WO2018043564A1

WO2018043564A1 - Optical filter and device using optical filter

Info

Publication number: WO2018043564A1
Application number: PCT/JP2017/031156
Authority: WO
Inventors: 達也葛西; 勝也長屋; 正子堀内; 大介重岡
Original assignee: Jsr株式会社
Priority date: 2016-08-31
Filing date: 2017-08-30
Publication date: 2018-03-08
Also published as: CN109642973A; JPWO2018043564A1; JP2021028726A; KR20210150591A; KR102434709B1; CN112946804B; JP7088261B2; CN109642973B; JP6791251B2; KR102388961B1; CN112946804A; KR20190040973A

Abstract

The present invention addresses the problem of providing an optical filter that achieves, at a high level, both color shading suppression and ghost suppression in a camera image, both of which cannot be sufficiently achieved by conventional optical filters. This optical filter is characterized by having a substrate satisfying requirements (a) to (c): (a) the substrate has a layer containing a compound (A) having an absorption maximum in a wavelength region of 650-760 nm inclusive; (b) a difference (X₂-X₁) between the shortest wavelength (X₁) and the second shortest wavelength (X₂) at which transmissivity becomes 10% in a wavelength region of 640 nm or more is 50 nm or more; and (c) transmissivities at wavelengths of 900 nm, 1000 nm, and 1100 nm are each 65% or less.

Description

Optical filter and device using optical filter

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

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

As such a near-infrared cut filter, those manufactured by various methods are conventionally used. For example, a near-infrared cut filter in which a transparent resin is used as a substrate and a near-infrared absorbing pigment is contained in the transparent resin is known (see, for example, Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not always have sufficient near-infrared absorption characteristics.

As a result of intensive studies, the applicant has used a transparent resin substrate containing a near-infrared-absorbing dye having an absorption maximum in a specific wavelength region, so that the near-infrared light has little change in optical characteristics even when the incident angle is changed. It has been found that a cut filter can be obtained, and Patent Document 2 proposes a near-infrared cut filter having both a wide viewing angle and a high visible light transmittance. Patent Document 3 discloses a near-infrared cut filter that uses a phthalocyanine dye having a specific structure to achieve both a high visible light transmittance and a long absorption maximum wavelength, both of which have been the conventional problems. It is described that can be obtained. However, in the near-infrared cut filters described in

Patent Documents

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

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

Further, Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass substrate and a layer containing a near-infrared absorbing pigment, but the color shading is sufficiently improved even with the configuration described in Patent Document 5. (For example, FIG. 5 of Patent Document 5 shows an optical characteristic graph when incident at 0 degrees and incident at 30 degrees. However, the visible light transmission band is also observed when incident at 30 degrees. A large wavelength shift is observed in the skirt region (630 to 700 nm).

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

It is an object of the present invention to provide an optical filter that can achieve a high level of color shading suppression and ghost suppression of camera images, which cannot be sufficiently achieved with conventional optical filters.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have a base material that has an absorption band with sufficient intensity in the vicinity of a wavelength of 700 nm and a wide absorption band in the near-infrared wavelength region of 900 nm or more. Has been found that an optical filter capable of achieving the intended near-infrared cut characteristics, visible light transmittance, color shading suppression effect and ghost suppression effect can be obtained, and the present invention has been completed. Examples of embodiments of the present invention are shown below.

[1] An optical filter having a substrate that satisfies the following requirements (a), (b), and (c), and that satisfies the following requirements (d) and (e):
(A) having a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm to 760 nm;
(B) The difference (X ₂ −X ₁ ) between the shortest wavelength (X ₁ ) with a transmittance of 10% and the second shortest wavelength (X ₂ ) in the wavelength region of 640 nm or more is 50 nm or more;
(C) The transmittance at a wavelength of 900 nm, the transmittance at a wavelength of 1000 nm, and the transmittance at a wavelength of 1100 nm are all 65% or less;
(D) In the wavelength range of 430 to 580 nm, the average transmittance when measured from the vertical direction of the optical filter is 75% or more;
(E) In the wavelength region of 1100 nm to 1200 nm, the average transmittance when measured from the vertical direction of the optical filter is 5% or less.

[2] The optical filter according to item [1], wherein the layer containing the compound (A) is a transparent resin layer.

[3] The optical filter according to item [1] or [2], wherein a dielectric multilayer film is provided on at least one surface of the substrate.

[4] The optical filter according to any one of items [1] to [3], wherein the base material further satisfies the following requirement (f):
(F) The minimum transmittance (T ₁ ) in the wavelength range of 690 to 720 nm is 5% or less.

[5] The optical filter according to any one of items [1] to [4], wherein the substrate further satisfies the following requirement (g):
(G) A compound (S) having an absorption maximum in a wavelength region of 1050 nm to 1200 nm is included.

[6] The item [5], wherein the compound (S) is at least one compound selected from the group consisting of compounds represented by the following formulas (I) and (II): Optical filter.

In formula (I) and formula (II),
R ¹ to R ³ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a —NR ^g R ^h group, a —SR ⁱ group, —SO ₂ R ⁱ group, —OSO ₂ R ⁱ group or any of the following L ^a to L ^h , wherein R ^g and R ^h are each independently a hydrogen atom, —C (O) R ⁱ group or the following L ^a to L ^e It represents either, R ⁱ represents any of the following L ^a ~ L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon C ^6-14 aromatic hydrocarbon group (L ^e ) C ^2-14 heterocyclic group (L ^f ) C ^1-12 alkoxy group (L ^g ) carbon number optionally having substituent L 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, At least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms,
Adjacent R ³ may form a ring which may have a substituent L,
n represents an integer of 0 to 4,
X represents an anion necessary to neutralize the charge,
M represents a metal atom,
Z represents D (R ⁱ ) ₄ , D represents a nitrogen atom, a phosphorus atom or a bismuth atom;
y represents 0 or 1.

[7] The optical filter according to any one of items [3] to [6], wherein the dielectric multilayer film is formed on both surfaces of the base material.

[8] The item [1] to [7], wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. The optical filter according to item 1.

[9] The transparent resin constituting the transparent resin layer is a cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate. Resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, Item characterized by being at least one resin selected from the group consisting of an allyl ester curable resin, a silsesquioxane ultraviolet curable resin, an acrylic ultraviolet curable resin, and a vinyl ultraviolet curable resin [ [2] to [8] Optical filter.

[10] The optical filter according to any one of items [1] to [9], wherein the base material contains a transparent resin substrate containing the compound (A) and the compound (S).

[11] The optical filter according to any one of items [1] to [10], which is for a solid-state imaging device.

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

[13] A camera module including the optical filter according to any one of items [1] to [11].

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

FIGS. 1A and 1B are schematic views showing examples of preferable configurations of the optical filter of the present invention. FIG. 2A is a schematic diagram illustrating a method for measuring the transmittance when measured from the vertical direction of the optical filter. FIG. 2B is a schematic diagram illustrating a method of measuring the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter. FIG. 3 is a spectral transmission spectrum of the substrate obtained in Example 1. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG. 5 is a spectral transmission spectrum of the substrate obtained in Example 2. FIG. 6 is a spectral transmission spectrum of the substrate obtained in Example 6. FIG. 7 is a spectral transmission spectrum of the base material obtained in Example 7. FIG. 8 is a spectral transmission spectrum of the base material (near infrared absorbing glass substrate) used in Comparative Example 3. FIG. 9 is a spectral transmission spectrum of the base material obtained in Comparative Example 4. FIG. 10 is a spectral transmission spectrum of the base material obtained in Comparative Example 5. It is a schematic diagram for demonstrating the color shading evaluation of the camera image performed in the Example and the comparative example. It is a schematic diagram for demonstrating the ghost evaluation of the camera image performed in the Example and the comparative example.

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

The optical filter of the present invention is characterized by having a base material that satisfies the requirements (a), (b), and (c) described later, and that satisfies the requirements (d) and (e) described later. The optical filter of the present invention preferably has a dielectric multilayer film on at least one surface of the substrate.

[Base material]
The substrate used in the present invention satisfies the following requirements (a), (b) and (c);
(A) having a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm to 760 nm;
(B) The difference (X ₂ −X ₁ ) between the shortest wavelength (X ₁ ) with a transmittance of 10% and the second shortest wavelength (X ₂ ) in the wavelength region of 640 nm or more is 50 nm or more;
(C) The transmittance (c1) at a wavelength of 900 nm, the transmittance (c2) at a wavelength of 1000 nm, and the transmittance (c3) at a wavelength of 1100 nm are all 65% or less.

The substrate preferably further satisfies at least one of the following requirements (f) to (h):
(F) The minimum transmittance (T ₁ ) in the wavelength region of 690 to 720 nm is 5% or less;
(G) including a compound (S) having an absorption maximum in a wavelength region of 1050 nm to 1200 nm;
(H) In the region where the wavelength is 600 nm or more, the shortest wavelength (Xc) at which the transmittance is 50% when the transmittance is more than 50% to 50% or less is in the wavelength range of 628 to 658 nm.

The following describes each requirement.

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

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

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

The absorption maximum wavelength of the compound (A) is preferably 660 nm or more and 755 nm or less, more preferably 670 nm or more and 750 nm or less, and further preferably 680 nm or more and 745 nm or less.

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

The total content of the compound (A) is, for example, a base material made of a transparent resin substrate containing the compound (A) or a curable resin on the transparent resin substrate containing the compound (A). In the case of using a base material on which a resin layer such as an overcoat layer made of, etc. is used, it is preferably 0.04 to 2.0 parts by weight, more preferably 0.06 to 2.0 parts by weight with respect to 100 parts by weight of the transparent resin. 1.5 parts by weight, more preferably 0.08 to 1.0 part by weight, and the compound (A) is contained as a base on a support such as a glass support or a resin support as a base. In the case of using a base material on which a transparent resin layer such as an overcoat layer made of a curable resin or the like is used, it is preferably 0.1% with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). 4 to 5.0 parts by weight, more preferably 0 6 to 4.0 parts by weight, more preferably 0.8 to 3.5 parts by weight.

<Requirement (b)>
The difference (X ₂ −X ₁ ) between the wavelengths X ₁ and X ₂ is preferably 53 nm or more, more preferably 55 nm or more, and further preferably 58 nm or more. Although an upper limit is not specifically limited, Since a visible transmittance | permeability may fall when a value is too large depending on the characteristic of a compound (A) and other near-infrared absorbers, it is preferable that it is 100 nm or less, for example. When the difference (X ₂ −X ₁ ) is in the above range, it has an absorption band with sufficient intensity (width) in the near-infrared wavelength region close to the visible region. It is preferable because color shading can be suppressed even under such a large incident angle condition.

The value of the wavelength (X ₁ + X ₂ ) / 2 between X ₁ and X ₂ can be said to be the center wavelength of the absorption band in the near infrared wavelength region close to the visible region, preferably 670 nm or more and 740 nm or less. Is 680 nm to 730 nm, more preferably 690 nm to 720 nm. It is preferable that the value of the wavelength represented by (X ₁ + X ₂ ) / 2 be in the above range because light in the wavelength region near the long wavelength end of the visible region can be cut more efficiently.

X ₁ preferably has a wavelength of 650 nm to 720 nm, more preferably a wavelength of 655 nm to 710 nm, and still more preferably a wavelength of 660 nm to 700 nm. X ₁ in such a range is preferable because it tends to provide a camera image with less noise and excellent color reproducibility.

<Requirement (c)>
All of the transmittances (c1), (c2) and (c3) are preferably 60% or less, more preferably 55% or less, and even more preferably 50% or less. The lower limit is not particularly limited, but depending on the properties of the near-infrared absorber, if the transmittance value in the near-infrared wavelength region is too low, the visible transmittance may decrease, or the thickness of the substrate may become extremely thick. For example, it is preferably 5% or more. It is preferable that the transmittances (c1), (c2), and (c3) are in the above ranges because a ghost suppressing effect at a practically sufficient level can be obtained.

The substrate may be a single layer or a multilayer as long as it has a layer containing the compound (A). In order to satisfy the requirement (C), the substrate preferably contains a near infrared absorber, and the near infrared absorber is contained in a different layer even if it is contained in the same layer as the compound (A). It may be.

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

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

The near-infrared absorber is not particularly limited as long as it has a wide absorption in the wavelength range of 900 to 1200 nm. For example, the near-infrared absorbing dye, the near-infrared absorbing fine particles, the conductive metal oxide, and the phosphate glass Examples thereof include transition metal components therein.

<Requirement (f)>
The T ₁ is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less. If T ₁ is in the above range, it can be said that the transmittance cut of the absorption band is sufficient, and flare around the light source can be suppressed in the camera image, which is preferable.

<Requirement (g)>
The substrate of the present invention preferably contains a near-infrared absorber, but when the near-infrared absorber is the compound (S), the absorption intensity and visible transmittance in the near-infrared wavelength region can be compatible at a high level. It is preferable because of its tendency.

≪Compound (S) ≫
The compound (S) is not particularly limited as long as it has an absorption maximum in a wavelength region of 1050 nm or more and 1200 nm or less, but is preferably a solvent-soluble dye compound, more preferably a diimonium compound or a metal dithiolate complex system. At least one compound selected from the group consisting of compounds, pyrrolopyrrole compounds, cyanine compounds, croconium compounds and naphthalocyanine compounds, more preferably selected from the group consisting of diimonium compounds and metal dithiolate complex compounds At least one compound selected from the group consisting of a diimonium compound represented by the following formula (I) and a metal dithiolate complex compound represented by the following formula (II). . By using such a compound (S), good near-infrared absorption characteristics and excellent visible light transmittance can be achieved.

In formula (I) and formula (II),
R ¹ to R ³ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a —NR ^g R ^h group, a —SR ⁱ group, —SO ₂ R ⁱ group, —OSO ₂ R ⁱ group or any of the following L ^a to L ^h , wherein R ^g and R ^h are each independently a hydrogen atom, —C (O) R ⁱ group or the following L ^a to L ^e It represents either, R ⁱ represents any of the following L ^a ~ L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) carbon C ^6-14 aromatic hydrocarbon group (L ^e ) C ^2-14 heterocyclic group (L ^f ) C ^1-12 alkoxy group (L ^g ) carbon number optionally having substituent L 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, At least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms,
Adjacent R ³ may form a ring which may have a substituent L,
n represents an integer of 0 to 4,
X represents an anion necessary to neutralize the charge,
M represents a metal atom,
Z represents D (R ⁱ ) ₄ , D represents a nitrogen atom, a phosphorus atom or a bismuth atom,
y represents 0 or 1.

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

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

X is an anion necessary for neutralizing the electric charge, and one molecule is required when the anion is divalent, and two molecules are required when the anion is monovalent. In the latter case, the two anions may be the same or different, but are preferably the same from the viewpoint of synthesis. Although X will not be restrict | limited especially if it is such an anion, The thing of following Table 1 can be mentioned as an example.

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

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

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

The M is preferably a transition metal, more preferably Ni, Pd, or Pt.

The D is preferably a nitrogen atom or a phosphorus atom, and the R ⁱ is preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, or an n-pentyl group. Group, n-hexyl group, n-heptyl group and phenyl group.

The absorption maximum wavelength of the compound (S) is preferably from 1060 nm to 1190 nm, more preferably from 1070 nm to 1180 nm, still more preferably from 1080 nm to 1170 nm. When the absorption maximum wavelength of the compound (S) is in such a range, unnecessary near-infrared rays can be efficiently cut, and an excellent ghost suppression effect can be obtained.

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

The content of the compound (S) is, for example, a base material made of a transparent resin substrate containing the compound (A) and the compound (S) or a transparent resin substrate containing the compound (S) as the base material. In the case of using a substrate on which a resin layer such as an overcoat layer made of a curable resin containing the compound (A) is laminated, it is preferably 0.01-2. 0 parts by weight, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight. Examples of the substrate include a glass support and a resin support as a base. On a substrate on which a transparent resin layer such as an overcoat layer composed of a curable resin containing the compound (A) and the compound (S) is laminated on a support, or on a transparent resin substrate containing the compound (A) Curable resin containing compound (S) in When a base material on which a resin layer such as an overcoat layer is used is used, it is preferably 0.1 to 5.0 with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). Parts by weight, more preferably 0.2 to 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight. When the content of the compound (S) is within the above range, an optical filter having both good near infrared absorption characteristics and high visible light transmittance can be obtained.

<Requirement (h)>
Xc is preferably 630 to 655 nm, more preferably 632 to 652 nm, and still more preferably 634 to 650 nm. If Xc is less than 628 nm, the transmittance in the wavelength region corresponding to red tends to be low, and color reproducibility tends to decrease. If it exceeds 658 nm, sufficient absorption intensity cannot be ensured, and the camera image Color shading tends to occur.

When the base material satisfies the requirement (h), even when a dielectric multilayer film is formed on the base material, it is possible to reduce the incident angle dependency of the optical characteristics in the vicinity of the visible wavelength to near infrared wavelength region. This is preferable because red reproducibility and color shading suppression effect can be achieved at a high level. Xc represents a wavelength that satisfies a predetermined condition when the spectral transmittance is evaluated from the short wavelength side toward the long wavelength side.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The other dye (X) is not particularly limited as long as it has a maximum absorption wavelength in the region of wavelength less than 650 nm or more than 760 nm and less than 1050 nm, but a dye having an absorption maximum wavelength in the region of more than 760 nm and less than 1050 nm is preferable. . Examples of such dyes include squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, octaphyrin compounds, diimonium compounds, pyrrolopyrrole compounds, and boron dipyrromethene (BODIPY). And at least one compound selected from the group consisting of a compound, a perylene compound, and a metal dithiolate compound.

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

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

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

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

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

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

The base material is an overcoat comprising a curable resin containing the compound (A) on a support such as a glass support or a base resin support or a transparent resin substrate containing no compound (A). In the case of a substrate on which a transparent resin layer such as a layer is laminated, for example, the resin solution containing the compound (A) is melt-molded or cast-molded on the support or the transparent resin substrate, preferably spin After coating by a method such as coating, slit coating or ink jetting, the solvent is dried and removed, and if necessary, further irradiation with light or heating is performed, whereby the compound (A) is formed on the support or the transparent resin substrate. The base material in which the transparent resin layer containing this was formed can be manufactured.

≪Melt molding≫
Specifically, as the melt molding, a method of melt molding a pellet obtained by melt-kneading a resin, a compound (A) and other components as necessary; a resin, a compound (A) and a necessary A method of melt-molding a resin composition containing other components as required; or obtained by removing the solvent from the resin composition containing compound (A), resin, solvent and other components as necessary Examples include a method of melt-molding pellets. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫
As the cast molding, a method of removing a solvent by casting a resin composition containing a compound (A), a resin, a solvent and other components as required on a suitable support; or a compound (A) and After removing a solvent by casting a curable composition containing a photocurable resin and / or a thermosetting resin and other components as necessary on an appropriate support, ultraviolet irradiation, heating, etc. It can also be produced by a method of curing by an appropriate method.

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

Examples of the support include phosphates containing copper components such as near-infrared absorbing glass plates (for example, “BS-11” manufactured by Matsunami Glass Industrial Co., Ltd. and “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., “AN100” manufactured by Asahi Glass Co., Ltd.), steel belt, steel drum, and transparent resin (for example, polyester) Film, cyclic olefin resin film) support.

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

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

[Optical filter]
The optical filter according to the present invention has a base material that satisfies the requirements (a), (b), and (c), and satisfies the following requirements (d) and (e):
(D) In the wavelength range of 430 to 580 nm, the average value (d1) of transmittance when measured from the vertical direction of the optical filter is 75% or more;
(E) In the wavelength region of 1100 nm to 1200 nm, the average value (e1) of transmittance when measured from the vertical direction of the optical filter is 5% or less.

Since the optical filter of the present invention satisfies the above requirements (d) and (e), it has excellent transmittance characteristics and near-infrared cut characteristics in the visible wavelength region, has little incident angle dependency, has a color shading suppression effect, and a ghost. It is an optical filter with excellent suppression effect.

<Requirement (d)>
The average value (d1) of the transmittance in the requirement (d) is preferably 78% or more, more preferably 80% or more, and further preferably 82% or more. When the average value (d1) of the transmittance is in this range, excellent imaging sensitivity can be achieved when the optical filter of the present invention is used as a solid-state imaging device.

<Requirement (e)>
The average value (e1) of the transmittance in requirement (e) is preferably 4% or less, more preferably 3% or less, and even more preferably 2% or less. When the average value (e1) of the transmittance is within this range, good black reproducibility can be achieved near the center of the camera image.

<Other properties and physical properties>
Since the optical filter of the present invention has the base material, the incident angle dependency of the optical characteristics can be reduced even in the form having the dielectric multilayer film. Specifically, in the wavelength range of 600 to 800 nm, the shortest wavelength value (Xa) at which the transmittance when measured from the vertical direction of the optical filter is 50%, and 30 ° with respect to the vertical direction of the optical filter. The absolute value | Xa−Xb | of the difference from the wavelength value (Xb) at which the transmittance when measured from the angle is 50% is preferably less than 20 nm, more preferably less than 15 nm, and even more preferably less than 10 nm. is there.

The thickness of the optical filter of the present invention is preferably thin in consideration of the recent trend of thinner and lighter solid-state imaging devices. Since the optical filter of the present invention includes the substrate, it can be thinned.

The thickness of the optical filter of the present invention is preferably 210 μm or less, more preferably 190 μm or less, further preferably 160 μm or less, particularly preferably 130 μm or less, and the lower limit is not particularly limited, but is preferably 20 μm or more.

[Dielectric multilayer film]
The optical filter of the present invention preferably has a dielectric multilayer film on at least one surface of the substrate. The dielectric multilayer film in the present invention is a film having the ability to reflect near-infrared rays or a film having an antireflection effect in the visible range. By having a dielectric multilayer film, a better visible light transmittance and near-infrared radiation are obtained. Cut characteristics can be achieved.

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

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

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

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

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

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

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

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

In the present invention, the material types constituting the high refractive index material layer and the low refractive index material layer, the high refractive index material layer, and the low refractive index in accordance with the absorption characteristics of the near infrared absorbers such as the compound (A) and the compound (S). By appropriately selecting the thickness of each layer of the rate material layer, the order of stacking, and the number of stacks, it has sufficient light cut characteristics in the near infrared wavelength region while ensuring sufficient transmittance in the visible region, In addition, it is possible to reduce the reflectance when near infrared rays are incident from an oblique direction.

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

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

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

The method of laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded or cast in the same manner as described above on a base material or a dielectric multilayer film. Examples of the method include molding.

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

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

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

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

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

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

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

Further, in order to improve the adhesion between the base material and the functional film and / or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, the corona is applied to the surface of the base material, the functional film or the dielectric multilayer film. Surface treatment such as treatment or plasma treatment may be performed.

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

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

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

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

In addition, about the resin synthesize | combined in the resin synthesis example 3 mentioned later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the said method.
(C) A part of the polyimide resin solution was added to anhydrous methanol to precipitate the polyimide resin, and filtered to separate from the unreacted monomer. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. Asked.

_{μ = {ln (t s /} t 0)} / C
t ₀ : Flowing time of solvent t _s : Flowing time of dilute polymer solution C: 0.5 g / dL
<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.

<Spectral transmittance>
The transmittance at each wavelength of the substrate, (T ₁ ), (X ₁ ), (X ₂ ) and (Xc), and the transmittance at each wavelength region of the optical filter, (Xa) and (Xb) Measurement was performed using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

Here, with respect to the transmittance when measured from the vertical direction of the optical filter, the light transmitted perpendicular to the filter is measured as shown in FIG. 2A, and the angle is 30 ° with respect to the vertical direction of the optical filter. As for the transmittance when measured from the above, the light transmitted at an angle of 30 ° with respect to the vertical direction of the filter as shown in FIG. 2B was measured.

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

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

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

As shown in FIG. 11, the positional relationship between the white plate 112 and the camera module was adjusted so that the white plate 112 occupied 90% or more of the area in the camera image 111 when shooting.

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

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

Note that, as shown in FIG. 12, when shooting, the light source 122 was adjusted to be the upper right end of the camera image 121.

[Synthesis example]
Compound (A) and compound (S) used in the following examples were synthesized by a generally known method. As general synthesis methods, for example, JP-A-60-228448, JP-A-1-14684, JP-A-1-228960, JP-A-4081149, “phthalocyanine -chemistry and function-” (I PC, 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.

<Resin synthesis example 1>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter also referred to as “DNM”) 100 g, 1-hexene (molecular weight regulator) 18 g and toluene (ring-opening polymerization solvent) 300 g were charged into a nitrogen-substituted reaction vessel. The solution was heated to 80 ° C. Next, 0.2 g of a toluene solution of triethylaluminum (0.6 mol / liter) and 0.9 g of a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were used as a polymerization catalyst. And the solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 g of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C., the hydrogenation reaction was performed by heating and stirring for 3 hours. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin A”). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

<Resin synthesis example 2>
In a 3 L four-necked flask, 35.12 g of 2,6-difluorobenzonitrile, 87.60 g of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g of potassium carbonate, N, N-dimethylacetamide (hereinafter referred to as “DMAc”). 443 g and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean Stark tube and a cooling tube were attached to the four-necked flask. Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum-dried overnight at 60 ° C. to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

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

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

In a container, 100 parts of resin A obtained in Resin Synthesis Example 1, compound (A-1) represented by the following formula (a-1) as compound (A) (maximum absorption wavelength 698 nm in dichloromethane) 0.04 And 0.04 parts of the compound (a-2) (absorption maximum wavelength 733 nm in dichloromethane) represented by the following formula (a-2), and the compound (s- 6) 0.07 part (absorption maximum wavelength in dichloromethane of 1093 nm) and methylene chloride were added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a base material composed of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. The spectral transmittance of this substrate was measured, and the transmittance at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength was determined. The results are shown in FIG. 3 and Table 5-1.

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

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

The dielectric multilayer films (I) and (II) were designed as follows.

Regarding the thickness and the number of layers of each layer, the wavelength-dependent characteristics of the base material refractive index and the applied compound (S) and compound (in order to achieve the antireflection effect in the visible range and the selective transmission / reflection performance in the near infrared range, Optimization was performed using optical thin film design software (Essential Macleod, Thin Film Center) according to the absorption characteristics of A). When performing optimization, in this example, the input parameters (Target values) to the software are as shown in Table 3 below.

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

The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 4 and Table 5-1. The average value of transmittance at a wavelength of 430 to 580 nm was 84%, the average value of transmittance at a wavelength of 1100 to 1200 nm was 1% or less, and the absolute value | Xa−Xb | was 2 nm.

Also, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1. The obtained camera images had good results in color shading and ghosting.

[Example 2]
In Example 2, an optical filter having a base material made of a transparent resin substrate was prepared according to the following procedure and conditions.

In Example 1, 0.04 part of the compound (A-3) represented by the following formula (a-3) (absorption maximum wavelength 703 nm in dichloromethane) as the compound (A) and the following formula (a-4) Compound (a-4) (absorption maximum wavelength in dichloromethane 736 nm) 0.08 part was used, and compound (s-8) described in Table 2-3 above as compound (S) (in dichloromethane) 0.06 parts of absorption maximum wavelength (1096 nm) and other dye (X) represented by the following formula (X-1) (X-1) (absorption maximum wavelength in dichloromethane: 887 nm) A base material made of a transparent resin substrate containing the compound (A) and the compound (S) was obtained in the same procedure and conditions as in Example 1 except that 0.01 part was used. The spectral transmittance of this substrate was measured, and the transmittance at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength was determined. The results are shown in FIG. 5 and Table 5-1.

Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). The multilayer film (III) is formed, and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as the second optical layer on the other surface of the base material (20 layers in total). A dielectric multilayer film (IV) was formed to obtain an optical filter having a thickness of about 0.105 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the base material refractive index. The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

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

In Example 1, 0.06 part of compound (a-4) as compound (A) and compound (a-5) represented by the following formula (a-5) (absorption maximum wavelength in dichloromethane: 713 nm) 0.06 Example 1 except that 0.08 part of the compound (s-13) described in Table 2-4 (maximum absorption wavelength 1096 nm in dichloromethane) was used as the compound (S). A transparent resin substrate containing the compound (A) and the compound (S) was obtained in the same procedure and conditions.

A resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm < ² >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) is formed on the other surface of the transparent resin substrate, and the resin layers are provided on both surfaces of the transparent resin substrate containing the compound (A) and the compound (S). A substrate was obtained. The spectral transmittance of this substrate was measured, and the transmittance at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength was determined. The results are shown in Table 5-1.

Resin composition (1): 60 parts by weight of tricyclodecane dimethanol diacrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30% )
Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). And a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as the second optical layer on the other surface of the substrate (20 layers in total). A dielectric multilayer film (VI) was formed to obtain an optical filter having a thickness of about 0.109 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

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

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

In the same manner as in Example 3, a resin layer made of the resin composition (2) having the following composition was formed on both surfaces of the obtained resin support, and the compound (A) and the compound ( A base material formed by forming a transparent resin layer containing S) was obtained. The spectral transmittance of this substrate was measured, and the transmittance at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength was determined. The results are shown in Table 5-1.

Resin composition (2): 100 parts by weight of tricyclodecane dimethanol diacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.10 parts by weight of compound (a-1), 0.10 parts by weight of compound (a-2) Parts, 1.75 parts by weight of compound (s-6), methyl ethyl ketone (solvent, TSC: 25%)
Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). And a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as the second optical layer on the other surface of the base material (total 20 layers). A dielectric multilayer film (VIII) was formed to obtain an optical filter having a thickness of about 0.109 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

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

On a transparent glass substrate “OA-10G (thickness 150 μm)” (manufactured by Nippon Electric Glass Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width, a resin composition (3) having the following composition was applied with a spin coater. The solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes. Under the present circumstances, the application | coating conditions of the spin coater were adjusted so that the thickness after drying might be set to 2 micrometers. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) is carried out using a conveyor type exposure machine, the resin composition (3) is cured, and a transparent resin layer containing the compound (A) and the compound (S) is provided. A base material made of a transparent glass substrate was obtained. The spectral transmittance of this substrate was measured, and the transmittance at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength was determined. The results are shown in Table 5-1.

Resin composition (3): 20 parts by weight of tricyclodecane dimethanol diacrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.20 part by weight of compound (a-1), compound (A-2) 0.20 part by weight, compound (s-6) 3.50 part by weight, methyl ethyl ketone (solvent, TSC: 35%)
Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). A multilayer film (IX) is formed, and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the base material (20 layers in total) A dielectric multilayer film (X) was formed to obtain an optical filter having a thickness of about 0.107 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Example 6]
In Example 6, an optical filter having a base material composed of a near-infrared absorbing glass substrate having a transparent resin layer containing the compound (A) on one side was prepared by the following procedure and conditions.

A resin composition (4) having the following composition was applied on a near infrared absorbing glass substrate “BS-11 (thickness 120 μm)” (manufactured by Matsunami Glass Industry Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width with a spin coater. Then, the solvent was volatilized and removed by heating at 80 ° C. for 2 minutes on a hot plate. Under the present circumstances, the application | coating conditions of the spin coater were adjusted so that the thickness after drying might be set to 2 micrometers. Next, exposure (exposure amount: 500 mJ / cm ² , 200 mW) is carried out using a conveyor type exposure machine, the resin composition (4) is cured, and the near-infrared absorbing glass substrate having a transparent resin layer containing the compound (A) A substrate consisting of The spectral transmittance of this substrate was measured, and the transmittance at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength was determined. The results are shown in FIG. 6 and Table 5-1.

Resin composition (4): 20 parts by weight of tricyclodecane dimethanol diacrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.15 part by weight of compound (a-3), compound (A-4) 0.30 part by weight, methyl ethyl ketone (solvent, TSC: 35%)
Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). A multilayer film (XI) is formed, and a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the substrate (20 layers in total). A dielectric multilayer film (XII) was formed to obtain an optical filter having a thickness of about 0.107 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Example 7]
In Example 7, an optical filter having a base material made of a transparent resin substrate containing the compound (A) and having a transparent resin layer containing near-infrared absorbing fine particles on both surfaces was prepared according to the following procedure and conditions.

In Example 2, a transparent resin substrate containing compound (A) was obtained by the same procedure and conditions as in Example 2 except that compound (S-8) and the other dye (X-1) were not used. It was.

The compound which forms the resin layer which consists of a resin composition (5) of the following composition on both surfaces of the obtained resin board | substrate like Example 3, and has a transparent resin layer containing near-infrared absorption fine particles on both surfaces A base material made of a transparent resin substrate containing (A) was obtained. The spectral transmittance of this substrate was measured, and the transmittance at (T ₁ ), (X ₁ ), (X ₂ ), (Xc) and each wavelength was determined. The results are shown in FIG. 7 and Table 5-1.

Resin composition (5): 100 parts by weight of tricyclodecane dimethanol diacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 35 parts by weight of near-infrared absorbing fine particle dispersion (YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd.) About 10 parts by weight in terms of solid content), methyl ethyl ketone (solvent, TSC: 30%)
Subsequently, in the same manner as in Example 1, a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total). And a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated as a second optical layer on the other surface of the base material (total 20 layers). A dielectric multilayer film (XIV) was formed to obtain an optical filter having a thickness of about 0.109 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the substrate as in Example 1. The spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Examples 8 to 13]
Resin, solvent, drying conditions of resin substrate, compound (A), compound (S), and other dye (X) were changed in the same manner as in Example 3 except for changing as shown in Table 5-1. Materials and optical filters were made. The optical properties of the obtained substrate and optical filter are shown in Table 5-1. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-1.

[Comparative Example 1]
In Example 1, except that the compound (S) and the compound (A) were not used, a substrate and an optical filter were prepared in the same manner as in Example 1, and optical characteristics were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 1 exhibits relatively good visible light transmittance, the optical property has a large incident angle dependency, and the base material has no absorption in the vicinity of 700 nm or in the near infrared wavelength region. Therefore, it was confirmed that the color shading suppression effect and the ghost suppression effect were inferior.

[Comparative Example 2]
An optical filter was prepared and the optical characteristics were evaluated in the same manner as in Example 1 except that a transparent glass substrate “OA-10G (thickness 150 μm)” (manufactured by Nippon Electric Glass Co., Ltd.) was used as the substrate. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 2 shows relatively good visible light transmittance, the optical property has a large incident angle dependency, and the base material has no absorption in the vicinity of 700 nm or near infrared wavelength region. Therefore, it was confirmed that the color shading suppression effect and the ghost suppression effect were inferior.

[Comparative Example 3]
An optical filter was prepared in the same manner as in Example 1 except that a near-infrared absorbing glass substrate “BS-11 (thickness 120 μm)” (manufactured by Matsunami Glass Industry Co., Ltd.) was used as a base material, and optical characteristics were evaluated. did. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. The spectral transmission spectrum of the substrate is shown in FIG. Although the optical filter obtained in Comparative Example 3 showed relatively good optical characteristics, it was confirmed that the absorption intensity in the vicinity of 700 nm of the substrate was not sufficient and the color shading suppression effect was poor.

[Comparative Example 4]
In Example 3, 0.08 part of compound (a-4) and 0.06 part of compound (a-5) were used as compound (A) without using compound (S), and dye (X— 1) Except having used 0.01 part, the base material and the optical filter were created like Example 3, and the optical characteristic was evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. The spectral transmission spectrum of the substrate is shown in FIG. Although the optical filter obtained in Comparative Example 5 showed relatively good optical characteristics, it was confirmed that the absorption intensity in the near-infrared wavelength region of the substrate was not sufficient and the ghost suppression effect was inferior.

[Comparative Example 5]
In Example 6, a substrate and an optical filter were prepared in the same manner as in Example 6 except that the resin composition (6) having the following composition was used instead of the resin composition (4).

Resin composition (6): 20 parts by weight of tricyclodecane dimethanol diacrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 0.15 part by weight of compound (a-1), methyl ethyl ketone (Solvent, TSC: 35%)
The optical properties of the obtained substrate and optical filter were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. The spectral transmission spectrum of the substrate is shown in FIG. Although the optical filter obtained in Comparative Example 5 showed relatively good optical properties, it was confirmed that the absorption intensity in the vicinity of 700 nm of the substrate was not sufficient and the color shading suppression effect was poor.

[Comparative Example 6]
In Example 3, 0.04 part of the compound (a-3) and 0.08 part of the compound (a-4) were used as the compound (A), and 0.01% of the compound (s-6) was used as the compound (S). A substrate and an optical filter were prepared in the same manner as in Example 3 except that the parts were used, and the optical characteristics were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 6 showed relatively good optical properties, it was confirmed that the absorption intensity in the near infrared wavelength region of the substrate was not sufficient and the ghost suppression effect was inferior.

[Comparative Example 7]
Example 3 except that 0.04 part of the compound (a-1) was used as the compound (A) and 0.07 part of the compound (s-6) was used as the compound (S) in Example 3. A substrate and an optical filter were prepared in the same manner as described above, and the optical characteristics were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 7 showed relatively good optical properties, it was confirmed that the absorption intensity in the vicinity of 700 nm of the substrate was not sufficient and the color shading suppression effect was inferior.

[Comparative Example 8]
In Example 3, 0.04 part of compound (a-1) was used as compound (A), and compound (s-14) described in Table 2-4 above (absorption in dichloromethane) was used as compound (S). A substrate and an optical filter were prepared in the same manner as in Example 3 except that 0.45 part of the maximum wavelength (1097 nm) was used, and the optical characteristics were evaluated. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 8 showed relatively good optical characteristics, it was confirmed that the absorption intensity in the vicinity of 700 nm of the substrate was not sufficient and the color shading suppression effect was inferior.

The construction of the base material and various compounds applied in the examples and comparative examples are as follows.

<Form of substrate>
Form (1): Transparent resin substrate containing compound (A) Form (2): Transparent resin substrate containing compound (A) has resin layers on both sides Form (3): Compound on both sides of resin support Form (4): having a transparent resin layer containing compound (A) on one side of the transparent glass substrate Form (5): compound on one side of the near-infrared absorbing glass substrate Form (6): having transparent resin layer containing near-infrared absorbing fine particles on both sides of transparent resin substrate containing compound (A) Form (7): containing compound (A) Transparent resin substrate (comparative example)
Form (8): Transparent glass substrate (comparative example)
Form (9): Near-infrared absorbing glass substrate (comparative example)
<Transparent resin>
Resin A: Cyclic polyolefin resin (resin synthesis example 1)
Resin B: Aromatic polyether resin (resin synthesis example 2)
Resin C: Polyimide resin (resin synthesis example 3)
Resin D: Cyclic olefin resin “Zeonor 1420R” (manufactured by Nippon Zeon Co., Ltd.)
<Glass substrate>
Glass substrate (1): Transparent glass substrate “OA-10G (thickness 150 μm)” cut to 60 mm length and 60 mm width (manufactured by Nippon Electric Glass Co., Ltd.)
Glass substrate (2): Near-infrared absorbing glass substrate “BS-11 (thickness 120 μm)” cut to a size of 60 mm length and 60 mm width (manufactured by Matsunami Glass Industry Co., Ltd.)
<Near-infrared absorbing dye>
<< Compound (A) >>
Compound (a-1): Compound (a-1) above (absorption maximum wavelength in dichloromethane 698 nm)
Compound (a-2): Compound (a-2) above (absorption maximum wavelength in dichloromethane: 733 nm)
Compound (a-3): Compound (a-3) described above (maximum absorption wavelength 703 nm in dichloromethane)
Compound (a-4): Compound (a-4) above (absorption maximum wavelength in dichloromethane 736 nm)
Compound (a-5): Compound (a-5) above (absorption maximum wavelength in dichloromethane of 713 nm)
Compound (a-6): A cyanine compound represented by the following formula (a-6) (absorption maximum wavelength in dichloromethane: 681 nm)

≪Compound (S) ≫
Compound (s-6): Compound (s-6) above (absorption maximum wavelength in dichloromethane of 1093 nm)
Compound (s-8): Compound (s-8) above (absorption maximum wavelength in dichloromethane of 1096 nm)
Compound (s-13): Compound (s-14) above (absorption maximum wavelength in dichloromethane of 1096 nm)
Compound (s-14): Compound (s-15) above (absorption maximum wavelength in dichloromethane of 1097 nm)
≪Other dye (X) ≫
Dye (X-1): the above dye (X-1) (absorption maximum wavelength in dichloromethane: 887 nm)
Dye (X-2): Dye represented by the following formula (X-2) (absorption maximum wavelength in dichloromethane: 811 nm)

<Solvent>
Solvent (1): Methylene chloride Solvent (2): N, N-dimethylacetamide Solvent (3): Cyclohexane / xylene (weight ratio: 7/3)
In Tables 5-1 and 5-2, the drying conditions of the (transparent) resin substrates of Examples and Comparative Examples are as follows. In addition, the coating film was peeled from the glass plate before drying under reduced pressure.

<Film drying conditions>
Condition (1): 20 ° C./8 hr → under reduced pressure 100 ° C./8 hr
Condition (2): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 140 ° C./8 hr
Condition (3): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 100 ° C./24 hr

1: Optical filter 2: Spectrophotometer 3: Light 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 the center of the white plate 114: Example of the edge of the white plate 121: Camera image 122: Light source 123: Example of ghost around the light source

Claims

An optical filter having a substrate satisfying the following requirements (a), (b) and (c) and satisfying the following requirements (d) and (e):
(A) having a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm to 760 nm;
(B) The difference (X 2 −X 1 ) between the shortest wavelength (X 1 ) with a transmittance of 10% and the second shortest wavelength (X 2 ) in the wavelength region of 640 nm or more is 50 nm or more;
(C) The transmittance at a wavelength of 900 nm, the transmittance at a wavelength of 1000 nm, and the transmittance at a wavelength of 1100 nm are all 65% or less;
(D) In the wavelength range of 430 to 580 nm, the average transmittance when measured from the vertical direction of the optical filter is 75% or more;
(E) In the wavelength region of 1100 nm to 1200 nm, the average transmittance when measured from the vertical direction of the optical filter is 5% or less.
The optical filter according to claim 1, wherein the layer containing the compound (A) is a transparent resin layer.
3. The optical filter according to claim 1, further comprising a dielectric multilayer film on at least one surface of the substrate.
The optical filter according to any one of claims 1 to 3, wherein the substrate further satisfies the following requirement (f):
(F) The minimum transmittance (T 1 ) in the wavelength range of 690 to 720 nm is 5% or less.
The optical filter according to any one of claims 1 to 4, wherein the substrate further satisfies the following requirement (g):
(G) A compound (S) having an absorption maximum in a wavelength region of 1050 nm to 1200 nm is included.
The optical filter according to claim 5, wherein the compound (S) is at least one compound selected from the group consisting of compounds represented by the following formulas (I) and (II).

[In Formula (I) and Formula (II),
R 1 to R 3 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, a —NR g R h group, a —SR i group, —SO 2 R i group, —OSO 2 R i group or any of the following L a to L h , wherein R g and R h are each independently a hydrogen atom, —C (O) R i group or the following L a to L e It represents either, R i represents any of the following L a ~ L e,
(L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms (L d ) carbon C 6-14 aromatic hydrocarbon group (L e ) C 2-14 heterocyclic group (L f ) C 1-12 alkoxy group (L g ) carbon number optionally having substituent L 1 to 12 acyl groups,
(L h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L. The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, At least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms,
Adjacent R 3 may form a ring which may have a substituent L,
n represents an integer of 0 to 4,
X represents an anion necessary to neutralize the charge,
M represents a metal atom,
Z represents D (R i ) 4 , D represents a nitrogen atom, a phosphorus atom or a bismuth atom;
y represents 0 or 1. )
7. The optical filter according to claim 3, wherein the dielectric multilayer film is formed on both surfaces of the base material.
The optical system according to any one of claims 1 to 7, wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. filter.
The transparent resin constituting the transparent resin layer is a cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin 9. At least one resin selected from the group consisting of a curable resin, a silsesquioxane ultraviolet curable resin, an acrylic ultraviolet curable resin, and a vinyl ultraviolet curable resin. The optical film according to any one of Over.
The optical filter according to any one of claims 1 to 9, wherein the substrate contains a transparent resin substrate containing the compound (A) and the compound (S).
The optical filter according to any one of claims 1 to 10, which is used for a solid-state imaging device.
A solid-state imaging device comprising the optical filter according to any one of claims 1 to 11.
A camera module comprising the optical filter according to any one of claims 1 to 11.