JPWO2019167876A1 - Optical filter and equipment using optical filter - Google Patents

Abstract

An object of the present invention is to achieve both color shading suppression and ghost suppression of a camera image and transmittance characteristics in the visible light wavelength region at a high level, and to maintain optical characteristics even when exposed to a high temperature for a long time. It is an object of the present invention to provide an optical filter having good heat resistance. The optical filter of the present invention is characterized by having a base material satisfying the requirement (a) and having a dielectric multilayer film formed on at least one surface of the base material: (a) wavelength 900 nm. It has a layer containing an organic pigment (S) having an absorption maximum in the region of 1200 nm or less.

Description

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

A CCD or CMOS image sensor, which is a solid-state image sensor for color images, is used in a solid-state image sensor such as a video camera, a digital still camera, or a mobile phone with a camera function. In these solid-state image sensors, a silicon photodiode having sensitivity to near infrared rays, which cannot be perceived by the human eye, is used in the light receiving portion thereof. In these solid-state image sensors, it is necessary to perform luminosity factor correction that makes the color tone natural to the human eye, and an optical filter (for example, near-infrared ray cut) that selectively transmits or cuts light in a specific wavelength region is required. Filter) is often used.

As such a near-infrared cut filter, those manufactured by various methods have been conventionally used. For example, a near-infrared cut filter in which a transparent resin is used as a base material and a near-infrared absorbing dye is contained in the transparent resin is known (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 Patent Document 2, the applicant uses a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength region, so that the optical characteristics do not change much even if the incident angle is changed. , Proposes a near-infrared cut filter with high visible light transmittance. Further, in Patent Document 3, by using a phthalocyanine dye having a specific structure, near-infrared rays that achieve both excellent visible light transmittance and long absorption maximum wavelength, which have been problems in the past, at a high level. It is stated that a cut filter can be obtained.

However, in the near-infrared cut filter described in Patent Documents 2 and 3, although the applied base material has an absorption band having sufficient strength in the vicinity of 700 nm, it is in the near-infrared wavelength region such as 900 to 1200 nm. Has almost no absorption. Therefore, the light rays in the near-infrared wavelength region are cut almost only by the reflection of the dielectric multilayer film, but in such a configuration, the internal reflection in the optical filter and the slight stray light due to the reflection between the optical filter and the lens are generated. , May cause ghosts and flares when shooting in a dark environment. In particular, in recent years, there has been a strong demand for higher image quality of cameras even in mobile devices such as smartphones, and there have been cases where conventional optical filters cannot be used suitably.

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

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 configuration described in Patent Document 5 also sufficiently improves color shading. Sometimes I couldn't. For example, FIG. 5 of Patent Document 5 shows optical characteristic graphs at 0-degree incident and 30-degree incident, but even at 30-degree incident, the region of the hem of the visible light transmission band (630 to 700 nm). ), A large wavelength shift is observed.

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

In addition to the above problems, in recent years, the demand for heat resistance has become more and more strict in view of the development in in-vehicle applications and the like. That is, it is required that changes in spectral characteristics can be suppressed as much as possible even when exposed to high temperatures for a long time.

As a method for improving the heat resistance and UV resistance of the dye described above, for example, a method of using the dye not as a dye (dissolved state) but as a pigment (particle dispersion state) is known (for example, Patent Documents 6 and 7). .. In Patent Document 7, regarding a near-infrared cut filter using a diimonium-based dye, which has a problem in heat resistance, the dye is dispersed in a dispersion medium (toluene) and then dissolved in a resin to be used (dye). It has been shown that heat resistance and UV resistance are improved when used as a. However, even if the technique of the above-mentioned prior literature is used, not only the absorption in the near-infrared region is not sufficient, but only a film having an extremely high haze value can be obtained, and the above-mentioned problems cannot be solved.

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

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

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

Further, the present inventors can obtain an optical filter having an extremely low haze value and excellent heat resistance by making the organic pigment into fine particles and setting the average particle size within a specific range. I found.
An example of the embodiment of the present invention completed based on these findings is 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 region having a wavelength of 900 nm or more and 1200 nm or less.

[2] The optical filter according to item [1], wherein the base material further satisfies the following requirement (b).
(B) It has a layer containing the compound (A) having an absorption maximum in a region having a wavelength 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 a squarylium compound, a phthalocyanine compound and a cyanine compound.

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

式（Ｉ）中、
Ｒ¹は、独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、カルボキシ基、リン酸基、−ＳＲⁱ基、−ＳＯ₂Ｒⁱ基、−ＯＳＯ₂Ｒⁱ基または下記Ｌ^a〜Ｌ^hのいずれかを表し、Ｒ²は、独立にハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−ＮＲ^gＲ^h基、−ＳＲⁱ基、−ＳＯ₂Ｒⁱ基、−ＯＳＯ₂Ｒⁱ基または下記Ｌ^a〜Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、−Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a〜Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a〜Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１〜１２の脂肪族炭化水素基
（Ｌ^b）炭素数１〜１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３〜１４の脂環式炭化水素基
（Ｌ^d）炭素数６〜１４の芳香族炭化水素基
（Ｌ^e）炭素数２〜１４の複素環基
（Ｌ^f）炭素数１〜１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１〜１２のアシル基
（Ｌ^h）置換基Ｌを有してもよい炭素数１〜１２のアルコキシカルボニル基
置換基Ｌは、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のハロゲン置換アルキル基、炭素数３〜１４の脂環式炭化水素基、炭素数６〜１４の芳香族炭化水素基および炭素数３〜１４の複素環基からなる群より選ばれる少なくとも１種であり、
ｎは０〜４の整数を表し、
Ｘは電荷を中和させるのに必要なアニオンを表す。

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 ~ Represents any of ^{L h , R 2} is an independent halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ It represents any of ^{R i} group, -OSO ₂ R ⁱ group or L ^{a to} L ^{h below, and R g} and R ^h are independently hydrogen atom, -C (O) R ⁱ group or L ^{a to} L below, respectively. represents either ^e, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L ^b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L ^d) carbon Aromatic hydrocarbon group of number 6 to 14 (L ^e ) Heterocyclic group having 2 to 14 carbon atoms (L ^f ) An alkoxy group having 1 to 12 carbon atoms (L ^g ) Substituent number of carbon atoms may be L. An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L ^h ) substituent L of 1 to 12 The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms and 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 from 0 to 4
X represents the anion required to neutralize the 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. Based resin, polysulfone based resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, A term characterized by being at least one resin selected from the group consisting of an allyl ester-based curable resin, a silsesquioxane-based ultraviolet curable resin, an acrylic-based ultraviolet curable resin, and a vinyl-based ultraviolet curable resin [ 6] The optical filter according to.

[8] The item is characterized in that 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). The optical filter according to any one of [1] to [7].

[9] The optical filter according to any one of items [1] to [8] for a solid-state image sensor.

[10] A solid-state image sensor including the optical filter according to any one of items [1] to [9].
[11] A camera module including 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 having excellent near-infrared cut characteristics, less dependence on incident angle, transmittance characteristics in the visible light wavelength range, color shading suppression effect, ghost suppression effect and heat resistance. Can be done.

1 (a) and 1 (b) are schematic views showing an example of a preferable configuration 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 an Example and a comparative example. It is a schematic diagram for demonstrating the ghost evaluation of the camera image performed in an Example and a comparative example.

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

The optical filter of the present invention is characterized by having a base material satisfying the requirement (a) described later and having 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 in consideration of the recent trend toward thinner and lighter solid-state image sensors. Since the optical filter of the present invention contains the base material, it can be made thinner.

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 region having a wavelength of 900 nm or more and 1200 nm or less.
Further, 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 region having a wavelength of 650 nm or more and 760 nm or less.
Each requirement will be described below.

<Requirement (a)>
In the requirement (a), the components constituting the layer containing the organic pigment (S) are not particularly limited, and examples thereof include transparent resins, sol-gel materials, and low-temperature cured glass materials, but they are easy to handle. From the viewpoint, it is preferably a transparent resin.

≪Organic pigment (S) ≫
The organic pigment (S) is not particularly limited as long as it is an organic pigment having an absorption maximum in the wavelength region of 900 nm or more and 1200 nm or less, and for example, the compound (S) having an absorption maximum in the wavelength region of 900 nm or more and 1200 nm or less. Can be obtained as a dispersion of the organic pigment (S) by dispersing the above 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 it is a compound having an absorption maximum in the region of a wavelength of 900 nm or more and 1200 nm or less, but is preferably a diimonium-based compound, a metal dithiolate complex-based compound, a pyrolopyrrole-based compound, or a cyanine-based compound. It is at least one compound selected from the group consisting of compounds, croconium compounds and naphthalocyanine compounds, and more preferably at least one compound selected from the group consisting of diimonium compounds and metal dithiolate complex compounds. Particularly preferably, it is a diimonium-based compound represented by the following formula (I). By using such a compound (S), good near-infrared absorption characteristics and excellent visible light transmittance can be imparted.

式（Ｉ）中、
Ｒ¹は、独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、カルボキシ基、リン酸基、−ＳＲⁱ基、−ＳＯ₂Ｒⁱ基、−ＯＳＯ₂Ｒⁱ基または下記Ｌ^a〜Ｌ^hのいずれかを表し、Ｒ²は、独立にハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−ＮＲ^gＲ^h基、−ＳＲⁱ基、−ＳＯ₂Ｒⁱ基、−ＯＳＯ₂Ｒⁱ基または下記Ｌ^a〜Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、−Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a〜Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a〜Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１〜１２の脂肪族炭化水素基
（Ｌ^b）炭素数１〜１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３〜１４の脂環式炭化水素基
（Ｌ^d）炭素数６〜１４の芳香族炭化水素基
（Ｌ^e）炭素数２〜１４の複素環基
（Ｌ^f）炭素数１〜１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１〜１２のアシル基
（Ｌ^h）置換基Ｌを有してもよい炭素数１〜１２のアルコキシカルボニル基
置換基Ｌは、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のハロゲン置換アルキル基、炭素数３〜１４の脂環式炭化水素基、炭素数６〜１４の芳香族炭化水素基および炭素数３〜１４の複素環基からなる群より選ばれる少なくとも１種であり、
ｎは０〜４の整数を表し、
Ｘは電荷を中和させるのに必要なアニオンを表す。

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 ~ Represents any of ^{L h , R 2} is an independent halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ It represents any of ^{R i} group, -OSO ₂ R ⁱ group or L ^{a to} L ^{h below, and R g} and R ^h are independently hydrogen atom, -C (O) R ⁱ group or L ^{a to} L below, respectively. represents either ^e, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L ^b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L ^d) carbon Aromatic hydrocarbon group of number 6 to 14 (L ^e ) Heterocyclic group having 2 to 14 carbon atoms (L ^f ) An alkoxy group having 1 to 12 carbon atoms (L ^g ) Substituent number of carbon atoms may be L. An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L ^h ) substituent L of 1 to 12 The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms and 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 from 0 to 4
X represents the anion required to neutralize the charge.

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

The R ² is preferably a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, or a hydroxyl group. , Amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino Group, pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, more preferably chlorine. Atomic, 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 , Pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, particularly preferably methyl group, ethyl group, n-propyl group, isopropyl group. ^{The number (value of n) of R 2} bonded to the same aromatic ring is not particularly limited as long as it is 0 to 4, but it is preferably 0 or 1.

The X is an anion required to neutralize the charge, X is one when X is a divalent anion, and two X when X is a monovalent anion. is there. In the latter case, the two anions may be the same or different, but they are preferably the same from a synthetic point of view. X is not particularly limited as long as it is such an anion, but as an example, those listed in Table 1 below can be mentioned.

Ｘとしては、ジイモニウム系化合物の耐熱性、耐光性および分光特性の観点から、上記表１中の（Ｘ−１０）、（Ｘ−１６）、（Ｘ−１７）、（Ｘ−２１）、（Ｘ−２２）、（Ｘ−２４）、（Ｘ−２８）が特に好ましい。

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

Examples of the diimonium-based 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. 4252961, Japanese Patent Application Laid-Open No. 2010-516823, Japanese Patent Application Laid-Open No. 63-165392. It can be synthesized by referring to the methods described in the publications and the like.

The absorption maximum wavelength of the compound (S) is preferably 920 nm or more and 1195 nm or less, more preferably 950 nm or more and 1190 nm or less, and further preferably 980 nm or more and 1180 nm or less. 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 suppressing 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 in the compound (S) is selected, the compound (S) dissolves in the dispersion medium and becomes a dye. In this case, not only the desired spectral characteristics cannot be obtained, but also the heat resistance and UV resistance are significantly lowered. Therefore, it is necessary to select a dispersion medium that has low solubility in compound (S) and does not dye. Whether or not the dispersion medium dyes the compound (S) is determined by adding the dispersion medium to the compound (S) and dropping it in the form of 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 substance 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, and alcohols such as isopropanol and ethanol are preferable. , 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-based compound, alcohols such as isopropanol and ethanol are particularly preferable from the viewpoint of storage stability of the dispersion. When a halogen solvent such as methylene chloride is used, the compound (S) is dyed, which is not preferable.

(3) Disperser Examples of the disperser used to disperse the compound (S) in a dispersion medium include bead mills, ball mills, vibrating ball mills, planetary ball mills, sand mills, colloid mills, jet mills and roller mills. ..
Further, the organic pigment (S) may be prepared by refining the primary particles of the compound (S) by so-called salt milling. As the salt milling method, for example, the method disclosed in JP-A-8-179111 can be adopted.

(4) Dispersant For the purpose of improving dispersion stability, the compound (S) may be dispersed using a known dispersant. Examples of the dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, and sorbitan fatty acid ester dispersants. , Polyester-based dispersant, (meth) acrylic-based dispersant, and the like. As commercially available products, for example, (meth) acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (all manufactured by Big Chemie (BYK)), Disperbyk-161, Disperbyk. Urethane-based dispersants such as -162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by Big Chemie (BYK)), Solspers 76500 (manufactured by Lubrizol Co., Ltd.), Solspers 24000 ( In addition to polyethyleneimine dispersants such as Lubrizol Co., Ltd.), polyester dispersants such as Ajispar PB821, Ajispar PB822, Ajispar PB880, and Ajispar PB881 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) LPN21324 (manufactured by Big Chemie (BYK)), Marialim SC series, Esleem AD series, Esleam C2093I (all manufactured by Nichiyu Co., Ltd.) and the like can be used. Further, as the (meth) acrylic dispersant, for example, Japanese Patent Application Laid-Open No. 2011-232735, Japanese Patent Application Laid-Open No. 2011-237769, Japanese Patent Application Laid-Open No. 2012-32767, International Publication No. 2011/129078 Pamphlet, International Publication No. 2012 The copolymer disclosed in Pamphlet No. / 001945 and the like can also be used. The dispersant can be used alone or in combination of two or more.

In the present invention, it is preferable to use a dispersant having an acidic functional group because the dispersion stability is good and the chemical action on the compound (S) is small. 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, and for example, an ethylenically unsaturated monomer having an acidic functional group. And other copolymers with copolymerizable ethylenically unsaturated monomers. In addition, examples of commercially available products include the above-mentioned Marialim 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 mass, more preferably 10 to 200 parts by mass, and further, with respect to 100 parts by mass of the organic pigment (S). It is preferably 20 to 150 parts by mass. When the content of the dispersant is within the above range, the dispersion stability of the dispersion is good, and the heat resistance, water resistance and adhesion of the base material and the optical filter are excellent, which is preferable.

In the present invention, it is preferable to perform the centrifugation treatment after the dispersion step. By the centrifugation treatment, coarse organic pigment particles having insufficient dispersion can be removed, the average particle size of the organic pigment can be reduced, and as a result, the haze of the optical filter can be reduced.

The time of the centrifugation is not particularly limited, but may be, for example, 1 minute or more and 60 minutes or less. The centrifugal acceleration of the centrifuge when performing centrifugation is not particularly limited, but can be, for example, 10 G or more and 50,000 G or less.

(5) Average Particle Size of Organic Pigment (S) The average particle size 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 size of the organic pigment (S) in the present invention is a value obtained by the measuring method described in Examples described later. When the average particle size of the organic pigment (S) is in the above range, an optical filter having an extremely low haze value and excellent heat resistance can be obtained.

(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 a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing S) is used, 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, and the base material is a glass support or a resin support as a base. When a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) is laminated on a support such as a body is used, the transparent resin containing the organic pigment (S) is used. With respect to 100 parts by mass of the resin forming the layer, preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 4.0 parts by mass, and particularly preferably 0.3 to 3.0 parts by mass. is there. 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 resin support as a base as a base material.

<Requirement (b)>
In the requirement (b), the components constituting the layer containing the compound (A) are not particularly limited, and examples thereof include transparent resins, sol-gel materials, low-temperature cured glass materials, etc., but they are easy to handle and the compounds ( From the viewpoint of compatibility with A), a transparent resin is preferable.

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

Squalylium compounds have excellent visible light transmittance, steep absorption characteristics, and high molar absorption coefficient, but may generate fluorescence that causes scattered light when absorbing light. In such a case, by using the squarylium compound and the other compound (A) in combination, it is possible to obtain an optical filter with less scattered light and better camera image quality.

The absorption maximum wavelength of 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 10. It is 60 nm, more preferably 15 to 55 nm, and even more preferably 20 to 50 nm. When the difference in absorption maximum wavelength is within the above range, scattered light due to fluorescence can be sufficiently reduced, and a wide absorption band around 700 nm and excellent visible light transmittance can be compatible with each other, which is preferable.

The content of the entire compound (A) is, as the base material, 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). When 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 is used, 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, still more preferably 0.08 to 1.0 parts by mass, and the base material is a glass support or a resin support as a base. When a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) and a compound (A) is laminated on a support such as a body is used, the compound (A) is used. With respect to 100 parts by mass of the resin forming the transparent resin layer containing the above, preferably 0.4 to 5.0 parts by mass, more preferably 0.6 to 4.0 parts by mass, still more preferably 0.8 to 3. 5 parts by mass.

The base material may be a single layer or a multilayer as long as it has a layer containing the organic pigment (S). Further, the compound (A) may be contained in the same layer as the organic pigment (S) or may be contained 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 substrate composed of a transparent resin substrate containing the organic pigment (S) and the compound (A), an organic pigment (S). ) And compound (A) on a transparent resin substrate on which a resin layer such as an overcoat layer made of a curable resin or the like is laminated, on a support such as a glass support or a base resin support. Examples thereof include a base material on which a transparent resin layer such as an overcoat layer made of a curable resin containing an organic pigment (S) and a 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) or the like 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) and an overcoat layer made of a curable resin containing a compound (A) on a support such as a glass support or a resin support as a base. Examples thereof include a base material on which and is laminated. In the present invention, it is preferable to provide an overcoat layer made of a curable resin or the like 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 of the above is more preferably 150 nm or less, and particularly preferably 100 nm or less.

<Other characteristics and physical characteristics>
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. By using a base material having such a transmission characteristic, a high light transmission characteristic can be achieved in the visible light region, and a highly sensitive camera function can be achieved.

The thickness of the base material can be appropriately selected depending on the desired application, and is not particularly limited, but is preferably 10 to 200 μm, more preferably 20 to 180 μm, and even more preferably 25 to 150 μm. When the thickness of the base material is within the above range, the optical filter using the base material can be made thinner and lighter, and can be suitably used for various applications such as a solid-state image sensor. In particular, when the base material made of the transparent resin substrate is used for 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 base material is not particularly limited as long as it does not impair the effects of the present invention, and is, for example, thermal stability and a film. The 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 the resin. Examples thereof include resins having a temperature of 110 to 370 ° C, more preferably 120 to 360 ° C. Further, when the glass transition temperature of the resin is 140 ° C. or higher, a film capable of forming a dielectric multilayer film by vapor deposition at a higher temperature can be obtained, which is particularly preferable.

As the transparent resin, when a resin plate having a thickness of 0.1 mm made of the resin 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 obtained substrate exhibits good transparency as an optical film.

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

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

The transparent resin may be used alone or in combination of two or more.

≪Cyclic polyolefin resin≫
The cyclic polyolefin 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.

式（Ｘ₀）中、Ｒ^x1〜Ｒ^x4はそれぞれ独立に、下記（i'）〜（ix'）より選ばれる原子または基を表し、ｋ^x、ｍ^xおよびｐ^xはそれぞれ独立に、０〜４の整数を表す。
（i'）水素原子
（ii'）ハロゲン原子
（iii'）トリアルキルシリル基
（iv'）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１〜３０の炭化水素基
（v'）置換または非置換の炭素数１〜３０の炭化水素基
（vi'）極性基（但し、（ii'）および（iv'）を除く。）
（vii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成されたアルキリデン基（但し、前記結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（vi'）より選ばれる原子または基を表す。）
（viii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（i'）〜（vi'）より選ばれる原子または基を表す。）
（ix'）Ｒ^x2とＲ^x3とが、相互に結合して形成された単環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1とＲ^x4は、それぞれ独立に前記（i'）〜（vi'）より選ばれる原子または基を表す。）

Wherein ^{_{(X 0), R x1 ~R}} x4 each independently represents an atom or a group selected from the following (i ') ~ (ix' ), k x, m x and p ^x are each independently 0 Represents an integer of ~ 4.
(I') Hydrogen atom (ii') Halogen atom (iii') Trialkylsilyl group (iv') Substituent or unsubstituted carbon number 1 having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. ~ 30 hydrocarbon groups (v') substituted or unsubstituted hydrocarbon groups (vi') polar groups with 1 to 30 carbon atoms (excluding (ii') and (iv'))
(Vii') Alkylidene groups formed by mutual bonding of ^{R x1} and R ^x2 or R ^x3 and R ^{x4 (however, R x1 to} R ^x4 not involved in the bond are independently described in (i'). ) ~ (Vi') represents an atom or group selected.)
(Viii') A monocyclic or polycyclic hydrocarbon ring or heterocycle formed by mutually bonding ^{R x1} and R ^x2 or R ^x3 and R ^{x4 (however, R x1 to} R not involved in the bond). ^x4 represents an atom or group independently selected from the above (i') to (vi').)
(Ix') A monocyclic hydrocarbon ring or heterocycle formed by bonding ^{R x2} and R ^{x3 to each other (however, R x1} and R ^{x4 that} are not involved in the bond are independently described in (i). Represents an atom or group selected from') to (vi').)

式（Ｙ₀）中、Ｒ^y1およびＲ^y2はそれぞれ独立に、前記（i'）〜（vi'）より選ばれる原子または基を表すか、Ｒ^y1とＲ^y2とが、相互に結合して形成された単環もしくは多環の脂環式炭化水素、芳香族炭化水素または複素環を表し、ｋ^yおよびｐ^yはそれぞれ独立に、０〜４の整数を表す。

In equation (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 resin preferably has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (1) and the structural unit represented by the following formula (2).

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

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

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

In the formula (2), R ^{1 to} R ⁴ and a to d are independently ^{synonymous with R 1 to} R ⁴ and a to d in the formula (1), and Y is a single bond, −SO ₂ -Or -CO-, R ⁷ and R ⁸ independently represent a halogen atom, a monovalent organic group or a nitro group having 1 to 12 carbon atoms, and g and h independently represent 0 to 4, respectively. It indicates an integer, and m indicates 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

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

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

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

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

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

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

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

≪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 and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It is preferably a polymer containing 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 groups or methacrylic groups in the molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. What is done can be mentioned. The acrylic ultraviolet curable resin is a base material in which a transparent resin layer containing the compound (A) and a curable resin is laminated on a glass support or a resin support as a base, or a compound ( When a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing A) is used, it can be particularly preferably used as the curable resin.

≪Epoxy resin≫
The epoxy resin is not particularly limited, but can be roughly classified into an ultraviolet curable type and a thermosetting type. The ultraviolet curable epoxy resin is synthesized from, for example, a composition containing a compound having one or more epoxy groups in the molecule and a compound that generates acid by ultraviolet rays (hereinafter, also referred to as "photoacid generator"). Examples of the thermosetting epoxy resin include those synthesized from a compound having one or more epoxy groups in the molecule and a composition containing an acid anhydride. Can be done. The epoxy-based ultraviolet curable resin contains, as the base material, a base material in which a transparent resin layer containing the compound (A) is laminated on a glass support or a resin support as a base, or a compound (A). When a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate is used, it can be particularly preferably used as the curable resin.

≪Commercial product≫
Examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic polyolefin resins include Arton manufactured by JSR Corporation, Zeonoa manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available products of the polyether sulfone-based resin include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate-based resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate-based resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available fluorene polyester-based resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include Acryviewer manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available products of the silsesquioxane-based ultraviolet curable resin include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Other pigments (X)>
The base material may further contain an organic pigment (S) and another dye (X) that does not correspond to the compound (A).

The other dye (X) is not particularly limited as long as it has a maximum absorption wavelength in the region of less than 650 nm or a wavelength of more than 760 nm and less than 900 nm, but a dye having a maximum absorption 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, octaphyllin compounds, diimonium compounds, pyrolopyrrole compounds, and borondipyrromethene (BODIPY). Examples thereof include at least one compound selected from the group consisting of a system compound, a perylene system compound and a metal dithiolate system compound.

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

<Other ingredients>
The base material may further contain an antioxidant, a near-ultraviolet absorber, a fluorescent 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-based compounds, indole-based compounds, benzotriazole-based compounds, and triazine-based compounds.

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

These other components may be mixed with a resin or the like when the base material is produced, or may be added when the resin is synthesized. The amount to be added is appropriately selected according to the desired characteristics, but is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the resin. It is a department.

<Manufacturing method of base material>
When the base material is a base material containing 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. By coating with a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding, a base material on which an overcoat layer is laminated can be produced.

The base material is made of a curable resin containing an organic pigment (S) on a support such as a glass support or a resin support as a base, or 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 is laminated, for example, it is preferable to melt-mold or cast-mold a resin solution containing the compound (A) on the support or the transparent resin substrate. After coating by a method such as spin coating, slit coating, or inkjet, the solvent is dried and removed, and if necessary, further light irradiation or heating is performed to obtain an organic pigment on the support or the transparent resin substrate. A base material on which a transparent resin layer containing (S) is formed can be produced.

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

≪Cast molding≫
The cast molding is a method of casting a resin composition containing an organic pigment (S), a resin, a solvent and, if necessary, other components on a suitable support to remove the solvent; 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, and then irradiated with ultraviolet rays. 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 an organic pigment (S), the base material can be obtained by peeling the coating film from the support after cast molding. Further, the base material is a curable resin containing an organic pigment (S) on a support such as a glass support or a resin support as a base, 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 the above is laminated, the base material can be obtained by not peeling off the coating film after cast molding.

The support includes a phosphate-based support containing a copper component such as a near-infrared absorbing glass plate (for example, "BS-11" manufactured by Matsunami Glass Industry Co., Ltd. or "NF-50T" manufactured by AGC 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. and "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, and further preferably 0.5 part 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 the residual solvent is within the above range, a transparent resin layer (transparent resin substrate) capable of easily exhibiting a desired function can be obtained, in which deformation of the base material and change in optical characteristics are unlikely to occur.

[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 an ability to reflect near infrared rays or a film having an antireflection effect in the visible light region, and having a dielectric multilayer film has a more excellent visible light transmittance. Infrared cut characteristics can be achieved.

In the present invention, the dielectric multilayer film may be provided on one side of the base material or on both sides. When it is provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when it is provided on both sides, it is possible to obtain an optical filter which has high strength and is less likely to warp or twist. When the optical filter is applied to a solid-state image sensor application, it is preferable that the optical filter has a small warp or twist. Therefore, it is preferable to provide a dielectric multilayer film on both sides of the resin substrate.

It is desirable that the dielectric multilayer film preferably has a reflection property over a wavelength range of 700 to 1100 nm, more preferably a wavelength of 700 to 1150 nm, and even more preferably 700 to 1200 nm.

As a form having dielectric multilayer films on both sides of the base material, it is based on the first optical layer having reflection characteristics mainly 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. With respect to the form in which the second optical layer having one side of the material and having the reflection characteristics mainly in the vicinity of 900 nm to 1150 nm is provided on the other side of the base material (see FIG. 1A) and the vertical direction of the optical filter. When measured from an angle of 5 °, a third optical layer having reflection characteristics mainly in the vicinity of a wavelength of 700 to 1150 nm is provided on one side of the base material, and a fourth optical layer having antireflection characteristics in the visible light region is provided. Examples thereof include a form having the base material on the other surface (see FIG. 1B).

Examples of the dielectric multilayer film include those in which high refractive index material layers and low refractive index material layers are alternately laminated. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of 1.7 to 2.5 is usually selected. Examples of such a material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide and the like as main components, and titanium oxide, tin oxide and /. Alternatively, those containing a small amount of cerium oxide or the like (for example, 0 to 10 parts by mass with respect to 100 parts by mass of the main component) can be mentioned.

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 1.2 to 1.6 is usually selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride and sodium hexafluoride.

The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a dielectric in which high refractive index material layers and low refractive index material layers are alternately laminated directly on a base material by a CVD method, a sputtering method, a vacuum vapor deposition method, an ion-assisted vapor deposition method, an ion plating method, or the like. 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 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 in this range, the optical film thickness in which the product (n × d) of the refractive index (n) and the film thickness (d) is calculated by λ / 4, the high refractive index material layer, and the low refraction The thickness of each layer of the index material layer becomes almost the same value, and there is a tendency that the blocking / transmitting of a specific wavelength can be easily controlled due to the relationship between the optical characteristics of reflection / refraction.

The total number of layers of the high-refractive index material layer and the low-refractive index material layer in the dielectric multilayer film is preferably 16 to 70 layers as a whole, more preferably 20 to 60 layers, and 24. It is particularly preferable to have ~ 50 layers. When the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and warpage of the optical filter and cracks of the dielectric multilayer film are reduced. can do.

In the present invention, the material species, the high refractive index material layer and the low refractive index material layer constituting the high refractive index material layer and the low refractive index material layer according to the absorption characteristics of the near infrared absorber such as the compound (A) and the organic pigment (S). By appropriately selecting the thickness of each layer of the refractive index material layer, the order of lamination, and the number of laminations, it has sufficient light-cutting characteristics in the near-infrared wavelength region while ensuring sufficient transmittance in the visible light region. Moreover, the reflectance when near-infrared light is incident from an oblique direction can be reduced.

Here, in order to optimize the above conditions, for example, optical thin film design software (for example, Ethential Macleod, manufactured by Thin Film Center) is used to achieve both an antireflection effect in the visible light region and a light ray cutting effect in the near infrared region. You can set the parameters so that you can. In the case of the above software, for example, when designing the first optical layer, the target transmittance at a wavelength of 400 to 700 nm is set to 100%, the value of Target Tolerance is set to 1, and the target transmittance at a wavelength of 705 to 950 nm is set to 0%. Parameter setting methods such as setting the value of Target Tolerance to 0.5 can be mentioned. These parameters can also change the value of Target Tolerance by further dividing the wavelength range according to various characteristics of the base material (i) and the like.

[Other functional membranes]
The optical filter of the present invention has a surface between the base material and the dielectric multilayer film, a surface opposite to the surface on which the dielectric multilayer film is provided, or a dielectric multilayer film, as long as the effects of the present invention are not impaired. Antireflection film, hard, for the purpose of improving the surface hardness of the base material and the dielectric multilayer film, improving chemical resistance, antistatic and scratch erasing on the surface opposite to the surface on which the base material of the film is provided. A functional film such as a coat film or an antistatic film can be appropriately provided.

The optical filter of the present invention may contain one layer made of the functional film, or may contain two or more layers. When the optical filter of the present invention contains two or more layers made of the functional film, it may contain 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 and the like is melt-molded or cast on a base material or a dielectric multilayer film in the same manner as described above. Examples thereof include a molding method.

It can also 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 the coating agent by irradiation with ultraviolet rays or the like.

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

In addition, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can be used, and the photopolymerization initiator and the thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more.

The proportion of the polymerization initiator in the curable composition 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 antireflection film, a hard coat film or an antistatic film which has excellent curing properties and handleability of the curable composition and has a desired hardness. it can.

Further, an organic solvent may be added to the curable composition as a solvent, 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 and 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 thereof include amides such as methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

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

Further, for the purpose of improving the adhesion between the base material and the functional film and / or the dielectric multilayer film and the adhesion between the functional film and the dielectric multilayer film, a corona is formed on 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 ray cutting ability. Therefore, it is useful for correcting the luminosity factor of a solid-state image sensor 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, automobile cameras, televisions, car navigation systems, mobile information terminals, video game machines, portable game machines. , Fingerprint authentication system, digital music player, etc. Further, it is also useful as a heat ray cut filter or the like attached to a glass plate or the like of an automobile or a building.

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

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In addition, "part" means "mass part" unless otherwise specified. The method for measuring each physical property value and the method for evaluating 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 and the like.
(A) Using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS, mass average molecular weight in terms of standard polystyrene. (Mw) and number average molecular weight (Mn) were measured.
(B) Using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: THF), the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured.

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

<Average particle size>
The average particle size of the organic pigment was measured by the following method. The prepared dispersion of organic pigment is diluted with a solvent having the same composition as the dispersion medium until the pigment concentration becomes 0.5% by mass, and this is dropped onto a glass plate to dry, and then a scanning electron microscope (SEM) (SEM) ( Observation was performed at "S4800" manufactured by Hitachi High-Technologies Corporation. 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 magnifications to calculate the average particle size. In addition, extremely large or small particles were excluded, and when the particle shape was not spherical, the longest diameter (major diameter) observed was defined as the particle diameter.

<Spectroscopic transmittance>
The transmittance of the base material and the optical filter in each wavelength range was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation. This transmittance was measured using the spectrophotometer under the condition that the light is vertically incident on the base material and the filter.

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

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

<Color shading evaluation of camera image>
The color shading evaluation when the optical filter was incorporated into 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 used as a D65 light source (standard light source device “Macbeth Judge II” manufactured by X-Rite). The image was taken below, and the difference in color between the center and the edge of the white plate in the camera image was evaluated according to the following criteria.

There is no problem at all and the acceptable level is A, there is a slight difference in color, but there is no practical problem as a high-quality camera module, and the acceptable level is B. There is a difference in color and it is not acceptable for high-quality camera module applications. The possible level was determined to be C, and the level that was unacceptable for general camera module applications due to a clear difference in color was determined to be D.

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

<Ghost evaluation of camera image>
The ghost evaluation when the optical filter was incorporated into 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 in a dark room (“Luminer Ace LA-150TX” manufactured by Hayashi Clock Industry Co., Ltd.). The degree of ghost generation around the light source in the image was evaluated according to the following criteria.

There is no problem at all and the acceptable level is A, some ghosts are recognized, but there is no practical problem as a high-quality camera module and the acceptable level is B, ghosts are generated and it is unacceptable for high-quality camera module applications. The possible level was determined to be C, and the level that was unacceptable for general camera module applications with a severe degree of ghost was determined to be D.

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

[Synthesis example]
Compound (A) and compound (S) used in the following examples were synthesized by a generally known method. Examples of the method include JP-A-60-228448, JP-A-1-146846, JP-A-1-228960, Patent No. 4081149, "Parthalocyanine-Chemistry and Function-" (IPC, 1997), Japanese Patent Application Laid-Open No. 2009-108267, Japanese Patent Application Laid-Open No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, and the like can be mentioned.

<Synthesis example 1>
8-Methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] 100 g of dodeca-3-ene (hereinafter also referred to as “DNM”), 18 g of 1-hexene (molecular weight modifier) and 300 g of toluene (solvent for ring-opening polymerization reaction) are charged in a nitrogen-substituted reaction vessel. , This 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 methanol-modified tungsten hexachloride toluene solution (concentration 0.025 mol / liter) were added to the solution in the reaction vessel as a polymerization catalyst. Was added, and the solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

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

1,000 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.} The hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ^{2 and a reaction temperature of 165 ° C.} After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter, also referred to as "resin A"). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

<Synthesis example 2>
In a reaction vessel equipped with a stirrer, thermometer and condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol at room temperature, 3-hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Company, Inc.) , Molecular weight: 222) 27.047 g, and Isophorone diisocyanate (manufactured by Ebonic, molecular weight: 222) 26.481 g are dissolved in 19 g of methyl ethyl ketone (MEK), 0.405 g of dioctyltin dilaurate is added, and then 70 with stirring. The temperature was raised to ° C. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate was additionally added, and the reaction was continued at 70 ° C. The reaction was terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ^{-1) had almost disappeared from 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).

[Example of preparation of organic pigment]
<Preparation Example 1>
Dispersant having 5 g of the compound (s-15) (absorption maximum wavelength 1083 nm in dichloromethane) and an acidic functional group shown in Table 2-4 above in a 0.25 L plastic container (Nikki Co., Ltd. "Marialim SC" -0505K ”), 95 g of isopropyl alcohol (IPA) as a dispersion medium, and 175 g of zirconia beads (“YTZ-0.05” manufactured by Nikkato Corporation) with a diameter of 0.05 mm were added to the paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) 1 hr dispersion processing was performed in. Then, the mixture was cooled to room temperature, and the 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, and zirconia beads having a diameter of 0.05 mm (Nikkato Corporation "YTZ-0. 05 ") 175 g was added, and 1 hr dispersion treatment was performed with a paint shaker. Then, the mixture was cooled to room temperature, and the zirconia beads were filtered off with a metal mesh to obtain an organic pigment dispersion (S-2).

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

<Preparation Example 4>
5 g of the compound (s-6) (absorption maximum wavelength in dichloromethane, 1093 nm) shown in Table 2-4 above, 95 g of methyl isobutyl ketone (MIBK) as a dispersion medium, and zirconia having a diameter of 0.05 mm in a 0.25 L plastic container. 175 g of beads (“YTZ-0.05” manufactured by Nikkato Corporation) were added and subjected to 1 hr dispersion treatment with a paint shaker. Then, the mixture was cooled to room temperature, and the 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 in a centrifuge (“Cool Centrifuge CR-22N” manufactured by himac) at a centrifugal acceleration of 36000 G for 10 minutes, and dispersed after the treatment. The liquid was filtered through a polypropylene filter (pore diameter 3 μm) to obtain an organic pigment dispersion liquid (S-5).

[Example 1]
In Example 1, an optical filter having a substrate having a transparent resin layer containing an organic pigment (S) formed on both sides of a transparent resin substrate containing the compound (A) was prepared by 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) as the compound (A) (absorption maximum wavelength in dichloromethane, 713 nm) and the following A solution having a resin concentration of 20% by mass was prepared by adding 0.06 g of the compound (a-2) represented by the formula (a-2) (absorption maximum wavelength in dichloromethane, 736 nm) and methylene chloride. 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 under reduced pressure at 100 ° C. 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.

上記式（ａ−１）中、ｉ−Ｐｒはイソプロピル基を示す。
得られた透明樹脂製基板の片面に、下記組成の樹脂組成物（１）をバーコーターで塗布し、オーブン中７０℃で３分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが３μｍとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光（露光量５００ｍＪ／ｃｍ²，２００ｍＷ）を行い、樹脂組成物（１）を硬化させ、透明樹脂製基板上に透明樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物（１）からなる透明樹脂層を形成し、化合物（Ａ）を含む透明樹脂製基板の両面に有機顔料（Ｓ）を含む透明樹脂層を有する基材を得た。

In the above formula (a-1), i-Pr represents an isopropyl group.
The 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, using a conveyer-type exposure apparatus performs exposure (exposure 500 mJ / cm ^2, 200 mW), the resin composition (1) is cured and to form a transparent resin layer on a transparent resin substrate. Similarly, a transparent resin layer made of the resin composition (1) is formed on the other surface of the transparent resin substrate, and the transparent resin substrate containing the compound (A) contains the organic pigment (S) on both sides. A substrate having a resin layer was obtained.

Resin composition (1): 100 g of tricyclodecanedimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 50 g of the 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 surface of the obtained substrate, and a dielectric multilayer film (II) is formed as a second optical layer on the other surface of the substrate. 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 vapor 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 vapor deposition temperature of 100 ° C. (20 layers in total). In both the dielectric multilayer films (I) and (II), the silica layer and the titania layer are formed in the order of the titania layer, the silica layer, the titania layer, ... the silica layer, the titania layer, and the silica layer from the substrate side. The layers were alternately laminated, and the outermost layer of the optical filter was a silica layer.

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

膜構成最適化の結果、実施例１では、誘電体多層膜（Ｉ）は、膜厚３１〜１５７ｎｍのシリカ層と膜厚１０〜９５ｎｍのチタニア層とが交互に積層されてなる、積層数２６の多層蒸着膜となり、誘電体多層膜（ＩＩ）は、膜厚３７〜１９４ｎｍのシリカ層と膜厚１２〜１１４ｎｍのチタニア層とが交互に積層されてなる、積層数２０の多層蒸着膜となった。最適化を行った膜構成の一例を下記表４に示す。

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

得られた光学フィルターの垂直方向から測定した分光透過率およびヘイズを測定し、各波長領域における光学特性を評価するとともに、上述した耐熱性を評価した。結果を図２および表５に示す。

The spectral transmittance and haze measured from the vertical direction of the obtained optical filter were measured, the optical characteristics in each wavelength region were evaluated, and the heat resistance described above was evaluated. The results are shown in FIG. 2 and Table 5.

In addition, a camera module was created using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Table 5. The camera images obtained gave 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): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), tricyclodecanedimethanol acrylate 50 g, 1-hydroxycyclohexylphenyl ketone 3 g, obtained in Preparation Example 1. Pigment dispersion (S-1) 50 g (2.5 g in terms of organic pigment (S)), isopropyl alcohol 117 g.

[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): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), 3-hydroxy-1-adamantyl acrylate 30 g, tricyclodecanedimethanol acrylate 20 g, 1-hydroxycyclohexylphenyl 3 g of methanol, 50 g of the 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 tricyclodecanedimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 50 g of the pigment dispersion (S-2) obtained in Preparation Example 2 (2.5 g in terms of organic pigment (S)). ), Methyl isobutyl ketone 117 g.

[Example 5]
Instead of the transparent resin substrate, a glass substrate (transparent glass substrate "OA-10G (thickness 150 μm)" (manufactured by Nippon Electric Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width is used, and the 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 the above. The results are shown in Table 5.

Resin composition (5): 100 g of tricyclodecanedimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl 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 (Zeonoa film ZF16 (thickness 100 μm)) (manufactured by Nippon Zeon Corporation) cut into 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. 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): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), 3-hydroxy-1-adamantyl acrylate 30 g, tricyclodecanedimethanol acrylate 20 g, 1-hydroxycyclohexylphenyl 3 g of methanol, 56 g of the pigment dispersion (S-3) obtained in Preparation Example 3 (2.8 g in terms of organic pigment (S)), 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): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), 3-hydroxy-1-adamantyl acrylate 30 g, tricyclodecanedimethanol acrylate 20 g, 1-hydroxycyclohexylphenyl 3 g of methanol, 52 g of the pigment dispersion (S-4) obtained in Preparation Example 4 (2.6 g in terms of organic pigment (S)), 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): Urethane acrylate compound (1) obtained in Synthesis Example 2 50 g (in terms of solid content), 3-hydroxy-1-adamantyl acrylate 30 g, tricyclodecanedimethanol acrylate 20 g, 1-hydroxycyclohexylphenyl 3 g of methanol, 50 g of the pigment dispersion (S-5) obtained in Preparation Example 5 (2.5 g in terms of organic pigment (S)), 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 above compound (a-1) (absorption maximum wavelength 713 nm in dichloromethane) and the above compound (a-2) (dichloromethane) as the compound (A). 0.06 g of absorption maximum wavelength 736 nm, 0.2 g of the compound (s-6) (absorption maximum wavelength 1093 nm in dichloromethane) and methylene chloride shown in Table 2-2 above were added to bring the resin concentration to 20. A mass% solution was prepared. The compound (s-6) was dissolved in methylene chloride and dyed. 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 under reduced pressure at 100 ° C. 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): Tricyclodecanedimethanol acrylate 100 g, 1-hydroxycyclohexylphenyl ketone 3 g, methyl ethyl ketone 154.5 g.

[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). The compound (s-15) was dissolved in methylene chloride and dyed. The results are shown in Table 5.

Resin composition (7): tricyclodecanedimethanol acrylate 100 g, 1-hydroxycyclohexylphenyl 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 configurations shown in Table 5 were adopted. The results are shown in Table 5.

表５中の基材の形態および各種化合物などの記号は下記の通りである。

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

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

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

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

10: Base material 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 of edge 121: Camera image 122: Light source 123: Example of ghost around the light source

Claims (11)

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 region having a wavelength of 900 nm or more and 1200 nm or less. The optical filter according to claim 1, wherein the base material further satisfies the following requirement (b).
(B) It has a layer containing the compound (A) having an absorption maximum in a region having a wavelength of 650 nm or more and 760 nm or less. The optical filter according to claim 2, wherein the compound (A) is at least one compound selected from the group consisting of a squarylium-based compound, a phthalocyanine-based compound, and a cyanine-based compound. The optical filter according to any one of claims 1 to 3, wherein the organic pigment (S) contains a diimonium-based 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 ~ Represents any of ^{L h , R 2} is an independent halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ It represents any of ^{R i} group, -OSO ₂ R ⁱ group or L ^{a to} L ^{h below, and R g} and R ^h are independently hydrogen atom, -C (O) R ⁱ group or L ^{a to} L below, respectively. represents either ^e, R ⁱ represents any of the following L ^a ~L ^e,
(L ^a) from 1 to 12 carbon atoms aliphatic hydrocarbon group (L ^b) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c) of 3 to 14 carbon atoms alicyclic hydrocarbon group (L ^d) carbon Aromatic hydrocarbon group of number 6 to 14 (L ^e ) Heterocyclic group having 2 to 14 carbon atoms (L ^f ) An alkoxy group having 1 to 12 carbon atoms (L ^g ) Substituent number of carbon atoms may be L. An alkoxycarbonyl group having 1 to 12 carbon atoms which may have an acyl group (L ^h ) substituent L of 1 to 12 The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms and 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 from 0 to 4
X represents the anion required to neutralize the charge. ) The optical filter according to any one of claims 1 to 4, wherein the average particle size of the organic pigment (S) is 200 nm or less. The optical filter according to any one of claims 1 to 5, 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, 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-based resin, polyether sulfone-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate-based resin, fluorinated aromatic polymer-based resin, (modified) acrylic-based resin, epoxy-based resin, allyl ester-based The sixth aspect of claim 6, wherein the resin is at least one selected from the group consisting of a curable resin, a silsesquioxane-based ultraviolet curable resin, an acrylic-based ultraviolet-curable resin, and a vinyl-based ultraviolet curable resin. Optical filter. Claims 1 to 1, wherein 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). 7. The optical filter according to any one of 7. The optical filter according to any one of claims 1 to 8, which is for a solid-state image sensor. A solid-state image sensor comprising the optical filter according to any one of claims 1 to 9. A camera module including the optical filter according to any one of claims 1 to 9.

Images