WO2019167876A1

WO2019167876A1 - Optical filter and device using optical filter

Info

Publication number: WO2019167876A1
Application number: PCT/JP2019/007035
Authority: WO
Inventors: 武志茂木; 嘉彦安藤; 達郎三井; 勝也長屋
Original assignee: Jsr株式会社
Priority date: 2018-02-27
Filing date: 2019-02-25
Publication date: 2019-09-06
Also published as: TW201945179A; JPWO2019167876A1; KR20200125604A; CN111684320A; CN111684320B; JP7207395B2

Abstract

The present invention addresses the problem of providing an optical filter that is capable of suppressing the color shading and the ghosting in a camera image while exhibiting high light transmittance characteristics in the visible light wavelength region, and has a suitable heat resistance so that the optical characteristics thereof can be maintained even after long term exposure to a high temperature. The optical filter according to the present invention is characterized by having a base material that satisfies a requirement (a), and having a dielectric multi-layer formed on at least one side of the base material. (a): The base material includes a layer containing an organic pigment (S) that has an absorption maximum in a wavelength range between 900 nm and 1200 nm, inclusive.

Description

Optical filter and device using optical filter

The present invention relates to an optical filter and an apparatus using the optical filter. Specifically, the present invention relates to an optical filter containing an organic pigment having absorption in a specific wavelength region, and a solid-state imaging device and a camera module using the optical filter.

A solid-state imaging device such as a video camera, a digital still camera, or a mobile phone with a camera function uses a CCD or CMOS image sensor, which is a solid-state imaging device for color images. For these solid-state imaging devices, silicon photodiodes having sensitivity to near infrared rays that cannot be sensed by human eyes at the light receiving portion 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, those manufactured by various methods are conventionally used. For example, a near-infrared cut filter in which a transparent resin is used as a substrate and a near-infrared absorbing pigment is contained in the transparent resin is known (see, for example, Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not always have sufficient near-infrared absorption characteristics.

In the patent document 2, the present applicant uses a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength region, so that there is little change in optical characteristics even when the incident angle is changed, and A near-infrared cut filter having a high visible light transmittance is proposed. Patent Document 3 discloses a near-infrared ray that uses a phthalocyanine dye having a specific structure to achieve both a high visible light transmittance and a long absorption maximum wavelength, both of which are conventional problems. It is described that a cut filter can be obtained.

However, in the near-infrared cut filters described in Patent Documents 2 and 3, the applied base material has a sufficiently strong absorption band in the vicinity of 700 nm, but in the near-infrared wavelength region of, for example, 900 to 1200 nm. Has almost no absorption. Therefore, light in the near-infrared wavelength region is cut almost only by the reflection of the dielectric multilayer film, but with such a configuration, slight stray light due to internal reflection in the optical filter and reflection between the optical filter and the lens is generated. When shooting in a dark environment, it may cause ghost and flare. In particular, in recent years, there has been a strong demand for high-quality cameras even for mobile devices such as smartphones, and conventional optical filters may not be used favorably.

On the other hand, an infrared shielding filter as in Patent Document 4 has been proposed as an optical filter using a base material having a wide absorption in the near infrared wavelength region. In Patent Document 4, a broad absorption in the near-infrared wavelength region is achieved mainly by applying a compound having a dithiolene structure, but the absorption intensity near 700 nm is not sufficient. In particular, when the camera module is used under a high incident angle condition (for example, 45 degree incidence) accompanying a recent reduction in the height of the camera module, image degradation may occur due to color shading.

Further, Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass base material and a layer containing a near-infrared absorbing dye, but the color shading is sufficiently improved even with the configuration described in Patent Document 5. There was a case that could not be done. For example, FIG. 5 of Patent Document 5 shows an optical characteristic graph at 0 ° incidence and at 30 ° incidence, but the region of the skirt portion of the visible light transmission band (630 to 700 nm) even at 30 ° incidence. ) A large wavelength shift is observed.

In order to solve the above-mentioned problems, the present inventors have examined the use of a dye having an absorption maximum in the near-infrared wavelength region of 900 to 1200 nm for the optical filter. However, since such dyes often have absorption in the visible light region of 430 to 580 nm as well as in the near infrared wavelength region, it has been a problem to improve both the ghost and the visible light transmittance. In addition, the above dyes sometimes have a problem of deterioration in optical properties due to low heat resistance and UV resistance. Specifically, in the drying process for volatilizing the solvent and the UV irradiation process for curing the curable resin, the near-infrared absorptance in the 900 to 1200 nm wavelength region and the 430 to 580 nm wavelength region due to the deterioration of the pigment. There is a problem that the desired spectral characteristics cannot be obtained. Therefore, it is important to improve heat resistance and UV resistance of a dye having an absorption maximum at 900 to 1200 nm.

In addition to the above-mentioned problems, in recent years, the demand for heat resistance has become increasingly severe in view of the development for in-vehicle applications. That is, it is required that the change in spectral characteristics can be suppressed as much as possible even when exposed to a high temperature for a long time.

As a method for improving the heat resistance and UV resistance of the above-mentioned pigment, for example, a method using a pigment as a pigment (particle dispersed state) instead of a dye (dissolved state) is known (for example, Patent Documents 6 and 7). . In Patent Document 7, a near-infrared cut filter using a diimonium dye having a problem of heat resistance is used by dissolving the dye in a dispersion medium (toluene) and then dispersing it in a resin (dye). It is shown that the heat resistance and UV resistance are improved as compared to the case of use as However, even if the techniques of the above-mentioned prior art are used, not only the absorption in the near infrared region is sufficient, but only a film having a very high haze value can be obtained, and the above-mentioned problems cannot be solved.

Japanese Patent Laid-Open No. 6-200113 JP 2011-100084 A International Publication No. 2015/025779 Pamphlet International Publication No. 2014/168190 Pamphlet International Publication 2014/030628 Pamphlet JP 2001-019898 A JP 2010-249964 A

The present invention achieves high levels of both color shading suppression and ghost suppression of camera images and transmittance characteristics in the visible light wavelength region, which could not be sufficiently achieved by conventional optical filters, and is exposed to high temperatures for a long time. It is an object of the present invention to provide an optical filter having good heat resistance that can maintain optical characteristics even in such a case.

As a result of intensive studies to solve the above problems, the present inventors have found that the substrate has a layer containing an organic pigment having an absorption maximum in a specific wavelength region, and on at least one surface of the substrate. By forming a dielectric multilayer film, it is possible to obtain an optical filter that can achieve near infrared cut characteristics, visible light transmittance, color shading suppression effect and ghost suppression effect while maintaining the transmittance in the visible light region. I found it.

In addition, the present inventors can obtain an optical filter excellent in heat resistance by maintaining the haze value at a very low level by making the organic pigment fine particles and making the average particle diameter in a specific range. I found.
Examples of embodiments of the present invention completed based on these findings are shown below.

[1] An optical filter having a base material satisfying the following requirement (a) and having a dielectric multilayer film on at least one surface of the base material:
(A) It has a layer containing an organic pigment (S) having an absorption maximum in a wavelength region of 900 nm to 1200 nm.

[2] The optical filter according to item [1], wherein the substrate further satisfies the following requirement (b):
(B) It has a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and 760 nm or less.

[3] The optical filter according to item [2], wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds.

[4] The optical filter according to any one of items [1] to [3], wherein the organic pigment (S) contains a diimonium compound represented by the following formula (I).

In formula (I),
R ¹ is independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxy group, a phosphoric acid group, -SR ⁱ group, -SO ₂ R ⁱ groups, -OSO ₂ R ⁱ group or a group represented by L ^a ~ R ² represents any one of R ^h and R ² independently represents 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 —SR ⁱ group, —SO ₂ R ⁱ group, —OSO ₂ R ⁱ group or any of the following L ^a to L ^h is represented, and R ^g and R ^h are each independently a hydrogen atom, —C (O) R ⁱ group or the following L ^a to L represents either ^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 C ^6-14 aromatic hydrocarbon group (L ^e ) C ^2-14 heterocyclic group (L ^f ) C ^1-12 alkoxy group (L ^g ) carbon number optionally having substituent L An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L ^h ) substituent L having 1 to 12 substituents. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. At least one selected from the group consisting of a halogen-substituted alkyl group, 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 Yes,
n represents an integer of 0 to 4,
X represents an anion necessary for neutralizing the electric charge.

[5] The optical filter according to any one of items [1] to [4], wherein the organic pigment (S) has an average particle size of 200 nm or less.

[6] The optical filter according to any one of items [1] to [5], wherein the layer containing the organic pigment (S) is a transparent resin layer.

[7] The transparent resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or a polyarylate. Resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, Item characterized by being at least one resin selected from the group consisting of an allyl ester curable resin, a silsesquioxane ultraviolet curable resin, an acrylic ultraviolet curable resin, and a vinyl ultraviolet curable resin [ [6] The optical filter according to [6].

[8] The item wherein the substrate contains a dispersant having an acidic functional group and the content thereof is 5 to 300 parts by mass with respect to 100 parts by mass of the organic pigment (S). The optical filter according to any one of [1] to [7].

[9] The optical filter according to any one of items [1] to [8], which is for a solid-state imaging device.

[10] A solid-state imaging device comprising the optical filter according to any one of items [1] to [9].
[11] A camera module comprising the optical filter according to any one of items [1] to [9].

According to the present invention, it is possible to provide an optical filter that has excellent near-infrared cut characteristics, little incident angle dependency, and excellent transmittance characteristics in the visible light wavelength region, color shading suppression effect, ghost suppression effect, and heat resistance. Can do.

FIGS. 1A and 1B are schematic views showing examples of preferable configurations of the optical filter of the present invention. FIG. 2 is a spectral transmission spectrum of the optical filter obtained in Example 1. It is a schematic diagram for demonstrating the color shading evaluation of the camera image performed in the Example and the comparative example. It is a schematic diagram for demonstrating the ghost evaluation of the camera image performed in the Example and the comparative example.

Hereinafter, the optical filter according to the present invention and an apparatus using the optical filter will be described in detail.

The optical filter of the present invention has a base material that satisfies the requirement (a) described below, and has a dielectric multilayer film on at least one surface of the base material.
The thickness of the optical filter of the present invention is preferably thin considering the recent trend of thinning and weight reduction of solid-state imaging devices. 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 210 μm or less, more preferably 190 μm or less, further preferably 160 μm or less, particularly preferably 130 μm or less, and the lower limit is not particularly limited, but is preferably 20 μm or more.

[Base material]
The base material used in the present invention satisfies the following requirement (a).
(A) It has a layer containing an organic pigment (S) having an absorption maximum in a wavelength region of 900 nm to 1200 nm.
Moreover, it is preferable that the base material further satisfies the following requirement (b).
(B) It has a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and 760 nm or less.
Hereinafter, each requirement will be described.

<Requirement (a)>
In the requirement (a), the component constituting the layer containing the organic pigment (S) is not particularly limited, and examples thereof include a transparent resin, a sol-gel material, a low-temperature-curing glass material, and the like. A transparent resin is preferable from the viewpoint.

≪Organic pigment (S) ≫
The organic pigment (S) is not particularly limited as long as it is an organic pigment having an absorption maximum in a wavelength region of 900 nm to 1200 nm. For example, the compound (S) having an absorption maximum in a wavelength region of 900 nm to 1200 nm. Can be obtained as a dispersion of the organic pigment (S) by dispersing it together with a dispersion medium and, if necessary, a dispersant and other additives by a known method.

(1) Compound (S)
The compound (S) is not particularly limited as long as the compound has an absorption maximum in a wavelength region of 900 nm or more and 1200 nm or less, but is preferably a diimonium compound, a metal dithiolate complex compound, a pyrrolopyrrole compound, or a cyanine compound. At least one compound selected from the group consisting of a compound, a croconium compound and a naphthalocyanine compound, more preferably at least one compound selected from the group consisting of a diimonium compound and a metal dithiolate complex compound, Particularly preferred are diimonium compounds represented by the following formula (I). By using such a compound (S), it is possible to impart good near infrared absorption characteristics and excellent visible light transmittance.

R ¹ is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, adamantyl group, trifluoromethyl group. , A pentafluoroethyl group, a 3-pyridinyl group, an epoxy group, a phenyl group, a benzyl group, and a fluorenyl group, and more preferably an isopropyl group, a sec-butyl group, a tert-butyl group, and a benzyl group.

R ² is preferably a 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, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino Group, pentafluoroethanoylamino group, tert-butanoylamino group, cyclohexylinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, more preferably chlorine Atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl Group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, tert-butanoylamino group, cyclohexyl group A cynoylamino group, particularly preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. The number of R ² bonded to the same aromatic ring (value of n) is not particularly limited as long as it is 0 to 4, but is preferably 0 or 1.

X is an anion necessary for neutralizing electric charge. When X is a divalent anion, X is one, and when X is a monovalent anion, X is two. is there. In the latter case, the two anions may be the same or different, but are preferably the same from the viewpoint of synthesis. Although X will not be specifically limited if it is such an anion, As an example, the thing of following Table 1 can be mentioned.

X is (X-10), (X-16), (X-17), (X-21), (X-21) in Table 1 above from the viewpoint of heat resistance, light resistance and spectral properties of the diimonium compound. X-22), (X-24) and (X-28) are particularly preferred.

Examples of the diimonium compound represented by the above formula (I) include those listed in Tables 2-1 to 2-4 below.

The compound (S) may be synthesized by a generally known method. For example, Japanese Patent No. 4168031, Japanese Patent No. 4225296, JP-T 2010-516823, JP-A No. 63-165392 It can be synthesized with reference to the method described in the publication.

The absorption maximum wavelength of the compound (S) is preferably 920 nm to 1195 nm, more preferably 950 nm to 1190 nm, and further preferably 980 nm to 1180 nm. When the absorption maximum wavelength of the compound (S) is in such a range, unnecessary near-infrared rays can be efficiently cut, and an excellent ghost suppression effect can be obtained.

(2) Dispersion medium The organic pigment (S) is preferably used by dispersing the compound (S) in a dispersion medium by a generally known method, for example, a method using a known disperser. In the present invention, when a dispersion medium having extremely high solubility with respect to the compound (S) is selected, the compound (S) is dissolved in the dispersion medium and becomes a dye. In this case, desired spectral characteristics cannot be obtained, and heat resistance and UV resistance are significantly reduced. Therefore, it is necessary to select a dispersion medium that has low solubility in the compound (S) and does not form a dye. Whether the dispersion medium dyes the compound (S) is determined by adding the dispersion medium to the compound (S) and dropping it into a glass plate so that the concentration of the compound (S) is 0.1% by mass. After drying, it can be confirmed by observing with a scanning electron microscope. When the compound (S) is present in the form of particles, it can be determined that it is pigmented, and when the particulate material is not confirmed, it can be determined that it is dyed.

The dispersion medium is not particularly limited as long as it does not dye the compound (S), but a solvent having a relatively high polarity is preferable from the viewpoint of safety in the dispersion process. For example, alcohols such as isopropanol and ethanol , Ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as butyl acetate and ethyl acetate, and ethers such as propylene glycol monomethyl ether.

When the compound (S) is a diimonium compound, alcohols such as isopropanol and ethanol are particularly preferable from the viewpoint of storage stability of the dispersion. Note that it is not preferable to use a halogen solvent such as methylene chloride because the compound (S) is dyed.

(3) Disperser Examples of the disperser used when dispersing the compound (S) in a dispersion medium include a bead mill, a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, and a roller mill. .
Further, the organic pigment (S) may be prepared by refining the primary particles of the compound (S) by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be employed.

(4) Dispersant For the purpose of improving dispersion stability, the compound (S) may be dispersed using a known dispersant. Examples of the dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkylphenyl ether-based dispersant, a polyethylene glycol diester-based dispersant, and a sorbitan fatty acid ester-based dispersant. , Polyester dispersants, (meth) acrylic dispersants, and the like. Examples of commercially available products include (meth) acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (manufactured by BYK (BYK)), Disperbyk-161, Disperbyk. -162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (manufactured by BYK Corporation), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.) and the like, Solsperse 24000 ( Polyethyleneimine-based dispersants such as Lubrizol Co., Ltd.), Ajisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 In addition to polyester dispersants such as those manufactured by Ajinomoto Fine Techno Co., Ltd., BYK-LPN21324 (manufactured by BYK Corporation), Mariarim SC series, Esliem AD series, Esliem C2093I (above, NOF Corporation) Etc.) can be used. Examples of the (meth) acrylic dispersant include, for example, JP 2011-232735 A, JP 2011-237769 A, JP 2012-32767 A, International Publication 2011/129078, International Publication 2012. Copolymers disclosed in the / 001945 pamphlet and the like can also be used. A dispersing agent can be used 1 type or in combination of 2 or more types.

In the present invention, it is preferable to use a dispersant having an acidic functional group in terms of good dispersion stability and small chemical action on the compound (S). The dispersant having an acidic functional group is not particularly limited as long as it is a dispersant having a carboxylic acid, a sulfonic acid, a phenolic hydroxyl group, or a salt thereof. For example, an ethylenically unsaturated monomer having an acidic functional group And other copolymerizable ethylenically unsaturated monomers. Examples of commercially available products include the above-mentioned Mariarim SC series, DISPERBYK-103, DISPERBYK-110, DISPERBYK-118, and the like.

The content of the dispersant can be appropriately selected depending on the type of the dispersant, but is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, and more preferably 100 parts by weight of the organic pigment (S). The amount is preferably 20 to 150 parts by mass. It is preferable for the content of the dispersant to be in the above range because the dispersion stability of the dispersion is good and the heat resistance, water resistance and adhesion of the substrate and optical filter are excellent.

In the present invention, it is preferable to perform a centrifugal separation process following the dispersion step. Centrifugation treatment can remove coarse organic pigment particles that are insufficiently dispersed, thereby reducing the average particle size of the organic pigment, and as a result, haze of the optical filter can be reduced.

Although it does not specifically limit as time of sputum centrifugation processing, For example, it is 1 minute or more and 60 minutes or less. Moreover, it is although it does not specifically limit as centrifugal acceleration of the centrifuge at the time of performing sputum centrifuge, For example, it can be set as 10 G or more and 50,000 G or less.

(5) Average particle diameter of organic pigment (S) The average particle diameter of the organic pigment (S) is preferably 200 nm or less, more preferably 5 to 190 nm, still more preferably 10 to 180 nm, and particularly preferably 15 to 150 nm. . Here, the average particle diameter of the organic pigment (S) in the present invention is a value obtained by the measurement method described in Examples described later. When the average particle diameter of the organic pigment (S) is in the above range, an optical filter excellent in heat resistance can be obtained while maintaining the haze value at an extremely low level.

(6) Content of organic pigment (S) The content of the entire organic pigment (S) is, for example, a base material made of a transparent resin substrate containing the organic pigment (S) or an organic pigment (S). When using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is used on a transparent resin substrate containing S), it is preferably 0.01 with respect to 100 parts by mass of the transparent resin. 2.0 parts by mass, more preferably 0.02 to 1.5 parts by mass, particularly preferably 0.03 to 1.0 parts by mass. As the substrate, a glass support or a resin support as a base is used. When using a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) is used on a support such as a body, a transparent resin containing the organic pigment (S) Preferably it is 0.1 with respect to 100 mass parts of resin which forms a layer. 5.0 parts by weight, more preferably 0.2 to 4.0 mass parts, and particularly preferably 0.3 to 3.0 parts by. When the content of the organic pigment (S) is within the above range, an optical filter having both good near infrared absorption characteristics and high visible light transmittance can be obtained. In the present invention, it is desirable to provide an overcoat layer made of a curable resin containing an organic pigment (S) on a support such as a glass support or a base resin support as a base material.

<Requirement (b)>
In the requirement (b), the component constituting the layer containing the compound (A) is not particularly limited, and examples thereof include a transparent resin, a sol-gel material, a low-temperature-curing glass material, and the like. A transparent resin is preferable from the viewpoint of compatibility with A).

<< Compound (A) >>
The compound (A) is not particularly limited as long as it is a compound having an absorption maximum in a wavelength region of 650 nm or more and 760 nm or less, but is preferably a solvent-soluble dye compound, and is a squarylium compound, a phthalocyanine compound, and a cyanine compound. It is more preferable that it is at least one selected from the group consisting of compounds, it is more preferable that a squarylium compound is included, and it is particularly preferable that there are two or more compounds including a squarylium compound. When the compound (A) is two or more types including a squarylium compound, two or more types of squarylium compounds having different structures may be used, or a combination of a squarylium compound and another compound (A) may be used. As the other compound (A), a phthalocyanine compound and a cyanine compound are particularly preferable.

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 during 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 660 nm or more and 755 nm or less, more preferably 670 nm or more and 750 nm or less, and further preferably 680 nm or more and 745 nm or less.

When the compound (A) is a combination of two or more kinds of compounds, the difference between the absorption maximum wavelengths of the compound (A) to be applied having the shortest absorption maximum wavelength and the longest absorption maximum wavelength is preferably 10 to The thickness is 60 nm, more preferably 15 to 55 nm, still more preferably 20 to 50 nm. It is preferable that the difference in absorption maximum wavelength is in the above-mentioned range because scattered light due to fluorescence can be sufficiently reduced and a wide absorption band near 700 nm and an excellent visible light transmittance can be compatible.

The total content of the compound (A) is, for example, a base material made of a transparent resin substrate containing the organic pigment (S) and the compound (A) or a transparent resin containing the compound (A) as the base material. When using a base material in which a resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) is laminated on a substrate, it is preferably 0.04 with respect to 100 parts by mass of the transparent resin. 2.0 parts by mass, more preferably 0.06 to 1.5 parts by mass, and still more preferably 0.08 to 1.0 parts by mass. As the substrate, a glass support or a resin support as a base is used. When using a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing the organic pigment (S) and the compound (A) is laminated on a support such as a body, the compound (A) 100 forming a transparent resin layer containing Relative to the amount unit, preferably 0.4 to 5.0 parts by mass, more preferably in a range of 0.6 to 4.0 mass parts, more preferably 0.8 to 3.5 mass parts.

The substrate may be a single layer or a multilayer as long as it has a layer containing an organic pigment (S). Moreover, the compound (A) may be contained in the same layer as the organic pigment (S) or in a different layer.

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

When the layer containing the organic pigment (S) and the layer containing the compound (A) are different, for example, an overcoat made of a curable resin containing the compound (A) on a transparent resin substrate containing the organic pigment (S) A base material on which a resin layer such as a layer is laminated, or a base material on which a resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) is laminated on a transparent resin substrate containing the compound (A) An overcoat layer made of a curable resin containing an organic pigment (S) on a support such as a glass support or a base resin support, and an overcoat layer made of a curable resin containing a compound (A) Can be mentioned. In the present invention, it is preferable to provide an overcoat layer made of a curable resin containing an organic pigment (S) on a transparent resin substrate containing the compound (A). In this case, the organic pigment (S) The average particle size is more preferably 150 nm or less, and particularly preferably 100 nm or less.

<Other properties and physical properties>
The average transmittance of the substrate in the wavelength region 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 light region, and a highly sensitive camera function can be achieved.

The thickness of the substrate can be appropriately selected according to the desired application and is not particularly limited, but is preferably 10 to 200 μm, more preferably 20 to 180 μm, and further preferably 25 to 150 μm. When the thickness of the substrate is in the above range, an optical filter using the substrate can be reduced in thickness and weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when a base material made of the transparent resin substrate 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.

<Transparent resin>
The transparent resin used for the transparent resin layer, the transparent resin substrate and the resin support constituting the substrate is not particularly limited as long as it does not impair the effects of the present invention. For example, thermal stability and film Glass transition temperature (Tg) is preferably 110 to 380 ° C., in order to obtain a film capable of forming a dielectric multilayer film by high temperature vapor deposition performed at a vapor deposition temperature of 100 ° C. or higher while ensuring moldability to Preferably, a resin having a temperature of 110 to 370 ° C., more preferably 120 to 360 ° C. is used. Further, it is particularly preferable that the glass transition temperature of the resin is 140 ° C. or higher because a film capable of depositing a dielectric multilayer film at a higher temperature can be obtained.

As a transparent resin, when a resin plate made of the resin having a thickness of 0.1 mm is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, More preferably 80 to 95% of the resin can be used. If a resin having a total light transmittance in such a range is used, the resulting substrate exhibits good transparency as an optical film.

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

Examples of transparent resins include cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, and polysulfones. Resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl Examples thereof include ester-based curable resins, silsesquioxane-based ultraviolet curable resins, acrylic-based ultraviolet curable resins, and vinyl-based ultraviolet curable resins.

Transparent resins may be used alone or in combination of two or more.

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

In the formula (X ₀ ), R ^x1 to R ^x4 each independently represents an atom or group selected from the following (i ′) to (ix ′), and k ^x , ^mx and p ^x are each independently 0 Represents an integer of ~ 4.
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom 30 to 30 hydrocarbon group (v ′) substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi ′) polar group (excluding (ii ′) and (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 which are not involved in the bond) ^x4 each independently represents an atom or group selected from (i ′) to (vi ′).
(Ix ′) A monocyclic hydrocarbon ring or heterocycle formed by bonding R ^x2 and R ^x3 to each other (provided that R ^x1 and R ^x4 not involved in the bonding are each independently the above (i Represents an atom or group selected from ') to (vi').

In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent 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 an integer of 0-4.

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

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

In the formula (2), in each of R ¹ ~ R ⁴ and a ~ d independently has the same meaning as R ¹ ~ R ⁴ and a ~ d of the formula (1), Y represents a single bond, -SO ₂ -Or -CO-, 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 represents 0 to 4 Represents an integer, and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

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

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

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

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

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

≪Fluorene polyester resin≫
The fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. For example, the fluorene polyester resin can be 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 (A) and a curable resin is laminated on a glass support or a resin support as a base, or a compound ( When using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is used on a transparent resin substrate containing A), it can be particularly preferably used as the curable resin.

≪Epoxy resin≫
Although it does not specifically limit as an epoxy-type resin, It can divide roughly into an ultraviolet curing type and a thermosetting type. As the ultraviolet curable epoxy resin, for example, synthesized from a composition containing a compound having one or more epoxy groups in the molecule and a compound that generates an acid by ultraviolet rays (hereinafter also referred to as “photo acid generator”). Examples of thermosetting epoxy resins include those synthesized from a composition containing one or more epoxy groups in the molecule and an acid anhydride. Can do. The epoxy ultraviolet curable resin contains, as the base material, a base material obtained by laminating a transparent resin layer containing the compound (A) on a glass support or a base resin support, and the compound (A). In the case of using a base material in which a resin layer such as an overcoat layer made of a curable resin is laminated on a transparent resin substrate to be used, it can be particularly suitably used as the curable resin.

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

<Other dye (X)>
The base material may further contain other pigment (X) not corresponding to the organic pigment (S) and the compound (A).

The other dye (X) is not particularly limited as long as the absorption maximum wavelength is in the region of wavelength less than 650 nm or more than 760 nm and less than 900 nm, but the dye having the absorption maximum wavelength in the region of more than 760 nm and less than 900 nm is preferable. . Examples of such dyes include squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, octaphyrin compounds, diimonium compounds, pyrrolopyrrole compounds, and boron dipyrromethene (BODIPY). And at least one compound selected from the group consisting of a compound, a perylene compound, and a metal dithiolate compound.

The content of the other dye (X) is, for example, when a base material made of a transparent resin substrate containing the other dye (X) is used as the base material, with respect to 100 parts by mass of the transparent resin. The amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.9 part by mass, particularly preferably 0.02 to 0.8 part by mass. Contains a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing other dye (X) is laminated on a support such as a resin support or an organic pigment (S) In the case of using a substrate in which a resin layer such as an overcoat layer made of a curable resin containing other dye (X) is used on a transparent resin substrate to be transparent, a transparent material containing other dye (X) is used. For 100 parts by mass of resin forming the resin layer Preferably 0.05 to 4.0 mass parts, more preferably 0.1 to 3.0 mass parts, and particularly preferably 0.2 to 2.0 parts by mass.

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

Examples of the near ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, triazine compounds, and the like.

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

In addition, these other components may be mixed with a resin or the like when producing a substrate, 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 with respect to 100 parts by weight of the resin. Part.

<Manufacturing method of substrate>
When the base material is a base material including a transparent resin substrate containing an organic pigment (S), the transparent resin substrate can be formed by, for example, melt molding or cast molding, and further if necessary. After forming, a substrate on which an overcoat layer is laminated can be produced by coating a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent.

The substrate is made of a curable resin containing an organic pigment (S) on a support such as a glass support or a base resin support or a transparent resin substrate containing no organic pigment (S). In the case of a substrate on which a transparent resin layer such as an overcoat layer is laminated, for example, preferably by melt molding or cast molding a resin solution containing the compound (A) on the support or the transparent resin substrate. Is applied by a method such as spin coating, slit coating, and ink jet, and then the solvent is dried and removed, and if necessary, light irradiation or heating is performed to form an organic pigment on the support or the transparent resin substrate. A substrate on which a transparent resin layer containing (S) is formed can be produced.

≪Melt molding≫
Specifically, as the melt molding, a method of melt molding pellets obtained by melt-kneading a resin, an organic pigment (S) and other components as necessary; a resin and an organic pigment (S) And a method of melt-molding a resin composition containing other components as necessary; or removing the solvent from the resin composition containing the organic pigment (S), the resin, the solvent and, if necessary, the other components The method of melt-molding the obtained pellet is mentioned. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫
As the cast molding, a method of removing a solvent by casting a resin composition containing an organic pigment (S), a resin, a solvent and, if necessary, other components on a suitable support; or an organic pigment (S ), A photocurable resin and / or a thermosetting resin, and if necessary, a curable composition containing other components is cast on a suitable support to remove the solvent, It can also be produced by a method of curing by an appropriate method such as heating.

When the base material is a base material made of a transparent resin substrate containing the organic pigment (S), the base material can be obtained by peeling the coating film from the support after cast molding. The base material is a curable resin containing an organic pigment (S) on a support such as a glass support or a base resin support or on a transparent resin substrate containing no organic pigment (S). In the case of a base material on which a transparent resin layer such as an overcoat layer made of, etc. is laminated, the base material can be obtained by not peeling the coating film after cast molding.

As the support, for example, a near-infrared absorbing glass plate (for example, a phosphate system containing a copper component such as “BS-11” manufactured by Matsunami Glass Industrial Co., Ltd. or “NF-50T” manufactured by AGC Sakai Techno Glass Co., Ltd.) Glass plate), transparent glass plate (for example, non-alkali glass plate such as “OA-10G” manufactured by Nippon Electric Glass Co., Ltd., “AN100” manufactured by Asahi Glass Co., Ltd.), steel belt, steel drum, and transparent resin (for example, polyester film) , Cyclic olefin resin film) support.

The amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the above method should be as small as possible. Specifically, the amount of the residual solvent is preferably 3 parts by mass or less, more preferably 1 part by mass or less, further preferably 0.5 parts by mass with respect to 100 parts by mass of the transparent resin layer (transparent resin substrate). It is as follows. When the amount of residual solvent is in the above range, a transparent resin layer (transparent resin substrate) that can easily exhibit a desired function is obtained, which hardly causes deformation of the base material or changes in optical properties.

[Dielectric multilayer film]
The optical filter of the present invention has a dielectric multilayer film on at least one surface of the substrate. The dielectric multilayer film in the present invention is a film having the ability to reflect near-infrared light or a film having an antireflection effect in the visible light region. Infrared cut characteristics can be achieved.

In the present invention, the dielectric multilayer film may be provided on one side of the substrate or on both sides. When it is provided on one side, it is possible to obtain an optical filter that is excellent in production cost and manufacturability and has high strength and is less likely to warp or twist when provided on both sides. When the optical filter is applied to a solid-state imaging device, it is preferable that the optical filter is less warped or twisted. Therefore, it is preferable to provide a dielectric multilayer film on both surfaces of the resin substrate.

The dielectric multilayer film preferably has reflection characteristics over the entire wavelength range of 700 to 1100 nm, more preferably 700 to 1150 nm, and even more preferably 700 to 1200 nm.

As a form having a dielectric multilayer film on both surfaces of the base material, the first optical layer mainly having a reflection characteristic in the vicinity of a wavelength of 700 to 950 nm when measured from an angle of 5 ° with respect to the vertical direction of the optical filter is used. A configuration (see FIG. 1 (a)) having a second optical layer on one side of the material and having a reflection characteristic mainly in the vicinity of 900 nm to 1150 nm on the other side of the substrate, and the vertical direction of the optical filter A fourth optical layer having a third optical layer having a reflection characteristic mainly in the vicinity of a wavelength of 700 to 1150 nm on one side of the substrate and having an antireflection characteristic in the visible light region. The form (refer FIG.1 (b)) which has on the other surface of a base material etc. are mentioned.

Examples of the dielectric multilayer film include those in which a high refractive index material layer and a low refractive index material layer are alternately laminated. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected. Examples of such 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 Alternatively, a material containing a small amount of cerium oxide or the like (eg, 0 to 10 parts by mass with respect to 100 parts by mass of the main component) can be used.

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

The thickness of each of the high refractive index material layer and the low refractive index material layer is usually preferably from 0.1λ to 0.5λ, where λ (nm) is the near infrared wavelength to be blocked. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is within this range, the optical thickness obtained by multiplying the refractive index (n) by the thickness (d) (n × d) by λ / 4, the high refractive index material layer, and the low refractive index. The thicknesses of the respective layers of the refractive index material layer are almost the same value, and there is a tendency that the blocking / transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection / refraction.

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, more preferably 20 to 60 layers, as a whole, 24 Particularly preferred is ˜50 layers. 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 high refractive index material layer, and the low refractive index are adjusted in accordance with the absorption characteristics of the near-infrared absorber such as the compound (A) or the organic pigment (S). Appropriate selection of the thickness of each refractive index material layer, the order of stacking, and the number of stacks ensure sufficient light-cutting characteristics in the near-infrared wavelength region while ensuring sufficient transmittance in the visible light region. And the reflectance when near-infrared rays inject from an oblique direction can be reduced.

Here, in order to optimize the above conditions, for example, optical thin film design software (for example, Essential Macleod, Thin Film Center) is used, and both the antireflection effect in the visible light region and the light cut effect in the near infrared region are compatible. Set the parameters so that you can. In the case of the above-mentioned software, for example, in designing the first optical layer, the target transmittance at a wavelength of 400 to 700 nm is set to 100%, the target Tolerance value is set to 1, and the target transmittance at a wavelength of 705 to 950 nm is set to 0%. Parameter setting method such as setting Target Tolerance value to 0.5 can be mentioned. These parameters can change the value of Target Tolerance by further finely dividing the wavelength range according to various characteristics of the substrate (i).

[Other functional membranes]
The optical filter of the present invention is within the range not impairing the effects of the present invention, between the base material and the dielectric multilayer film, the surface opposite to the surface on which the dielectric multilayer film is provided, or the dielectric multilayer film. On the opposite side of the surface of the film where the substrate is provided, an anti-reflection film, a hard layer is used for the purpose of improving the surface hardness of the substrate or the dielectric multilayer film, improving the chemical resistance, antistatic and scratching. Functional films such as a coating film and an antistatic film can be provided as appropriate.

The optical filter of the present invention may include one layer made of the functional film or 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 for laminating the functional film is not particularly limited, but a coating agent containing an antireflection agent, a hard coating agent and / or an antistatic agent, etc. is melt-molded or cast in the same manner as described above on a base material or a dielectric multilayer film. Examples of the method include molding.

Also, the coating agent can be produced by applying the coating agent on a base material or a dielectric multilayer film with a bar coater or the like and then curing it by ultraviolet irradiation or the like.

Examples of the coating agent include curable compositions containing ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins. Specific examples of the curable resin contained in the curable composition include vinyl compounds, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate resins.

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

In the curable composition, the mixing ratio of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, when the total amount of the curable composition is 100 parts by mass. More preferably, it is 1 to 5 parts by mass. 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 the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- 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, in order to improve the adhesion between the base material and the functional film and / or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, the corona is applied to the surface of the base material, the functional film or the dielectric multilayer film. Surface treatment such as treatment or plasma treatment may be performed.

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

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

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. “Part” means “part by mass” unless otherwise specified. Moreover, the measurement method of each physical property value and the evaluation method of the physical property are as follows.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
(A) Weight average molecular weight in terms of standard polystyrene using a gel permeation chromatography (GPC) apparatus manufactured by WATERS (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) (Mw) and number average molecular weight (Mn) were measured.
(B) Standard polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a GPC apparatus (HLC-8220 type, column: TSKgelα-M, developing solvent: THF) manufactured by Tosoh Corporation.

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

<Average particle size>
The average particle diameter of the organic pigment was measured by the following method. The prepared dispersion liquid of the organic pigment is diluted with a solvent having the same composition as the dispersion medium until the pigment concentration becomes 0.5% by mass, dropped on a glass plate and dried, and then scanned with an electron microscope (SEM) ( Observation was performed with Hitachi High-Technologies Corporation “S4800”. SEM images were taken from a plurality of fields of view, and the particle size of 100 arbitrarily selected particles was measured on a scale and converted into a magnification to calculate an average particle size. In addition, extremely large or small particles were excluded, and when the particle shape was not spherical, the longest diameter (major axis) observed was taken as the particle diameter.

<Spectral transmittance>
The transmittance in each wavelength region of the substrate and the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation. The transmittance is measured using the spectrophotometer under the condition that light is incident on the substrate and the filter perpendicularly.

<Haze>
The haze of the substrate and the optical filter was measured using a haze meter (Haze Guard II) manufactured by Toyo Seiki Seisakusho Co., Ltd. Measurements were taken at three different locations and the average value was used.

<Heat resistance>
The optical filter was treated under the conditions of 85 ° C. × 1000 hr, and the average transmittance at wavelengths of 430 to 580 nm before and after the treatment was measured. The transmittance maintenance ratio calculated by the following formula was used as an index of heat resistance. The higher the maintenance factor, the better the heat resistance.
Transmittance maintenance rate (%) = (average transmittance from 430 to 580 nm after treatment) / (average transmittance from 430 to 580 nm before treatment) × 100

<Camera image color shading evaluation>
The color shading evaluation when the optical filter was incorporated in the camera module was performed by the following method. A camera module is created in the same manner as in Japanese Patent Application Laid-Open No. 2016-110067, and a white plate having a size of 300 mm × 400 mm is formed using the created camera module as a D65 light source (standard light source device “Macbeth Judge II” manufactured by X-Rite) Images were taken below, and the difference in color between the center and edge of the white plate in the camera image was evaluated according to the following criteria.

There is no problem at all and an acceptable level is A, and a slight difference in color is recognized, but there is no problem in practical use as a high-quality camera module. The possible level was determined as C, and the level unacceptable for general camera module use with a clear color difference was determined as D.

As shown in FIG. 3, the positional relationship between the white plate 112 and the camera module was adjusted so that the white plate 112 occupied 90% or more of the area in the camera image 111 when shooting.

<Ghost evaluation of camera images>
Ghost evaluation when the optical filter was incorporated in the camera module was performed by the following method. A camera module is created in the same manner as in Japanese Patent Application Laid-Open No. 2016-110067, and the camera module is used to take a picture under a halogen lamp light source (“Luminer Ace LA-150TX” manufactured by Hayashi Watch Industry Co., Ltd.) in a dark room. The degree of ghost generation around the light source in the image was evaluated according to the following criteria.

Acceptable level with no problem at all, A slight ghost is recognized, but acceptable as a high-quality camera module, practically acceptable level is B, ghost is generated and unacceptable for high-quality camera module application The possible level was determined as C, and the level of ghosts was determined to be unacceptable for general camera module applications as D.

Note that, as shown in FIG. 4, when shooting, the light source 122 was adjusted to be the upper right end of the camera image 121.

[Synthesis example]
Compound (A) and compound (S) used in the following examples were synthesized by a generally known method. Examples of the method include, for example, JP-A-60-228448, JP-A-1-146646, JP-A-1-228960, and Japanese Patent No. 4081149, “Phthalocyanine—Chemistry and Function” (IPC, 1997), JP 2009-108267 A, JP 2010-241873 A, JP 3699464 A, JP 4740631 A, and the like.

<Synthesis Example 1>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter also referred to as “DNM”) 100 g, 1-hexene (molecular weight regulator) 18 g and toluene (ring-opening polymerization solvent) 300 g were charged into a nitrogen-substituted reaction vessel. The solution was heated to 80 ° C. Next, 0.2 g of a toluene solution of triethylaluminum (0.6 mol / liter) and 0.9 g of a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were used as a polymerization catalyst. 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%.

1,000 g of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C., the hydrogenation reaction was performed by heating and stirring for 3 hours. 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.

<Synthesis Example 2>
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol at room temperature, 3-hydroxy-1-adamantyl acrylate (Mitsubishi Gas Chemical Co., Ltd.) , Molecular weight: 222) 27.047 g and isophorone diisocyanate (manufactured by Evonik, molecular weight: 222) 26.481 g were dissolved in 19 g of methyl ethyl ketone (MEK), and 0.405 g of dioctyltin dilaurate was added thereto, followed by stirring with stirring. The temperature was raised to ° C. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution was clarified, 27.047 g of 3-hydroxy-1-adamantyl acrylate was additionally charged, and the reaction was continued at 70 ° C. The reaction was completed after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) almost disappeared in the infrared absorption spectrum. The reaction mixture was purified by silica gel column chromatography using ethyl acetate / hexane as an eluent, and then diluted with isopropyl alcohol to obtain urethane acrylate compound (I) (50% by mass solution).

[Preparation example of organic pigment]
<Preparation Example 1>
In a 0.25 L plastic container, 5 g of the compound (s-15) shown in Table 2-4 (maximum absorption wavelength 1083 nm in dichloromethane), a dispersant having an acidic functional group (“Marialim SC manufactured by NOF Corporation”) -0505K ") 5 g, isopropyl alcohol (IPA) 95 g as dispersion medium, and 175 g of zirconia beads having a diameter of 0.05 mm (" YTZ-0.05 "manufactured by Nikkato Co., Ltd.) were added, and a paint shaker (manufactured by Toyo Seiki Seisakusho) The dispersion process was performed for 1 hr. Thereafter, the mixture was cooled to room temperature, and zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-1).

<Preparation Example 2>
In a 0.25 L plastic container, 5 g of the compound (s-15) shown in Table 2-4 above, 95 g of methyl isobutyl ketone (MIBK) as a dispersion medium, 0.05 mm diameter zirconia beads (“YTZ-0. 05 ") 175 g was charged and dispersed for 1 hr with a paint shaker. Thereafter, the mixture was cooled to room temperature, and zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-2).

<Preparation Example 3>
In a 0.25 L plastic container, 5 g of the compound (s-4) shown in Table 2-4 (maximum absorption wavelength 1100 nm in dichloromethane), 95 g of methyl isobutyl ketone (MIBK) as a dispersion medium, zirconia having a diameter of 0.05 mm 175 g of beads (“YTZ-0.05” manufactured by Nikkato Co., Ltd.) was added and dispersed for 1 hr using a paint shaker. Thereafter, the mixture was cooled to room temperature, and zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-3).

<Preparation Example 4>
In a 0.25 L plastic container, 5 g of the compound (s-6) shown in Table 2-4 (maximum absorption wavelength 1093 nm in dichloromethane), 95 g of methyl isobutyl ketone (MIBK) as a dispersion medium, zirconia having a diameter of 0.05 mm 175 g of beads (“YTZ-0.05” manufactured by Nikkato Co., Ltd.) was added and dispersed for 1 hr using a paint shaker. Thereafter, the mixture was cooled to room temperature, and zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-4).

<Preparation Example 5>
The organic pigment dispersion (S-1) obtained in Preparation Example 1 was centrifuged at a centrifugal acceleration of 36000 G for 10 minutes in a centrifuge (“cooled centrifuge CR-22N” manufactured by himac), and the dispersion after the treatment The liquid was filtered through a polypropylene filter (pore size: 3 μm) to obtain an organic pigment dispersion (S-5).

[Example 1]
In Example 1, an optical filter having a substrate formed by forming a transparent resin layer containing an organic pigment (S) on both surfaces of a transparent resin substrate containing a compound (A) was prepared according to the following procedure and conditions.

In a container, 100 g of the resin A obtained in Synthesis Example 1, 0.07 g of the compound (A-1) represented by the following formula (a-1) (absorption maximum wavelength 713 nm in dichloromethane) as the compound (A) and 0.06 g of the compound (a-2) represented by the formula (a-2) (absorption maximum wavelength 736 nm in dichloromethane) and methylene chloride were added to prepare a solution having a resin concentration of 20% by mass. 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 transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

In the above formula (a-1), i-Pr represents an isopropyl group.
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 3 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 3 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the transparent resin layer was formed on the substrate made from transparent resin. Similarly, a transparent resin layer made of the resin composition (1) is formed on the other surface of the transparent resin substrate, and the organic pigment (S) is transparent on both surfaces of the transparent resin substrate containing the compound (A). A substrate having a resin layer was obtained.

Resin composition (1): 100 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexyl phenyl ketone, 50 g of pigment dispersion (S-1) obtained in Preparation Example 1 (2.5 g in terms of organic pigment (S)) ), 117 g of isopropyl alcohol.

Subsequently, a dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained base material, and a dielectric multilayer film (II) is formed as a second optical layer on the other side of the base material. Thus, an optical filter having a thickness of about 0.105 mm was obtained.

The dielectric multilayer film (I) is formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100 ° C. (26 layers in total). 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. (20 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 of each layer, the wavelength-dependent characteristics of the base material refractive index and the applied organic pigment (S) and the anti-reflection effect in the visible light region and the selective transmission / reflection performance in the near-infrared region can be achieved. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) in accordance with the absorption characteristics of the compound (A). When performing optimization, in this example, the input parameters (Target values) to the software are as shown in Table 3 below.

As a result of the optimization of the film configuration, in Example 1, the dielectric multilayer film (I) is formed by alternately stacking a silica layer having a film thickness of 31 to 157 nm and a titania layer having a film thickness of 10 to 95 nm. The dielectric multi-layer film (II) is a multi-layer vapor-deposited film having 20 layers, in which a silica layer having a thickness of 37 to 194 nm and a titania layer having a thickness of 12 to 114 nm are alternately stacked. It was. An example of the optimized film configuration is shown in Table 4 below.

The spectral transmittance and haze measured from the vertical direction of the obtained optical filter were measured to evaluate the optical characteristics in each wavelength region and the heat resistance described above. The results are shown in FIG.

Also, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5. The obtained camera images showed good results in shading and ghosting.

[Example 2]
An optical filter was obtained and evaluated in the same manner as in Example 1 except that the resin composition (2) shown below was used instead of the resin composition (1). The results are shown in Table 5.

Resin composition (2): 50 g of urethane acrylate compound (1) obtained in Synthesis Example 2 (converted to solid content), 50 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexyl phenyl ketone, obtained in Preparation Example 1 50 g of pigment dispersion (S-1) (2.5 g in terms of organic pigment (S)), 117 g of isopropyl alcohol.

[Example 3]
An optical filter was obtained in the same manner as in Example 1 except that the resin composition (3) shown below was used instead of the resin composition (1), and the same evaluation was performed. The results are shown in Table 5.

Resin composition (3): 50 g of urethane acrylate compound (1) obtained in Synthesis Example 2 (in terms of solid content), 30 g of 3-hydroxy-1-adamantyl acrylate, 20 g of tricyclodecane dimethanol acrylate, 1-hydroxycyclohexylphenyl 3 g of ketone, 50 g of pigment dispersion (S-1) obtained in Preparation Example 1 (2.5 g in terms of organic pigment (S)), 117 g of isopropyl alcohol.

[Example 4]
An optical filter was obtained and evaluated in the same manner as in Example 1 except that the resin composition (4) shown below was used instead of the resin composition (1). The results are shown in Table 5.

Resin composition (4): 100 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexyl phenyl ketone, 50 g of the pigment dispersion (S-2) obtained in Preparation Example 2 (2.5 g in terms of organic pigment (S)) ), 117 g of methyl isobutyl ketone.

[Example 5]
Instead of the transparent resin substrate, a glass substrate (a transparent glass substrate “OA-10G (thickness 150 μm) cut to 60 mm length and 60 mm width)” (manufactured by Nippon Electric Glass Co., Ltd.) was used. Resin composition (1) An optical filter was obtained and evaluated in the same manner as in Example 1 except that the resin composition (5) shown below was used instead of 1. The results are shown in Table 5.

Resin composition (5): 100 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexyl phenyl ketone, 50 g of the pigment dispersion (S-2) obtained in Preparation Example 2 (2.5 g in terms of organic pigment (S)) ), Compound (a-1) 0.5 g, compound (a-2) 0.4 g, methyl isobutyl ketone 112 g.

[Example 6]
Optical in the same manner as in Example 5 except that a transparent resin film (Zeonor film ZF16 (thickness 100 μm)) (manufactured by Nippon Zeon Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width was used instead of the glass substrate. A filter was obtained and evaluated, and the results are shown in Table 5.

[Example 7]
An optical filter was obtained and evaluated in the same manner as in Example 3 except that the resin composition (6) shown below was used instead of the resin composition (1). The results are shown in Table 5.

Resin composition (6): 50 g of urethane acrylate compound (1) obtained in Synthesis Example 2 (in terms of solid content), 30 g of 3-hydroxy-1-adamantyl acrylate, 20 g of tricyclodecane dimethanol acrylate, 1-hydroxycyclohexylphenyl 3 g of ketone, 56 g of the pigment dispersion (S-3) obtained in Preparation Example 3 (2.8 g in terms of organic pigment (S)), and 117 g of isopropyl alcohol.

[Example 8]
An optical filter was obtained and evaluated in the same manner as in Example 3 except that the resin composition (7) shown below was used instead of the resin composition (1). The results are shown in Table 5.

Resin composition (7): 50 g of urethane acrylate compound (1) obtained in Synthesis Example 2 (converted to solid content), 30 g of 3-hydroxy-1-adamantyl acrylate, 20 g of tricyclodecane dimethanol acrylate, 1-hydroxycyclohexylphenyl 3 g of ketone, 52 g of pigment dispersion (S-4) obtained in Preparation Example 4 (2.6 g in terms of organic pigment (S)), and 117 g of isopropyl alcohol.

[Example 9]
An optical filter was obtained and evaluated in the same manner as in Example 3 except that the resin composition (8) shown below was used instead of the resin composition (1). The results are shown in Table 5.

Resin composition (8): 50 g of urethane acrylate compound (1) obtained in Synthesis Example 2 (converted to solid content), 30 g of 3-hydroxy-1-adamantyl acrylate, 20 g of tricyclodecane dimethanol acrylate, 1-hydroxycyclohexylphenyl 3 g of ketone, 50 g of the pigment dispersion (S-5) obtained in Preparation Example 5 (2.5 g in terms of organic pigment (S)), and 117 g of isopropyl alcohol.

[Comparative Example 1]
In a container, 100 parts of the resin A obtained in Synthesis Example 1, 0.07 g of the compound (a-1) (absorption maximum wavelength 713 nm in dichloromethane) as the compound (A) and the compound (a-2) (dichloromethane) 0.06 g of absorption maximum wavelength in water (736 nm) and 0.2 g of compound (s-6) (absorption maximum wavelength of 1093 nm in dichloromethane) described in Table 2-2 above and methylene chloride were added to give a resin concentration of 20 A mass% solution was prepared. Compound (s-6) was dissolved in methylene chloride to form a dye. 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 transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

An optical filter was obtained and evaluated in the same manner as in Example 1 except that the obtained transparent resin substrate was used and the resin composition (6) shown below was used instead of the resin composition (1). went. The results are shown in Table 5.

Resin composition (6): 100 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexyl phenyl ketone, 154.5 g of methyl ethyl ketone.

[Comparative Example 2]
An optical filter was obtained and evaluated in the same manner as in Example 5 except that the resin composition (7) shown below was used instead of the resin composition (5). Compound (s-15) was dissolved in methylene chloride to form a dye. The results are shown in Table 5.

Resin composition (7): Tricyclodecane dimethanol acrylate 100 g, 1-hydroxycyclohexyl phenyl ketone 3 g, compound (s-15) 2.5 g, compound (a-1) 0.5 g, compound (a-2) 0 .4 g, methylene chloride 155 g.

[Comparative Examples 3 to 4]
An optical filter was obtained and evaluated in the same manner as in Example 1 except that the configuration shown in Table 5 was adopted. The results are shown in Table 5.

The symbols of the base material form and various compounds in Table 5 are as follows.

<Form of substrate>
Form (1): A transparent resin substrate containing a compound (A) has a transparent resin layer containing an organic pigment (S) on both sides. Form (2): Transparent glass substrate (“OA-10G manufactured by Nippon Electric Glass Co., Ltd.) (Thickness 150 μm) ”) having a transparent resin layer containing an organic pigment (S) on both sides. Form (3): Compound (A) on both sides of a resin support (“ Zeonor Film ZF16 ”manufactured by Nippon Zeon Co., Ltd.) And a transparent resin layer containing an organic pigment (S) Form (4): having a transparent resin layer containing an organic pigment (S) on both sides of a resin support Form (5): Compound (A) and Compound (S Form (6): having a transparent resin layer containing compound (S) on both sides of the transparent glass substrate Form (7): made of transparent resin containing compound (A) Has resin layers on both sides of the substrate

<Transparent resin>
Resin A: Cyclic polyolefin resin (resin synthesis example 1)
Monomer A: Tricyclodecane dimethanol acrylate Monomer B: Urethane acrylate compound (1) obtained in Synthesis Example 2
Monomer C: 3-hydroxy-1-adamantyl acrylate

<Diluted solvent>
Dilution solvent (1): Isopropyl alcohol Dilution solvent (2): Methyl isobutyl ketone Dilution solvent (3): Methyl ethyl ketone Dilution solvent (4): Methylene chloride

10: Substrate 11: First optical layer 12: Second optical layer 13: Third optical layer 14: Fourth optical layer 111: Camera image 112: White plate 113: Example of central portion of white plate 114: White plate Example 121: Camera image 122: Light source 123: Example of a ghost around the light source

Claims

An optical filter having a base material satisfying the following requirement (a) and having a dielectric multilayer film formed on at least one surface of the base material:
(A) It has a layer containing an organic pigment (S) having an absorption maximum in a wavelength region of 900 nm to 1200 nm.
The optical filter according to claim 1, wherein the substrate further satisfies the following requirement (b):
(B) It has a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and 760 nm or less.
3. The optical filter according to claim 2, wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds.
The optical filter according to any one of claims 1 to 3, wherein the organic pigment (S) contains a diimonium compound represented by the following formula (I).

[In the formula (I),
R 1 is independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxy group, a phosphoric acid group, -SR i group, -SO 2 R i groups, -OSO 2 R i group or a group represented by L a ~ R 2 represents any one of R h and R 2 independently represents 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 —SR i group, —SO 2 R i group, —OSO 2 R i group or any of the following L a to L h is represented, and R g and R h are each independently a hydrogen atom, —C (O) R i group or the following L a to L represents either 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 C 6-14 aromatic hydrocarbon group (L e ) C 2-14 heterocyclic group (L f ) C 1-12 alkoxy group (L g ) carbon number optionally having substituent L An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L h ) substituent L having 1 to 12 substituents. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. At least one selected from the group consisting of a halogen-substituted alkyl group, 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 Yes,
n represents an integer of 0 to 4,
X represents an anion necessary for neutralizing the electric charge. )
The optical filter according to any one of claims 1 to 4, wherein an average particle diameter of the organic pigment (S) is 200 nm or less.
6. The optical filter according to claim 1, wherein the layer containing the organic pigment (S) is a transparent resin layer.
The transparent resin constituting the transparent resin layer is a cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, 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 7. The resin according to claim 6, wherein the resin 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. Optical filter.
The base material contains a dispersant having an acidic functional group, and the content thereof is 5 to 300 parts by mass with respect to 100 parts by mass of the organic pigment (S). 8. The optical filter according to any one of 7 above.
The optical filter according to any one of claims 1 to 8, which is used for a solid-state imaging device.
A solid-state imaging device comprising the optical filter according to any one of claims 1 to 9.
A camera module comprising the optical filter according to any one of claims 1 to 9.