JP6358114B2 - 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. Specifically, the present invention relates to an optical filter (two-wavelength bandpass filter) that selectively transmits visible light and part of near-infrared light, including a compound having specific absorption, and a solid-state imaging device and camera module using the optical filter. .

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

  As such a near-infrared cut filter, what was conventionally manufactured by various methods is used. For example, Patent Document 1 describes a near-infrared cut filter using a substrate made of a transparent resin and containing a near-infrared absorber in the transparent resin, and Patent Document 2 describes a glass containing copper ions. A near-infrared cut filter using a substrate is described.

  On the other hand, in recent years, an attempt has been made to provide a camera module with a sensing function such as motion capture using near infrared rays or distance recognition (space recognition). In such applications, it is necessary to selectively transmit visible light and part of near-infrared light. Therefore, it is impossible to use a near-infrared cut filter that uniformly blocks near-infrared light as in the prior art.

  As an optical filter that selectively transmits visible light and some near-infrared rays, Toa Riken Laboratories Co., Ltd. and Ceratech Japan Co., Ltd. sell filters with a dielectric multilayer film on a glass substrate. Yes.

JP-A-6-200113 Japanese Patent No. 5036229

  In an optical filter that is commercially available as an optical filter that selectively transmits visible light and part of near infrared light, the spectral characteristics change greatly when the light is incident obliquely. In particular, if the incident angle dependence of the optical filter is large on the short wavelength side of the near-infrared selective transmission band, the signal-to-noise ratio (S / N ratio) of near-infrared rays used for the sensing function during oblique incidence deteriorates, and the camera There is a problem that the image quality and particularly the color reproducibility at the edge of the image are adversely affected. FIG. 1 shows an example of a spectral transmission spectrum of a conventional two-wavelength bandpass filter. However, when the incident angle is 30 degrees, the near-infrared selective transmission band is significantly shifted by a short wavelength, and the wavelength that should originally be cut by light rays. It is confirmed that the transmittance in the region (near 750 to 800 nm in the example of this figure) becomes high. Therefore, the near-infrared selective transmission band has little dependency on the incident angle on the short wavelength side, and good near-infrared ray S / N ratio, camera image quality, selective transmission of visible rays and some near-infrared rays. The appearance of an optical filter that satisfies all of the above has been desired.

  An object of the present invention is to provide an optical filter having a function of selectively transmitting visible light and part of near-infrared light and having little incident angle dependence on the short wavelength side of the near-infrared selective transmission band, and the optical filter It is providing the apparatus using this.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that the substrate of the optical filter has a transparent resin layer containing a compound having a specific structure and a dielectric multilayer film, so that visible light and The present inventors have found that an optical filter having excellent near-infrared ray transmission characteristics and having a small incident angle dependency on the short wavelength side of the near-infrared selective transmission band can be obtained, and the present invention has been completed. Examples of embodiments of the present invention are shown below.

  [1] A substrate and a dielectric multilayer film on at least one surface of the substrate, and the substrate has a transparent resin layer containing a compound (S) represented by the following formula (S1) An optical filter that selectively transmits visible light and some near infrared rays.

式（Ｓ１）中、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、−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 formula (S1), X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or —NR ⁸ —.
R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a —NR ^g R ^h group, a —SO ₂ R ⁱ group, or —OSO. It represents either ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h each independently represents a hydrogen atom, one of the -C (O) R ⁱ groups or the following L ^a ~L ^e , R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon the number 6 to 14 aromatic hydrocarbon group (L ^e) carbon atoms, which may have a number Hajime Tamaki 3 to 14 (L ^f) an alkoxy group having 1 to 12 carbon atoms (L ^g) substituents L carbon 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms that may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms.

  [2] The optical filter according to item [1], wherein the compound (S) has an absorption maximum at a wavelength of 750 nm to 850 nm.

  [3] The optical according to item [1] or [2], wherein the transparent resin layer contains, in addition to the compound (S), a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm. filter.

  [4] 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 resin Item [1] to [3], which is at least one resin selected from the group consisting of a curable resin, a silsesquioxane ultraviolet curable resin, an acrylic ultraviolet curable resin, and a vinyl ultraviolet curable resin. The optical filter according to any one of the above.

[5] The optical filter according to any one of [1] to [4], wherein the base material includes a transparent resin substrate containing the compound (S).
[6] The optical filter according to any one of items [1] to [5], which is for a solid-state imaging device.
[7] A solid-state imaging device comprising the optical filter according to any one of items [1] to [5].
[8] A camera module comprising the optical filter according to any one of items [1] to [5].

  According to the present invention, it is possible to provide an optical filter that is excellent in transmission characteristics of visible light and part of near-infrared light and has little incident angle dependency on the short wavelength side of the near-infrared selective transmission band.

FIG. 1 shows an example of a spectral transmission spectrum of a conventional two-wavelength bandpass filter. FIG. 2A is a schematic diagram illustrating a method for 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. 3 is a spectral transmission spectrum of the substrate obtained in Example 1. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG. 5 is a spectral transmission spectrum of the substrate obtained in Example 2. FIG. 6 is a spectral transmission spectrum of the optical filter obtained in Example 2. FIG. 7 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 1. FIG. 8 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 2.

Hereinafter, the present invention will be specifically described.
[Optical filter]
The optical filter of the present invention has a base material (i) having a transparent resin layer containing a specific compound (S) described later, and a dielectric multilayer film, and selectively transmits visible light and some near infrared rays. It is a filter that allows transmission. Thus, since the optical filter of the present invention uses the transparent resin layer containing the compound (S) and the dielectric multilayer film in combination, it has excellent transmittance characteristics and is incident on the short wavelength side of the near-infrared selective transmission band. It is an optical filter with little angular dependence.

  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, particularly preferably. 85% or more. When the average transmittance is within this range in this wavelength region, excellent imaging sensitivity can be achieved when the optical filter of the present invention is used as a solid-state imaging device.

  The optical filter of the present invention has a light blocking band Za, a light transmitting band Zb, and a light blocking band Zc in a region having a wavelength of 650 nm or more. However, the wavelength of each band is Za <Zb <Zc. In “Za <Zb <Zc”, the center wavelength of each band satisfies this equation.

  Za is the longest, with the transmittance measured from the vertical direction of the optical filter at a wavelength of 650 nm or more and 900 nm or less, from the shortest wavelength Za1 that is more than 20% to 20% or less, and from less than 20% to 20% or more. It refers to the wavelength band up to the wavelength Za2.

  Zb is from 40% to 40% from the shortest wave length Zb1 at which the transmittance when measured from the vertical direction of the optical filter at wavelengths of 750 nm to 1050 nm is from 40% to 40%. It refers to the wavelength band up to the longest wavelength Zb2.

  Zc refers to the wavelength band from the shortest wavelength Zc1 at which the transmittance when measured from the vertical direction of the optical filter at a wavelength of 820 nm or more is more than 20% to 20% or less to the wavelength Zc2 that is Zc1 + 200 nm.

  When the optical filter of the present invention is used for a solid-state imaging device having a near-infrared sensing function, the maximum transmittance of the light ray (near-infrared) transmission band Zb is preferably higher, and the minimum transmission of the light-rejection bands Za and Zc. A lower rate is preferred. In such a case, it is possible to achieve excellent near-infrared sensing performance, and it is possible to effectively cut off light beams having unnecessary wavelengths, and to improve the color reproducibility of the camera image.

  The maximum transmittance when measured from the vertical direction of the optical filter in the light transmission band Zb is preferably 55% or more, more preferably 57% or more, still more preferably 60% or more, and particularly preferably 63% or more. The minimum transmittance when measured from the vertical direction of the optical filter in the light blocking zones Za and Zc is preferably 15% or less, more preferably 10% or less, still more preferably 8% or less, and particularly preferably 5% or less. . When the maximum transmittance in Zb and the minimum transmittance in Za and Zc are in the above ranges, a camera image with low noise and excellent color reproducibility can be obtained while achieving high near-infrared sensing performance.

  The width of the light transmission band Zb is defined by the difference Xb−Xa between the wavelength value (Xa) on the shortest wavelength side and the wavelength value (Xb) on the longest wavelength side that has a transmittance of 50% among the Zb. The value of Xb-Xa is preferably 5 to 150 nm, more preferably 10 to 140 nm, and particularly preferably 15 to 130 nm. The value of the central wavelength Y of Zb represented by Y = (Xa + Xb) / 2 is preferably 750 to 950 nm, more preferably 760 to 940 nm, still more preferably 770 to 930 nm, and particularly preferably 780 to 920 nm. . If the values of Xb-Xa and Y are in this range, an optical filter that is superior in near-infrared sensing sensitivity and color reproducibility of the camera image can be obtained.

  The optical filter of the present invention is the wavelength value on the shortest wavelength side where the transmittance is 50% in the band corresponding to Zb in the transmittance curve measured from an angle of 30 ° with respect to the vertical direction of the optical filter. The absolute value | Xa−Xa ′ | of the difference between (Xa ′) and Xa is preferably less than 30 nm, more preferably less than 25 nm, and particularly preferably less than 20 nm. When the value of | Xa−Xa ′ | is within this range, it is possible to obtain an optical filter having a small incident angle dependency of spectral characteristics, and when the optical filter is used for a camera module having a sensing function. Even when light is incident on the filter obliquely, a good near infrared S / N ratio and camera image quality can be achieved at the same time. Such an optical filter can be obtained by forming a dielectric multilayer film on the substrate (i) so as to selectively transmit visible light and part of near infrared light.

  The optical filter of the present invention has an average transmittance of 60% or more, more preferably 65% or more, and particularly preferably 70% when measured from the vertical direction in the wavelength range of Y-10 nm to Y + 10 nm. That's it. A filter having such transmission characteristics can achieve high light transmission characteristics in the visible region and the target near-infrared region, and can achieve both a camera function and a near-infrared sensing function at a good level.

  The optical filter of the present invention has the shortest wavelength value (Xd) 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 the vertical direction of the optical filter. It is preferable that the absolute value of the difference from the wavelength value (Xe) at which the transmittance when measured from an angle of 30 ° is 50% is small. The absolute value of the difference between (Xd) and (Xe) is preferably less than 25 nm, more preferably less than 15 nm, and particularly preferably less than 10 nm. Such an optical filter can be obtained by forming a dielectric multilayer film on the substrate (i) so as to selectively transmit visible light and part of near infrared light.

  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, it can be thinned.

  The thickness of the optical filter of the present invention is preferably, 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, and the lower limit is not particularly limited, but for example, 20 μm It is desirable to be.

[Base material (i)]
The base material (i) may be a single layer or a multilayer, and may have a transparent resin layer containing at least one compound (S) as a near infrared absorber. When the base material (i) is a single layer, for example, a base material made of a transparent resin substrate (ii) containing the compound (S) can be mentioned, and this transparent resin substrate (ii) is the transparent resin layer. It becomes. In the case of a multilayer, for example, a support such as a glass support or a base resin support or an overcoat layer made of a curable resin containing the compound (S) on the transparent resin substrate (ii) Examples include a substrate on which a transparent resin layer is laminated, and a substrate on which a resin layer such as an overcoat layer made of a curable resin is laminated on a transparent resin substrate (ii) containing the compound (S). . From the standpoints of manufacturing cost and ease of optical property adjustment, and further the achievement of scratch-removing effect of the resin support and the transparent resin substrate (ii) and the improvement of scratch resistance of the substrate (i), the compound (S A substrate in which a resin layer such as an overcoat layer made of a curable resin is laminated on a transparent resin substrate (ii) containing) is particularly preferable.

Hereinafter, the layer containing the compound (S) and the transparent resin is also referred to as “transparent resin layer”, and the other resin layers are also simply referred to as “resin layers”.
In the region of a wavelength of 750 nm or more, the lowest transmittance (Tb) 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.

  The shortest wavelength (Xf) at which the transmittance measured from the vertical direction of the substrate (i) in the region of a wavelength of 750 nm or more is less than 50% to 50% or more is preferably 770 to 900 nm, more preferably 775 to 890 nm. Especially preferably, it is 780-880 nm.

  If (Tb) and (Xf) of the base material (i) are in such a range, unnecessary near infrared rays near the near infrared selective transmission band can be selectively and efficiently cut, and the sensing near infrared S S The / N ratio can be improved, and when the dielectric multilayer film is formed on the substrate (i), the incident angle dependency of the optical characteristics on the short wavelength side of the near infrared selective transmission band can be reduced.

  In the region of wavelength 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 substrate (i) in the wavelength region of 600 nm or more is from 50% to 50% is preferably 610 to 670 nm, more preferably 620 to 665 nm. Especially preferably, it is 630-660 nm.

  If (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, it is possible to reduce the incident angle dependency of the optical characteristics in the vicinity of the visible wavelength to the near infrared wavelength region.

  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 can be achieved in the visible range and the target near-infrared range, and both the camera function and the near-infrared sensing function can be achieved at a good level.

  The thickness of the base material (i) can be appropriately selected according to a desired application, and is not particularly limited. However, it is desirable and preferably selected appropriately so as to reduce the incident angle dependency of the obtained optical filter. Is 10 to 200 μm, more preferably 20 to 180 μm, and particularly preferably 30 to 150 μm.

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

In addition to the compound (S), the substrate (i) may further contain a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm.
When the compound (A) and the compound (S) are used in combination, these compounds may be contained in the same layer or in different layers. When they are contained in the same layer, for example, the compound (A) and the compound (S) are both contained in the same transparent resin substrate (ii) and on a support such as a glass support. (A) and the base material with which the transparent resin layer containing compound (S) is laminated | stacked can be mentioned, When it is contained in a separate layer, for example, the substrate made of transparent resin containing compound (A) (Ii) A base material on which a transparent resin layer containing the compound (S) is laminated, or a transparent resin layer containing the compound (A) on the transparent resin substrate (ii) containing the compound (S) Can be mentioned.

  The compound (A) and the compound (S) are more preferably contained in the same layer. In such a case, the compound (A) and the compound (S) are more contained than in the case where they are contained in separate layers. It becomes easier to control the content ratio.

<Compound (S)>
The compound (S) is a squarylium compound represented by the following formula (S1). By using such a compound (S), sharp absorption near the absorption maximum and high visible light transmittance can be achieved simultaneously. Furthermore, many organic dyes usually generate fluorescence. However, as a result of extensive studies by the applicant, it has been found that the compound (S) can suppress the fluorescence intensity extremely low. Therefore, when the optical filter of the present invention having a transparent resin layer containing the compound (S) is used in a camera module having a near-infrared sensing function, malfunction of the sensing function due to dye fluorescence can be prevented.

式（Ｓ１）中、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、−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のいずれかを表す。
（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 formula (S1), X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or —NR ⁸ —.
R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a —NR ^g R ^h group, a —SO ₂ R ⁱ group, or —OSO. It represents either ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h each independently represents a hydrogen atom, one of the -C (O) R ⁱ groups or the following L ^a ~L ^e , R ⁱ represents any of the following L ^a ~L ^e.
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon the number 6 to 14 aromatic hydrocarbon group (L ^e) carbon atoms, which may have a number Hajime Tamaki 3 to 14 (L ^f) an alkoxy group having 1 to 12 carbon atoms (L ^g) substituents L carbon 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms that may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms.

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

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

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

X is preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.
The compound (S) can also represent the structure 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 structure description method, and both represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium compound is represented by a description method such as the following formula (S1).

さらに、例えば、下記式（Ｓ１）で表される化合物と下記式（Ｓ３）で表される化合物は、同一の化合物であると見なすことができる。

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

化合物（Ｓ）は、前記式（Ｓ１）の要件を満たせば特に構造は限定されない。中央の四員環に結合している左右の置換基は同一であっても異なっていてもよいが、同一であった方が合成上容易であるため好ましい。化合物（Ｓ）の具体例としては、下記表１に記載の化合物（ｓ−１）〜（ｓ−３０）を挙げることができる。

The structure of the compound (S) is not particularly limited as long as it satisfies the requirement of the formula (S1). The left and right substituents bonded to the central four-membered ring may be the same or different, but it is preferable that they are the same because synthesis is easier. Specific examples of the compound (S) include compounds (s-1) to (s-30) described in Table 1 below.

  The absorption maximum wavelength of the compound (S) is preferably from 750 nm to 850 nm, more preferably from 755 nm to 845 nm, still more preferably from 760 nm to 840 nm, particularly preferably from 765 nm to 835 nm. When the absorption maximum wavelength of the compound (S) is in such a range, unnecessary near infrared rays in the vicinity of the near infrared selective transmission band can be selectively and 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, etc. Can be synthesized with reference to the method described in the above.

  The content of the compound (S) is, for example, a substrate made of a transparent resin substrate (ii) containing the compound (S) or a transparent resin substrate containing the compound (S) as the substrate (i). (Ii) When using a substrate on which a resin layer such as an overcoat layer made of a curable resin or the like is laminated, preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the transparent resin. , More preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. As the base material (i), a compound is used as a glass support or a resin support as a base. In the case of using a base material on which a transparent resin layer such as an overcoat layer made of a curable resin containing (S) is used, with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (S) And preferably 0.1 to 5.0 parts by weight, more preferably 0. 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 and transmission characteristics and high visible light transmittance can be obtained.

<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. More preferably, it is at least one selected from the above, more preferably contains a squarylium compound, more preferably contains at least one squarylium compound and another compound (A), and other compound (A). Particularly preferred are phthalocyanine compounds and cyanine compounds.

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

  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. When the base material (i) contains the compound (A) in addition to the compound (S), the dependence on the incident angle in the visible region is reduced in addition to the short wavelength side of the near-infrared selective transmission band when an optical filter is used. This makes it easier to reduce the absolute value of the difference between the above (Xd) and (Xe).

  The content of the compound (A) is, for example, a substrate made of a transparent resin substrate (ii) containing the compound (A) or a transparent resin substrate containing the compound (S) as the substrate (i). (Ii) When using a substrate on which a resin layer such as an overcoat layer made of a curable resin or the like is laminated, preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the transparent resin. , More preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. As the base material (i), a compound is used as a glass support or a resin support as a base. In the case of using a substrate on which a transparent resin layer such as an overcoat layer made of a curable resin containing (S) is used, with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A) And preferably 0.1 to 5.0 parts by weight, more preferably 0. To 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight.

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

  Other dyes (X) are not particularly limited as long as the absorption maximum wavelength is less than 650 nm or more than 850 nm. For example, squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds And at least one compound selected from the group consisting of a porphyrin compound and a metal dithiolate compound. Depending on the absorption characteristics of the compound (S) and the target near-infrared transmission wavelength, the long wavelength of the near-infrared transmission band in addition to the visible wavelength range can be obtained by using the compound (S) in combination with the other dye (X). Also on the side, the dependency on the incident angle can be reduced, and good infrared sensing performance can be achieved.

  The content of the other dye (X) is, for example, a base material made of a transparent resin substrate (ii) containing the other dye (X) or the other dye (X) as the base material (i). In the case of using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on the transparent resin substrate (ii) to be contained, it is preferably 0.01 to 100 parts by weight of the transparent resin To 1.5 parts by weight, more preferably 0.02 to 1.0 parts by weight, particularly preferably 0.03 to 0.7 parts by weight, and serves as a glass support or base as the substrate (i). When using a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin or the like is laminated on a resin support, a transparent resin layer containing the other dye (X) Is preferably 0.1-4. Parts by weight, more preferably 0.2 to 3.0 parts by weight, particularly preferably 0.3 to 2.0 parts by weight. When the content of the other dye (X) is within the above range, both good near-infrared absorption characteristics and high visible light transmittance can be achieved.

<Transparent resin>
The transparent resin layer and the transparent resin substrate (ii) to be laminated on a resin support or glass support can be formed using a transparent resin. As transparent resin used for the said base material (i), 1 type may be individual and 2 or more types may be sufficient.

  The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, it ensures thermal stability and moldability to a film, and dielectrics are formed by high-temperature deposition performed at a deposition temperature of 100 ° C. or higher. In order to use as a base material which can form a body multilayer film, the resin whose glass transition temperature (Tg) becomes like this. Preferably it is 110-380 degreeC, More preferably, it is 110-370 degreeC, More preferably, it is 120-360 degreeC. Moreover, it is especially preferable that the glass transition temperature of the resin is 140 ° C. or higher because a film (transparent resin layer and transparent resin substrate (ii)) on which the dielectric multilayer film can be deposited at a higher temperature can be obtained. Specifically, Tg can be measured by the method described in the Examples below.

  As the transparent resin, when a resin support made of the resin and having a thickness of 0.1 mm is formed, the total light transmittance (JIS K7375) of the resin support is preferably 75% or more, more preferably Resins that can be 78% or more, particularly preferably 80% or more can be used. If a resin having a total light transmittance in such a range is used, the obtained base material (i) exhibits good transparency as an optical film.

  When a solvent-soluble resin is used as the transparent resin, the polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000, Preferably it is 30,000-250,000, and a number average molecular weight (Mn) is 10,000-150,000 normally, Preferably it is 20,000-100,000. Specifically, Mw and Mn can be measured by the methods described in the following examples.

  Examples of transparent resins include cyclic (poly) olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, and polyarylate resins. Resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins Examples thereof include resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins.

≪Cyclic (poly) olefin resin≫
The cyclic (poly) olefin resin is 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 are preferred.

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

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

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

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

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

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

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

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。

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

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

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

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

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

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

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

<Other ingredients>
The base material (i) may further contain additives such as an antioxidant, a near-ultraviolet absorber, a fluorescence quencher, and a metal complex compound as long as the effects of the present invention are not impaired. Moreover, when manufacturing base material (i) by the cast molding mentioned later, manufacture of base material (i) can be made easy by adding a leveling agent and an antifoamer. These other components may be used alone or in combination of two or more.

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

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

<Method for producing substrate (i)>
When the base material (i) is a base material including a transparent resin substrate (ii) containing the compound (S), the transparent resin substrate (ii) is formed by, for example, melt molding or cast molding. In addition, if necessary, a substrate on which an overcoat layer is laminated can be produced by coating a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding. .

  Transparent resin layer such as an overcoat layer in which the base material (i) is a glass support, a resin support as a base, or a curable resin containing the compound (S) on a transparent resin substrate (ii) Is a laminated substrate, for example, by melt-molding or cast-molding a resin solution containing the compound (S) on a glass support or base resin support or transparent resin substrate (ii), Preferably, the solvent is dried and removed after coating by a method such as spin coating, slit coating, and ink jet, and if necessary, further irradiation with light or heating is performed, whereby a glass support or a resin support as a base or A base material having a transparent resin layer formed on a transparent resin substrate (ii) can be produced.

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

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

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

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

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

  The amount of residual solvent in the transparent resin layer (transparent resin substrate (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 0.8% by weight with respect to the weight of the transparent resin layer (transparent resin substrate (ii)). 5% by weight or less. When the amount of residual solvent is in the above range, a transparent resin layer (transparent resin substrate (ii)) that can easily exhibit a desired function is obtained, in which deformation and characteristics are hardly changed.

[Dielectric multilayer film]
The dielectric multilayer film constituting the optical filter of the present invention is a film having the ability to cut unnecessary near infrared rays by reflection and transmit the necessary near infrared rays. In the present invention, the dielectric multilayer film may be provided on one side of the substrate (i) or on both sides. When it is provided on one side, it is excellent in production cost and manufacturability, and when it is provided on both sides, an optical filter having high strength and less warpage can be obtained.

  When the optical filter of the present invention is applied to uses such as a solid-state imaging device, it is preferable that the warp of the optical filter is smaller. Therefore, it is preferable to provide the dielectric multilayer film on both surfaces of the substrate (i). The dielectric multilayer films may have the same or different spectral characteristics. When the spectral characteristics of the dielectric multilayer films provided on both surfaces are the same, the transmittance of the light blocking zones Za and Zc can be efficiently reduced in the near-infrared wavelength region, and the spectral characteristics of the dielectric multilayer films provided on both surfaces. When the values are different, there is a tendency that the light blocking band Zc can be easily extended to the longer wavelength side.

  Examples of the dielectric multilayer film include those in which high refractive index material layers and low refractive index material layers are alternately stacked. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as the main components, and titanium oxide, tin oxide, and / or Or what contains a small amount (for example, 0-10 weight% with respect to a main component) of cerium oxide etc. is mentioned.

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

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

  The physical film thickness of each of the high-refractive index material layer and the low-refractive index material layer is preferably 5 to 500 nm, although it depends on the refractive index of each layer, and is the total physical film thickness of the dielectric multilayer film. The value is preferably 1.0 to 8.0 μm for the entire optical filter.

  The total number of stacked 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. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and the warpage of the optical filter and cracks in the dielectric multilayer film can be reduced. can do.

  In the present invention, the material type constituting the high-refractive index material layer and the low-refractive index material layer, the thickness of each layer of the high-refractive index material layer and the low-refractive index material layer, the order of stacking, and the number of stacks are appropriately selected. Thus, it is possible to obtain an optical filter having a light blocking band and a light transmission band of a desired wavelength in the near infrared wavelength range while ensuring a sufficient transmittance in the visible range.

  Here, in order to optimize the above conditions, for example, optical thin film design software (for example, Essential Macleod, manufactured by Thin Film Center) is used, and the transmittance in the wavelength range where light transmission is desired to be suppressed in the near-infrared wavelength range. The parameter may be set so as to increase the transmittance in the wavelength region where light is to be transmitted. For example, when a light transmission band is provided in the vicinity of 800 nm by a dielectric multilayer film formed on both surfaces, the above-described software is used, and the target transmittance of one dielectric multilayer film at a wavelength of 720 to 760 nm is 0%, 780 to 820 nm. The target transmittance of each wavelength region is set to 100%, the Target Tolerance value of each wavelength region is set to 0.5 or less, and the target transmittance of the other dielectric multilayer film at wavelengths of 780 to 820 nm is set to 100%. And a parameter setting method in which the target transmittance at 850 to 1100 nm is set to 0% and the Target Tolerance value of each wavelength region is set to 0.5 or less.

[Other functional membranes]
As long as the optical filter of the present invention does not impair the effects of the present invention, the optical filter between the substrate (i) and the dielectric multilayer film is on the side opposite to the surface on which the dielectric multilayer film of the substrate (i) is provided. On the surface or the surface opposite to the surface on which the substrate (i) of the dielectric multilayer film is provided, the surface hardness of the substrate (i) or the dielectric multilayer film is improved, the chemical resistance is improved, the antistatic A functional film such as an antireflection film, a hard coat film, or an antistatic film can be appropriately provided for the purpose of scratch removal.

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

  The method of laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melted in the base material (i) or the dielectric multilayer film as described above. Examples of the method include molding or cast molding.

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

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

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

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

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

These solvents may be used alone or in combination of two or more.
The thickness of the functional film is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 0.7 to 5 μm.

  Further, for the purpose of improving 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 Surface treatment such as corona treatment or plasma treatment may be applied to the surface of the multilayer film.

[Use of optical filter]
The optical filter of the present invention has a wide viewing angle and can selectively transmit visible light and some near infrared rays. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS image sensor having both a camera function and a near-infrared sensing function. Especially digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automotive cameras, night vision cameras, motion capture, laser rangefinders, virtual fittings, license plates It is useful for recognition devices, televisions, car navigation systems, portable information terminals, video game machines, portable game machines, fingerprint authentication systems, digital music players, and the like.

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

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

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

  (A) Weight of standard polystyrene conversion using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS Average molecular weight (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 type, column: TSKgel α-M, developing solvent: tetrahydrofuran) manufactured by Tosoh Corporation. .
In addition, about the resin synthesize | combined in the resin synthesis example 3 mentioned later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the said method.

(C) A part of the polyimide resin solution was put into anhydrous methanol to precipitate a polyimide resin, and filtered to separate unreacted monomers. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. 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 Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.

<Spectral transmittance>
(Ta), (Xc), (Tb) and (Xf) of the substrate, and transmittance in each wavelength region of the optical filter, (Xa), (Xb), (Xd), (Xe) and (Xa ′) ) Was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

  Here, with respect to the transmittance when measured from the vertical direction of the optical filter, the light transmitted perpendicularly to the filter was measured as shown in FIG. In addition, with respect to the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter, light transmitted at an angle of 30 ° with respect to the vertical direction of the filter was measured as shown in FIG.

  This transmittance is measured using the spectrophotometer under the condition that light is perpendicularly incident on the substrate and the filter, except when measuring (Xa ′) and (Xe). . In the case of measuring (Xa ') and (Xe), the measurement is performed 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]
The compound (S) and the compound (A) used in the following examples can be synthesized by a generally known method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475. Publication, Japanese Patent No. 3094037, Japanese Patent No. 3703869, Japanese Patent Application Laid-Open No. 60-228448, Japanese Patent Application Laid-Open No. 1-146846, Japanese Patent Application Laid-Open No. 1-281960, Japanese Patent No. 4081149, Japanese Patent Application Laid-Open No. Sho 63- No. 124054, “Phthalocyanine -Chemistry and Function” (IPC, 1997), JP 2007-169315, JP 2009-108267, JP 2010-241873, JP 3699464, It can be synthesized by referring to the method described in Japanese Patent No. 4740631. Yes.

<Resin synthesis example 1>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] 100 parts of dodec-3-ene, 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel, and this solution was heated to 80 ° C. Heated. Next, 0.2 parts of a toluene solution of triethylaluminum (concentration 0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) 0 as a polymerization catalyst were added to the solution in the reaction vessel. .9 parts was added and the solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

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-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin 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, 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean Stark tube and a cooling tube were attached to the four-necked flask. Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum-dried overnight at 60 ° C. 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>
To a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, a Dean-Stark tube and a condenser tube, was added 1,4-bis (4-amino-α, α under a nitrogen stream. -Dimethylbenzyl) benzene (27.66 g, 0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl (7.38 g, 0.02 mol) were added, and γ-butyrolactone (68.65 g) and N, It was dissolved in 17.16 g of N-dimethylacetamide. The resulting solution was 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 As a result, 0.50 g (0.005 mol) of triethylamine was added all at once. After completion of the addition, the temperature was raised to 180 ° C. and refluxed for 6 hours while distilling off the distillate as needed. After refluxing for 6 hours, it was air-cooled until the internal temperature reached 100 ° C., diluted by adding 143.6 g of DMAc, and cooled with stirring to obtain 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight. . A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and dried in a vacuum dryer 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 a logarithmic viscosity of 0.87.

[Example 1]
In Example 1, an optical filter having a base material 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, 0.03 part of compound (s-5) (absorption maximum wavelength in dichloromethane of 770 nm) described in Table 1 above as compound (S), and methylene chloride Was added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a base material composed 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), (Xc), and (Xf) were obtained. The results are shown in FIG.

Subsequently, the dielectric multilayer film (I) is formed on one surface of the obtained base material, and the dielectric multilayer film (II) is further formed on the other surface of the base material, so that the optical thickness is about 0.104 mm. A filter 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 24 layers). The dielectric multilayer film (II) is formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100 ° C. (18 layers in total). In both of the dielectric multilayer films (I) and (II), the silica layer and the titania layer are in 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 outermost layer of the optical filter was a silica layer.

The dielectric multilayer films (I) and (II) were designed as follows.
Regarding the thickness and the number of layers, the wavelength dependence characteristics of the refractive index of the base material and the absorption characteristics of the applied compound (S) so as to achieve an antireflection effect in the visible range and selective transmission / reflection performance in the near infrared range. Was optimized using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When performing optimization, in this example, the input parameters (Target values) to the software are as shown in Table 2 below.

  As a result of the optimization of the film configuration, in Example 1, the dielectric multilayer film (I) was formed by alternately laminating a silica layer having a film thickness of 13 to 174 nm and a titania layer having a film thickness of 9 to 200 nm. The dielectric multi-layer film (II) is a multi-layer vapor-deposited film having 18 layers, in which a silica layer having a film thickness of 41 to 198 nm and a titania layer having a film thickness of 12 to 122 nm are alternately stacked. It was. Table 3 shows an example of the optimized film configuration.

  The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. The average transmittance at wavelengths of 430 to 580 nm is 90%, Xa is 826 nm, Xb is 902 nm, Y is 864 nm, the average transmittance is 89% in the wavelength range of wavelengths Y-10 nm to Y + 10 nm, and the absolute value | Xa−Xa ′ | Was 20 nm, and the absolute value | Xd−Xe | was 25 nm.

[Example 2]
In Example 1, 0.03 part of compound (s-11) (absorption maximum wavelength 776 nm in dichloromethane) described in Table 1 above was used instead of 0.03 part of compound (s-5), and As a compound (A), 0.03 part of a compound (a-1) represented by the following formula (a-1) (absorption maximum wavelength 698 nm in dichloromethane) and a compound represented by the following formula (a-2) ( a-2) Transparent resin substrate containing compound (S) and compound (A) under the same procedure and conditions as in Example 1 except that 0.03 part (absorption maximum wavelength in dichloromethane: 733 nm) was used A substrate consisting of The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in FIG.

続いて、実施例１と同様に、得られた基材の片面にシリカ（ＳｉＯ₂）層とチタニア（ＴｉＯ₂）層とが交互に積層されてなる（合計２４層）誘電体多層膜（ＩＩＩ）を形成し、さらに基材のもう一方の面にシリカ（ＳｉＯ₂）層とチタニア（ＴｉＯ₂）層とが交互に積層されてなる（合計１８層）誘電体多層膜（ＩＶ）を形成し、厚さ約０．１０４ｍｍの光学フィルターを得た。誘電体多層膜の設計は、基材屈折率の波長依存性を考慮した上で、下記表４のような設計パラメーターを用いて行った。

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on one side of the obtained substrate (24 layers in total). And a dielectric multilayer film (IV) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on the other surface of the substrate (18 layers in total). An optical filter having a thickness of about 0.104 mm was obtained. The dielectric multilayer film was designed using design parameters as shown in Table 4 below in consideration of the wavelength dependence of the base material refractive index.

  As a result of the optimization of the film configuration, in Example 2, the dielectric multilayer film (III) is formed by alternately laminating a silica layer having a film thickness of 27 to 198 nm and a titania layer having a film thickness of 10 to 121 nm. The dielectric multilayer film (IV) is a multilayer deposited film having 18 layers, in which a silica layer having a film thickness of 41 to 198 nm and a titania layer having a film thickness of 12 to 122 nm are alternately stacked. It was. Table 5 shows an example of the optimized film configuration.

  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.

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

  In Example 1, 0.03 part of compound (s-14) (absorption maximum wavelength 795 nm in dichloromethane) described in Table 1 above was used instead of 0.03 part of compound (s-5). A transparent resin substrate containing the compound (S) was obtained by the same procedure and conditions as in Example 1.

A resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (S) was obtained. . The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.

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, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (VI) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on the other surface of the substrate (18 layers in total). An optical filter having a thickness of about 0.108 mm was obtained. 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 as in Example 1. The spectral transmittance of this optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.

[Example 4]
In Example 3, in place of 0.03 part of compound (s-14), 0.01 part of compound (s-5) described in Table 1 above and compound (s-21) described in Table 1 above (in dichloromethane) The base material which has a resin layer on both surfaces of the transparent resin board | substrate containing a compound (S) in the same procedure and conditions as Example 3 except having used 0.02 part of absorption maximum wavelength in 782 nm. . The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (VIII) formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (18 layers in total) on the other surface of the substrate. An optical filter having a thickness of about 0.108 mm was obtained. 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 as in Example 1. The spectral transmittance of this optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.

[Example 5]
In Example 3, 0.04 part of the compound (s-11) described in Table 1 above was used instead of 0.03 part of the compound (s-14), and the following formula was used as the compound (A). 0.02 part of compound (a-3) represented by (a-3) (maximum absorption wavelength 703 nm in dichloromethane) and compound (a-4) represented by the following formula (a-4) (in dichloromethane) Except that 0.06 part of absorption maximum wavelength (736 nm) was used, a base material having resin layers on both surfaces of a transparent resin substrate containing the compound (S) was obtained in the same procedure and conditions as in Example 3. The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.

続いて、実施例１と同様に、得られた基材の片面にシリカ（ＳｉＯ₂）層とチタニア（ＴｉＯ₂）層とが交互に積層されてなる（合計２４層）誘電体多層膜（ＩＸ）を形成し、さらに基材のもう一方の面にシリカ（ＳｉＯ₂）層とチタニア（ＴｉＯ₂）層とが交互に積層されてなる（合計１８層）誘電体多層膜（Ｘ）を形成し、厚さ約０．１０８ｍｍの光学フィルターを得た。誘電体多層膜の設計は、実施例１と同様に基材屈折率の波長依存性等を考慮した上で、実施例２と同じ設計パラメーターを用いて行った。この光学フィルターの分光透過率を測定し、各波長領域における光学特性を評価した。結果を表７に示す。

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (X) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on the other surface of the substrate (18 layers in total). An optical filter having a thickness of about 0.108 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 2 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. The results are shown in Table 7.

[Example 6]
In Example 6, an optical filter having a base material composed of a resin substrate having a transparent resin layer containing the compound (S) on both surfaces was prepared according to the following procedure and conditions.

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

A resin layer made of the resin composition (2) having the following composition is formed on both surfaces of the obtained resin substrate in the same manner as in Example 2, and the resin substrate having a transparent resin layer containing the compound (S) on both surfaces. A base material was obtained. The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.
Resin composition (2): 100 parts by weight of tricyclodecane dimethanol acrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.75 part by weight of compound (s-5), 0.75 part by weight of compound (a-2) , 0.75 parts by weight of compound (a-3), methyl ethyl ketone (solvent, TSC: 25%)

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (XII) in which silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated (18 layers in total) on the other surface of the substrate. An optical filter having a thickness of about 0.110 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 2 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.

[Example 7]
In Example 7, an optical filter having a base material composed of a transparent glass substrate having a transparent resin layer containing the compound (S) on one side was prepared by the following procedure and conditions.

On a transparent glass substrate “OA-10G (thickness 200 μm)” (manufactured by Nippon Electric Glass Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width, a resin composition (3) having the following composition was applied by a spin coater, The solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes. Under the present circumstances, the application | coating conditions of the spin coater were adjusted so that the thickness after drying might be set to 2 micrometers. Next, it exposes (exposure amount 500mJ / cm < ² >, 200mW) using a conveyor type exposure machine, hardens the resin composition (3), and consists of a transparent glass substrate which has a transparent resin layer containing a compound (S). A substrate was obtained. The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.

Resin composition (3): 20 parts by weight of tricyclodecane dimethanol acrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 1.5 parts by weight of compound (s-5), compound ( a-2) 1.5 parts by weight, compound (a-3) 1.5 parts by weight, methyl ethyl ketone (solvent, TSC: 35%)
Subsequently, similarly to Example 1, a dielectric multilayer film (XIII) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (XIV) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on the other surface of the substrate (18 layers in total). An optical filter having a thickness of about 0.110 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 2 in consideration of the wavelength dependence of the base material refractive index as in Example 1. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.

[Comparative Example 1]
In Example 1, a substrate was prepared in the same manner as in Example 1 except that the compound (S) was not used. Subsequently, as in Example 1, a dielectric multilayer film (XV) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on one side of the obtained base material (24 layers in total). And a dielectric multilayer film (XVI) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on the other surface of the substrate (18 layers in total). An optical filter having a thickness of about 0.106 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the base material refractive index. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

[Comparative Example 2]
In the same manner as in Example 1 except that near-infrared absorbing glass substrate “BS-6 (thickness 210 μm)” (manufactured by Matsunami Glass Industry Co., Ltd.) was used as the base material, silica (SiO ₂ ) Layer and titania (TiO ₂ ) layer are alternately laminated (24 layers in total) to form a dielectric multilayer film (XVII), and further, a silica (SiO ₂ ) layer and titania on the other surface of the substrate A dielectric multilayer film (XVIII) formed by alternately laminating (TiO ₂ ) layers (18 layers in total) was formed, and an optical filter having a thickness of about 0.216 mm was obtained. The dielectric multilayer film was designed using design parameters as shown in Table 6 below in consideration of the wavelength dependence of the base material refractive index. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

[Comparative Example 3]
In Example 1, 0.03 part of the compound (a-2) and 0.03 part of the compound (a-3) were used instead of the compound (S). Made the material. The spectral transmittance of the substrate was measured, and (Ta), (Tb), (Xc), and (Xf) were obtained. The results are shown in Table 7.

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on one side of the obtained base material (24 in total). Dielectric multilayer film (XIX) Further, a dielectric multilayer film (XXX) is formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers on the other surface of the substrate (18 layers in total), An optical filter having a thickness of about 0.106 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 2 in consideration of the wavelength dependence of the refractive index of the substrate. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.

[Comparative Example 4]
A silica (SiO ₂ ) layer on one side of the base material 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 the base material. And a titania (TiO ₂ ) layer are alternately laminated (a total of 24 layers) to form a dielectric multilayer film (XXI), and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) are formed on the other surface of the substrate. ₂ ) Dielectric multilayer film (XXII) was formed by alternately laminating layers (total 20 layers), and an optical filter having a thickness of about 0.206 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the base material refractive index. The spectral transmittance and reflectance of this optical filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 7.

[Examples 8 to 13]
A substrate and an optical filter were prepared in the same manner as in Example 5 except that the resin, the solvent, the drying conditions for the resin substrate, the compound (S), and the compound (A) were changed as shown in Table 7. Table 7 shows the optical properties of the obtained substrate and optical filter.

The configurations of the base materials and various compounds applied in the examples and comparative examples are as follows.
<Form of substrate>
Form (1): Transparent resin substrate containing compound (S) Form (2): Having resin layers on both sides of transparent resin substrate containing compound (S) Form (3): Compound (on both sides of resin substrate) Form (4): having a transparent resin layer containing compound (S) on one side of a glass substrate Form (5): transparent resin substrate containing no compound (S) (Comparison) Example)
Form (6): Near-infrared absorbing glass substrate (comparative example)
Form (7): Glass substrate (comparative example)
<Transparent resin>
Resin A: Cyclic olefin 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 Nippon Zeon Co., Ltd.)
<Glass substrate>
Glass substrate (1): Transparent glass substrate “OA-10G (thickness: 200 μm)” cut to 60 mm length and 60 mm width (manufactured by Nippon Electric Glass Co., Ltd.)
Glass substrate (2): Near-infrared absorbing glass substrate “BS-6 (thickness 210 μm)” cut to a size of 60 mm length and 60 mm width (manufactured by Matsunami Glass Industry Co., Ltd.)
<Compound (S)>
Compound (s-5): Compound (s-5) described in Table 1 above (absorption maximum wavelength in dichloromethane: 770 nm)
Compound (s-11): Compound (s-11) described in Table 1 above (absorption maximum wavelength in dichloromethane: 776 nm)
Compound (s-14): Compound (s-14) described in Table 1 above (absorption maximum wavelength in dichloromethane of 795 nm)
Compound (s-21): Compound (s-21) described in Table 1 above (absorption maximum wavelength in dichloromethane: 782 nm)
Compound (s-23): Compound (s-23) described in Table 1 above (absorption maximum wavelength in dichloromethane of 784 nm)
<Compound (A)>
Compound (a-1): The above compound (a-1) (maximum absorption wavelength 698 nm in dichloromethane)
Compound (a-2): Compound (a-2) above (absorption maximum wavelength in dichloromethane: 733 nm)
Compound (a-3): Compound (a-3) above (absorption maximum wavelength in dichloromethane: 703 nm)
Compound (a-4): Compound (a-4) above (absorption maximum wavelength 736 nm in dichloromethane)
<Solvent>
Solvent (1): Methylene chloride Solvent (2): N, N-dimethylacetamide Solvent (3): Cyclohexane / xylene (weight ratio: 7/3)

<Resin substrate drying conditions>
In Table 7, the (transparent) resin substrate drying conditions of Examples and Comparative Examples are as follows. In addition, the coating film was peeled from the glass plate before drying under reduced pressure.
Condition (1): 20 ° C./8 hr → under reduced pressure 100 ° C./8 hr
Condition (2): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 140 ° C./8 hr
Condition (3): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 100 ° C./24 hr

<Composition for resin layer formation>
The resin composition for forming the resin layer in the examples of Table 7 is as follows.
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, TSC: 30%)
Resin composition (2): Tricyclodecane dimethanol acrylate 100 parts by weight, 1-hydroxycyclohexyl phenyl ketone 4 parts by weight, (s-5) 0.75 parts by weight, compound (a-2) 0.75 parts by weight, 0.75 part by weight of compound (a-3), methyl ethyl ketone (solvent, TSC: 25%)
Resin composition (3): 20 parts by weight of tricyclodecane dimethanol acrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 1.5 parts by weight of (s-5), compound (a -2) 1.5 parts by weight, compound (a-3) 1.5 parts by weight, methyl ethyl ketone (solvent, TSC: 35%)

  The optical filter of the present invention includes a digital still camera, a smartphone camera, a mobile phone camera, a digital video camera, a wearable device camera, a PC camera, a surveillance camera, an automobile camera, a night vision camera, a motion capture, a laser rangefinder, It can be suitably used for virtual try-on, license plate recognition device, television, car navigation, portable information terminal, personal computer, video game machine, portable game machine, fingerprint authentication system, digital music player, and the like.

1: Optical filter 2: Spectrophotometer 3: Light

Claims (8)

A dielectric multilayer film on at least one surface of the substrate and the substrate;
An optical filter that selectively transmits visible light and part of near infrared light, wherein the substrate has a transparent resin layer containing a compound (S) represented by the following formula (S1).

[In the formula (S1), X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or —NR ⁸ —;
R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a —NR ^g R ^h group, a —SO ₂ R ⁱ group, or —OSO. It represents either ₂ R ⁱ group or a group represented by L ^a ~L ^h, R ^g and R ^h each independently represents a hydrogen atom, one of the -C (O) R ⁱ groups or the following L ^a ~L ^e , R ⁱ represents any of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon the number 6 to 14 aromatic hydrocarbon group (L ^e) carbon atoms, which may have a number Hajime Tamaki 3 to 14 (L ^f) an alkoxy group having 1 to 12 carbon atoms (L ^g) substituents L carbon 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms that may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, It is at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms. ]   The optical filter according to claim 1, wherein the compound (S) has an absorption maximum at a wavelength of 750 nm to 850 nm.   3. The optical filter according to claim 1, wherein the transparent resin layer contains a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm, in addition to the compound (S).   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 resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins The at least 1 sort (s) of resin selected from the group which consists of a silsesquioxane type | system | group ultraviolet curable resin, an acrylic type ultraviolet curable resin, and a vinyl type ultraviolet curable resin. Optical filter.   The optical filter according to claim 1, wherein the base material contains a transparent resin substrate containing the compound (S).   The optical filter according to claim 1, which is for a solid-state imaging device.   The solid-state imaging device which comprises the optical filter of any one of Claims 1-5.   A camera module comprising the optical filter according to claim 1.

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