JP6627864B2 - Optical filter and device using optical filter - Google Patents

Description

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

  In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, CCDs and CMOS image sensors, which are solid-state imaging devices for color images, are used. Silicon photodiodes having sensitivity to near infrared rays that cannot be detected by human eyes are used. In these solid-state imaging devices, it is necessary to perform luminosity correction to make the color look natural to the human eye, and an optical filter (for example, a near-infrared ray cut-off device) that selectively transmits or cuts a light beam in a specific wavelength region is required. Filter) is often used.

  Conventionally, as such a near-infrared cut filter, one manufactured by various methods has been used. For example, a near-infrared cut filter in which a transparent resin is used as a base material and a near-infrared absorbing dye is contained in the transparent resin is known (for example, see Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not always have sufficient near-infrared absorption characteristics.

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

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

JP-A-6-200113 JP 2005-338395 A JP 2011-100084 A

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

  An object of the present invention is to provide an optical filter which has little dependence on an incident angle and can reduce multiple reflection when near-infrared light is incident from an oblique direction.

  The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by applying a combination of two or more compounds having an absorption maximum in a specific wavelength range, a desired near-infrared cut characteristic, visible transmission The present inventors have found that an optical filter capable of achieving a reduction in the ratio and multiple reflection light in the near-infrared wavelength region can be obtained, and have completed the present invention. Examples of embodiments of the present invention are shown below.

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

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

  [3] The item [1] or [1], wherein the compound (S) is at least one selected from the group consisting of a squarylium-based compound, a cyanine-based compound, a pyrrolopyrrole-based compound, and a metal dithiolate-based compound. The optical filter according to 2).

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

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

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

式（Ｉ）および（ＩＩ）中、波線で表した部分が中央四員環との結合部位を表し、
Ｘは、独立に酸素原子、硫黄原子、セレン原子、テルル原子または−ＮＲ⁸−を表し、
Ｒ¹〜Ｒ⁸は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−ＮＲ^gＲ^h基、−ＳＲⁱ基、−ＳＯ₂Ｒⁱ基、−ＯＳＯ₂Ｒⁱ基または下記Ｌ^a〜Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、−Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a〜Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a〜Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１〜１２の脂肪族炭化水素基
（Ｌ^b）炭素数１〜１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３〜１４の脂環式炭化水素基
（Ｌ^d）炭素数６〜１４の芳香族炭化水素基
（Ｌ^e）炭素数３〜１４の複素環基
（Ｌ^f）炭素数１〜１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１〜１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１〜１２のアルコキシカルボニル基
置換基Ｌは、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のハロゲン置換アルキル基、炭素数３〜１４の脂環式炭化水素基、炭素数６〜１４の芳香族炭化水素基および炭素数３〜１４の複素環基からなる群より選ばれる少なくとも１種である。

In the formulas (I) and (II), a portion represented by a wavy line represents a binding site to the central four-membered ring,
X is independently oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ - represents,
R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -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 the following L ^a ~L ^e represents either, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) An aromatic hydrocarbon group having 6 to 14 carbon atoms (L ^e ), a heterocyclic group having 3 to 14 carbon atoms (L ^f ), an alkoxy group having 1 to 12 carbon atoms (L ^g ), and a carbon atom which may have a substituent L. 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.

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

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

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

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

  According to the present invention, it is possible to provide an optical filter which is excellent in near-infrared cut characteristics, has little incident angle dependence, and has excellent transmittance characteristics in a visible wavelength region and an excellent effect of reducing multiple reflection light in a near-infrared wavelength region. it can.

FIG. 1A is a schematic diagram illustrating that a light beam that is multiply reflected between an optical filter and a lens is incident on a solid-state imaging device. FIG. 1B is a schematic diagram showing that light beams that are multiply reflected inside the optical filter are incident on the solid-state imaging device. FIG. 1C is a schematic diagram illustrating that light beams that are multiple-reflected between the optical filter and the solid-state imaging device enter the solid-state imaging device. FIG. 1D is a schematic diagram illustrating that light beams that are multiple-reflected between the optical filter and the solid-state imaging device enter the solid-state imaging device. FIG. 2A is a schematic diagram illustrating a method of measuring the transmittance when measured from the vertical direction of the optical filter. FIG. 2B is a schematic diagram illustrating a method of measuring the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter. FIG. 2C is a schematic diagram illustrating a method of measuring the reflectance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter. FIG. 2D is a schematic view showing a method of measuring the reflectance when measured from an angle of 5 ° with respect to the vertical direction of the evaporation monitor glass. FIGS. 3A and 3B are schematic views showing an example of a preferred configuration of the optical filter of the present invention. FIG. 4 is a spectral transmission spectrum of the substrate obtained in Example 1. FIG. 5A is a spectral reflection spectrum measured at an angle of 5 ° with respect to the vertical direction of the dielectric multilayer film (I) prepared in Example 1, and FIG. 3 is a spectral reflection spectrum measured from an angle of 5 ° with respect to the vertical direction of the dielectric multilayer film (II) prepared in 1. FIG. 6 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG. 7 shows the optical filter obtained in Example 1 having a light incident surface on the side of the dielectric multilayer film (II) (second optical layer) closer to 30 ° with respect to the vertical direction of the optical filter. It is a spectral reflection spectrum measured from an angle. FIG. 8 is a spectral transmission spectrum of the substrate obtained in Example 2. FIG. 9 is a spectral transmission spectrum of the optical filter obtained in Example 2. FIG. 10 shows that the optical filter obtained in Example 2 has an angle of 30 ° with respect to the vertical direction of the optical filter when the light incident surface is on the dielectric multilayer (IV) (second optical layer) side. It is a spectral reflection spectrum measured from an angle.

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

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

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

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

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

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

  The dielectric multilayer film preferably has a reflection characteristic over the entire wavelength range of 700 to 1100 nm, more preferably has a reflection characteristic over the entire wavelength range of 700 to 1150 nm, particularly preferably 700 to 1200 nm. The first optical layer mainly having a reflection characteristic at a wavelength of about 700 to 950 nm when measured from an angle of 5 ° with respect to the vertical direction of the optical filter as a form having a dielectric multilayer film on both surfaces of the substrate (i). On one surface of the base material (i), and has a reflection characteristic mainly at around 900 nm to 1150 nm when measured from the angle of 5 ° with respect to the vertical direction of the optical filter on the other surface of the base material (i). 3A having a second optical layer (see FIG. 3A) or a third optical element having a reflection characteristic mainly at a wavelength of about 700 to 1150 nm when measured from an angle of 5 ° with respect to the vertical direction of the optical filter. An embodiment in which a layer is provided on one surface of the substrate (i) and a fourth optical layer having antireflection properties in the visible region is provided on the other surface of the substrate (i) (see FIG. 3B). Can be

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

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

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

[Substrate (i)]
The base material (i) may be a single layer or a multilayer, and has a transparent resin layer containing at least one compound (A) and at least one compound (S). What is necessary is just to have a transparent resin layer containing the transparent resin layer containing the compound (S). When the substrate (i) is a single layer, for example, a substrate composed of a transparent resin substrate (ii) containing the compound (A) and the compound (S) can be mentioned. This transparent resin substrate (ii) Becomes the transparent resin layer. In the case of a multilayer, for example, a transparent resin layer such as an overcoat layer made of a curable resin containing the compound (A) and the compound (S) on a support such as a glass support or a resin support serving as a base. , A substrate in which a resin layer such as an overcoat layer made of a curable resin or the like containing the compound (A) is laminated on a transparent resin substrate (iii) containing the compound (S), A base material in which a resin layer such as an overcoat layer made of a curable resin or the like containing a compound (S) is laminated on a transparent resin substrate (iv) containing A), containing a compound (A) and a compound (S) Examples of the base material include a transparent resin substrate (ii) on which a resin layer such as an overcoat layer made of a curable resin or the like is laminated. The compound (A) is preferred in view of the manufacturing cost, the ease of adjusting the optical properties, the ability to achieve a scrubbing effect of the resin support and the transparent resin substrate (ii), the improvement of the scratch resistance of the substrate (i), and the like. ) And a compound (S) containing a resin layer such as an overcoat layer made of a curable resin on a transparent resin substrate (ii). When a glass support is used as the support of the substrate (i), a glass support containing no near-infrared absorber is particularly preferable from the viewpoint of the strength of the substrate and a reduction in thickness.

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

  The shortest wavelength (Xc) at which the transmittance measured from the vertical direction of the base material (i) in the region of a wavelength of 600 nm or more is from 50% to 50% is preferably 610 to 670 nm, more preferably 620 to 665 nm. And particularly preferably 630 to 660 nm.

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

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

  When the (Tb) of the substrate (i) is in such a range, the visible light transmittance is kept high, and when a dielectric multilayer film is formed on the substrate (i), the (Tb) becomes oblique. It is possible to reduce the reflectance when infrared light enters.

  The average transmittance of the substrate (i) at a wavelength of 430 to 580 nm is preferably 75% or more, more preferably 78% or more, and particularly preferably 80% or more. When a substrate having such transmission characteristics is used, high light transmission characteristics in the visible region can be achieved, and a highly sensitive camera function can be achieved.

  The thickness of the substrate (i) can be appropriately selected according to the desired use, and is not particularly limited, but is preferably selected as appropriate so as to reduce the incident angle dependence of the obtained optical filter, and is preferable. Is 10 to 200 μm, more preferably 15 to 180 μm, and particularly preferably 20 to 150 μm.

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

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

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

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

  The content of the compound (A) may be, for example, as the base material (i), a base material composed of a transparent resin substrate (ii) containing the compound (A) and the compound (S) or a compound (A). When a base material in which a resin layer such as an overcoat layer made of a curable resin containing the compound (S) is laminated on a transparent resin substrate (iv) to be used, the transparent resin is used for 100 parts by weight of the transparent resin. , Preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. A base material in which a transparent resin layer such as an overcoat layer made of a curable resin or the like containing the compound (A) and the compound (S) is laminated on a resin support as a support or a base, or the compound (S) Curable resin containing compound (A) on transparent resin substrate (iii) containing When a substrate on which a resin layer such as an overcoat layer made of a resin is laminated is used, preferably 0.1 to 5.0 parts by weight based on 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). Parts by weight, more preferably 0.2 to 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight.

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

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

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

式（Ｉ）および（ＩＩ）中、波線で表した部分が中央四員環との結合部位を表し、
Ｘは、独立に酸素原子、硫黄原子、セレン原子、テルル原子または−ＮＲ⁸−を表し、
Ｒ¹〜Ｒ⁸は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−ＮＲ^gＲ^h基、−ＳＲⁱ基、−ＳＯ₂Ｒⁱ基、−ＯＳＯ₂Ｒⁱ基または下記Ｌ^a〜Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、−Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a〜Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a〜Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１〜１２の脂肪族炭化水素基
（Ｌ^b）炭素数１〜１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３〜１４の脂環式炭化水素基
（Ｌ^d）炭素数６〜１４の芳香族炭化水素基
（Ｌ^e）炭素数３〜１４の複素環基
（Ｌ^f）炭素数１〜１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１〜１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１〜１２のアルコキシカルボニル基
置換基Ｌは、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のハロゲン置換アルキル基、炭素数３〜１４の脂環式炭化水素基、炭素数６〜１４の芳香族炭化水素基および炭素数３〜１４の複素環基からなる群より選ばれる少なくとも１種である。

In the formulas (I) and (II), a portion represented by a wavy line represents a binding site to the central four-membered ring,
X is independently oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ - represents,
R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -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 the following L ^a ~L ^e represents either, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) An aromatic hydrocarbon group having 6 to 14 carbon atoms (L ^e ), a heterocyclic group having 3 to 14 carbon atoms (L ^f ), an alkoxy group having 1 to 12 carbon atoms (L ^g ), and a carbon atom which may have a substituent L. 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.

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

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

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

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

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

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

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

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

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

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

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

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

  The content of the compound (S) may be, for example, a content of the base material (i) including the base material composed of the transparent resin substrate (ii) containing the compound (A) and the compound (S) or the compound (S). When a base material in which a resin layer such as an overcoat layer made of a curable resin containing the compound (A) is laminated on a transparent resin substrate (iii) to be used, the transparent resin is used in an amount of 100 parts by weight. , Preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. A base material in which a transparent resin layer such as an overcoat layer made of a curable resin or the like containing the compound (A) and the compound (S) is laminated on a resin support as a support or a base, or a compound (A). Curing resin containing compound (S) on transparent resin substrate (iv) containing In the case of using a substrate on which a resin layer such as an overcoat layer made of such a material is laminated, preferably 0.1 to 5 parts by weight based on 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). 0 parts by weight, more preferably 0.2 to 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight. When the content of the compound (S) is within the above range, an optical filter having both good near-infrared absorption characteristics and high visible light transmittance can be obtained.

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

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

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

  The transparent resin is not particularly limited as long as it does not impair the effects of the present invention, but, for example, secures heat stability and moldability to a film, and obtains dielectric properties by high-temperature deposition performed at a deposition temperature of 100 ° C. or more. In order to form a film capable of forming a body 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 is exemplified. Further, it is particularly preferable that the resin has a glass transition temperature of 140 ° C. or higher, since a film on which a dielectric multilayer film can be formed by vapor deposition at a higher temperature is obtained.

  When a resin plate having a thickness of 0.1 mm made of the resin is formed as the transparent resin, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, Particularly preferably 80 to 95%. If a resin having a total light transmittance in such a range is used, the obtained substrate shows good transparency as an optical film.

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

  Examples of the transparent resin include a cyclic (poly) olefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide (aramid) resin, and a polyarylate resin. Resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin Resins, allyl ester-based curable resins, silsesquioxane-based UV-curable resins, acrylic UV-curable resins, and vinyl-based UV-curable resins can be mentioned.

≪Cyclic (poly) olefin resin≫
As the cyclic (poly) olefin-based resin, at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ) And a resin obtained by hydrogenating the resin.

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

In the formula (X ₀ ), R ^{x1 to} R ^x4 each independently represent an atom or a group selected from the following (i ′) to (ix ′), and k ^x , ^mx and p ^x each independently represent 0 Or represents a positive integer.
(I ') hydrogen atom (ii') halogen atom (iii ') trialkylsilyl group (iv') substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom To 30 hydrocarbon groups (v ') substituted or unsubstituted C1-C30 hydrocarbon groups (vi') polar groups (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 participating in the bonding are each independently the above-mentioned (i ′) ) Represents an atom or a group selected from (vi ′).)
(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 ^{and x4} independently represents an atom or a group selected from the above (i ') to (vi').)
(Ix ′) R ^x2 and R ^x3 are bonded to each other to form a monocyclic hydrocarbon ring or heterocyclic ring (provided that R ^x1 and R ^x4 that do not participate in the bond are each independently the above-mentioned (i ') Represents an atom or group selected from (vi').)

式（Ｙ₀）中、Ｒ^y1およびＲ^y2はそれぞれ独立に、前記（i'）〜（vi'）より選ばれる原子または基を表すか、Ｒ^y1とＲ^y2とが、相互に結合して形成された単環もしくは多環の脂環式炭化水素、芳香族炭化水素または複素環を表し、ｋ^yおよびｐ^yはそれぞれ独立に、０または正の整数を表す。

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

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

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

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

式（２）中、Ｒ¹〜Ｒ⁴およびａ〜ｄはそれぞれ独立に、前記式（１）中のＲ¹〜Ｒ⁴およびａ〜ｄと同義であり、Ｙは、単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、Ｒ⁷およびＲ⁸はそれぞれ独立に、ハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｇおよびｈはそれぞれ独立に、０〜４の整数を示し、ｍは０または１を示す。但し、ｍが０のとき、Ｒ⁷はシアノ基ではない。

In the formula (2), 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 = indicates O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group or a nitro group having 1 to 12 carbon atoms, g and h are each independently 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

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

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

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

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

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

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

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

≪Fluorinated aromatic polymer resin≫
The fluorinated aromatic polymer-based resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. The polymer is preferably a polymer containing a repeating unit containing at least one bond, and can be synthesized by, for example, a 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 a molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. Can be listed. The acrylic ultraviolet-curable resin is a substrate (i) in which a transparent resin layer containing a compound (S) and a curable resin is laminated on a glass support or a resin support serving as a base. When 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 (ii) containing the compound (S) is used, it is particularly preferably used as the curable resin. be able to.

≪Commercial item≫
Commercially available transparent resins include the following commercially available products. Commercial products of the cyclic (poly) olefin resin include Arton manufactured by JSR Corporation, Zeonor manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. . Examples of commercially available polyethersulfone-based resins include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. 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. Commercially available fluorene polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Ltd. Examples of commercially available fluorene polyester-based resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include Acryviewer manufactured by Nippon Shokubai Co., Ltd. Commercial products of the silsesquioxane-based ultraviolet curable resin include Nippon Steel Chemical Co., Ltd.'s Silplus.

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

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

  These additives may be mixed with a resin or the like when producing the base material (i), or may be added when synthesizing the resin. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the resin. Department.

<Method for producing substrate (i)>
When the base material (i) is a base material including the transparent resin substrates (ii) to (iv), the transparent resin substrates (ii) to (iv) are formed by, for example, melt molding or cast molding. Producing a substrate having an overcoat layer laminated thereon by coating a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent after molding, if necessary. Can be.

  The substrate (i) is formed by laminating a transparent resin layer such as an overcoat layer made of a curable resin containing the compound (A) and the compound (S) on a glass support or a resin support serving as a base. In the case of a base material, for example, a resin solution containing the compound (A) and the compound (S) is melt-molded or cast-molded on a glass support or a resin support serving as a base, preferably by spin coating or slitting. After coating with a method such as ink-jet, the solvent is dried and removed, and if necessary, light irradiation or heating is performed to form a transparent resin layer on a glass support or a resin support serving as a base. Substrate can be manufactured.

≪Molten molding≫
As the melt molding, specifically, a method in which a resin, a compound (A), a compound (S) and the like are melt-kneaded and a pellet obtained by melt-molding; a resin, a compound (A) and a compound (S) Or a method of melt-forming pellets obtained by removing a solvent from a resin composition containing compound (A), compound (S), resin and solvent. Is mentioned. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

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

  When the substrate (i) is a substrate composed of a transparent resin substrate (ii) containing the compound (A) and the compound (S), the substrate (i) is supported after cast molding. The substrate (i) can be obtained by peeling a coating film from a body, and the base material (i) is formed on a support such as a glass support or a resin support serving as a base. When a transparent resin layer such as an overcoat layer made of a curable resin or the like containing S) is a substrate laminated thereon, the substrate (i) is prepared by removing a coating film after casting. Obtainable.

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

  Further, a glass plate, a method of coating the resin composition on an optical component such as quartz or transparent plastic and drying the solvent, or a method of coating the curable composition and curing and drying, and the like. A transparent resin layer may be formed on the component.

  The amount of residual solvent in the transparent resin layer (transparent resin substrate (ii)) obtained by the above method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.1% by weight or less, based on the weight of the transparent resin layer (transparent resin substrate (ii)). 5% by weight or less. When the amount of the residual solvent is in the above range, a transparent resin layer (transparent resin substrate (ii)) which is less likely to deform or change its properties and can easily exhibit desired functions can be obtained.

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

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

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

  The thickness of each of the high-refractive-index material layer and the low-refractive-index material layer is usually preferably 0.1 λ to 0.5 λ, where λ (nm) is the near-infrared wavelength to be cut off. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is in this range, the optical film thickness obtained by calculating the product (n × d) of the refractive index (n) and the film thickness (d) by λ / 4, the high refractive index material layer and the low refractive index The thickness of each layer of the refractive index material layer becomes substantially the same, and there is a tendency that the cutoff and transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection and refraction.

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

  In the present invention, the material types of the high refractive index material layer and the low refractive index material layer, and the high refractive index material layer and the low refractive index material layer, are adjusted according to the absorption characteristics of the compound (A) and the compound (S). By appropriately selecting the thickness, the order of lamination, and the number of laminations, while ensuring sufficient transmittance in the visible region, having sufficient light-cutting characteristics in the near-infrared wavelength region, It is possible to reduce the reflectance when infrared light enters.

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

[Other functional films]
The optical filter of the present invention is provided between the substrate (i) and the dielectric multilayer film, on the side opposite to the surface on which the dielectric multilayer film is provided, of the substrate (i) as long as the effects of the present invention are not impaired. The surface or the surface of the dielectric multilayer film opposite to the surface on which the substrate (i) is provided, has an improved surface hardness of the substrate (i) and the dielectric multilayer film, an improved chemical resistance, an antistatic property, A functional film such as an antireflection film, a hard coat film, or an antistatic film can be provided as appropriate for the purpose of, for example, erasing scratches.

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

  The method for laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent is melted on the substrate (i) or the dielectric multilayer film in the same manner as described above. Molding or cast molding may be used.

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

  Examples of the coating agent include an ultraviolet (UV) / electron beam (EB) curable resin and a thermosetting resin. Specifically, vinyl compounds, urethane, urethane acrylate, acrylate, 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.

  Further, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. One type of polymerization initiator may be used alone, or two or more types may be used in combination.

  In the curable composition, the proportion 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 compounding ratio of the polymerization initiator is within the above range, the curable composition has excellent curing characteristics and handleability, and an antireflection film having a desired hardness, a functional film such as a hard coat film or an antistatic film can be obtained. it can.

Further, an organic solvent may be added as a solvent to the curable composition, and a known organic solvent can be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; 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- Amides such as methylpyrrolidone can be mentioned.
These solvents may be used alone or in combination of two or more.

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

  Further, in order to increase the adhesion between the base material (i) and the functional film and / or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, the base material (i), the functional film or the dielectric film may be used. The surface of the multilayer film may be subjected to a surface treatment such as a corona treatment or a plasma treatment.

[Use of optical filter]
The optical filter of the present invention has a wide viewing angle and has excellent near-infrared cut ability and the like. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS image sensor of a camera module. In particular, digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, personal digital assistants, video game machines, and portable game machines , Fingerprint authentication system, digital music player, etc. Further, it is useful as a heat ray cut filter mounted on a glass plate or the like of an automobile or a building.

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

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In addition, "part" means "part by weight" unless otherwise specified. The method for measuring each physical property value and the method for evaluating the physical properties 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, 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) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a GPC apparatus (HLC-8220, column: TSKgelα-M, developing solvent: THF) manufactured by Tosoh Corporation.

For the resin synthesized in Resin Synthesis Example 3 described later, the logarithmic viscosity was measured by the following method (c) instead of the measurement of the molecular weight by the above method.
(C) A part of the polyimide resin solution was poured into anhydrous methanol to precipitate a polyimide resin, which was separated by filtration from unreacted monomers. 0.1 g of the polyimide obtained by vacuum drying at 80 ° C. for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. was determined using a Canon-Fenske viscometer by the following formula. I asked.
_{μ = {ln (t s /} t 0)} / C
t ₀ : Flowing time of solvent t _s : Flowing time of dilute polymer solution C: 0.5 g / dL

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nanotechnology Co., Ltd., the temperature was measured at a rate of 20 ° C./min under a nitrogen stream.

<Spectral transmittance>
(Ta), (Xc), and (Tb) of the base material, and the transmittances (Xa) and (Xb) of the optical filter in each wavelength range were measured by a spectrophotometer (U- 4100).

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

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

[Synthesis example]
Compound (A) and compound (S) used in the following Examples were synthesized by a generally known method. As a general synthesis method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Application Laid-Open No. 60-228448, Japanese Patent Application 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, JP-A-2009 -108267, Japanese Patent Application Laid-Open No. 2010-241873, Japanese Patent No. 3699466, Japanese Patent No. 4740631, and the like.

<Resin synthesis example 1>
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] Dodeca-3-ene (hereinafter also referred to as "DNM") 100 parts, 1-hexene (molecular weight modifier) 18 parts and toluene (ring opening polymerization reaction solvent) 300 parts by nitrogen substitution. The solution was charged into a container and heated to 80 ° C. Subsequently, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / l) and a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol / l) were added to the solution in the reaction vessel as a polymerization catalyst. 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-opened polymer solution. The polymerization conversion in this polymerization reaction was 97%.

このようにして得られた開環重合体溶液１，０００部をオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．１２部添加し、水素ガス圧１００ｋｇ／ｃｍ²、反応温度１６５℃の条件下で、３時間加熱撹拌して水素添加反応を行った。得られた反応溶液（水素添加重合体溶液）を冷却した後、水素ガスを放圧した。この反応溶液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添加重合体（以下「樹脂Ａ」ともいう。）を得た。得られた樹脂Ａは、数平均分子量（Ｍｎ）が３２，０００、重量平均分子量（Ｍｗ）が１３７，０００であり、ガラス転移温度（Ｔｇ）が１６５℃であった。

1,000 parts of the ring-opened polymer solution thus obtained was charged into an autoclave, and 0.12 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution. Then, the mixture was heated and stirred for 3 hours under a condition of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. to perform a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), the pressure of hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and collect a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter, also referred to as “resin A”). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

<Resin synthesis example 2>
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, and 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 equipped with a nitrogen inlet 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 obtained solution was reacted at 140 ° C. for 3 hours, and generated water was removed from the Dean-Stark tube as needed. When generation of water was no longer observed, the temperature was gradually raised to 160 ° C., and the reaction was continued at the same temperature for 6 hours. After cooling to room temperature (25 ° C.), the generated salt was removed with a filter paper, and the filtrate was reprecipitated by throwing into methanol, and the filtrate (residue) was isolated by filtration. The obtained residue was vacuum-dried at 60 ° C. overnight to obtain a white powder (hereinafter also referred to as “resin B”) (yield: 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

<Resin synthesis example 3>
Under a nitrogen stream, 1,4-bis (4-amino-α, α) was placed in a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with side tubes, a Dean-Stark tube, and a cooling tube. -Dimethylbenzyl) benzene (27.66 g, 0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl 7.38 g (0.02 mol) were added, and 68.65 g of γ-butyrolactone and N, It was dissolved in 17.16 g of N-dimethylacetamide. The obtained solution is cooled to 5 ° C. using an ice water bath, and while maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an imidization catalyst And 0.50 g (0.005 mol) of triethylamine was added all at once. After the addition was completed, the temperature was raised to 180 ° C., and the mixture was refluxed for 6 hours while distilling off the distillate as needed. After the completion of the reaction, the mixture was air-cooled until the internal temperature reached 100 ° C., diluted with 143.6 g of N, N-dimethylacetamide, and cooled with stirring to obtain 264.16 g of a polyimide resin solution having a solid content of 20% by weight. Got. A part of this polyimide resin solution was poured into 1 L of methanol to precipitate polyimide. After washing the filtered polyimide with methanol, it was dried in a vacuum drier at 100 ° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). The IR spectrum of the obtained resin C was measured, 1704 cm ^-1 characteristic of imido group, absorption of 1770 cm ^-1 were observed. Resin C had a glass transition temperature (Tg) of 310 ° C. and was measured for logarithmic viscosity to be 0.87.

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

  In a container, 100 parts of resin A obtained in Resin Synthesis Example 1, 0.02 part of compound (s-11) (maximum absorption wavelength in dichloromethane of 776 nm in dichloromethane) shown in Table 1 above as compound (S), and compound (S) 0.03 parts of the compound (a-1) represented by the following formula (a-1) (maximum absorption wavelength in dichloromethane: 698 nm) as A) and the compound (a-2) represented by the following formula (a-2) 0.03 parts (maximum absorption wavelength in dichloromethane: 733 nm) and methylene chloride were added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a substrate made of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm. The spectral transmittance of the substrate was measured, and (Ta), (Tb) and (Xc) were determined. The results are shown in FIG.

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

The dielectric multilayer film (I) is formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100 ° C. (a total of 26 layers). The dielectric multilayer film (II) is formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer at a deposition temperature of 100 ° C. (a total of 20 layers). In each of the dielectric multilayer films (I) and (II), the silica layer and the titania layer are arranged in the order of the titania layer, the silica layer, the titania layer,..., The silica layer, the titania layer, and the silica layer from the substrate side. The layers were alternately laminated, and the outermost layer of the optical filter was a silica layer.

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

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

  The spectral transmittance of the obtained optical filter was measured in the vertical direction and at an angle of 30 ° from the vertical direction, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. When the spectral reflectance of the obtained optical filter was measured at an angle of 30 ° from the vertical direction of each surface, the light incident surface was changed to the dielectric multilayer film (II) side (second optical layer side). In this case, it was confirmed that the value of the minimum reflectance at a wavelength of 815 to 935 nm was small. FIG. 7 shows the spectral reflectance spectrum measured from an angle of 30 ° from the vertical direction of the optical filter when the light incident surface is on the dielectric multilayer film (II) side. The average value of the transmittance at a wavelength of 430 to 580 nm is 88%, the average value of the transmittance at a wavelength of 800 to 1000 nm is 1% or less, at least when measured from an angle of 30 ° with respect to the vertical direction at a wavelength of 815 to 935 nm. The minimum value of the reflectance measured from one surface was 61%, and the absolute value | Xa-Xb | was 3 nm.

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

Subsequently, in the same manner as in Example 1, on one surface of the obtained base material, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer were alternately laminated as a first optical layer (a total of 26 layers). A multi-layer film (III) is formed, and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on the other surface of the base material as a second optical layer (a total of 20 layers). A dielectric multilayer film (IV) was formed to obtain an optical filter having a thickness of about 0.104 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate. The spectral transmittance of the obtained optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. When the spectral reflectance of the obtained optical filter was measured at an angle of 30 ° from the vertical direction of each surface, the light incident surface was set to the dielectric multilayer (IV) side (second optical layer side). In this case, it was confirmed that the value of the minimum reflectance at a wavelength of 815 to 935 nm was small. FIG. 10 shows the spectral reflectance spectrum measured from an angle of 30 ° from the vertical direction of the optical filter when the light incident surface is on the dielectric multilayer film (IV) side.

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

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

On one surface of the obtained transparent resin substrate, a resin composition (1) having the following composition was applied with a bar coater, and heated in an oven at 70 ° C. for 2 minutes to 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, exposure (exposure amount: 500 mJ / cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) and form a resin layer on a transparent resin substrate. Similarly, a resin layer made of the resin composition (1) is formed on the other surface of the transparent resin substrate, and the transparent resin substrate containing the compound (S) and the compound (A) has resin layers on both surfaces. A substrate was obtained. The spectral transmittance of this substrate was measured, and (Ta), (Tb), and (Xc) were determined. Table 5 shows the results.

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

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

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

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

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

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

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

[Example 5]
In Example 5, an optical filter having a substrate made of a transparent glass substrate having a transparent resin layer containing the compound (S) and the compound (A) on one surface was prepared by the following procedure and conditions.

A transparent glass substrate “OA-10G (thickness: 200 μm)” (manufactured by NEC Corporation) cut into a size of 60 mm in length and 60 mm in width was coated with a resin composition (3) having the following composition by a spin coater, The mixture was heated on a hot plate at 80 ° C. for 2 minutes to remove the solvent by volatilization. At this time, the application conditions of the spin coater were adjusted so that the thickness after drying was 2 μm. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) is performed using a conveyor-type exposure machine to cure the resin composition (3) and to have a transparent resin layer containing the compound (S) and the compound (A). A substrate made of a transparent glass substrate was obtained. The spectral transmittance of the substrate was measured, and (Ta), (Tb) and (Xc) were determined. Table 5 shows the results.

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

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

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

[Comparative Example 1]
A substrate and an optical filter were prepared in the same manner as in Example 1 except that the compound (S) and the compound (A) were not used. Table 5 shows the optical characteristics of the obtained substrate and optical filter.

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

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

The constitution of the base material and various compounds applied in the examples and comparative examples are as follows.
<Form of base material>
Form (1): Transparent resin substrate containing compound (S) and compound (A) Form (2): Transparent resin substrate containing compound (S) and compound (A) having resin layers on both surfaces (3) ): Transparent resin layer containing compound (S) and compound (A) on both surfaces of resin substrate Form (4): Transparent resin layer containing compound (S) and compound (A) on one surface of glass substrate Form (5): Transparent resin substrate not containing compound (S) and compound (A) (Comparative Example)
Form (6): having a resin layer on both surfaces of a transparent resin substrate containing compound (A) (Comparative Example)
Form (7): glass substrate (comparative example)

<Transparent resin>
Resin A: cyclic olefin-based resin (resin synthesis example 1)
Resin B: aromatic polyether resin (resin synthesis example 2)
Resin C: polyimide resin (resin synthesis example 3)
Resin D: Cyclic olefin resin "Zeonor 1420R" (manufactured by Zeon Corporation)

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

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

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

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

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

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

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

1: Optical filter 2: Spectrophotometer 3: Light 4: Lens 5: Solid-state imaging device 6: Multiple reflection light 7: Reflection mirror 8: Dielectric multilayer film 9: Glass for evaporation monitor (back surface is treated with anti-reflection film)
10: Substrate (i)
11: first optical layer 12: second optical layer 13: third optical layer 14: fourth optical layer

Claims (8)

Having a substrate and a dielectric multilayer film on at least one surface of the substrate,
The substrate has a transparent resin layer containing a compound (A) having an absorption maximum at a wavelength of from 600 nm to less than 750 nm and a compound (S) having an absorption maximum at a wavelength of from 750 nm to 1050 nm, or A) having a transparent resin layer containing A) and a transparent resin layer containing the compound (S);
Satisfy the following requirement (a) ,
The compound (S) is a squarylium-based compound represented by the following formula (Z):
The optical filter, wherein the compound (A) is at least one compound selected from the group consisting of a squarylium-based compound, a phthalocyanine-based compound, and a cyanine-based compound.
(A) In the wavelength range of 800 to 1000 nm, the average value of the transmittance when measured from the vertical direction of the optical filter is 5% or less.

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

[In the formulas (I) and (II), a portion represented by a wavy line represents a binding site to the central four-membered ring,
X is independently oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ - represents,
R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -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 the following L ^a ~L ^e represents either, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms
(L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms
(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms
(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms
(L ^e ) a heterocyclic group having 3 to 14 carbon atoms
(L ^f ) an alkoxy group having 1 to 12 carbon atoms
(L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L;
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L
The substituent L is 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, or an aromatic hydrocarbon 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. ] The optical filter according to claim 1, further satisfying the following requirement (b):
(B) In the wavelength range of 430 to 580 nm, the average value of the transmittance measured from the vertical direction of the optical filter is 75% or more. The optical filter according to claim 1 or 2, characterized in that on both sides of the substrate having a dielectric multilayer film. The transparent resin is a cyclic (poly) olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, polysulfone resin , Polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester-curable resin , silsesquioxane-based ultraviolet curing resin, claim 1-3, characterized in that at least one resin selected from the group consisting of acrylic ultraviolet-curable resin and a vinyl-based UV-curable resin Item 2. The optical filter according to item 1. The optical filter according to any one of claims 1 to 4 , wherein the base material includes a transparent resin substrate containing the compound (A) and the compound (S). The optical filter according to any one of claims 1 to 5 , which is used for a solid-state imaging device. A solid-state imaging device including an optical filter according to any one of claims 1-5. Camera module comprising an optical filter according to any one of claims 1-5.

Images