present invention. Here, the camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, and the like, and outputs images and distance information as electrical signals.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. “Parts” means “parts by weight” unless otherwise specified. Moreover, the measurement method of each physical property value and the evaluation method of the physical property are as follows.

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

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

  (B) Standard polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF) manufactured by Tosoh Corporation.

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

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

  Here, with respect to the transmittance when measured from the vertical direction of the optical filter, the light 1 transmitted perpendicularly to the optical filter 2 is measured by the spectrophotometer 3 as shown in FIG. With respect to the transmittance when measured from an angle of 30 degrees with respect to the direction, the spectrophotometer 3 transmits light 1 ′ transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. In the transmittance when measured and measured from an angle of 60 degrees with respect to the vertical direction of the optical filter, light 1 transmitted at an angle of 60 degrees with respect to the vertical direction of the optical filter 2 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 reflectance when measured from an angle of 5 degrees with respect to the vertical direction of the optical filter, the light 11 reflected at an angle of 5 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. A total of 3 measurements were taken.

  The near-infrared absorbing dye used in the following examples was synthesized by a generally known method. Examples of general synthesis methods include, for example, Japanese Patent No. 336697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open No. 1-146846, JP-A-1-228960, JP-A-4081149, JP-A-63-124054, “Phthalocyanine—Chemistry and Function” (IPC, 1997), JP-A-2007-169315, JP2009. -108267, Unexamined-Japanese-Patent No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, etc. can be mentioned.

  The near-infrared absorbing dye used in the following examples was synthesized by a generally known method. Examples of general synthesis methods include, for example, Japanese Patent No. 336697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open No. 1-146846, JP-A-1-228960, JP-A-4081149, JP-A-63-124054, “Phthalocyanine—Chemistry and Function” (IPC, 1997), JP-A-2007-169315, JP2009. -108267, Unexamined-Japanese-Patent No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, etc. can be mentioned.

<Resin synthesis example 1>
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask. Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried 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>
100 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] dodec-3-ene (hereinafter also referred to as “DNM”) represented by the following formula (8). , 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel, and this solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel. 9 parts was added and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of hydrogen gas pressure of 100 kg / cm ² and reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin 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 base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.

<Preparation of transparent resin substrate>
In a container, 100 parts by weight of the resin A obtained in Resin Synthesis Example 1, 0.08 part of the compound (a-17), 0.16 part of the compound (b-39) and the compound (A) as the compound (A) a-47) 0.20 part, 3.50 parts of a light absorber “CIR-RL” (hereinafter referred to as “compound (B-1)”) manufactured by Nippon Carlit as the compound (B), 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, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.050 mm, a length of 200 mm, and a width of 200 mm.

<Preparation of substrate and optical filter>
A resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .

Resin composition (1): 60 parts by weight of tricyclodecane dimethanol acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, near-infrared absorbing fine particle dispersion (manufactured by Sumitomo Metal Mining Co., Ltd.) YMF-02A, (absorption maximum 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%)
On both surfaces of the obtained base material, using an ion-assisted vacuum deposition apparatus, an antireflection layer [silica (SiO ₂ : refractive index 1.46 of 550 nm) layer and titania (TiO ₂ ) shown in Table 14 below. ₂ : Dielectric multilayer film formed by alternately laminating layers having a refractive index of 2.48) of 550 nm] was formed at a deposition temperature of 120 ° C. to obtain an optical filter having a thickness of 0.054 mm.

  Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. Also, the absolute value (Δn) of the difference between the equivalent admittance of the dielectric multilayer film (I) including the base material of the obtained optical filter and the refractive index of air is set at 10 nm intervals in the wavelength range of 420 to 1000 nm. As a result of calculation, the average value of the absolute values (Δn) was 0.31.

[Example 2]
In Example 2, an optical filter having a base material including a transparent glass substrate was produced according to the following procedure and conditions.

<Preparation of resin solution (D-1)>
In a container, 100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 2.00 parts of the compound (a-17), 4.00 parts of the compound (b-39) and the compound (A) as the compound (A) a-47) As a compound (B), 15.00 parts of the above compound (B-1) and dichloromethane were added to prepare a solution having a resin concentration of 10% by weight. Then, it filtered with the Millipore filter with a hole diameter of 5 micrometers, and obtained the resin solution (D-1).

<Preparation of substrate and optical filter>
The resin composition (1) was applied to one side of a near-infrared absorbing glass substrate “BS-11” (thickness: 80 μm) manufactured by Matsunami Glass Industry Co., Ltd., cut to a size of 200 mm in length and 200 mm in width with a bar coater. And heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 4 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the glass substrate.

  Next, the resin solution (D-1) is applied onto the resin layer under the condition that the thickness after drying is 2 μm using a spin coater, and heated on a hot plate at 80 ° C. for 5 minutes to remove the solvent. Volatile removal was performed to form a transparent resin layer, which was then baked in an oven at 230 ° C. for 20 minutes to obtain a base material having a length of 200 mm and a width of 200 mm.

An antireflection layer was provided on both surfaces of the obtained substrate in the same manner as in Example 1 to obtain an optical filter having a thickness of 0.086 mm.
Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

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

<Preparation of transparent resin substrate>
In a container, 100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 0.08 part of the compound (a-47) as the compound (A), and 0.08 part of the compound (B-1) as the compound (B). 30 parts 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, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.050 mm, a length of 200 mm, and a width of 200 mm.

<Preparation of substrate and optical filter>
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 volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 4 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
An optical filter having a thickness of 0.058 mm provided with antireflection layers on both sides of the obtained base material in the same manner as in Example 1 except that the design (I) was changed to the design (II) shown in Table 15 below. Got.

  Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. In addition, the absolute value (Δn) of the difference between the equivalent admittance of the dielectric multilayer film (II) including the substrate of the obtained optical filter and the refractive index of air is set at 10 nm intervals in the wavelength range of 420 to 1000 nm. As a result of calculation, the average value of the absolute values (Δn) was 0.22.

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

<Preparation of resin solution (D-2)>
In a container, 100 parts by weight of resin A obtained in Resin Synthesis Example 1, 10.00 parts of compound (a-47) as compound (A), and compound (B-1) 22. A solution having a resin concentration of 10% by weight was prepared by adding 50 parts and dichloromethane. Then, it filtered with the Millipore filter with the hole diameter of 5 micrometers, and obtained the resin solution (D-2).

<Preparation of resin composition (2)>
30 parts by weight of isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.), 20 parts by weight of 1,9-nonanediol diacrylate, 20 parts by weight of methacrylic acid, glycidyl methacrylate 30 Parts by weight, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals) and Sun-Aid SI-110 main agent (Sanshin Chemical) (Made by Kogyo Co., Ltd.) 1 part by weight was mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid concentration was 50 wt%, and then filtered through a Millipore filter having a pore size of 0.2 μm to obtain a resin composition (2) Was prepared.

<Preparation of substrate and optical filter>
After applying the resin composition (2) to one side of a near-infrared absorbing glass substrate “BS-11” (thickness: 80 μm) manufactured by Matsunami Glass Industry Co., Ltd., cut to a size of 200 mm length and 200 mm width, The solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes to form a resin layer functioning as an adhesive layer with the transparent resin layer described later. At this time, the spin coater coating conditions were adjusted so that the resin layer had a thickness of about 0.8 μm. Next, the resin solution (D-2) is applied on the resin layer under the condition that the film thickness after drying is 2 μm using a spin coater, and heated on a hot plate at 80 ° C. for 5 minutes to remove the solvent. Volatile removal was performed to form a transparent resin layer. Subsequently, it exposed using the conveyor type exposure machine from the glass surface side (exposure amount 1J / cm < ² >, illumination intensity 200mW), and it baked for 20 minutes at 230 degreeC after that in an oven, and obtained the base material of length 200mm and width 200mm.

An antireflection layer was provided on both surfaces of the obtained substrate in the same manner as in Example 3 to obtain an optical filter having a thickness of 0.086 mm.
Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

[Example 5]
In Example 5, an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.

<Preparation of transparent resin substrate>
In a container, 100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 0.142 parts of the compound (a-47) as the compound (A), and 2. 14 parts 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, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.070 mm, a length of 200 mm, and a width of 200 mm.

<Preparation of substrate and optical filter>
A resin composition (3) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .

Resin composition (3): 60 parts by weight of tricyclodecane dimethanol diacrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30% )
An antireflection layer was provided on both surfaces of the obtained substrate in the same manner as in Example 3 to obtain an optical filter having a thickness of 0.074 mm.

  Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

[Example 6]
In Example 6, an optical filter having a base material composed of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.

<Preparation of transparent resin substrate>
In a container, 100 parts by weight of the resin A obtained in Resin Synthesis Example 1, 0.029 part of the compound (a-17) and 0.057 part of the compound (b-39) as a compound (A), 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, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.070 mm, a length of 200 mm, and a width of 200 mm.

<Preparation of substrate and optical filter>
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 volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 6 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .

An antireflection layer was provided on both surfaces of the obtained substrate in the same manner as in Example 3 to obtain an optical filter having a thickness of 0.082 mm.
Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

[Example 7]
In Example 7, an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.

<Preparation of transparent resin substrate>
In a container, 100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 0.06 part of the compound (a-17) and 0.12 part of the compound (b-39) as the compound (A), compound (B) As a result, 1.20 parts of the above compound (B-1) 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, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.050 mm, a length of 200 mm, and a width of 200 mm.

<Preparation of substrate and optical filter>
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 volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .

  An optical filter having a thickness of 0.054 mm provided with antireflection layers on both sides of the obtained base material in the same manner as in Example 1 except that the design (I) was changed to the design (III) shown in Table 16 below. Got.

  Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. In addition, the absolute value (Δn) of the difference between the equivalent admittance of the dielectric multilayer film (III) including the base material of the obtained optical filter and the refractive index of air is set at 10 nm intervals in the wavelength range of 420 to 1000 nm. As a result of calculation, the average value of the absolute values (Δn) was 0.16.

[Example 8]
In Example 8, an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.

<Preparation of transparent resin substrate>
In a container, 100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 0.10 parts of the compound (a-17), 0.20 parts of the compound (b-39) and the compound (A) a-47) 0.25 part, 1.50 parts of the above compound (B-1) as compound (B), 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, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.040 mm, a length of 200 mm, and a width of 200 mm.

<Preparation of substrate and optical filter>
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 volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .

An antireflection layer was provided on both surfaces of the obtained substrate in the same manner as in Example 7 to obtain an optical filter having a thickness of 0.044 mm.
Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

[Example 9]
In Example 9, an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.

<Preparation of transparent resin substrate>
In a container, 100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 0.036 parts of the compound (a-17), 0.162 parts of the compound (b-39) and the compound (A) a-47) 0.064 parts, compound (a-63) 0.080 parts, compound (a-89) 0.064 parts, compound (B) as compound (B-1) 0.852 parts As well as dichloromethane, a solution having a resin 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, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.050 mm, a length of 200 mm, and a width of 200 mm.

<Preparation of substrate and optical filter>
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 volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .

An antireflection layer was provided on both surfaces of the obtained substrate in the same manner as in Example 7 to obtain an optical filter having a thickness of 0.054 mm.
Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIGS.

[Comparative Example 1]
In Comparative Example 1, an optical filter having a near-infrared reflective layer on both sides was produced according to the following procedure and conditions.

<Preparation of transparent resin substrate>
In a container, 100 parts by weight of the resin A obtained in Resin Synthesis Example 1, 0.057 parts of the compound (a-17) and 0.114 parts of the compound (b-39) as a compound (A), 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, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.070 mm, a length of 200 mm, and a width of 200 mm.

<Preparation of substrate and optical filter>
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 volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .

A near-infrared cut layer [silica (SiO ₂ : refractive index of 1.46 at 550 nm) layer and titania (designed with IV) shown in Table 17 below is formed on both surfaces of the obtained substrate using an ion-assisted vacuum deposition apparatus. TiO ₂ : Dielectric multilayer film in which 550 nm refractive index 2.48) layers are alternately laminated] was formed at a deposition temperature of 120 ° C. to obtain an optical filter having a thickness of 0.079 mm.

  Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. Further, the absolute value (Δn) of the difference between the equivalent admittance of the dielectric multilayer film (IV) including the base material of the obtained optical filter (light incident side: layers 1 to 26 in Table 17) and the refractive index of air. ) Was calculated at intervals of 10 nm in the wavelength range of 420 to 1000 nm. As a result, the average value of the absolute values (Δn) was 1.28. On the other hand, the absolute value (Δn) of the difference between the equivalent admittance of the dielectric multilayer film (IV) including the base material of the obtained optical filter (light emission side: layers 27 to 46 in Table 17) and the refractive index of air. ) Was calculated at intervals of 10 nm in the wavelength range of 420 to 1000 nm. As a result, the average value of the absolute values (Δn) was 0.47.

  The optical filter obtained in Comparative Example 1 was thin, the optical density of 800 nm to 1200 nm was high and the near-infrared shielding performance was good, but did not satisfy the requirement (b), the reflected light was strong, It was unsuitable as an optical filter.

[Comparative Example 2]
In Comparative Example 2, an optical filter composed of a near-infrared absorbing glass substrate having antireflection layers on both sides was produced according to the following procedure and conditions.

<Production of optical filter>
An antireflection layer was provided on both sides of a near-infrared absorbing glass substrate “BS-11” (thickness 90 μm) manufactured by Matsunami Glass Industrial Co., Ltd. cut to a size of 200 mm in length and 200 mm in width in the same manner as in Example 7. An optical filter having a thickness of 0.091 mm was obtained.

  Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

  The optical filter obtained in Comparative Example 2 was thin, satisfied the requirement (b), and was good with little reflected light. However, the optical density at 800 nm to 1200 nm was low, and the near-infrared shielding performance was insufficient. It was unsuitable as an optical filter.

[Comparative Example 3]
In Comparative Example 3, an optical filter composed of a near-infrared absorbing glass substrate having an antireflection layer on one side and a near-infrared reflecting layer on the other side was produced by the following procedure and conditions.

<Production of optical filter>
A near-infrared cut layer of the design (V) shown in Table 18 below on both sides of a near-infrared absorbing glass substrate “BS-11” (thickness 90 μm) manufactured by Matsunami Glass Industrial Co., Ltd. cut to a size of 200 mm in length and 200 mm in width. And antireflection layer [dielectric multilayer film in which silica (SiO ₂ : 550 nm refractive index 1.46) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layers are alternately laminated, near-infrared cut Layer: layers 1 to 40, antireflection layer: layers 41 to 49] were formed at a deposition temperature of 120 ° C. to obtain an optical filter having a thickness of 0.095 mm.

  Spectral transmittance from angles of 30 ° and 60 ° to the vertical direction of the obtained optical filter and from the vertical direction, spectral reflectance from an angle of 5 ° to the vertical direction of the optical filter, The spectral reflectance from an angle of 5 ° with respect to the vertical direction on the surface was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIGS. Further, the absolute value (Δn) of the difference between the equivalent admittance of the dielectric multilayer film (V) including the base material of the obtained optical filter (light incident side: layers 1 to 40 in Table 18) and the refractive index of air. ) Was calculated at intervals of 10 nm in the wavelength range of 420 to 1000 nm. As a result, the average value of the absolute values (Δn) was 1.26.

  The optical filter obtained in Comparative Example 3 was thin and had a near-infrared shielding performance, but did not satisfy the requirement (b), the reflected light was strong, and it was unsuitable as an optical filter.

The symbols for the constitution of the substrate and various compounds in Table 19 are as follows.

<Optical filter configuration>
Form (1): Form consisting of a resin substrate having an antireflection layer and a resin layer containing near-infrared absorbing fine particles on both sides Form (2): Near-infrared absorbing fine particles having an antireflective layer on both sides Form consisting of a near-infrared absorbing glass substrate having a resin layer containing: Form (3): Form consisting of a near-infrared absorbing glass substrate having an antireflection layer on both sides and a resin layer on one side Form (4): Reflecting on both sides Form consisting of resin substrate having prevention layer and resin layer Form (5): Form consisting of resin substrate having near-infrared cut layers on both sides (comparative example)
Form (6): Form consisting of a near-infrared absorbing glass substrate having antireflection layers on both sides (comparative example)
Form (7): Form consisting of a near-infrared absorbing glass substrate having an antireflection layer on one side and a near-infrared cut layer on one side (comparative example)

<Glass substrate>
Glass substrate (1): Near-infrared absorbing glass substrate “BS-11” (manufactured by Matsunami Glass Industry Co., Ltd.)
<Resin composition>
Resin composition (1): 60 parts by weight of tricyclodecane dimethanol acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, near-infrared absorbing fine particle dispersion (manufactured by Sumitomo Metal Mining Co., Ltd.) 117 parts by weight (about 33 parts by weight in terms of solid content), methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)
Resin composition (2): Isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.), 1,9-nonanediol diacrylate 20 parts by weight, methacrylic acid 20 Parts by weight, 30 parts by weight of glycidyl methacrylate, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by Ciba Specialty Chemicals) and Sun-Aid SI -110 base agent (manufactured by Sanshin Chemical Industry Co., Ltd.) 1 part by weight, propylene glycol monomethyl ether acetate (solvent, solid content concentration (TSC) 50%)
Resin composition (3): 60 parts by weight of tricyclodecane dimethanol diacrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30% )

<Near-infrared absorbing dye>
<< Compound (A) >>
Compound (a-17) (Maximum absorption wavelength in dichloromethane: 713 nm, weight absorption coefficient of maximum absorption wavelength: 4 × 10 ² L · cm ⁻¹ · g ⁻¹ , maximum weight absorption coefficient at 430 nm to 580 nm is 5 L · cm ^{− 1} · g ^-1 )
Compound (b-39) (maximum absorption wavelength in dichloromethane: 736 nm, weight absorption coefficient of maximum absorption wavelength: 1.1 × 10 ² L · cm ⁻¹ · g ⁻¹ , maximum weight absorption coefficient at 430 nm to 580 nm is 2 L · cm ^-1 · g ^-1 )
Compound (a-47) (maximum absorption wavelength in dichloromethane: 776 nm, weight absorption coefficient of maximum absorption wavelength: 5 × 10 ² L · cm ⁻¹ · g ⁻¹ , maximum weight absorption coefficient at 430 nm to 580 nm is 7 L · cm ^{− 1} · g ^-1 )
Compound (a-63) (maximum absorption wavelength in dichloromethane of 868 nm, weight absorption coefficient of maximum absorption wavelength of 3.3 × 10 ² L · cm ⁻¹ · g ⁻¹ , maximum weight absorption coefficient at 430 nm to 580 nm of 9 L · cm ^-1 · g ^-1 )
Compound (a-89) (maximum absorption wavelength in dichloromethane of 822 nm, weight absorption coefficient of maximum absorption wavelength of 5.7 × 10 ² L · cm ⁻¹ · g ⁻¹ , maximum weight absorption coefficient at 430 nm to 580 nm of 9 L · cm ^-1 · g ^-1 )
≪Compound (B) ≫
Compound (B-1): Light absorber “CIR-RL” manufactured by Nippon Carlit Co., Ltd. (absorption maximum wavelength in dichloromethane of 1095 nm, weight absorption coefficient of maximum absorption wavelength of 9.8 × 10 L · cm ⁻¹ · g ⁻¹ The maximum weight extinction coefficient at 430 nm to 580 nm is 4 L · cm ⁻¹ · g ⁻¹ )

1, 1 ', 1''... Light 2 ... Optical filter 3 ... Spectrophotometer 11 ... Reflected light

Claims (17)

It has a base material satisfying the following requirement (a) and an antireflection layer formed on at least one surface of the base material, and satisfies the following requirements (b), (c) and (d) Features optical filters:
(A) having a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and less than 950 nm;
(B) In the region of wavelength 420 nm or more and 1000 nm or less, the average value Rfa _-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 And the average value Rf _b-5 of the reflectance of light incident from an oblique direction with respect to 5 degrees is 6% or less;
(C) In the region of wavelength 430 nm or more and 580 nm or less, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter and the light of non-polarized light incident from an oblique direction of 30 degrees with respect to the vertical direction The average value T _a-30 of the transmittance and the average value T _a-60 of the transmittance of the non-polarized light incident from an oblique direction of 60 degrees with respect to the vertical direction are both 20% or more;
(D) In the region of wavelength 800 nm or more and 1200 nm or less, the average value OD _a-0 of the optical density (OD value) with respect to the 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) with respect to the light and the average value OD _a-60 of the optical density (OD value) with respect to light incident from an oblique direction of 60 degrees with respect to the vertical direction are 1. 5 or more.   The optical filter according to claim 1, further comprising an antireflection layer on both surfaces of the base material.   The optical filter according to claim 1, wherein the optical filter has a thickness of 100 μm or less.   The optical filter according to claim 1, wherein the layer containing the compound (A) is a transparent resin layer.   5. The optical according to claim 1, wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. filter.   The optical filter according to any one of claims 1 to 5, wherein the substrate contains a compound (B) having an absorption maximum in a wavelength region of 950 nm to 1800 nm.   The compound (B) is selected from the group consisting of near-infrared absorbing fine particles, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, cyanine compounds, diimonium compounds, metal dithiolate compounds, and pyrrolopyrrole compounds. The optical filter according to claim 6, wherein the optical filter is at least one compound selected.   The optical filter according to any one of claims 1 to 7, wherein the compound (A) includes a compound having an absorption maximum in a wavelength region of 650 nm or more and less than 800 nm.   The optical filter according to any one of claims 1 to 8, wherein the compound (A) includes a compound having an absorption maximum in a wavelength region of 800 nm or more and less than 950 nm.   8. The compound according to claim 1, wherein the compound (A) includes a compound having an absorption maximum in a region of a wavelength of 650 nm or more and less than 800 nm and a compound having an absorption maximum in a region of a wavelength of 800 nm or more and less than 950 nm. The optical filter according to claim 1. The near-infrared absorbing fine particles are selected from the group consisting of first fine particles composed of a compound represented by the following formula (P-1) and second fine particles composed of a compound represented by the following formula (P-2). The optical filter according to claim 7, wherein the optical filter is at least one kind.
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 , and n is 1 when A is an alkali metal or NH ₄ . , A is 2 when alkaline earth metal. ]
M _x W _y O _z (P-2)
[In the formula (P-2), M is H, alkali metal, alkaline earth metal, 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 and I, x, y and z are 0.001 ≦ x / y ≦ 1 and 2.2 ≦ z / y ≦ 3. Satisfy the condition of 0. ]   The resin constituting the transparent resin layer is a cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polysulfone resin Resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane resin UV curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin, And by sol-gel method The optical filter according to claim 4, characterized in that at least one resin selected from the group consisting of made silica from the resin as a main component.   The optical filter according to any one of claims 1 to 12, wherein the base material includes a substrate made of a fluorophosphate glass layer or a phosphate glass layer containing a copper component. In the case where the optical filter is incident from the vertical direction, in the case where the optical filter is incident from the direction of 30 ° with respect to the vertical direction and in the case where the optical filter is incident from the direction of 60 ° with respect to the vertical direction,
Change rate of ratio of R (red) transmittance derived from the following formula (1), change rate of ratio of G (green) transmittance derived from the following formula (2), and B derived from the following formula (3) 14. The optical filter according to claim 1, wherein a change rate of a ratio of (blue) transmittance is in a range of 0.6 to 1.1.
(R transmittance ratio) = (R transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (1)
(G transmittance ratio) = (G transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (2)
(B transmittance ratio) = (B transmittance) × 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (3)
[In the formulas (1) to (3), the R transmittance is an average transmittance at a wavelength of 580 to 650 nm, the G transmittance is an average transmittance at a wavelength of 500 to 580 nm, and the B transmittance is an average transmittance at a wavelength of 420 to 500 nm. is there. ]   The base material for optical filters used for the optical filter of any one of Claims 1-14.   An image pickup apparatus comprising the optical filter according to claim 1.   A camera module comprising the optical filter according to claim 1.