KR102434709B1 - Optical filter and device using optical filter - Google Patents

Abstract

It is an object to provide an optical filter capable of achieving both color shading suppression and ghost suppression of a camera image at a high level, which cannot be sufficiently achieved with conventional optical filters. The optical filter of the present invention is characterized in that it has a substrate satisfying the requirements (a) to (c): (a) a layer comprising the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and 760 nm or less; have; (b) the difference (X 2 -X 1 ) between the shortest wavelength (X ₁ ) and the second shortest wavelength (X ₂ ) at which the transmittance is 10% in the region of wavelength 640 nm or more (X ₂ -X ₁ ) is 50 nm or more; (c) The transmittance|permeability in wavelength 900nm, 1000nm, and 1100nm are all 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, it relates to an optical filter containing a compound having absorption in a specific wavelength region, and a solid-state imaging device and camera module using the optical filter.

CCD and CMOS image sensors, which are solid-state imaging devices for color images, are used in solid-state imaging devices such as video cameras, digital still cameras, and cellular phones with camera functions. Silicon photodiodes with sensitivity to near-infrared rays that cannot be detected are used. In these solid-state imaging devices, it is necessary to perform a visibility correction that makes a natural color tone seen by the human eye, so when an optical filter that selectively transmits or cuts light in a specific wavelength region (for example, a near-infrared cut filter) is used. there are many

As such a near-infrared cut filter, what was conventionally manufactured by various methods is used. For example, a near-infrared cut filter using a transparent resin as a base material and containing a near-infrared absorbing dye in the transparent resin is known (see, for example, Patent Document 1). However, the near-infrared absorption characteristic of the near-infrared cut filter of patent document 1 may not necessarily be enough.

As a result of intensive studies, the present applicant found that, by using a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength region, a near-infrared cut filter with little change in optical properties even when the angle of incidence is changed, In Patent Document 2, a near-infrared cut filter having a wide viewing angle and high visible light transmittance is proposed. Further, in Patent Document 3, it is described that by using a phthalocyanine-based dye having a specific structure, a near-infrared cut filter capable of achieving both excellent visible transmittance and longer wavelength of the absorption maximum wavelength, which were conventional problems, can be obtained at a high level. However, in the near-infrared cut filter described in Patent Documents 2 and 3, the applied substrate has an absorption band of sufficient intensity in the vicinity of 700 nm, but hardly has absorption in the near-infrared wavelength region such as 900 to 1200 nm, for example. Therefore, light in the near-infrared wavelength region is cut almost exclusively by reflection of the dielectric multilayer film, but in such a configuration, some stray light due to internal reflection in the optical filter or reflection between the optical filter and the lens causes shooting in a dark environment. When performing, it may cause ghosts or flares. In particular, in recent years, even for mobile devices such as smartphones, high image quality of cameras has been strongly demanded, and conventional optical filters may not be suitable for use.

On the other hand, as an optical filter using the base material which has broad absorption in a near-infrared wavelength region, the infrared-shielding filter like patent document 4 is proposed. In Patent Document 4, broad absorption in the near-infrared wavelength region is achieved by mainly applying a compound having a dithiolene structure, but the absorption intensity in the vicinity of 700 nm is not sufficient. In particular, image deterioration due to color shading may occur in use in high incidence angle conditions (eg, 45 degree incidence) accompanying a reduction in camera module height in recent years.

In addition, Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass substrate and a layer containing a near-infrared absorbing dye. For example, in FIG. 5 of Patent Document 5, optical characteristic graphs at 0 degree incidence and 30 degree incidence are shown, and even at 30 degrees incidence, a large wavelength shift in the region (630 to 700 nm) of the lower end of the visible light transmission band is shown. is observed).

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

An object of the present invention is to provide an optical filter capable of achieving both color shading suppression and ghost suppression of a camera image at a high level, which cannot be sufficiently achieved with conventional optical filters.

As a result of intensive studies to solve the above problems, the present inventors have applied a base material having an absorption band of sufficient intensity in the vicinity of a wavelength of 700 nm and a broad absorption band in a near-infrared wavelength region of 900 nm or more, thereby achieving the desired near-infrared cut characteristic. It discovered that the optical filter which can achieve the visible light transmittance, the color shading suppression effect, and the ghost suppression effect is obtained, and came to complete this invention. Examples of aspects of the present invention are shown below.

[1] An optical filter having a substrate satisfying the following requirements (a), (b) and (c), and also satisfying the following requirements (d) and (e):

(a) has a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and 760 nm or less;

(b) the difference (X 2 -X 1 ) between the shortest wavelength (X ₁ ) and the second shortest wavelength (X ₂ ) at which the transmittance is 10% in the region of wavelength 640 nm or more (X ₂ -X ₁ ) 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 region of 430 to 580 nm, the average value of transmittance when measured from the vertical direction of the optical filter is 75% or more;

(e) In the wavelength range of 1100 nm to 1200 nm, the average value of 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 at least one surface of the substrate has a dielectric multilayer film.

[4] The optical filter according to any one of items [1] to [3], wherein the substrate further satisfies the following requirement (f):

(f) The minimum value T ₁ of the transmittance|permeability in the area|region of wavelength 690-720 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) The compound (S) which has an absorption maxima in the wavelength region of 1050 nm or more and 1200 nm or less is contained.

[6] The optical filter according to 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).

In formulas (I) and (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, a -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any of the following L ^a to L ^h , R ^g and R ^h each independently represent a hydrogen atom, a -C(O)R ⁱ group, or any of the following L ^a to L ^e , R ⁱ represents any of the following L ^a to 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 ) aromatic hydrocarbon group having 6 to 14 carbon atoms

(L ^e ) heterocyclic group having 2 to 14 carbon atoms

(L ^f ) Alkoxy group having 1 to 12 carbon atoms

(L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L;

(L ^h ) Alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L

The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. At least one selected from the group,

Adjacent R ³ may form a ring which may have a substituent L,

n represents an integer of 0 to 4,

X represents the anion required 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 [3] to [6], wherein the dielectric multilayer film is formed on both surfaces of the substrate.

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

[9] The transparent resin constituting the transparent resin layer is a cyclic polyolefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a fluorene polycarbonate-based resin, a fluorene polyester-based resin, and a polycarbonate. Resins, polyamide-based resins, polyarylate-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorinated aromatic polymer-based resins, (modified ) at least one resin selected from the group consisting of acrylic resins, epoxy resins, allyl ester-based curable resins, silsesquioxane-based UV-curable resins, acrylic UV-curable resins, and vinyl-based UV-curable resins. The optical filter according to any one of [2] to [8].

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

[11] The optical filter according to any one of [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 [1] to [11].

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

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in a near-infrared cut characteristic, there is little incident angle dependence, and it can provide the optical filter excellent in the transmittance|permeability characteristic in a visible wavelength region, the color shading suppression effect, and the ghost suppression effect.

1(a), (b) is a schematic diagram which shows the example of the preferable structure of the optical filter of this invention.
Fig. 2(a) is a schematic diagram showing a method of measuring transmittance when measured from the vertical direction of the optical filter. Fig. 2(b) is a schematic diagram showing a method of measuring transmittance when measured from an angle of 30° with respect to the vertical direction of the optical filter.
3 : is the spectral transmission spectrum of the base material obtained in Example 1. FIG.
4 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG.
5 : is the spectral transmission spectrum of the base material obtained in Example 2. FIG.
Fig. 6 is a spectral transmission spectrum of the substrate obtained in Example 6.
Fig. 7 is a spectral transmission spectrum of the substrate obtained in Example 7.
Fig. 8 is a spectral transmission spectrum of the substrate (near-infrared absorbing glass substrate) used in Comparative Example 3;
9 is a spectral transmission spectrum of the substrate obtained in Comparative Example 4.
Fig. 10 is a spectral transmission spectrum of the substrate obtained in Comparative Example 5;
It is a schematic diagram for demonstrating the color shading evaluation of the camera image performed by the Example and the comparative example.
It is a schematic diagram for demonstrating the ghost evaluation of the camera image performed by the Example and the comparative example.

Hereinafter, an 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 in that it has a description that satisfies the requirements (a), (b) and (c) described later, and also satisfies the requirements (d) and (e) described later. Moreover, it is preferable that the optical filter of this invention has a dielectric multilayer film on at least one surface of the said base material.

[write]

The substrate used in the present invention satisfies the following requirements (a), (b) and (c);

(a) has a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and 760 nm or less;

(b) the difference (X 2 -X 1 ) between the shortest wavelength (X ₁ ) and the second shortest wavelength (X ₂ ) at which the transmittance is 10% in the region of wavelength 640 nm or more (X ₂ -X ₁ ) 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.

In addition, it is preferable that the substrate further satisfies at least one of the following requirements (f) to (h):

(f) the minimum value (T ₁ ) of the transmittance in the region having a wavelength of 690 to 720 nm is 5% or less;

(g) contains the compound (S) having an absorption maximum in a wavelength region of 1050 nm or more and 1200 nm or less;

(h) The shortest wavelength Xc at which the transmittance becomes 50% when the transmittance is greater than 50% to 50% or less in a region having a wavelength of 600 nm or more is in the wavelength range of 628 to 658 nm.

Hereinafter, each requirement is demonstrated.

<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, and a low-temperature hardened glass material, which are easy to handle. However, it is preferable that it is a transparent resin from a compatibility viewpoint with a compound (A).

≪Compound (A)≫

Although the compound (A) is not particularly limited as long as it is a compound having an absorption maximum in the wavelength region of 650 nm or more and 760 nm or less, it is preferably a solvent-soluble dye compound, and a group consisting of a squarylium compound, a phthalocyanine compound and a cyanine compound It is more preferable that it is at least 1 type selected from, It is more preferable to contain a squarylium type compound, It is especially preferable that it is 2 or more types containing a squarylium type compound. When the compound (A) contains two or more squarylium-based compounds, two or more squarylium-based compounds having different structures may be used, or a combination of the squarylium-based compound and other compounds (A) may be used. As another compound (A), a phthalocyanine type compound and a cyanine type compound are especially preferable.

Although the squarylium-based compound has excellent visible light transmittance, a sharp absorption characteristic, and a high molar extinction coefficient, fluorescence that causes scattered light may be generated upon absorption of light. In such a case, by using a squarylium-type compound in combination with another compound (A), there is little scattered light and the optical filter with better camera image quality can be obtained.

The absorption maximum wavelength of a compound (A) becomes like this. Preferably they are 660 nm or more and 755 nm or less, More preferably, they are 670 nm or more and 750 nm or less, More preferably, they are 680 nm or more and 745 nm or less.

When the compound (A) is a combination of two or more compounds, the difference between the absorption maximum wavelength between the shortest absorption maximum wavelength and the longest absorption maximum wavelength among the compounds (A) to be applied is preferably 10 to 60 nm, more preferably preferably 15 to 55 nm, more preferably 20 to 50 nm. When the difference in absorption maximum wavelength exists in the said range, while being able to fully reduce the scattered light by fluorescence, since it can make compatible the wide absorption band of 700 nm vicinity, and the outstanding visible light transmittance, it is preferable.

The content of the entire compound (A) is, as the above-mentioned substrate, for example, a substrate including a transparent resin substrate containing the compound (A), or a transparent resin substrate containing the compound (A), a curable resin, etc. When using a substrate on which a resin layer such as an overcoat layer containing to 1.0 parts by weight, and as the substrate, a substrate in which a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) is laminated on a support such as a glass support or a resin support serving as a base is used. Preferably, 0.4 to 5.0 parts by weight, more preferably 0.6 to 4.0 parts by weight, still more preferably 0.8 to 3.5 parts by weight with respect to 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). is wealth

<Requirement (b)>

The difference between the wavelengths X ₁ and X ₂ (X ₂ -X ₁ ) is preferably 53 nm or more, more preferably 55 nm or more, still more preferably 58 nm or more. Although an upper limit is not specifically limited, Since visible transmittance may fall when a value is too large depending on the characteristic of a compound (A) or another near-infrared absorber, it is preferable that it is 100 nm or less, for example. When the difference (X ₂ -X ₁ ) is in the range as described above, an absorption band of sufficient intensity (width) is obtained in the near-infrared wavelength region close to the visible region, and for example, an incident angle such as an incident angle of 45 degrees It is preferable because color shading can be suppressed even under large conditions.

The value (X ₁ +X ₂ )/2 of the wavelength intermediate between X ₁ and X ₂ can be said to be the central wavelength of the absorption band in the near-infrared wavelength region close to the visible region, preferably 670 nm or more and 740 nm Hereinafter, more preferably, they are 680 nm or more and 730 nm or less, More preferably, they are 690 nm or more and 720 nm or less. When the value of the wavelength expressed by (X ₁ +X ₂ )/2 is in the above range, light in the wavelength region near the long wavelength end of the visible region can be more efficiently cut, which is preferable.

Said X ₁ becomes like this. Preferably they are wavelength 650 nm or more and 720 nm or less, More preferably, they are wavelength 655 nm or more and 710 nm or less, More preferably, they are wavelength 660 nm or more and 700 nm or less. When X ₁ is in such a range, it is preferable because there is a tendency for a camera image having little noise and excellent color reproducibility to be obtained.

<Requirement (c)>

The transmittances (c1), (c2) and (c3) are all preferably 60% or less, more preferably 55% or less, and still more preferably 50% or less. The lower limit is not particularly limited, but depending on the characteristics of the near-infrared absorber, if the value of the transmittance 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, 5 % or more is preferable. When the transmittances (c1), (c2) and (c3) are within the above ranges, it is preferable that the ghost suppression effect of a practically sufficient level can be obtained.

A single layer may be sufficient as the said base material, as long as it has a layer containing a compound (A), and a multilayer may be sufficient as it. Moreover, in order to satisfy the requirement (C), it is preferable that the said base material contains a near-infrared absorber, and this near-infrared absorber may be contained in the same layer as compound (A), or may be contained in another layer.

When the layer containing the compound (A) and the layer containing the near-infrared absorber are the same, for example, a substrate comprising a transparent resin substrate containing the compound (A) and the near-infrared absorber, the compound (A) and the near-infrared absorber A resin layer such as an overcoat layer containing a curable resin or the like is laminated on a transparent resin substrate containing and a substrate on which a transparent resin layer such as an overcoat layer made of a resin or the like was laminated.

When the layer containing the compound (A) and the layer containing the near-infrared absorber are different, for example, an overcoat layer containing a curable resin containing the compound (A) on a transparent resin substrate containing the near-infrared absorber, etc. A substrate on which a resin layer is laminated, a substrate on which a resin layer such as an overcoat layer containing a curable resin containing a near-infrared absorber, etc. is laminated on a transparent resin substrate containing the compound (A), a glass support or a resin serving as a base On a substrate including an overcoat layer containing a curable resin containing the compound (A) and the like, and an overcoat layer containing a curable resin containing a near-infrared absorber, etc. laminated on a support such as a support, a glass substrate containing a near-infrared absorber The base material etc. on which resin layers, such as an overcoat layer containing curable resin etc. containing a compound (A), were laminated|stacked are mentioned.

The near-infrared absorber is not particularly limited as long as it has broad absorption in a wavelength range of 900 to 1200 nm, and examples include a near-infrared absorbing dye, near-infrared absorbing fine particles, conductive metal oxides, and transition metal components in phosphoric acid glass. have.

<Requirement (f)>

Said T ₁ becomes like this. Preferably it is 3 % or less, More preferably, it is 2 % or less, More preferably, it is 1 % or less. When T ₁ is in the above range, it can be said that the transmittance cut of the absorption band is sufficient, and it is preferable because the flare around the light source in the camera image can be suppressed.

<Requirement (g)>

The base material of the present invention preferably contains a near-infrared absorber. If the near-infrared absorber is the compound (S), it is preferable because absorption intensity in the near-infrared wavelength region and visible transmittance tend to be compatible at a high level.

≪Compound (S)≫

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

In formulas (I) and (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, a -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any of the following L ^a to L ^h , R ^g and R ^h each independently represent a hydrogen atom, a -C(O)R ⁱ group, or any of the following L ^a to L ^e , R ⁱ represents any of the following L ^a to 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 ) aromatic hydrocarbon group having 6 to 14 carbon atoms

(L ^e ) heterocyclic group having 2 to 14 carbon atoms

(L ^f ) Alkoxy group having 1 to 12 carbon atoms

(L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L;

(L ^h ) Alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L

The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. At least one selected from the group,

Adjacent R ³ may form a ring which may have a substituent L,

n represents an integer of 0 to 4,

X represents the anion required 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, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, adamantyl group, trifluoro They are a methyl group, a pentafluoroethyl group, 3-pyridinyl group, an epoxy group, a phenyl group, a benzyl group, and a fluorenyl group, More preferably, they are an isopropyl group, sec-butyl group, tert- butyl group, and a benzyl group.

R ² is preferably a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a hydroxyl group, Amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoro loethanoylamino group, tert-butanoylamino group, cyclohexinoylamino 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, pentafluoro They are a loethanoylamino group, a tert-butanoylamino group, and a cyclohexinoylamino group, Especially preferably, they are a methyl group, an ethyl group, n-propyl group, and an isopropyl group. Although the number (value of n) of R< ² > couple|bonded with the same aromatic ring will not be restrict|limited if it is 0-4, It is preferable that it is 0 or 1.

X is an anion required to neutralize the charge, and when the anion is divalent, one molecule is required, and when the anion is monovalent, two molecules are required. In the latter case, the two anions may be the same or different, but the same is preferable from the viewpoint of synthesis. X is not particularly limited as long as it is such an anion, and examples thereof include those listed in Table 1 below.

[Table 1]

As X, (X-10), (X-16), (X-17), (X-21), (X-22) in the said Table 1 from a viewpoint of the heat resistance, light resistance, and spectral characteristic of a dimonium-type compound. ), (X-24) and (X-28) are particularly preferred.

Examples of the dimonium-based compound represented by the formula (I) include those shown in Tables 2-1 to 2-4 below.

[Table 2-1]

[Table 2-2]

[Table 2-3]

[Table 2-4]

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 , when adjacent R ³ groups form a ring, it is preferably a heterocyclic ring in which at least one sulfur atom or nitrogen atom is contained in the ring.

As said M, Preferably it is a transition metal, More preferably, they are Ni, Pd, and Pt.

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

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

The compound (S) may be synthesized by a generally known method, for example, Japanese Patent No. 4168031 , Japanese Patent No. 4252961 , Japanese Patent Publication No. 2010-516823 , Japanese Patent Application Laid-Open No. 63-165392 It can synthesize|combine with reference to the method etc. which are described in the publication etc. of a publication.

The content of the compound (S) is, as the above-mentioned substrate, for example, on a substrate including a transparent resin substrate containing the compound (A) and the compound (S), or on a transparent resin substrate containing the compound (S). When using a base material in which a resin layer such as an overcoat layer containing a curable resin or the like containing the compound (A) is laminated, preferably 0.01 to 2.0 parts by weight, more preferably 0.01 to 2.0 parts by weight based on 100 parts by weight of the transparent resin. A curable resin containing the compound (A) and the compound (S) on a support such as a glass support or a resin support serving as a base as the substrate, in an amount of 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight, etc. A resin layer such as an overcoat layer containing a curable resin containing the compound (S) or the like is laminated on a substrate on which a transparent resin layer such as an overcoat layer containing In the case of using the base material, it is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.0 parts by weight, particularly preferably 0.1 to 5.0 parts by weight, based on 100 parts by weight of the resin for forming the transparent resin layer containing the compound (A). 0.3 to 3.0 parts by weight. When content of a compound (S) exists in the said range, the optical filter which made the favorable near-infrared absorption characteristic and high visible light transmittance compatible can be obtained.

<Requirement (h)>

Xc is preferably 630 to 655 nm, more preferably 632 to 652 nm, still more preferably 634 to 650 nm. When Xc is less than 628 nm, the transmittance in the wavelength region corresponding to red decreases and color reproducibility tends to decrease. tends to

When the substrate satisfies the above requirement (h), even when a dielectric multilayer film is formed on the substrate, it is possible to reduce the dependence of the incident angle on the optical properties in the vicinity of a visible wavelength to a near-infrared wavelength region, and red reproducibility and color Since the shading suppression effect can be compatible at a high level, it is preferable. In addition, Xc represents a wavelength which satisfies a predetermined condition when the spectral transmittance is evaluated from the short wavelength side toward the long wavelength side.

<Other characteristics and properties>

The average transmittance of the substrate in the region having a wavelength of 430 to 580 nm is preferably 75% or more, more preferably 78% or more, and particularly preferably 80% or more. If a substrate having such a transmission characteristic is used, high light transmission characteristic can be achieved in a visible region, and a high-sensitivity camera function can be achieved.

The thickness of the substrate can be appropriately selected depending on the desired use, and is not particularly limited, but is preferably 10 to 200 µm, more preferably 20 to 180 µm, still more preferably 25 to 150 µm. When the thickness of the base material is within the above range, an optical filter using the base material can be reduced in thickness and weight, and can be suitably used for various uses such as solid-state imaging devices. In particular, when the substrate including the transparent resin substrate is used for a lens unit such as a camera module, it is preferable because the lens unit can be reduced in size and weight.

<Transparent resin>

The transparent resin used in the transparent resin layer, the transparent resin substrate, and the resin support constituting the base material is not particularly limited as long as the effects of the present invention are not impaired, but for example, thermal stability and In order to ensure moldability and to obtain a film capable of forming a dielectric multilayer film by high-temperature deposition performed at a deposition temperature of 100°C or higher, the glass transition temperature (Tg) is preferably 110 to 380°C, more preferably 110 to 370°C, more preferably 120 to 360°C. Moreover, since the film which can vapor-deposit and form a dielectric multilayer film at higher temperature that the glass transition temperature of the said resin is 140 degreeC or more is obtained, it is especially preferable.

As the transparent resin, when a resin plate having a thickness of 0.1 mm containing the resin is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95%, More preferably, resin used as 80 to 95% can be used. When 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 the gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000, preferably 30,000 to 250,000, and the number average molecular weight (Mn) is usually 10,000 to 150,000 , preferably 20,000 to 100,000.

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

Transparent resin may be used individually by 1 type, and may be used in combination of 2 or more type.

≪Cyclic polyolefin resin≫

As cyclic polyolefin-type resin, resin obtained from the at least 1 sort(s) of monomer chosen from the group which consists of a monomer represented by a following formula (X ₀ ), and a monomer represented by a following formula (Y ₀ ), and obtained by hydrogenating the said resin Resin is preferred.

In formula (X ₀ ), R ^x1 to R ^x4 each independently represent an atom or group selected from the following (i') to (ix'), and k ^x , m ^x and p ^x are each independently 0 or Represents a positive integer.

(i') hydrogen atom

(ii') halogen atom

(iii') trialkylsilyl group

(iv') a substituted or unsubstituted C1-C30 hydrocarbon group having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom

(v') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms

(vi') polar group (with the proviso that (iv') is excluded.)

(vii') R ^x1 and R ^x2 or R ^x3 and R ^x4 are an alkylidene group formed by combining with each other (provided that R ^x1 to R ^x4 not involved in the bond are each independently selected from the above (i') to ( 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 heterocycle (provided that R ^x1 to R ^x4 not involved in the bond are each independently An atom or group selected from (i') to (vi') is represented.)

(ix') R ^x2 and R ^x3 are bonded to each other to form a monocyclic hydrocarbon ring or a heterocyclic ring (provided that R ^x1 and R ^x4 not involved in the bonding are each independently selected from the above (i') to (vi') ) represents an atom or group selected from.)

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

≪Aromatic polyether-based resin≫

It is preferable that aromatic polyether-type resin has at least 1 sort(s) of structural unit chosen from the group which consists of a structural unit represented by following formula (1), and a structural unit represented by following formula (2).

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

In Formula (2), R ¹ to R ⁴ and a to d are each independently the same as R ¹ to R ⁴ and a to d in Formula (1), and Y is 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, g and h each independently represent an integer of 0 to 4; m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

Further, 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 (3) and a structural unit represented by the following formula (4). .

In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z is 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 the same as R ⁷ , R ⁸ , Y, m, g and h in Formula (2), R ⁵ , R ⁶ , Z, n, e and f are each independently the same as R ⁵ , R ⁶ , Z, n, e and f in the formula (3).

≪Polyimide-based resin≫

It does not restrict|limit especially as a polyimide-type resin, What is necessary is just a high molecular compound containing an imide bond in a repeating unit, For example, it describes in Unexamined-Japanese-Patent No. 2006-199945 and Unexamined-Japanese-Patent No. 2008-163107. It can be synthesized in any way.

≪Fluorene polycarbonate-based resin≫

The fluorene polycarbonate-based resin is not particularly limited, and any polycarbonate resin containing a fluorene moiety may be used. For example, it may be synthesized by the method described in Japanese Patent Laid-Open No. 2008-163194. can

≪Fluorene polyester-based resin≫

It does not restrict|limit especially as fluorene polyester-type resin, What is necessary is just a polyester resin containing a fluorene moiety, For example, it describes in Unexamined-Japanese-Patent No. 2010-285505 and Unexamined-Japanese-Patent No. 2011-197450. It can be synthesized in any way.

≪Fluorinated Aromatic Polymer Resin≫

The fluorinated aromatic polymer-based resin is not particularly limited, but at least one bond selected from the group consisting of an aromatic ring having at least one fluorine atom and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond; It is preferable that it is a polymer containing the repeating unit which contains, and it can synthesize|combine by the method described in Unexamined-Japanese-Patent No. 2008-181121, for example.

≪Acrylic ultraviolet curable resin≫

Although it does not restrict|limit especially as an acryl-type ultraviolet curable resin, What is synthesize|combined from the resin composition containing the compound which has one or more acryl group or methacryl group in a molecule|numerator, and the compound which decomposes|disassembles by ultraviolet-ray to generate active radicals is 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 serving as a base as the substrate, or a transparent resin containing compound (A) When using a base material in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated on a substrate, it can be particularly suitably used as the curable resin.

≪Epoxy resin≫

Although it does not restrict|limit especially as an epoxy resin, It can distinguish largely into an ultraviolet curable type and a thermosetting type. Examples of the ultraviolet curable epoxy resin include those synthesized from a composition containing a compound having one or more epoxy groups in a molecule and a compound that generates an acid by ultraviolet rays (hereinafter also referred to as “photoacid generator”). And, as a thermosetting type epoxy resin, what synthesize|combined from the composition containing the compound which has one or more epoxy groups in a molecule|numerator, and an acid anhydride is mentioned, for example. The epoxy-based UV-curable resin is a substrate in which a transparent resin layer containing the compound (A) is laminated on a glass substrate or a resin substrate serving as a base as the substrate, or on a transparent resin substrate containing the compound (A) When using a base material on which a resin layer such as an overcoat layer containing a curable resin or the like is laminated, it can be particularly suitably used as the curable resin.

≪Commercial product≫

As a commercial item of transparent resin, the following commercial items etc. are mentioned. As a commercial item of cyclic polyolefin resin, JSR Co., Ltd. product Aton, Nippon Zeon Co., Ltd. product Zeonoa, Mitsui Chemical Co., Ltd. product APEL, Polyplastics Co., Ltd. product TOPAS, etc. are mentioned. As a commercial item of polyether sulfone-type resin, Sumitomo Chemical Co., Ltd. Sumica Excel PES etc. are mentioned. As a commercial item of polyimide-type resin, the Mitsubishi Gas Chemical Co., Ltd. product neo-annealing L etc. are mentioned. As a commercial item of polycarbonate-type resin, Teijin Co., Ltd. product Pure Ace etc. are mentioned. As a commercial item of fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. Upijetta EP-5000 etc. are mentioned. As a commercial item of fluorene polyester-type resin, Osaka Gas Chemical Co., Ltd. product OKP4HT etc. are mentioned. As a commercial item of an acrylic resin, the Nippon Shokubai Co., Ltd. Accribua etc. are mentioned. As a commercial item of a silsesquioxane type|system|group ultraviolet curable resin, the Shin-Nippon Chemical Co., Ltd. product Silplus etc. are mentioned.

<Other pigment (X)>

The above description may further contain other dyes (X) that do not correspond to the compound (A) and the compound (S).

The other dye (X) is not particularly limited as long as it is a dye having an absorption maximum wavelength of less than 650 nm or a wavelength of more than 760 nm and less than 1050 nm, but a dye having an absorption maximum wavelength of more than 760 nm and less than 1050 nm is preferable. As such a dye, for example, a squarylium-based compound, a phthalocyanine-based compound, a cyanine-based compound, a naphthalocyanine-based compound, a croconium-based compound, an octapyrine-based compound, a dimonium-based compound, a pyrrolopyrrole compound, boron dipyrrome and at least one compound selected from the group consisting of a ten (BODIPY)-based compound, a perylene-based compound, and a metal dithiolate-based compound.

The content of the other dye (X) is preferably based on 100 parts by weight of the transparent resin when using a base material including, for example, a transparent resin substrate containing the other dye (X) as the base material. is 0.005 to 1.0 parts by weight, more preferably 0.01 to 0.9 parts by weight, particularly preferably 0.02 to 0.8 parts by weight, and as the substrate, other dyes ( A substrate on which a transparent resin layer such as an overcoat layer containing a curable resin containing X) is laminated, or a transparent resin substrate containing the compound (A), a curable resin containing another dye (X), etc. When using a base material on which a resin layer such as an overcoat layer is laminated, it is preferably 0.05 to 4.0 parts by weight, more preferably 0.05 to 4.0 parts by weight, based on 100 parts by weight of the resin for forming the transparent resin layer containing the other pigment (X). preferably 0.1 to 3.0 parts by weight, particularly preferably 0.2 to 2.0 parts by weight.

<Other ingredients>

The said base material is the range which does not impair the effect of this invention WHEREIN: As another component, you may contain antioxidant, a near-ultraviolet absorber, a fluorescence quencher, etc. further. These other components may be used individually by 1 type, and may use 2 or more types together.

As said near ultraviolet absorber, an azomethine type compound, an indole type compound, a benzotriazole type compound, a triazine type compound, etc. are mentioned, for example.

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

In addition, when manufacturing a base material, these other components may be mixed with resin etc., and may be added when synthesize|combining resin. Moreover, although the addition amount is suitably selected according to the desired characteristic, it is 0.01-5.0 weight part normally with respect to 100 weight part of resin, Preferably it is 0.05-2.0 weight part.

<Method for manufacturing base material>

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 if necessary, After molding, the substrate on which the overcoat layer is laminated can be prepared by coating a coating agent such as an antireflection agent, a hard coating agent and/or an antistatic agent.

The substrate is an overcoat layer containing a curable resin containing the compound (A), etc. on a support such as a glass substrate or a resin substrate serving as a base, or on a transparent resin substrate not containing the compound (A) When the transparent resin layer is a laminated substrate, for example, melt molding or cast molding a resin solution containing the compound (A) on the support or the transparent resin substrate, preferably spin coating, slit coating, After coating by an inkjet method or the like, the solvent is dried and removed, and, if necessary, further light irradiation or heating is performed to form a transparent resin layer containing compound (A) on the support or the transparent resin substrate. can be manufactured.

≪Melt molding≫

As said melt molding, specifically, the method of melt-molding the pellet obtained by melt-kneading resin, compound (A), and other components as needed; a method of melt-molding a resin composition containing a resin, the compound (A) and, if necessary, other components; Or the method of melt-molding the pellet obtained by removing a solvent from the resin composition containing a compound (A), resin, a solvent, and other components as needed, etc. are mentioned. Examples of the melt molding method include injection molding, melt extrusion molding or blow molding.

≪Cast molding≫

Examples of the cast molding include a method in which a resin composition containing the compound (A), a resin, a solvent and, if necessary, other components is cast on a suitable support to remove the solvent; Alternatively, a curable composition comprising the compound (A), a photocurable resin and/or a thermosetting resin, and, if necessary, other components is cast on a suitable support to remove the solvent, followed by an appropriate method such as ultraviolet irradiation or heating. It can also be manufactured by the method of hardening, etc.

When the substrate is a substrate including a transparent resin substrate containing the compound (A), the substrate can be obtained by peeling the coating film from the support after casting, and the substrate is a glass support or a base. A substrate in which a transparent resin layer such as an overcoat layer containing a curable resin or the like containing the compound (A) is laminated on a support such as a resin support or the like or on a transparent resin substrate not containing the compound (A) In this case, the base material can be obtained by not peeling a coating film after cast molding.

Examples of the support include a near-infrared absorbing glass plate (for example, a phosphate-based glass plate containing a copper component such as “BS-11” manufactured by Matsunami Glass Kogyo Co., Ltd. or “NF-50T” manufactured by AGC Techno Glass Co., Ltd.); A transparent glass plate (for example, an alkali-free glass plate such as "OA-10G" manufactured by Nippon Denki Glass Co., Ltd. or "AN100" manufactured by Asahi Glass Corporation), a steel belt, a steel drum and a transparent resin (eg, polyester film, cyclic olefin) system resin film) support body is mentioned.

In addition, the transparent resin layer on the optical component by a method of coating the resin composition on an optical component such as a glass plate, quartz, or transparent plastic to dry the solvent, or coating the curable composition to cure and dry it. can also be formed.

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

[Optical filter]

The optical filter according to the present invention is characterized in that it has a substrate satisfying the above requirements (a), (b) and (c), and also satisfies the following requirements (d) and (e):

(d) the average value (d1) of transmittance when measured from the vertical direction of the optical filter in the wavelength region of 430 to 580 nm is 75% or more;

(e) In the wavelength range 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 is excellent in transmittance characteristics and near-infrared cut characteristics in the visible wavelength region, has little incident angle dependence, and has a color shading suppression effect and a ghost suppression effect. is an excellent optical filter.

<Requirement (d)>

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

<Requirement (e)>

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

<Other characteristics and properties>

Since the optical filter of this invention has the said base material, also in the form which has a dielectric multilayer film, the dependence of the incident angle of an optical characteristic can be reduced. Specifically, in the wavelength range of 600 to 800 nm, the value Xa of the shortest wavelength at which the transmittance is 50% when measured from the vertical direction of the optical filter, and an angle of 30° with respect to the vertical direction of the optical filter The absolute value |Xa-Xb| of the difference of the value (Xb) of the wavelength at which the transmittance is 50% when measured from , is preferably less than 20 nm, more preferably less than 15 nm, still more preferably less than 10 nm.

The thickness of the optical filter of the present invention is preferably thin in view of recent trends such as thickness reduction and weight reduction of solid-state imaging devices. Since the optical filter of this invention contains the said base material, thickness reduction is possible.

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

[Dielectric Multilayer Film]

It is preferable that the optical filter of this invention has a dielectric multilayer film on at least one surface of the said base material. The dielectric multilayer film in the present invention is a film having an ability to reflect near infrared rays or a film having an antireflection effect in the visible region, and by having the dielectric multilayer film, more excellent visible light transmittance and near infrared cut characteristics can be achieved.

In the present invention, the dielectric multilayer film may be provided on one side or both sides of the substrate. When installing on one side, it is excellent in manufacturing cost and manufacturing easiness, and when installing on both sides, it has high intensity|strength, and it can obtain the optical filter which curvature or distortion is hard to generate|occur|produce. When an optical filter is applied to a solid-state imaging device use, it is preferable to provide a dielectric multilayer film on both surfaces of a resin substrate from the point where the bending and twisting of an optical filter are more preferable.

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

A form having a dielectric multilayer film on both surfaces of a substrate, wherein, when measured from an angle of 5° with respect to the vertical direction of the optical filter, a first optical layer having a reflection characteristic mainly in the vicinity of a wavelength of 700 to 950 nm is provided on one side of the substrate, A form having a second optical layer having a reflection characteristic mainly in the vicinity of 900 nm to 1150 nm on the other side of the substrate (see Fig. 1 (a)) or when measured from an angle of 5° with respect to the vertical direction of the optical filter In the form of 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 a fourth optical layer having an antireflection characteristic in the visible region on the other side of the substrate (FIG. 1) (b) see) and the like.

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

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

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

The thickness of each layer of the high-refractive-index material layer and the low-refractive-index material layer is preferably 0.1λ to 0.5λ when the near-infrared wavelength to be blocked is usually λ (nm). The value of lambda (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. If the thickness is within this range, the product (n × d) of the refractive index (n) and the film thickness (d) is calculated as λ/4, and the thickness of each layer of the high refractive index material layer and the low refractive index material layer is It becomes almost the same value, and there exists a tendency that blocking and transmission of a specific wavelength can be controlled easily from the relationship of the optical characteristic of reflection and refraction.

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

In the present invention, according to the absorption characteristics of the near-infrared absorber such as compound (A) or compound (S), the material species constituting the high refractive index material layer and the low refractive index material layer, the high refractive index material layer and each layer of the low refractive index material layer By appropriately selecting the thickness, the order of lamination, and the number of laminations, after securing sufficient transmittance in the visible region, sufficient ray cut characteristics in the near-infrared wavelength region can be obtained, and the reflectance when near-infrared rays are incident from the oblique direction can be reduced. have.

Here, in order to optimize the above conditions, for example, using optical thin film design software (eg, Essential Macleod, manufactured by Thin Film Center), the anti-reflection effect in the visible region and the ray cut effect in the near-infrared region are compatible. You just need to set the parameters to do this. In the case of the above software, for example, when designing the first optical layer, the target transmittance at a wavelength of 400 to 700 nm is set to 100%, the target tolerance value is set to 1, and then the target transmittance at a wavelength of 705 to 950 nm is set. A parameter setting method such as 0% and a target tolerance value of 0.5 may be mentioned. These parameters may further finely divide the wavelength range according to various characteristics of the substrate (i) and change the value of the target tolerance.

[Other function film]

The optical filter of the present invention, within the scope of not impairing the effects of the present invention, between the substrate and the dielectric multilayer film, on the surface opposite to the surface on which the dielectric multilayer film of the substrate is provided, or on the surface opposite to the surface on which the substrate of the dielectric multilayer film is provided. , For the purpose of improving the surface hardness of the substrate or dielectric multilayer film, improving chemical resistance, preventing static electricity, and removing scratches, functional films such as an antireflection film, a hard coat film or an antistatic film can be provided as appropriate.

The optical filter of this invention may contain one layer containing the said functional film, and may contain two or more layers. When the optical filter of this invention contains two or more layers of the layer containing the said functional film, two or more layers of the same layer may be included, and two or more layers of different layers may be included.

The method for laminating the functional film is not particularly limited, but a method of melt-molding or cast-molding in the same manner as above for a substrate or a dielectric multilayer film with a coating agent such as an antireflection agent, a hard coating agent and/or an antistatic agent, etc. can be mentioned.

In addition, the curable composition including the coating agent or the like can be applied on a substrate or a dielectric multilayer film with a bar coater or the like, and then cured by UV irradiation or the like.

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins and thermosetting resins, and specifically, vinyl compounds, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylic. A rate-type resin etc. are mentioned. As said curable composition containing these coating agents, a vinyl type, a urethane type, a urethane acrylate type, an acrylate type, an epoxy type, and an epoxy acrylate type curable composition etc. are mentioned.

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

In the said curable composition, when the compounding ratio of a polymerization initiator makes whole quantity of curable composition 100 weight%, Preferably it is 0.1 to 10 weight%, More preferably, it is 0.5 to 10 weight%, More preferably, it is 1 to 5 weight%. % by weight. When the mixing ratio of the polymerization initiator is in the above range, it is excellent in curing characteristics and handleability of the curable composition, and functional films such as an antireflection film, a hard coat film and an antistatic film having a desired hardness can be obtained.

In addition, an organic solvent may be added to the said curable composition as a solvent, and a well-known thing can be used as an organic solvent. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene 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; and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

These solvents may be used individually by 1 type, and may use 2 or more types together.

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.

In addition, in order to improve the adhesion between the substrate and the functional film and/or the multilayer dielectric film or the adhesion between the functional film and the multilayer dielectric film, the surface of the substrate, the functional film or the dielectric multilayer film may be subjected to a surface treatment such as corona treatment or plasma treatment. .

[Use of optical filter]

The optical filter of this invention has a wide viewing angle, and has the outstanding near-infrared cutting ability, etc. Therefore, it is useful as an object for visibility correction|amendment of solid-state image sensors, such as a CCD of a camera module and a CMOS image sensor. In particular, digital still cameras, smart phone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, portable information terminals, video game consoles, portable game consoles, fingerprints Useful for authentication systems, digital music players, etc. Moreover, it is useful also as a hot-ray cut filter etc. which are attached to the glass plate of automobiles, buildings, etc.

[Solid-State Imaging Device]

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

Example

Hereinafter, the present invention will be described more specifically based on Examples, but the present invention is not limited to these Examples at all. In addition, "part" means "part by weight" unless otherwise indicated. In addition, the measuring method of each physical property value, and the evaluation method of a physical property are as follows.

<Molecular Weight>

The molecular weight of resin considered the solubility with respect to the solvent of each resin, etc., and measured by the method of following (a) or (b).

(a) Using a gel permeation chromatography (GPC) apparatus manufactured by Waters Corporation (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene), the weight average molecular weight in terms of standard polystyrene ( Mw) and number average molecular weight (Mn) were measured.

(b) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: THF).

In addition, about the resin synthesize|combined by the resin synthesis example 3 mentioned later, not the measurement of the molecular weight by the said method, but the measurement of the logarithmic viscosity by the following method (c) was performed.

(c) A part of the polyimide resin solution was poured into anhydrous methanol to precipitate a polyimide resin, and filtered to separate from unreacted monomers. 0.1 g of polyimide obtained by vacuum drying at 80°C for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30°C was calculated by the following formula using a Canon-Penske viscometer. saved

μ={ln(t _s /t ₀ )}/C

t ₀ : solvent flow time

t _s : flow time of the dilute polymer solution

C: 0.5 g/dL

<Glass transition temperature (Tg)>

Using a differential scanning calorimeter (DSC6200) manufactured by SII Technologies, Inc., it was measured at a rate of temperature increase: 20° C. per minute and a nitrogen stream.

<Spectral transmittance>

Transmittance in each wavelength of the substrate, (T ₁ ), (X ₁ ), (X ₂ ) and (Xc), and transmittance in each wavelength region of the optical filter, (Xa) and (Xb) Measurement was made using a spectrophotometer (U-4100) manufactured by Hitachi High Technologies, Inc.

Here, in the transmittance when measured from the vertical direction of the optical filter, light transmitted perpendicular to the filter is measured as shown in FIG. In the transmittance of , the light transmitted at an angle of 30° with respect to the vertical direction of the filter was measured as shown in FIG. 2(b).

In addition, this transmittance|permeability is measured using the spectrophotometer under the condition that light is incident perpendicularly to a board|substrate and a filter except the case where (Xb) is measured. 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.

<Evaluation of color shading of camera images>

The color shading evaluation at the time of inserting an optical filter into a camera module was performed by the following method. A camera module was manufactured in the same manner as in Japanese Patent Laid-Open No. 2016-110067, and a white plate of 300 mm × 400 mm size was used as a D65 light source (standard light source device “Macbeth Jersey II” manufactured by X-Rite) using the camera module produced. It imaged under the following reference|standards and evaluated the difference of the color tone in the center part and edge part of the white plate in a camera image.

A level that is acceptable without any problem, A level that is acceptable for a high-definition camera module with a slight difference in color tone but no practical problem as a high-definition camera module. Due to the difference, a level that is unacceptable even for general camera module use was judged as D.

In addition, 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 occupies 90% or more of the area of the camera image 111 when shooting was performed.

<Ghost evaluation of camera images>

The ghost evaluation at the time of inserting an optical filter into a camera module was performed by the following method. A camera module was manufactured in the same manner as in Japanese Patent Laid-Open No. 2016-110067, and using the camera module produced, photographed under a halogen lamp light source (“Lumina Ace LA-150TX” manufactured by Hayashi Tokee Kogyo Co., Ltd.) in a dark room, and the camera The following criteria evaluated the ghost generation|occurrence|production state around the light source in an image.

Level A is acceptable without any problem, level B that is acceptable for high-definition camera module with little ghosting but practically no problem, level C is unacceptable for high-definition camera module use because ghost is generated, and the degree of ghost is The level was so severe that it was unacceptable even for general camera module use.

In addition, as shown in FIG. 12, when performing imaging|photography, it adjusted so that the light source 122 might become the upper right end of the camera image 121. In addition, as shown in FIG.

[Synthesis Example]

Compound (A) and compound (S) used in the following Examples were synthesized by a generally known method. As a general synthesis method, For example, Unexamined-Japanese-Patent No. 60-228448, Unexamined-Japanese-Patent No. 1-146846, Unexamined-Japanese-Patent No. 1-228960, Unexamined-Japanese-Patent No. 4081149, "Phthalocyanine-Chemistry Department," for example. Function -" (IPC, 1997), Unexamined-Japanese-Patent No. 2009-108267, Unexamined-Japanese-Patent No. 2010-241873, Unexamined-Japanese-Patent No. 3699464, Unexamined-Japanese-Patent No. 4740631, etc. are mentioned. can

<Resin Synthesis Example 1>

100 g of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^{2,5.1 7,10} ]dodeca-3-ene (hereinafter also referred to as “DNM”) represented by the following formula (a); 18 g of 1-hexene (molecular weight modifier) and 300 g of toluene (solvent for ring-opening polymerization) were put into a nitrogen-substituted reaction vessel, and the solution was heated at 80°C. Then, 0.2 g of a triethylaluminum toluene solution (0.6 mol/liter) and 0.9 g of a methanol-modified tungsten hexachloride toluene solution (concentration 0.025 mol/liter) were added to the solution in the reaction vessel as a polymerization catalyst, This solution was subjected to a ring-opening polymerization reaction by heating and stirring at 80°C for 3 hours to obtain a ring-opening polymer solution. The polymerization conversion ratio in this polymerization reaction was 97%.

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

<Resin Synthesis Example 2>

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 “ DMAc") 443 g and toluene 111 g were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube, and a cooling tube were installed in the four-neck flask. Next, after replacing the inside of the flask with nitrogen, the resulting solution was reacted at 140°C for 3 hours, and the resulting water was removed from time to time from the Dean-Stark tube. When the production of water was no longer observed, the temperature was gradually increased to 160°C, and the reaction was carried out at the same temperature for 6 hours. After cooling to room temperature (25° C.), the resulting 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 at 60 degreeC overnight, and white powder (henceforth "resin B") was obtained (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>

1,4-bis(4-amino-α,α-dimethylbenzyl) in a 500 mL 5-neck flask equipped with a thermometer, stirrer, nitrogen inlet tube, side tube-equipped dropping funnel, Dean-Stark tube and cooling tube under a nitrogen stream 27.66 g of benzene and 7.38 g of 4,4'-bis(4-aminophenoxy)biphenyl were added, and dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide. The obtained solution was cooled to 5°C using an ice-water bath, and 22.62 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.50 g of triethylamine as an imidization catalyst were added at once while maintaining the same temperature. did. After completion of the addition, the temperature was raised to 180°C, and the distillate was distilled off at any time, while refluxing for 6 hours. After completion of the reaction, after completion of the reaction, the mixture was air-cooled until the internal temperature reached 100° C., diluted by adding 143.6 g of N,N-dimethylacetamide, and cooled while stirring to obtain 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight. . A part of this polyimide resin solution was poured into 1 L of methanol, and polyimide was precipitated. After wash|cleaning the polyimide separated by filtration with methanol, it was made to dry in 100 degreeC vacuum dryer for 24 hours, and white powder (henceforth "resin C" is also mentioned.) was obtained. When the IR spectrum of the obtained resin C was measured, absorption of 1704 cm ^-1 and 1770 cm ^-1 peculiar to the imide group was seen. Resin C had a glass transition temperature (Tg) of 310°C, and when the logarithmic viscosity was measured, it was 0.87.

[Example 1]

In Example 1, an optical filter having a substrate including a transparent resin substrate was produced under the following procedures and conditions.

In a container, 100 parts of Resin A obtained in Resin Synthesis Example 1, 0.04 parts of compound (a-1) represented by the following formula (a-1) as compound (A) (maximum absorption wavelength in dichloromethane 698 nm) and the following formula 0.04 parts of compound (a-2) represented by (a-2) (maximum absorption wavelength in dichloromethane 733 nm), compound (s-6) described in Table 2-2 above as compound (S) (in dichloromethane Absorption maximum wavelength 1093 nm), 0.07 parts and methylene chloride were added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on the smooth glass plate, and after drying at 20 degreeC for 8 hours, it peeled 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 comprising 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 base material was measured, and the transmittance|permeability in (T1), ( _X1 ), (X2), (Xc), _{and each} wavelength was calculated|required. The results are shown in FIG. 3 and Table 5-1.

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

The dielectric multilayer film (I) is formed by alternately stacking 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 stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (20 layers in total). In any of the dielectric multilayer films (I) and (II), the silica layer and the titania layer are formed from a titania layer, a silica layer, a titania layer, ... It was laminated|stacked alternately in order of a silica layer, a titania layer, and a silica layer, and made the silica layer into the outermost layer of an optical filter.

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

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

[Table 3]

As a result of the film configuration optimization, in Example 1, the dielectric multilayer film (I) is a multilayer deposited film having a laminate number of 26, in which 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 are alternately laminated, The dielectric multilayer film (II) was a multilayer vapor deposition film having a stack number of 20 in which a silica layer having a film thickness of 37 to 194 nm and a titania layer having a film thickness of 12 to 114 nm were alternately laminated. Table 4 below shows an example of the optimized film configuration.

[Table 4]

The spectral transmittance measured from the vertical direction and the angle of 30 degrees from the perpendicular direction of the obtained optical filter was measured, and the optical characteristic in each wavelength range was evaluated. The results are shown in FIG. 4 and Table 5-1. The average value of the transmittance|permeability in wavelength 430-580 nm was 84 %, the average value of the transmittance|permeability in wavelength 1100-1200 nm was 1 % or less, and absolute value |Xa-Xb| was 2 nm.

Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-1. The obtained camera image was a good result in color shading and ghosting.

[Example 2]

In Example 2, an optical filter having a substrate including a transparent resin substrate was produced under the following procedures and conditions.

In Example 1, as the compound (A), 0.04 parts of a compound (a-3) represented by the following formula (a-3) (a maximum absorption wavelength of 703 nm in dichloromethane) and a compound represented by the following formula (a-4) Compound (a-4) (maximum absorption wavelength in dichloromethane 736 nm) using 0.08 parts, compound (S) described in Table 2-3 above as compound (s-8) (maximum absorption wavelength in dichloromethane: 1096 nm) 0.06 The same procedure as in Example 1 except that part was used and 0.01 parts of the dye (X-1) represented by the following formula (X-1) (maximum absorption wavelength in dichloromethane 887 nm) was used as the other dye (X). and a substrate including a transparent resin substrate containing the compound (A) and the compound (S) under the conditions. The spectral transmittance of this base material was measured, and the transmittance|permeability in (T1), ( _X1 ), (X2), (Xc), _{and each} wavelength was calculated|required. The results are shown in FIG. 5 and Table 5-1.

Subsequently, in the same manner as in Example 1, a multilayer dielectric film (III) in which 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 substrate (26 layers in total) A dielectric multilayer film (IV) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers as a second optical layer on the other side of the substrate (a total of 20 layers) was formed to have a thickness of about An optical filter of 0.105 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the substrate. The spectral transmittance measured from the vertical direction and the angle of 30 degrees from the perpendicular direction of the obtained optical filter was measured, and the optical characteristic in each wavelength range was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-1.

[Example 3]

In Example 3, an optical filter having a substrate including a transparent resin substrate having a resin layer on both surfaces was produced under the following procedures and conditions.

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

The resin composition (1) of the following composition was apply|coated to the single side|surface of the obtained transparent resin board|substrate with a bar coater, and it heated at 70 degreeC in oven for 2 minutes, and volatilized removal of the solvent. At this time, the application|coating conditions of the bar 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) was performed using a conveyor type exposure machine, the resin composition (1) was hardened, and the resin layer was formed on the transparent resin substrate. Similarly, a resin layer containing the resin composition (1) is formed on the other side of the transparent resin substrate, and a substrate having a resin layer on both sides of the transparent resin substrate containing the compound (A) and the compound (S) is applied. got it The spectral transmittance of this base material was measured, and the transmittance|permeability in (T1), ( _X1 ), (X2), (Xc), _{and each} wavelength was calculated|required. 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-hydroxycyclohexylphenyl ketone, methyl ethyl ketone (solvent, solid content concentration ( TSC): 30%)

Subsequently, in the same manner as in Example 1, a dielectric multilayer film (V) in which silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as a first optical layer on one side of the obtained substrate (26 layers in total) A dielectric multilayer film (VI) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers as a second optical layer on the other side of the substrate (a total of 20 layers) was formed to have a thickness of about An optical filter of 0.109 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the base refractive index and the like in the same manner as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 degrees from the perpendicular direction of the obtained optical filter was measured, and the optical characteristic in each wavelength range was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-1.

[Example 4]

In Example 4, an optical filter having a base material in which a transparent resin layer containing the compound (A) is formed on both surfaces of a resin support was produced under the following procedures and conditions.

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

On both surfaces of the obtained resin support, in the same manner as in Example 3, a resin layer containing the resin composition (2) of the following composition was formed, and the compound (A) and the compound (S) were included on both surfaces of the resin support. A base material formed by forming a transparent resin layer to be used was obtained. The spectral transmittance of this base material was measured, and the transmittance|permeability in (T1), ( _X1 ), (X2), (Xc), _{and each} wavelength was calculated|required. The results are shown in Table 5-1.

Resin composition (2): 100 parts by weight of tricyclodecanedimethanol diacrylate, 4 parts by weight of 1-hydroxycyclohexylphenyl ketone, 0.10 parts by weight of compound (a-1), 0.10 parts by weight of compound (a-2); Compound (s-6) 1.75 parts by weight, methyl ethyl ketone (solvent, TSC: 25%)

Subsequently, in the same manner as in Example 1, a multilayer dielectric film (VII) in which 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 substrate (26 layers in total) A dielectric multilayer film (VIII) formed by alternately stacking a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a second optical layer on the other side of the substrate (a total of 20 layers) was formed to form a thickness of about An optical filter of 0.109 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the base refractive index and the like in the same manner as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 degrees from the perpendicular direction of the obtained optical filter was measured, and the optical characteristic in each wavelength range was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-1.

[Example 5]

In Example 5, an optical filter having a substrate including a transparent glass substrate having a transparent resin layer containing the compound (A) on one side was produced under the following procedures and conditions.

On a transparent glass substrate "OA-10G (thickness 150 um)" (manufactured by Nippon Denki Glass Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width, the resin composition (3) of the following composition was applied with a spin coater and hot The solvent was removed by volatilization by heating at 80°C for 2 minutes on the plate. At this time, the 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 performed using a conveyor type exposure machine, the resin composition (3) is cured, and a transparent glass substrate having a transparent resin layer containing the compound (A) and the compound (S) is obtained. A substrate containing The spectral transmittance of this base material was measured, and the transmittance|permeability in (T1), ( _X1 ), (X2), (Xc), _{and each} wavelength was calculated|required. The results are shown in Table 5-1.

Resin composition (3): 20 parts by weight of tricyclodecanedimethanol diacrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexylphenyl ketone, 0.20 parts by weight of compound (a-1) , 0.20 parts by weight of compound (a-2), 3.50 parts by weight of compound (s-6), methyl ethyl ketone (solvent, TSC: 35%)

Subsequently, in the same manner as in Example 1, a dielectric multilayer film (IX) in which silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated as a first optical layer on one side of the obtained substrate (26 layers in total) A dielectric multilayer film (X) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers as a second optical layer on the other side of the substrate (a total of 20 layers) was formed, and a thickness of about An optical filter of 0.107 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the base refractive index and the like in the same manner as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 degrees from the perpendicular direction of the obtained optical filter was measured, and the optical characteristic in each wavelength range was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-1.

[Example 6]

In Example 6, the optical filter which has a base material containing the near-infrared absorption glass substrate which has a transparent resin layer containing a compound (A) on one side was produced by the following procedure and conditions.

A resin composition (4) of the following composition was applied with a spin coater on a near-infrared absorption glass substrate "BS-11 (thickness 120 μm)" (manufactured by Matsunami Glass Kogyo Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width. and heated on a hot plate at 80° C. for 2 minutes to remove the solvent by volatilization. At this time, the 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 performed using a conveyor type exposure machine, the resin composition (4) is cured, and a substrate comprising a near-infrared absorbing glass substrate having a transparent resin layer containing the compound (A) got it The spectral transmittance of this base material was measured, and the transmittance|permeability in (T1), ( _X1 ), (X2), (Xc), _{and each} wavelength was calculated|required. The results are shown in FIG. 6 and Table 5-1.

Resin composition (4): 20 parts by weight of tricyclodecanedimethanol diacrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexylphenyl ketone, 0.15 parts by weight of compound (a-3) , 0.30 parts by weight of compound (a-4), methyl ethyl ketone (solvent, TSC: 35%)

Subsequently, in the same manner as in Example 1, a dielectric multilayer film (XI) in which 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 substrate (26 layers in total) A dielectric multilayer film (XII) formed by alternately stacking a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a second optical layer on the other side of the substrate (a total of 20 layers) is formed, and the thickness is about An optical filter of 0.107 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the base refractive index and the like in the same manner as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 degrees from the perpendicular direction of the obtained optical filter was measured, and the optical characteristic in each wavelength range was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-1.

[Example 7]

In Example 7, an optical filter having a base material including a transparent resin substrate containing the compound (A) and having a transparent resin layer containing near-infrared absorbing fine particles on both surfaces was produced under the following procedures and conditions.

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

Compound (A) having a resin layer comprising a resin composition (5) of the following composition on both surfaces of the obtained resin substrate in the same manner as in Example 3, and having a transparent resin layer containing near-infrared absorbing fine particles on both surfaces ) to obtain a substrate comprising a transparent resin substrate containing The spectral transmittance of this base material was measured, and the transmittance|permeability in (T1), ( _X1 ), (X2), (Xc), _{and each} wavelength was calculated|required. 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-hydroxycyclohexylphenyl ketone, 35 parts by weight of near-infrared absorbing fine particle dispersion (YMF-02A manufactured by Sumitomo Kinzoku Kozan Co., Ltd.) parts (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 multilayer dielectric film (XIII) in which 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 substrate (26 layers in total) A dielectric multilayer film (XIV) formed by alternately stacking a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a second optical layer on the other side of the substrate (a total of 20 layers) is formed to have a thickness of about An optical filter of 0.109 mm was obtained. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the base refractive index and the like in the same manner as in Example 1. The spectral transmittance measured from the vertical direction and the angle of 30 degrees from the perpendicular direction of the obtained optical filter was measured, and the optical characteristic in each wavelength range was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-1.

[Examples 8 to 13]

The description was carried out in the same manner as in Example 3 except that the resin, solvent, drying conditions of the resin substrate, compound (A), compound (S), and other dyes (X) were changed as shown in Table 5-1. and an optical filter. Table 5-1 shows the optical properties of the obtained substrate and optical filter. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. 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 base material and an optical filter were prepared in the same manner as in Example 1, and the optical properties were evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-2. The optical filter obtained in Comparative Example 1 exhibits relatively good visible light transmittance, but has a large incident angle dependence of optical properties, and since the substrate has no absorption in the vicinity of 700 nm or near infrared wavelength region, color shading suppression effect and ghost suppression effect was confirmed to fall.

[Comparative Example 2]

Except having used the transparent glass substrate "OA-10G (thickness 150 um)" (made by Nippon Denki Glass Co., Ltd.) as a base material, it carried out similarly to Example 1, and produced the optical filter, and the optical characteristic was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-2. The optical filter obtained in Comparative Example 2 exhibits relatively good visible light transmittance, but has a large incident angle dependence of optical properties, and since the substrate has no absorption in the vicinity of 700 nm or near-infrared wavelength region, color shading suppression effect and ghost suppression effect was confirmed to fall.

[Comparative Example 3]

An optical filter was produced in the same manner as in Example 1 except that a near-infrared absorbing glass substrate "BS-11 (thickness 120 um)" (manufactured by Matsunami Glass Kogyo Co., Ltd.) was used as the base material, and the optical properties were evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-2. In addition, the spectral transmission spectrum of the substrate is shown in FIG. 8 . Although the optical filter obtained in Comparative Example 3 showed comparatively good optical properties, it was confirmed that the absorption intensity of the substrate near 700 nm was not sufficient, and the color shading suppression effect was inferior.

[Comparative Example 4]

In Example 3, without using compound (S), 0.08 parts of compound (a-4) and 0.06 parts of compound (a-5) were used as compound (A), and 0.01 parts of dye (X-1) was used. Except that, it carried out similarly to Example 3, the base material and the optical filter were produced, and the optical characteristic was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-2. Also, the spectral transmission spectrum of the substrate is shown in FIG. 9 . Although the optical filter obtained by the comparative example 5 showed comparatively favorable optical characteristic, the absorption intensity in the near-infrared wavelength region of a base material was not enough, and it was confirmed that the ghost suppression effect is inferior.

[Comparative Example 5]

In Example 6, a base material and an optical filter were produced 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-hydroxycyclohexylphenyl ketone, 0.15 parts by weight of compound (a-1) , methyl ethyl ketone (solvent, TSC: 35%)

The optical properties of the obtained substrate and optical filter were evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-2. Moreover, the spectral transmission spectrum of a base material is shown in FIG. Although the optical filter obtained in Comparative Example 5 showed comparatively good optical properties, it was confirmed that the absorption intensity of the substrate near 700 nm was not sufficient, and the effect of suppressing color shading was inferior.

[Comparative Example 6]

Example 3, except that 0.04 parts of compound (a-3) and 0.08 parts of compound (a-4) were used as compound (A), and 0.01 parts of compound (s-6) was used as compound (S). It carried out similarly to 3, the base material and the optical filter were produced, and the optical characteristic was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-2. Although the optical filter obtained by the comparative example 6 showed comparatively favorable optical characteristic, the absorption intensity in the near-infrared wavelength region of a base material was not enough, and it was confirmed that the ghost suppression effect is inferior.

[Comparative Example 7]

In Example 3, except that 0.04 parts of compound (a-1) was used as compound (A) and 0.07 parts of compound (s-6) was used as compound (S), it was carried out in the same manner as in Example 3; was produced, and the optical properties were evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 7 showed comparatively good optical properties, it was confirmed that the absorption intensity of the substrate near 700 nm was not sufficient, and the color shading suppression effect was inferior.

[Comparative Example 8]

In Example 3, 0.04 parts of compound (a-1) was used as compound (A), and compound (s-14) described in Table 2-4 above as compound (S) (maximum absorption wavelength in dichloromethane of 1097 nm) Except having used 0.45 part, it carried out similarly to Example 3, the base material and the optical filter were produced, and the optical characteristic was evaluated. Moreover, the camera module was produced using the obtained optical filter, and evaluation of the color shading and ghost of a camera image was performed. The results are shown in Table 5-2. Although the optical filter obtained in Comparative Example 8 exhibited comparatively good optical properties, it was confirmed that the absorption intensity of the substrate near 700 nm was not sufficient, and the color shading suppression effect was inferior.

The composition of the substrate applied in Examples and Comparative Examples, various compounds, and the like are as follows.

<Form of description>

Form (1): Transparent resin substrate containing compound (A)

Aspect (2): A resin layer is provided on both surfaces of the transparent resin substrate containing the compound (A).

Aspect (3): has transparent resin layer containing compound (A) on both surfaces of a resin support body

Aspect (4): has a transparent resin layer containing compound (A) on one surface of a transparent glass substrate

Aspect (5): It has a transparent resin layer containing a compound (A) on one surface of a near-infrared absorption glass substrate

Aspect (6): A transparent resin layer containing near-infrared absorbing fine particles is provided on both surfaces of a transparent resin substrate containing the compound (A).

Form (7): Transparent resin substrate not containing compound (A) (comparative example)

Form (8): transparent glass substrate (comparative example)

Form (9): Near-infrared absorption glass substrate (comparative example)

<Transparent resin>

Resin A: Cyclic polyolefin resin (resin synthesis example 1)

Resin B: Aromatic polyether-based resin (resin synthesis example 2)

Resin C: polyimide-based resin (resin synthesis example 3)

Resin D: Cyclic olefin resin "Zeonoa 1420R" (made by Nippon Zeon Co., Ltd.)

<Glass substrate>

Glass substrate (1): A transparent glass substrate “OA-10G (150 μm thick)” cut to a size of 60 mm in length and 60 mm in width (manufactured by Nippon Denki Glass Co., Ltd.)

Glass substrate (2): Near-infrared absorption glass substrate "BS-11 (thickness 120 μm)" cut to a size of 60 mm in length and 60 mm in width (manufactured by Matsunami Glass Kogyo Co., Ltd.)

<Near-infrared absorbing dye>

≪Compound (A)≫

Compound (a-1): the compound (a-1) (maximum absorption wavelength in dichloromethane 698 nm)

Compound (a-2): the compound (a-2) (maximum absorption wavelength 733 nm in dichloromethane)

Compound (a-3): the compound (a-3) (maximum absorption wavelength 703 nm in dichloromethane)

Compound (a-4): the compound (a-4) (maximum absorption wavelength in dichloromethane 736 nm)

Compound (a-5): the compound (a-5) (maximum absorption wavelength in dichloromethane 713 nm)

Compound (a-6): a cyanine-based compound represented by the following formula (a-6) (maximum absorption wavelength in dichloromethane 681 nm)

≪Compound (S)≫

Compound (s-6): the compound (s-6) (maximum absorption wavelength in dichloromethane 1093 nm)

Compound (s-8): the compound (s-8) (maximum absorption wavelength in dichloromethane 1096 nm)

Compound (s-13): the compound (s-14) (maximum absorption wavelength in dichloromethane 1096 nm)

Compound (s-14): the compound (s-15) (maximum absorption wavelength in dichloromethane 1097 nm)

≪Other Pigments (X)≫

Dye (X-1): said dye (X-1) (maximum absorption wavelength 887 nm in dichloromethane)

Dye (X-2): a dye represented by the following formula (X-2) (maximum absorption wavelength in dichloromethane 811 nm)

<solvent>

Solvent (1): methylene chloride

Solvent (2): N,N-dimethylacetamide

Solvent (3): cyclohexane/xylene (weight ratio: 7/3)

In Table 5-1 and Table 5-2, the drying conditions of the (transparent) resin substrate of an Example and a comparative example are as follows. In addition, before drying under reduced pressure, the coating film was peeled from the glass plate.

<Film drying conditions>

Condition (1): 20℃/8hr → 100℃/8hr under reduced pressure

Condition (2): 60℃/8hr→80℃/8hr→140℃/8hr under reduced pressure

Condition (3): 60℃/8hr→80℃/8hr→100℃/24hr under reduced pressure

[Table 5-1]

[Table 5-2]

1: Optical filter
2: Spectrophotometer
3: light
10: description
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 central part of the white plate
114: Example of the end of the white plate
121: camera image
122: light source
123: Example of ghost around light source

Claims (11)

An optical filter having a substrate satisfying the following requirements (a), (b), (c) and (g), and also satisfying the following requirements (d) and (e):
(a) has a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 nm or more and 760 nm or less;
(b) the difference (X 2 -X 1 ) between the shortest wavelength (X ₁ ) and the second shortest wavelength (X ₂ ) at which the transmittance is 10% in the region of wavelength 640 nm or more (X ₂ -X ₁ ) 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;
(g) contains the compound (S) having an absorption maximum in a wavelength region of 1050 nm or more and 1200 nm or less;
(d) in the wavelength region of 430 to 580 nm, the average value 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 of transmittance when measured from the vertical direction of the optical filter is 5% or less;
The description is (i) or (ii):
(i) a first resin layer containing the compound (A) and the compound (S) is laminated on a glass support or a resin support, the compound ( The content of S) is 0.1 parts by weight to 5.0 parts by weight;
(ii) A second resin layer containing compound (S) is laminated on a transparent resin substrate containing compound (A). The optical filter according to claim 1, wherein at least one surface of the substrate has a dielectric multilayer film. The optical filter according to claim 1 or 2, characterized in that the substrate further satisfies the following requirement (f):
(f) The minimum value T ₁ of the transmittance|permeability in the area|region of wavelength 690-720 nm is 5 % or less. The optical filter according to claim 1 or 2, 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 formulas (I) and (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, a -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any of the following L ^a to L ^h , R ^g and R ^h each independently represent a hydrogen atom, a -C(O)R ⁱ group, or any of the following L ^a to L ^e , R ⁱ represents any of the following L ^a to 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 ) aromatic hydrocarbon group having 6 to 14 carbon atoms
(L ^e ) heterocyclic group having 2 to 14 carbon atoms
(L ^f ) Alkoxy group having 1 to 12 carbon atoms
(L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L;
(L ^h ) Alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L
The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. At least one selected from the group,
Adjacent R ³ may form a ring which may have a substituent L,
n represents an integer of 0 to 4,
X represents the anion required 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.] The optical filter according to claim 2, wherein the dielectric multilayer film is formed on both surfaces of the substrate. The optical filter according to claim 1 or 2, wherein the compound (A) is at least one compound selected from the group consisting of a squarylium compound, a phthalocyanine compound, and a cyanine compound. The transparent resin according to claim 1 or 2, wherein the first resin layer may contain a transparent resin, and the transparent resin contained in the first resin layer or the transparent resin substrate is a cyclic polyolefin-based resin or an aromatic polyether. Resin, polyimide-based resin, fluorene polycarbonate-based resin, fluorene polyester-based resin, polycarbonate-based resin, polyamide-based resin, polyarylate-based resin, polysulfone-based resin, polyethersulfone-based resin Resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate-based resin, fluorinated aromatic polymer-based resin, (modified) acrylic resin, epoxy-based resin, allyl ester-based curable resin, silsesquioxane-based UV-curable resin , An optical filter, characterized in that at least one resin selected from the group consisting of an acrylic UV-curable resin and a vinyl-based UV-curable resin. The optical filter according to claim 1 or 2, which is for a solid-state imaging device. A solid-state imaging device comprising the optical filter according to claim 1 or 2 . A camera module provided with the optical filter of Claim 1 or 2. delete

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