TW201945179A - Optical filter and device using optical filter - Google Patents

Abstract

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

Description

Optical filter and device using the same

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

In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, charge-coupled devices (Charge-Coupled Devices) have been used as solid-state imaging elements for color images. CCD) image sensor or Complementary Metal-Oxide-Semiconductor (CMOS) image sensor. In these solid-state imaging devices, a silicon photodiode having a sensitivity to near-infrared rays which cannot be perceived by human eyes is used in a light receiving portion thereof. In these solid-state imaging elements, it is necessary to perform visual sensitivity correction that becomes natural tones when viewed by human eyes. In many cases, an optical filter (for example, a near-infrared cut-off filter) that selectively transmits or cuts light in a specific wavelength region is used.

As such a near-infrared cut-off filter, manufacturers using various methods have been used heretofore. For example, a near-infrared cut filter using a transparent resin as a base material and containing a near-infrared absorbing pigment in the transparent resin is known (for example, refer to Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not have sufficient near-infrared absorption characteristics.

In the patent document 2, the present applicant proposed a transparent resin substrate containing a near-infrared absorbing pigment having a maximum absorption in a specific wavelength region, and even if the incident angle was changed, the change in optical characteristics was small, and Near infrared cut-off filter with high visible light transmittance. Further, Patent Document 3 describes that by using a phthalocyanine dye having a specific structure, it is possible to obtain a long wavelength that is excellent in both the visible light transmittance and the maximum absorption wavelength, which is a high-level problem that has been achieved in the past. Near infrared cut-off filter.

However, in the near-infrared cut-off filters described in Patent Documents 2 and 3, the applied substrate has a sufficiently strong absorption band near 700 nm, but for example, a near-infrared wavelength such as 900 nm to 1200 nm There is almost no absorption in the area. Therefore, although the light in the near-infrared wavelength region is almost cut off only by the reflection of the dielectric multilayer film, in this configuration, there is an internal reflection in the optical filter or a reflection between the optical filter and the lens. The stray light causes ghost or flare when shooting in a dark environment. Especially in recent years, a mobile device such as a smart phone is also strongly required to improve the image quality of the camera. Therefore, there are cases where the conventional optical filter cannot be used satisfactorily.

On the other hand, as an optical filter used for a substrate having a wide-width absorption in a near-infrared wavelength region, an infrared shielding filter like that of Patent Document 4 is proposed. In Patent Document 4, a wide absorption in the near-infrared wavelength region is mainly achieved by using a compound having a dithiolene structure, but the absorption intensity in the vicinity of 700 nm is insufficient. In particular, when using a camera module in recent years with a low profile and a high incidence angle condition (for example, a 45-degree incident), image degradation due to chromatic aberration may occur.

In addition, Patent Document 5 discloses a near-infrared cut-off filter having a near-infrared absorbing glass substrate and a layer containing a near-infrared absorbing pigment. However, even with the configuration described in Patent Document 5, there is a problem that the color difference cannot be sufficiently improved. (Color shading). For example, FIG. 5 of Patent Document 5 shows graphs of optical characteristics at 0-degree incidence and 30-degree incidence. However, even at 30-degree incidence, it is in a region (630 nm to 700 nm) at the edge of the visible light transmission band. ) A large wavelength shift is observed.

In order to solve the above problems, the present inventors have investigated pigments having an absorption maximum in a near-infrared wavelength region such as 900 nm to 1200 nm for use in optical filters. However, in many cases, such a pigment has absorption in the near-infrared wavelength region and also in the visible light region from 430 nm to 580 nm, so improvement of ghosting and visible light transmittance are both issues. Furthermore, the said dye may have a problem that the fall of optical characteristics by low heat resistance or ultraviolet (UV) resistance may become a problem. Specifically, in the drying step for volatilizing the solvent or the UV irradiation step for curing the curable resin, the pigment is deteriorated, and the near-infrared ray absorptivity in the wavelength range of 900 nm to 1200 nm and 430 nm to 580 exist. There is a problem that the transmittance in the nm wavelength region is lowered, so that desired spectral characteristics cannot be obtained. Therefore, it is important to improve the heat resistance or UV resistance of the pigment having the maximum absorption at 900 nm to 1200 nm.

Furthermore, in addition to the problems described above, in recent years, in view of developments in automotive applications and the like, requirements for heat resistance have become increasingly strict. That is, it is required that the change in the spectral characteristics can be suppressed as much as possible even when exposed to high temperatures for a long time.

As a method of improving the heat resistance or UV resistance of the pigment, for example, a method of using the pigment in a form of a pigment (particle dispersed state) instead of a dye (dissolved state) is known (for example, Patent Document 6, Patent Document 7) . Patent Document 7 shows that a near-infrared cut filter of a diimmonium-based pigment having a problem in heat resistance is disclosed. The pigment is dispersed in a dispersion medium (toluene) and then dispersed in a resin. When dissolving and using (using as a dye), heat resistance or UV resistance is improved. However, even if the technique of the existing document is used, not only the absorption in the near-infrared region is insufficient, but also a film having a very high haze value can be obtained, and the problem cannot be solved.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 6-200113
[Patent Document 2] Japanese Patent Laid-Open No. 2011-100084
[Patent Document 3] International Publication No. 2015/025779
[Patent Document 4] International Publication No. 2014/168190
[Patent Document 5] International Publication No. 2014/030628
[Patent Document 6] Japanese Patent Laid-Open No. 2001-019898
[Patent Document 7] Japanese Patent Laid-Open No. 2010-249964

[Problems to be Solved by the Invention]
An object of the present invention is to provide a high-level solution that satisfies chromatic aberration suppression and ghosting suppression of a camera image and transmittance characteristics in a visible light wavelength region, which have not been sufficiently realized in a conventional optical filter. An optical filter that can maintain good optical properties even when exposed to high temperatures for a long time.
[Means for solving problems]

The present inventors have conducted active investigations in order to solve the above problems, and as a result, have found that the substrate has a layer containing an organic pigment having a maximum absorption in a specific wavelength region and is provided on at least one surface of the substrate By forming a dielectric multilayer film, it is possible to obtain an optical filter that can maintain the transmittance in the visible light region and achieve near-infrared cutoff characteristics, visible light transmittance, chromatic aberration suppression effect, and ghost suppression effect.

Furthermore, the present inventors have found that by micronizing the organic pigment and setting the average particle diameter to a specific range, it is possible to obtain an optical filter having an extremely low level of haze value and excellent heat resistance.
Examples of aspects of the present invention completed based on these findings are shown below.

[1] An optical filter, comprising a substrate that satisfies the following requirement (a), and a dielectric multilayer film on at least one side of the substrate:
(A) A layer including an organic pigment (S) having a maximum absorption in a region having a wavelength of 900 nm or more and 1200 nm or less.

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

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

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

[Chemical 1]



In formula (I),
R ¹ independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxyl group, a phosphate group, an -SR ⁱ group, an -SO ₂ R ⁱ group, an -OSO ₂ R ⁱ group, or the following L ^a to L ^h R ² independently represents a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -NR ^g R ^h group, a -SR ⁱ group, a -SO ₂ R ⁱ group, -OSO ₂ R ⁱ or the following group L ^a ~ L ^h is any one of, R ^g, and R ^h each independently represent a hydrogen atom, -C (O) R ⁱ or the following group L ^a ~ L ^e is any one of, R ⁱ represents L ^a ~ L ^e following any one,
(L ^a ) aliphatic hydrocarbon group (L ^b ) having 1 to 12 carbon atoms, halogen-substituted alkyl group (L ^c ) having 1 to 12 carbon atoms, alicyclic hydrocarbon group (L ^d ) having 3 to 14 carbon atoms, and 6 to 14 carbon atoms Aromatic hydrocarbon group (L ^e ) heterocyclic group (L ^f ) having 2 to 14 carbon atoms alkoxy group (L ^g ) having 1 to 12 carbon atoms may have 1 to 12 carbon atoms (L ^h ) The alkoxycarbonyl substituent L having 1 to 12 carbons which may have the substituent L is selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, and 3 to 14 carbon atoms. At least one of the group consisting of an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms,
n represents an integer from 0 to 4,
X represents the anion required to neutralize the charge.

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

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

[7] The optical filter according to item [6], wherein the transparent resin constituting the transparent resin layer is selected from the group consisting of a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin,茀 Polycarbonate resin, 茀 Polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, polyfluorene resin, polyether fluorene resin, polyparaphenylene resin, polyfluorene Amine resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester hardening resins, sesquisilicones At least one resin in the group consisting of an oxane-based ultraviolet curing resin, an acrylic ultraviolet curing resin, and a vinyl ultraviolet curing resin.

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

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

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

According to the present invention, it is possible to provide an optical filter having excellent near-infrared cutoff characteristics, small incident angle dependence, and excellent transmittance characteristics in the visible wavelength region, chromatic aberration suppression effect, ghost suppression effect, and heat resistance.

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

The optical filter of the present invention includes a substrate that satisfies the requirement (a) described later, and has a dielectric multilayer film on at least one surface of the substrate.
In consideration of the recent trend toward thinner and lighter solid-state imaging devices, the thickness of the optical filter of the present invention is preferably thin. Since the optical filter of the present invention includes the base material, it can be reduced in thickness.

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, and even more preferably 130 μm or less. The lower limit is not particularly limited, and preferably 20 μm or more.

[Substrate]
The substrate used in the present invention satisfies the following requirement (a).
(A) A layer including an organic pigment (S) having a maximum absorption in a region having a wavelength of 900 nm or more and 1200 nm or less.
The substrate preferably further satisfies the following requirement (b).
(B) A layer including the compound (A) having a maximum absorption in a region having a wavelength of 650 nm or more and 760 nm or less.
Hereinafter, each necessary condition will be described.

<Requirement (a)>
In the required condition (a), the components constituting the layer containing the organic pigment (S) are not particularly limited, and examples thereof include transparent resins, sol-gel materials, and low-temperature-curable glass materials. However, in terms of ease of handling, It is preferably a transparent resin.

"Organic Pigment (S)"
The organic pigment (S) is not particularly limited as long as it is an organic pigment having the maximum absorption in a region of a wavelength of 900 nm to 1200 nm. For example, a known method can be used to set the wavelength of 900 nm to 1200 nm. The compound (S) having the maximum absorption in the region of is dispersed with a dispersion medium and, if necessary, a dispersant or other additive, and is obtained as a dispersion of an organic pigment (S).

(1) Compound (S)
The compound (S) is not particularly limited as long as it has a maximum absorption in a region with a wavelength of 900 nm to 1200 nm, but it is preferably selected from the group consisting of a diimmonium compound and a metal dithiolate. At least one compound selected from the group consisting of a compound compound, a pyrrolopyrrole compound, a cyanine compound, a croconium compound, and a naphthalocyanine compound, further preferably selected from a diimmonium system The at least one compound in the group consisting of the compound and the metal dithiolate complex compound is particularly preferably a diimmonium compound represented by the following formula (I). By using such a compound (S), good near-infrared absorption characteristics and excellent visible light transmittance can be imparted.

[Chemical 2]



In formula (I),
R ¹ independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxyl group, a phosphate group, an -SR ⁱ group, an -SO ₂ R ⁱ group, an -OSO ₂ R ⁱ group, or the following L ^a to L ^h R ² independently represents a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -NR ^g R ^h group, a -SR ⁱ group, a -SO ₂ R ⁱ group, -OSO ₂ R ⁱ or the following group L ^a ~ L ^h is any one of, R ^g, and R ^h each independently represent a hydrogen atom, -C (O) R ⁱ or the following group L ^a ~ L ^e is any one of, R ⁱ represents L ^a ~ L ^e following any one,
(L ^a ) aliphatic hydrocarbon group (L ^b ) having 1 to 12 carbon atoms, halogen-substituted alkyl group (L ^c ) having 1 to 12 carbon atoms, alicyclic hydrocarbon group (L ^d ) having 3 to 14 carbon atoms, and 6 to 14 carbon atoms Aromatic hydrocarbon group (L ^e ) heterocyclic group (L ^f ) having 2 to 14 carbon atoms alkoxy group (L ^g ) having 1 to 12 carbon atoms may have 1 to 12 carbon atoms (L ^h ) The alkoxycarbonyl substituent L having 1 to 12 carbons which may have the substituent L is selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, and 3 to 14 carbon atoms. At least one of the group consisting of an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms,
n represents an integer from 0 to 4,
X represents the anion required to neutralize the charge.

The R ^{1 is} preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, cyclohexyl, adamantyl, or trifluoromethyl. Group, pentafluoroethyl, 3-pyridyl, epoxy, phenyl, benzyl, and fluorenyl, more preferably isopropyl, second butyl, third butyl, and benzyl.

The R ^{2 is} preferably a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, a third butyl group, a cyclohexyl group, a phenyl group, or a hydroxyl group. , Amino, dimethylamino, cyano, nitro, methoxy, ethoxy, n-propoxy, n-butoxy, ethenylamino, propionylamino, N-methyl Ethylamino, trifluoromethylamino, pentafluoroethylamino, tributylamino, cyclohexylamino, n-butylsulfonyl, methylthio, ethylthio, N-propylthio, n-butylthio, more preferably chlorine atom, fluorine atom, methyl, ethyl, n-propyl, isopropyl, third butyl, hydroxyl, dimethylamino, methoxy, Ethoxy, ethylamino, propylamino, trifluoromethylamino, pentafluoroethylamino, tributylamino, cyclohexylamino, especially methyl , Ethyl, n-propyl, isopropyl. The number (the value of n) of R ² bonded to the same aromatic ring is not particularly limited as long as it is 0 to 4, and is preferably 0 or 1.

The X is an anion necessary for neutralizing the electric charge. When X is a divalent anion, X is one, and when X is a monovalent anion, X is two. In the latter case, the two anions may be the same or different, but from the viewpoint of synthesis, they are preferably the same. X is not particularly limited as long as it is such an anion, and examples thereof include anions described in Table 1 below.

[Table 1]



As X, (X-10), (X-16), (X-17), (X- 21), (X-22), (X-24), (X-28) are particularly preferred.

Examples of the diimmonium-based compound represented by the formula (I) include compounds described in the following Tables 2-1 to 2-4.

[table 2-1]

[Table 2-2]

[Table 2-3]

[Table 2-4]

The compound (S) may be synthesized by a generally known method. For example, refer to Japanese Patent No. 4168031, Japanese Patent No. 4296961, Japanese Patent Publication No. 2010-516823, and Japanese Patent. It is synthesized by the method described in JP-A-63-165392 and the like.

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

(2) Dispersion medium The organic pigment (S) is preferably used by dispersing the compound (S) in a dispersion medium by a generally known method such as a method using a known disperser. In the present invention, when a dispersion medium having a significantly high solubility in the compound (S) is selected, the compound (S) is dissolved in the dispersion medium to be dyed. In this case, not only the desired spectral characteristics cannot be obtained, but also the heat resistance or UV resistance is significantly reduced. Therefore, it is necessary to select a dispersion medium that has low solubility in the compound (S) and does not dye. Whether the compound (S) is dyed by the dispersion medium can be added to the compound (S) so that the concentration of the compound (S) becomes 0.1% by mass. The dispersion medium is dropped onto a glass plate and dried. An electron microscope was used for observation to confirm. When the compound (S) is present in a particulate form, it can be judged to be pigmented, and when no particulate matter is confirmed, it can be judged to be dyed.

The dispersion medium is not particularly limited as long as the compound (S) is dyed. In terms of safety in the dispersion process, a relatively polar solvent is preferred. Examples include isopropyl alcohol. Alcohols such as alcohol and ethanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Esters such as butyl acetate and ethyl acetate; Ethers such as propylene glycol monomethyl ether.

When the compound (S) is a diimmonium-based compound, alcohols such as isopropyl alcohol and ethanol are particularly preferred in terms of storage stability of the dispersion. In addition, when a halogen solvent such as dichloromethane is used, the compound (S) is not preferable because it is dyed.

(3) Disperser As the disperser used when the compound (S) is dispersed in a dispersion medium, for example, a bead mill, a ball mill, a vibration ball mill, a planetary ball mill, a sand mill, and a colloid mill ( Colloid Mill), jet mill and roller mill.
Furthermore, the organic pigment (S) can also be prepared by miniaturizing the primary particles of the compound (S) by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Patent Laid-Open No. 8-179111 can be used.

(4) The dispersant may be used for the purpose of improving the dispersion stability, and the compound (S) is dispersed using a known dispersant. Examples of the dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, and a polyoxyethylene alkylphenyl ether-based dispersant. , Polyethylene glycol diester-based dispersant, sorbitan fatty acid ester-based dispersant, polyester-based dispersant, (meth) acrylic-based dispersant, and the like. As commercially available products, for example, except Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK -LPN22102 (above manufactured by BYK) and other (meth) acrylic dispersants, Disperbyk-161, Disperbyk-162, Disparby Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above manufactured by BYK) ), Solsperse 76500 (made by Lubrizol Co., Ltd.) and other urethane-based dispersants, Solsperse 24000 (Lubrizol (Stock ) (Manufactured by the company) and other polyethyleneimine-based dispersants, Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (above Other than polyester dispersants such as Ajinomoto Fine-Techno , Also can use BYK-LPN21324 (made by BYK), Mariam SC series (Malialim SC series), esleam AD series (Esleam AD series), Islam C2093I (Esleam C2093I) (above, manufactured by Nippon Oil Corporation), etc. As the (meth) acrylic dispersant, for example, Japanese Patent Laid-Open No. 2011-232735, Japanese Patent Laid-Open No. 2011-237769, Japanese Patent Laid-Open No. 2012-32767, and International Publication No. 2011 can also be used. Copolymers disclosed in Handbook No./129078, International Publication No. 2012/001945, and the like. One kind of dispersant may be used, or two or more kinds may be used in combination.

In the present invention, it is preferable to use a dispersant having an acidic functional group because of its good dispersion stability and its small chemical effect on the compound (S).
The dispersant having an acidic functional group is not particularly limited as long as it is a dispersant having a carboxylic acid, a sulfonic acid, a phenolic hydroxyl group, or a salt thereof, and examples thereof include ethylenically unsaturated monomers having an acidic functional group. And other copolymerizable ethylenically unsaturated monomers. In addition, as commercially available products, the above-mentioned marialim SC series (malialim SC series), DISPERBYK-103, DISPERBYK-110, and DISPARBYK ( DISPERBYK) -118 and so on.

The content of the dispersant may be appropriately selected according to the type of the dispersant, and is preferably 5 parts by mass to 300 parts by mass, more preferably 10 parts by mass to 200 parts by mass with respect to 100 parts by mass of the organic pigment (S), and furthermore It is preferably 20 parts by mass to 150 parts by mass. When the content of the dispersant is within the above range, the dispersion stability of the dispersion is good, and the substrate, or the optical filter is excellent in heat resistance, water resistance, and adhesion, and is therefore preferred.

In the present invention, it is preferable to perform a centrifugal separation treatment after the dispersing step. The centrifugal separation process can remove coarse organic pigment particles that are not sufficiently dispersed, thereby reducing the average particle diameter of the organic pigment, and as a result, the haze of the optical filter can be reduced.

The time for the centrifugal separation treatment is not particularly limited, and may be, for example, 1 minute or more and 60 minutes or less. The centrifugal acceleration of the centrifugal separator during centrifugal separation is not particularly limited, and may be, for example, 10 G or more and 50,000 G or less.

(5) The average particle diameter of the organic pigment (S) The average particle diameter of the organic pigment (S) is preferably 200 nm or less, more preferably 5 nm to 190 nm, still more preferably 10 nm to 180 nm, and even more preferably 15 nm to 150 nm. Here, the average particle diameter of the organic pigment (S) in this invention is a value calculated | required by the measuring method as described in the Example mentioned later. When the average particle diameter of the organic pigment (S) is in the above range, an optical filter having an extremely low level of haze value and excellent heat resistance can be obtained.

(6) Content of Organic Pigment (S) The content of the entire organic pigment (S) is, for example, a substrate using a transparent resin substrate containing an organic pigment (S), or a transparent resin containing an organic pigment (S). When a base material comprising a resin layer such as an overcoat layer such as a curable resin is laminated on the substrate to be used as the base material, it is preferably 0.01 to 2.0 parts by mass, more preferably 100 parts by mass of the transparent resin. 0.02 parts by mass to 1.5 parts by mass, particularly preferably 0.03 parts by mass to 1.0 part by mass, are laminated on a support such as a glass support or a resin support used as a base to contain a curable resin containing an organic pigment (S) When a substrate made of a transparent resin layer such as an overcoat layer is used as the substrate, it is preferably 0.1 to 5.0 parts by mass relative to 100 parts by mass of the resin forming the transparent resin layer containing the organic pigment (S). It is more preferably 0.2 parts by mass to 4.0 parts by mass, and even more preferably 0.3 to 3.0 parts by mass. When the content of the organic pigment (S) is within the above range, an optical filter having both good near-infrared absorption characteristics and high visible light transmittance can be obtained. In the present invention, as the substrate, it is desirable to provide an overcoat layer containing a curable resin or the like containing an organic pigment (S) on a support such as a glass support or a resin support that serves as a base.

<Requirement (b)>
In the required condition (b), the components constituting the layer containing the compound (A) are not particularly limited, and examples thereof include transparent resins, sol-gel materials, and low-temperature-curable glass materials. From the viewpoint of compatibility, a transparent resin is preferred.

"Compound (A)"
The compound (A) is not particularly limited as long as it has a maximum absorption in a region of 650 nm to 760 nm, but is preferably a solvent-soluble pigment compound, and more preferably selected from the group consisting of lactone At least one selected from the group consisting of a salt-based compound, a phthalocyanine-based compound, and a cyanine-based compound, and further preferably contains a squuronic acid salt-based compound, and particularly preferably contains two or more kinds of a squuronic acid salt. . In the case where the compound (A) is two or more kinds including a squarylium salt compound, the squamylium salt compound having a different structure may be two or more kinds, or the squamylium salt compound and A combination of other compounds (A). As other compounds (A), phthalocyanine-based compounds and cyanine-based compounds are particularly preferred.

Squaryl ylide compounds have excellent visible light transmission, steep absorption characteristics, and high molar absorption coefficients. However, there are cases where fluorescent light that causes scattered light is generated when light is absorbed. In such a case, an optical filter having less scattered light and a better camera image quality can be obtained by using a squarylium compound and another compound (A) in combination.

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

In the case where the compound (A) is a combination of two or more compounds, the difference between the maximum absorption wavelengths of the shortest maximum absorption wavelength and the longest maximum absorption wavelength in the applied compound (A) is preferably 10 nm to 60 nm , More preferably 15 nm to 55 nm, and further preferably 20 nm to 50 nm. When the difference between the maximum absorption wavelengths is within the above range, it is preferable to sufficiently reduce scattered light due to fluorescence, and to achieve a wide absorption band around 700 nm and excellent visible light transmittance.

The content of the entire compound (A) is, for example, a substrate containing a transparent resin substrate containing an organic pigment (S) and the compound (A), or an organic compound-containing layer is laminated on the transparent resin substrate containing the compound (A). When a base material formed by a resin layer such as an overcoat layer such as a curable resin of pigment (S) is used as the base material, it is preferably 0.04 to 2.0 parts by mass, more preferably 100 parts by mass of transparent resin. 0.06 parts by mass to 1.5 parts by mass, and more preferably 0.08 parts by mass to 1.0 part by mass. The support layer containing an organic pigment (S) and a compound (A) is laminated on a support such as a glass support or a resin support used as a base. When a substrate made of a transparent resin layer such as an overcoat layer such as a curable resin is used as the substrate, it is preferably 0.4 parts by mass to 100 parts by mass of the resin forming the transparent resin layer containing the compound (A). 5.0 parts by mass, more preferably 0.6 parts by mass to 4.0 parts by mass, and even more preferably 0.8 parts by mass to 3.5 parts by mass.

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

When the layer containing the organic pigment (S) is the same as the layer containing the compound (A), for example, a substrate including a transparent resin substrate containing the organic pigment (S) and the compound (A), A substrate made of a pigment (S) and a compound (A) transparent resin substrate laminated with a resin layer including an overcoat layer such as a curable resin, etc., on a support such as a glass support or a resin support that becomes a base The laminate includes a base material including a transparent resin layer such as an overcoat layer such as a curable resin such as an organic pigment (S) and a compound (A).

When the layer containing the organic pigment (S) is different from the layer containing the compound (A), for example, a layer containing a curable resin containing the compound (A) is laminated on a transparent resin substrate containing the organic pigment (S). A substrate made of a resin layer such as an overcoat layer or the like, or a substrate formed by laminating a resin layer such as an overcoat layer containing a curable resin containing an organic pigment (S) on a transparent resin substrate containing the compound (A) An outer coating containing a curable resin containing an organic pigment (S) and the like, and an outer coating containing a curable resin containing a compound (A) are laminated on a support such as a glass support or a resin-based support that becomes a base. Layered substrates. In the present invention, it is preferable to provide an overcoat layer containing a curable resin containing an organic pigment (S) on a transparent resin substrate containing the compound (A). In this case, an organic pigment is more preferred. The average particle diameter of (S) is 150 nm or less, and particularly preferably 100 nm or less.

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

The thickness of the substrate can be appropriately selected depending on the intended use and is not particularly limited, but is preferably 10 μm to 200 μm, more preferably 20 μm to 180 μm, and further preferably 25 μm to 150 μm. When the thickness of the substrate is within the above range, the optical filter using the substrate can be made thinner and lighter, and can be preferably used for various applications such as solid-state imaging devices. In particular, when a substrate including the transparent resin substrate is used for a lens unit such as a camera module, it is preferable to reduce the weight and weight of the lens unit.

＜ Transparent resin ＞
The transparent resin used as the transparent resin layer, the transparent resin substrate, and the resin support constituting the substrate is not particularly limited as long as the effects of the present invention are not impaired, for example, to ensure thermal stability and molding The film has moldability and is a film capable of forming a dielectric multilayer film by high-temperature vapor deposition at a vapor deposition temperature of 100 ° C or higher. The glass transition temperature (Tg) is preferably 110 ° C to 380 ° C, more preferably 110 ° C to 370 ° C, and even more preferably 120 ° C to 360 ° C. In addition, if the glass transition temperature of the resin is 140 ° C. or higher, a film that can be deposited at a higher temperature to form a dielectric multilayer film is particularly preferred.

As a transparent resin, when a resin plate having a thickness of 0.1 mm including the resin is formed, the total light transmittance of the resin plate (Japanese Industrial Standards (JIS) K7105) is preferably 75%. ~ 95%, more preferably 78% to 95%, even more preferably 80% to 95% of the resin. When a resin having a total light transmittance within the above range is used, the obtained substrate exhibits good transparency as an optical film.

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

Examples of the transparent resin include a cyclic polyolefin resin, an aromatic polyether resin, a polyfluorene resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, and a polyfluorene. Amine (aromatic polyfluorene) resin, polyarylate resin, polyfluorene resin, polyether fluorene resin, polyparaphenylene resin, polyfluorene amine imine resin, polyethylene naphthalate (Polyethylene naphthalate (PEN)) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester hardening resin, silsesquioxane ultraviolet curing resin, Acrylic UV-curable resin and vinyl UV-curable resin.

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

<< Cyclic Polyolefin Resin >>
The cyclic polyolefin resin is preferably at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ) A resin obtained and a resin obtained by hydrogenating the resin.

[Chemical 3]



In the formula (X ₀ ), R ^x1 to R ^x4 each independently represent an atom or a group selected from the following (i ') to (ix'), and k ^x , m ^x and p ^x each independently represent 0 to 4 Integer.
(I ') a hydrogen atom (ii') a halogen atom (iii ') a trialkylsilyl group (iv') a substituted or unsubstituted carbon having a linker containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom 1 to 30 hydrocarbon group (v ') substituted or unsubstituted hydrocarbon group (vi') polar group having 1 to 30 carbon atoms (except (ii ') and (iv'))
(Vii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other by an alkylene group (wherein R ^x1 to R ^x4 which do not participate in the bonding are independently selected from (i Atoms or radicals in ') to (vi'))
(Viii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring (wherein, R ^x1 to R ^x4 not participating in the bonding are independent of each other) The ground represents an atom or a group selected from the above (i ') to (vi'))
(Ix ') R ^x2 and R ^x3 are bonded to each other to form a monocyclic hydrocarbon ring or heterocyclic ring (wherein R ^x1 and R ^x4 which do not participate in the bonding are independently selected from (i') Atom or radical in ~ (vi '))

[Chemical 4]



In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or a group selected from the above (i ′) to (vi ′), or a monocyclic ring formed by bonding R ^y1 and R ^{y2 to} each other Or polycyclic alicyclic hydrocarbons, aromatic hydrocarbons or heterocyclic rings, k ^y and p ^y each independently represent an integer of 0 to 4.

《Aromatic Polyether Resin》
The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

[Chemical 5]



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.

[Chemical 6]



In formula (2), R ¹ to R ⁴ and a to d each independently have the same meaning as R ¹ to R ⁴ and a to d in formula (1), and Y represents a single bond, -SO ₂ -or -CO-, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, g and h each independently represent an integer of 0 to 4, and m represents 0 or 1. However, when m is 0, R ^{7 is} not a cyano group.

The aromatic polyether resin preferably further has at least one structure 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). unit.

[Chemical 7]



In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, -O-, -S-, -SO _2- , -CO-, -CONH -, -COO- or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1.

[Chemical 8]



Formula ^{(4), R 7, R 8, Y} , m, g , and h are each independently with (2) the formula wherein R ^{7, R 8, Y, m} , g , and h are the same meanings, R ⁵ , R ⁶ , Z, n, e, and f each independently have the same meaning as R ⁵ , R ⁶ , Z, n, e, and f in the formula (3).

"Polyimide resin"
The polyfluorene-imide-based resin is not particularly limited as long as it is a polymer compound containing a fluoreneimide bond in a repeating unit. For example, it can be disclosed in Japanese Patent Laid-Open No. 2006-199945 or Japanese Patent Laid-Open No. 2008 -163107 to synthesize.

"茀 Polycarbonate resin"
The fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene site, and can be synthesized, for example, by a method described in Japanese Patent Laid-Open No. 2008-163194.

"茀 polyester resin"
The fluorene polyester resin is not particularly limited, as long as it is a polyester resin containing a fluorene site, for example, it can be described in Japanese Patent Laid-Open No. 2010-285505 or Japanese Patent Laid-Open No. 2011-197450. Method to synthesize.

《Fluorinated Aromatic Polymer Resin》
The fluorinated aromatic polymer-based resin is not particularly limited, but preferably contains an aromatic ring having at least one fluorine atom and a group selected from the group consisting of an ether bond, a ketone bond, a fluorene bond, a fluorene bond, and a fluorimine The polymer of a repeating unit of at least one bond in the group consisting of a bond and an ester bond can be synthesized, for example, by a method described in Japanese Patent Laid-Open No. 2008-181121.

《Acrylic UV-curable Resin》
The acrylic ultraviolet curing resin is not particularly limited, and examples thereof include a resin composition containing a compound having one or more acrylic groups or methacrylic groups in a molecule, and a compound that is decomposed by ultraviolet rays to generate active radicals. Synthesizers. A substrate formed by laminating a transparent resin layer containing the compound (A) and a curable resin on a resin support used on a glass support or as a base, or a transparent resin substrate containing the compound (A) When a base material including a resin layer such as an overcoat layer such as a curable resin is used as the base material, an acrylic ultraviolet curable resin is particularly preferably used as the curable resin.

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

"Commercial goods"
As a commercial item of a transparent resin, the following commercial items etc. are mentioned. Examples of commercially available cyclic polyolefin resins include Arton manufactured by JSR Corporation, Zeonor manufactured by Zeon Corporation, Mitsui Chemical Co., Ltd. ) Manufactured by APEL and TOPAS manufactured by Polyplastics. Examples of commercially available products of the polyether fluorene resin include Sumikaexcel PES manufactured by Sumitomo Chemical Co., Ltd. and the like. Examples of commercially available products of polyimide-based resins include Neopulim L manufactured by Mitsubishi Gas Chemical Co., Ltd. and the like. Examples of commercially available polycarbonate-based resins include PURE-ACE manufactured by Teijin Corporation. As a commercially available product of rhenium polycarbonate resin, Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited. Examples of commercially available products of fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemicals Co., Ltd. and the like. Examples of commercially available products of acrylic resins include Acryviewa (manufactured by Nihon Catalytic Corp.). Examples of commercially available products of the silsesquioxane-based ultraviolet curable resin include Silplus manufactured by Nippon Steel Chemical Co., Ltd. and the like.

＜ Other pigments (X) ＞
The substrate may further include other pigments (X) that are not equivalent to the organic pigment (S) and the compound (A).

The other pigment (X) is not particularly limited as long as it is a pigment having a maximum absorption wavelength of less than 650 nm or a region exceeding 760 nm and less than 900 nm, but the maximum absorption wavelength is preferably more than 760 Pigments in the region below 900 nm. Examples of such a pigment include a compound selected from the group consisting of a stilbene ylide compound, a phthalocyanine compound, a cyanine compound, a naphthalocyanine compound, a ketonium compound, an octameric porphyrin compound, and a diamine. At least one compound selected from the group consisting of an ammonium compound, a pyrrolopyrrole compound, a borodipyrrole (BODIPY) compound, a hydrazone compound, and a metal dithiolate compound.

As for the content of the other pigment (X), for example, when a substrate containing a transparent resin substrate containing the other pigment (X) is used as the substrate, it is preferably 0.005 parts by mass to 1.0 with respect to 100 parts by weight of the transparent resin. Mass parts, more preferably 0.01 parts by mass to 0.9 parts by mass, and even more preferably 0.02 parts by mass to 0.8 parts by mass. The layer is formed on a support such as a glass support or a resin support used as a base, and contains other pigments (X ) A substrate made of a transparent resin layer such as an overcoat layer such as a curable resin, or an overcoat containing a curable resin containing other pigments (X) on a transparent resin substrate containing an organic pigment (S) When a substrate made of a resin layer such as a layer is used as the substrate, it is preferably from 0.05 to 4.0 parts by mass, more preferably 0.1 to 100 parts by weight of the resin forming the transparent resin layer containing the other pigment (X). Part by mass to 3.0 parts by mass, particularly preferably 0.2 to 2.0 parts by mass.

＜ Other ingredients ＞
As long as the effect of the present invention is not impaired, the substrate may further contain an antioxidant, a near-ultraviolet absorber, a fluorescent matting agent, and the like as other components. These other components may be used alone or in combination of two or more.

Examples of the near-ultraviolet absorber include methylimine-based compounds, indole-based compounds, benzotriazole-based compounds, and triazine-based compounds.

Examples of the antioxidant include 2,6-di-third-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-third-butyl-5, 5'-dimethyldiphenylmethane, tetra [methylene-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] methane and tris (2,4-di -Third butylphenyl) phosphite and the like.

In addition, these other components may be mixed together with a resin or the like when manufacturing a base material, or may be added when a synthetic resin is used. In addition, the amount to be added is appropriately selected according to desired characteristics, but it is usually 0.01 to 5.0 parts by mass, and preferably 0.05 to 2.0 parts by mass based on 100 parts by mass of the resin.

<Method for manufacturing base material>
When the substrate is a substrate including a transparent resin substrate containing an organic pigment (S), the transparent resin substrate may be formed by, for example, melt molding or casting, and may be coated after molding if necessary. A coating agent such as an anti-reflection agent, a hard coating agent, and / or an antistatic agent, thereby manufacturing a substrate with an overcoat layer.

A layer containing a curable resin containing an organic pigment (S) is laminated on the substrate on a support such as a glass support or a resin support serving as a base or on a transparent resin substrate containing no organic pigment (S). In the case of a substrate made of a transparent resin layer such as an overcoat layer, for example, the resin solution containing the compound (A) can be melt-molded or cast-molded on the support or the transparent resin substrate. The solvent is dried and removed after coating by spin coating, slit coating, inkjet, or the like, and further light irradiation or heating is performed as necessary to produce organic-containing materials formed on the support or the transparent resin substrate. Base material of transparent resin layer of pigment (S).

"Melting"
Specific examples of the melt-molding include a method of melt-molding pellets obtained by melt-kneading a resin, an organic pigment (S), and other components as needed; and a method containing the resin, the organic pigment (S), and A method for melt-molding a resin composition of other components as needed; or a method for melt-molding particles obtained by removing a solvent from a resin composition containing an organic pigment (S), a resin, a solvent, and other components as necessary Wait. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

《Casting and Forming》
As said casting molding, it can also manufacture by the method etc. which cast the resin composition containing an organic pigment (S), resin, a solvent, and other components as needed on a suitable support body, and remove | eliminates the solvent. Method; or a curable composition containing an organic pigment (S), a photo-curable resin and / or a thermo-curable resin, and other components as needed is cast on a suitable support and the solvent is removed, and then irradiated with ultraviolet Or a suitable method such as heating to harden it.

When the substrate is a substrate including a transparent resin substrate containing an organic pigment (S), the substrate can be obtained by peeling a coating film from a support after casting, and the substrate is An overcoat layer containing a hardening resin containing an organic pigment (S) is laminated on a support such as a glass support or a resin support serving as a base or a transparent resin substrate containing no organic pigment (S). In the case of a substrate made of a transparent resin layer, the substrate can be obtained by not peeling the coating film after casting.

Examples of the support include a near-infrared-absorbing glass plate (for example, "BS-11" manufactured by Songlang Glass Industry Co., Ltd. or "NF-50T" manufactured by AGC Techno Glass). Copper-based phosphate-based glass plates), clear glass (for example, alkali-free glass plates such as "OA-10G" manufactured by Nippon Electric Glass Co., Ltd. or "AN100" manufactured by Asahi Glass Co., Ltd., steel strips, steel drums, and transparent resin (For example, a polyester film, a cyclic olefin resin film).

The amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.5 part by mass or less with respect to 100 parts by mass 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 less likely to undergo deformation of the substrate or change in optical characteristics, and can easily perform desired functions can be obtained.

[Dielectric multilayer film]
The optical filter of the present invention has a dielectric multilayer film on at least one side of the substrate. The dielectric multilayer film of the present invention is a film having the ability to reflect near infrared rays or a film having an anti-reflection effect in the visible light region. By having a dielectric multilayer film, it is possible to achieve more excellent visible light transmittance and near infrared rays. Cut-off characteristics.

In the present invention, the dielectric multilayer film may be provided on one side of the substrate or on both sides. When provided on one side, it is excellent in manufacturing cost or ease of manufacture, and when provided on both sides, an optical filter having high strength and less prone to warping or distortion can be obtained. When the optical filter is applied to a solid-state imaging device, it is preferable that the warp or distortion of the optical filter is small. Therefore, it is preferable to provide a dielectric multilayer film on both surfaces of the resin substrate.

The dielectric multilayer film desirably has reflection characteristics throughout the entire range of preferably 700 nm to 1100 nm, more preferably 700 nm to 1150 nm, and further preferably 700 nm to 1200 nm.

As a form of having a dielectric multilayer film on both sides of the base material (i), there can be mentioned: a single-side surface of the base material is measured at an angle of 5 ° from the vertical direction with respect to the optical filter, and is mainly measured at a wavelength The form of the first optical layer having a reflective property near 700 nm to 950 nm, and the second optical layer having a reflective property near 900 nm to 1150 nm on the other surface of the substrate (see FIG. 1 (a)) ; Or a third optical layer having a reflection characteristic in the vicinity of a wavelength of 700 nm to 1150 nm when measuring at an angle of 5 ° with respect to the vertical direction of the optical filter on one side of the substrate, A form of a fourth optical layer having anti-reflection characteristics in a visible light region on one surface (see FIG. 1 (b)) and the like.

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

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 generally 1.2 to 1.6 is selected. Examples of such a material include silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

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

Generally, if the wavelength of the near-infrared light to be blocked is set to λ (nm), the thickness of each layer of the high-refractive-index material layer and the low-refractive-index material layer is preferably a thickness of 0.1λ to 0.5λ. The value of λ (nm) is, for example, 700 nm to 1400 nm, and preferably 750 nm to 1300 nm. If the thickness is within this range, the product of the refractive index (n) and the film thickness (d) (n × d) is calculated from λ / 4, the optical film thickness calculated with λ / 4, and the thickness of the optical film thickness with the high refractive index material layer and the low refractive index material layer. The thickness of each layer has approximately the same value, and depending on the relationship between the optical characteristics of reflection and refraction, there is a tendency that the blocking and transmission of a specific wavelength can be easily controlled.

As a whole of the optical filter, the total number of laminated layers of the high-refractive-index material layer and the low-refractive-index material layer in the dielectric multilayer film is preferably 16 to 70, more preferably 20 to 60, and most preferably 24 to 50 layers. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, or the total number of layers is within the above-mentioned range, a sufficient manufacturing margin can be ensured, and the warpage of the optical filter can be reduced. Curved or cracked dielectric multilayer film.

In the present invention, the types of materials constituting the high-refractive index material layer and the low-refractive index material layer, and the high-refractive index material layer are appropriately selected in accordance with the absorption characteristics of the near-infrared absorber such as the compound (A) or the organic pigment (S). And low-refractive-index material layer thickness, the order of lamination, and the number of laminations, which can ensure sufficient transmittance in the visible light region, have sufficient light cutoff characteristics in the near-infrared wavelength region, and reduce near-infrared Reflectance when incident from oblique direction.

Here, in order to optimize the conditions, for example, only optical film design software (for example, Essential Macleod, manufactured by Thin Film Center) may be used in order to take into account anti-reflection in the visible light region. The effect and the light cut-off effect in the near infrared region can be set by parameters. In the case of the software, for example, when designing the first optical layer, set the target transmittance at a wavelength of 400 nm to 700 nm to 100%, and set the value of the target tolerance (Target Tolerance) to 1. The parameter setting method is to set a target transmittance at a wavelength of 705 nm to 950 nm to 0% and a target tolerance value to 0.5. Regarding these parameters, it is also possible to finely divide the wavelength range in accordance with various characteristics of the base material (i) and change the value of the target tolerance.

[Other functional films]
The optical filter of the present invention can improve the surface hardness of the substrate or the dielectric multilayer film, improve the chemical resistance, resist static electricity, and eliminate damage. The optical filter of the present invention can be used within a range that does not impair the effects of the present invention. Appropriately between the substrate and the dielectric multilayer film, the surface of the substrate opposite to the surface on which the dielectric multilayer film is provided, or the surface of the dielectric multilayer film on the side opposite to the surface on which the substrate is disposed Provide functional films such as anti-reflection film, hard coating film, or antistatic film.

The optical filter of the present invention may include one layer containing the functional film, or may include two or more layers. When the optical filter of the present invention includes two or more layers containing the functional film, the same may be included in two or more layers, or two or more different layers may be included.

The method of laminating the functional film is not particularly limited, and examples thereof include an antireflective agent, a hard coating agent, and / or an antistatic agent on a substrate or a dielectric multilayer film in the same manner as described above. Method of melt coating or casting molding of the coating agent.

Furthermore, it can also manufacture by coating the said coating agent on a base material or a dielectric multilayer film by a bar coater, etc., and hardening by ultraviolet irradiation etc.

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

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

In the curable composition, when the total amount of the curable composition is 100 parts by mass, the blending ratio of the polymerization initiator is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 10 parts by mass. It is more preferably 1 to 5 parts by mass. When the blending ratio of the polymerization initiator is within the above range, the hardening composition and the handleability are excellent, and a functional film such as an antireflection film, a hard coating film, or an antistatic film having a desired hardness can be obtained.

Further, an organic solvent may be added to the curable composition as a solvent, and a known one may be used as the 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; ethyl acetate Esters such as esters, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether Aromatic hydrocarbons such as benzene, toluene, and xylene; fluorenamines such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

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

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

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

[Use of optical filter]
The optical filter of the present invention has a wide viewing angle and has an excellent near-infrared cut-off function and the like. Therefore, it is effectively used for the correction of the visual acuity of a solid-state imaging element such as a CCD image sensor or a CMOS image sensor of a camera module. Particularly effective for digital still cameras, cameras for smartphones, cameras for mobile phones, digital cameras, cameras for wearable devices, personal computer (PC) cameras, surveillance cameras, automotive cameras, televisions, automobiles Navigation, portable information terminals, video game consoles, portable game consoles, fingerprint authentication systems, digital music players, etc. Furthermore, it is also effectively used as an infrared cut-off filter or the like mounted on a glass plate or the like in an automobile or a building.

[Solid imaging device]
A solid-state imaging device according to the present invention includes the optical filter according to the present invention. Here, the solid-state imaging device is an image sensor including a solid-state imaging element such as a CCD image sensor, a CMOS image sensor, or the like. Specifically, the solid-state imaging device can be used for a digital still camera, a smartphone camera, and a mobile phone. Phone camera, wearable device camera, digital video camera, etc. For example, the camera module of the present invention includes the optical filter of the present invention.
[Example]

Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples. In addition, unless otherwise specified, "part" means "mass part". In addition, the measurement method of each physical property value and the evaluation method of a physical property are as follows.

＜ Molecular weight ＞
The molecular weight of the resin is measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
(A) A gel permeation chromatography (GPC) device manufactured by Waters Corporation (type 150C, column: H-type column manufactured by Tosoh Corporation, development solvent: o-dichlorobenzene) , Determine the mass average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene.
(B) Using a GPC device manufactured by Tosoh Corporation (HLC-8220, column: TSKgel α-M, developing solvent: Tetrahydrofuran (THF)), the weight average molecular weight (Mw) of standard polystyrene conversion and Number average molecular weight (Mn).

＜ Glass transition temperature (Tg) ＞
The measurement was performed under a nitrogen gas flow using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies Co., Ltd. at a temperature rising rate: 20 ° C / min.

＜ Average particle size ＞
The average particle diameter of the organic pigment is measured by the following method. The prepared organic pigment dispersion was diluted with a solvent having the same composition as the dispersion medium until the pigment concentration became 0.5% by mass, and the solution was added dropwise to a glass plate and dried. Then, a scanning electron microscope (scanning electron microscope, SEM) ("S4800" manufactured by Hitachi High-technologies Co., Ltd.). The SEM image was captured with multiple fields of view, and the particle diameter was measured on a scale with respect to 100 particles selected arbitrarily, and the ratio was converted to calculate the average particle diameter. In addition, except for extremely large or extremely small particles, the longest diameter (longest diameter) observed when the particle shape is not spherical is taken as the particle diameter.

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

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

＜ Heat resistance ＞
The optical filter was processed under the conditions of 85 ° C. × 1000 hr, and the average transmittance at a wavelength of 430 nm to 580 nm before and after the processing was measured. The maintenance factor of the transmittance calculated by the following formula was used as an index of heat resistance. The higher the value of the retention rate, the better the heat resistance.

Maintenance of transmittance (%) = (average transmittance of 430 nm to 580 nm after treatment) / (average transmittance of 430 nm to 580 nm before treatment) × 100

<Color difference evaluation of camera image>
The color difference evaluation when the optical filter is assembled into the camera module is performed by the following method. A camera module was manufactured by the same method as in Japanese Patent Laid-Open No. 2016-110067, and the manufactured camera module was used in a D65 light source (a standard light source device "Macbeth Judge II manufactured by X-Rite" company). ”) And photographed a white plate with a size of 300 mm × 400 mm. The following criteria were used to evaluate the difference in hue between the central portion and the end portion of the white plate in the camera image.

A completely acceptable level without problems is judged to be A, and a certain acceptable level is recognized as a high-quality camera module without any problem in practical terms. It is judged to be B, and different shades are allowed as A level that cannot be tolerated for the use of a high-quality camera module is determined to be C, and a level that has a noticeable difference in color tone and cannot be tolerated for general camera module use is determined to be D.

In addition, as shown in FIG. 3, the positional relationship between the white plate 112 and the camera module is adjusted such that the white plate 112 occupies more than 90% of the area of the camera image 111 during shooting.

<Ghost evaluation of camera image>
Ghost evaluation when the optical filter is assembled into a camera module is performed by the following method. A camera module was manufactured by the same method as in Japanese Patent Laid-Open No. 2016-110067, and the manufactured camera module was used in a dark room with a halogen light source ("Luminar Ace" ) LA-150TX "). The following criteria were used to evaluate the occurrence of ghosting around the light source in the camera image.

The allowable level without any problem is judged to be A, and the allowable level where a few ghosts can be confirmed but there is no problem in practical use as a high-quality camera module is judged to be B, and the ghost is considered to be high-resolution A level that is unacceptable for the use of a high-quality camera module is determined to be C, and a level that is severe enough to be unacceptable for general camera module applications is determined to be D.

In addition, as shown in FIG. 4, when shooting, the light source 122 is adjusted so that it becomes the upper right end of the camera image 121.

[Synthesis example]
The compound (A) and the compound (S) used in the following examples were synthesized by a generally known method. Examples of the method include: Japanese Patent Laid-Open No. 60-228448; Japanese Patent Laid-Open No. 1-146846; Japanese Patent Laid-Open No. 1-228960; Japanese Patent No. 4081149; -Chemistry and Function- "(IPC, 1997), Japanese Patent Laid-Open No. 2009-108267, Japanese Patent Laid-Open No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4746031, etc. Methods.

<Synthesis example 1>
The 8-methyl-represented by the following formula (a) -8- methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene (hereinafter also referred to as "DNM" ) 100 g, 18 g of 1-hexene (molecular weight regulator), and 300 g of toluene (a solvent for the ring-opening polymerization reaction) were put into a reaction vessel substituted with nitrogen, and the solution was heated to 80 ° C. Next, 0.2 g of a toluene solution of triethylaluminum (0.6 mol / L) as a polymerization catalyst and a toluene solution of tungsten hexachloride modified by methanol (concentration: 0.025 mol / L) were added to the solution in the reaction vessel. ) 0.9 g, and the solution was heated and stirred at 80 ° C. for 3 hours, thereby performing a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

[Chemical 9]



1,000 g of the ring-opened polymer solution obtained in the above manner was charged into an autoclave, and 0.12 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution. Hydrogenation was performed by heating and stirring for 3 hours under the conditions of a hydrogen pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After the obtained reaction solution (hydrogenated polymer solution) was cooled, the hydrogen was depressurized. This reaction solution was poured into a large amount of methanol, and the coagulum was separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The number average molecular weight (Mn) of the obtained resin A was 32,000, the weight average molecular weight (Mw) was 137,000, and the glass transition temperature (Tg) was 165 ° C.

<Synthesis example 2>
In a reaction vessel having a stirring device, a thermometer, and a condenser, at room temperature, 0.0194 g of 2,6-di-third-butyl-4-cresol and 3-hydroxy-1-adamantyl acrylate ( Made by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222) 27.047 g and isophorone diisocyanate (manufactured by Evonik, molecular weight: 222) 26.481 g is dissolved in 19 g of methyl ethyl ketone (MEK), After adding 0.405 g of dioctyltin dilaurate, the temperature was raised to 70 ° C while stirring. After it was confirmed that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate was additionally added, and the reaction was continued at 70 ° C. After confirming that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group in the infrared absorption spectrum almost disappeared, the reaction was completed. The reaction mixture was purified by silica gel column chromatography using ethyl acetate / hexane as an eluent, and then diluted with isopropanol to obtain an acrylic urethane compound (I) ( 50% by mass solution).

[Preparation Example of Organic Pigment]
<Preparation Example 1>
In a 0.25 L plastic container, put 5 g of the compound (s-15) described in Table 2-4 (maximum absorption wavelength of 1083 nm in dichloromethane) and a dispersant (Nippon Oil) with an acidic functional group. Co., Ltd. "Marialim SC-0505K (malialim SC-0505K)") 5 g, 95 g of isopropanol (IPA) as a dispersion medium, and 0.05 mm diameter zirconia beads (manufactured by NIKKATO) "YTZ-0.05") 175 g, and dispersed for 1 hr with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Then, it cooled to room temperature, and the zirconia bead was taken out with the metal mesh sieve, and the organic pigment dispersion liquid (S-1) was obtained.

<Preparation Example 2>
In a 0.25 L plastic container, put 5 g of the compound (s-15) described in Table 2-4, 95 g of methyl isobutyl ketone (MIBK) as a dispersion medium, and zirconia beads with a diameter of 0.05 mm. ("YTZ-0.05" manufactured by NIKKATO) 175 g, and dispersed for 1 hr with a paint shaker. Then, it cooled to room temperature, and the zirconia bead was taken out with the metal mesh sieve, and the organic pigment dispersion liquid (S-2) was obtained.

<Preparation Example 3>
In a 0.25 L plastic container, 5 g of the compound (s-4) (maximum absorption wavelength of 1100 nm in dichloromethane) described in Table 2-4 and methyl isobutanone ( MIBK) 95 g, 0.05 mm diameter zirconia beads ("YTZ-0.05" manufactured by NIKKATO) 175 g, were dispersed by a paint shaker for 1 hr. Then, it cooled to room temperature, and the zirconia bead was taken out with the metal mesh sieve, and the organic pigment dispersion liquid (S-3) was obtained.

<Preparation Example 4>
In a 0.25 L plastic container, 5 g of the compound (s-6) (maximum absorption wavelength 1093 nm in dichloromethane) described in Table 2-4 and methyl isobutyl ketone (as a dispersion medium) were charged. MIBK) 95 g, 0.05 mm diameter zirconia beads ("YTZ-0.05" manufactured by NIKKATO) 175 g, were dispersed by a paint shaker for 1 hr. Then, it cooled to room temperature, and the zirconia bead was taken out with the metal mesh sieve, and the organic pigment dispersion liquid (S-4) was obtained.

<Preparation Example 5>
The organic pigment dispersion liquid (S-1) obtained in Preparation Example 1 was subjected to a centrifugal acceleration of 36,000 G for 10 minutes by a centrifugal separation device ("cooling centrifuge CR-22N" manufactured by Himac). The organic pigment dispersion liquid (S-5) was obtained by centrifugation and filtering the processed dispersion liquid through a polypropylene filter (pore size: 3 μm).

[Example 1]
In Example 1, the following procedures and conditions were used to produce an optical filter having a transparent resin layer containing an organic pigment (S) on both sides of a transparent resin substrate containing a compound (A) Made of substrate.

100 g of resin A obtained in Synthesis Example 1 and compound (a-1) represented by the following formula (a-1) (maximum absorption wavelength in dichloromethane 713) as compound (A) were added to a container. nm) 0.07 g and compound (a-2) represented by the following formula (a-2) (maximum absorption wavelength 736 nm in dichloromethane) 0.06 g and dichloromethane to prepare a resin concentration of 20 mass %The solution. The obtained solution was cast onto a smooth glass plate and dried at 20 ° C. for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

[Chemical 10]

[Chemical 11]



In the formula (a-1), i-Pr represents isopropyl.
A resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater, and heated in an oven at 70 ° C. for 3 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 3 μm. Next, exposure was performed using a conveyor type exposure machine (exposure amount 500 mJ / cm ² , 200 mW), and the resin composition (1) was hardened to form a transparent resin layer on a transparent resin substrate. Similarly, a transparent resin layer containing a resin composition (1) is also formed on the other surface of the transparent resin substrate, and an organic pigment (S) is contained on both sides of the transparent resin substrate containing the compound (A). Substrate of transparent resin layer.

Resin composition (1): 100 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 50 g of pigment dispersion liquid (S-1) obtained in Preparation Example 1 (using organic pigments (S) is 2.5 g), and 117 g of isopropanol.

Then, a dielectric multilayer film (I) as a first optical layer is formed on one side of the obtained substrate, and a dielectric multilayer film (2) as a second optical layer is formed on the other surface of the substrate ( II), and an optical filter having a thickness of about 0.105 mm was obtained.

The dielectric multilayer film (I) is formed by alternately stacking a silicon dioxide (SiO ₂ ) layer and a titanium dioxide (TiO ₂ ) layer at a vapor deposition temperature of 100 ° C. (a total of 26 layers).
The dielectric multilayer film (II) is formed by alternately stacking a silicon dioxide (SiO ₂ ) layer and a titanium dioxide (TiO ₂ ) layer at a deposition temperature of 100 ° C. (a total of 20 layers). In any one of the dielectric multilayer film (I) and the dielectric multilayer film (II), the silicon dioxide layer and the titanium dioxide layer are formed from a substrate side with a titanium dioxide layer, a silicon dioxide layer, a titanium dioxide layer, ... The silicon dioxide layer, the titanium dioxide layer, and the silicon dioxide layer are laminated alternately in this order, and the outermost layer of the optical filter is a silicon dioxide layer.

The design of the dielectric multilayer film (I) and the dielectric multilayer film (II) was performed as follows.
The thickness and number of each layer are combined with the wavelength-dependent characteristics of the refractive index of the substrate or the organic pigment (S) to achieve the anti-reflection effect in the visible region and the selective transmission and reflection performance in the near-infrared region. ) And the absorption characteristics of compound (A) were optimized using optical film design software (Core MacLeod, manufactured by Film Center Corporation). When performing optimization, in this embodiment, the input parameters (target values) for the software are set as shown in Table 3 below.

[table 3]
table 3

As a result of optimization of the film configuration, in Example 1, the dielectric multilayer film (I) was alternately laminated with a silicon dioxide layer having a film thickness of 31 nm to 157 nm and a titanium dioxide layer having a film thickness of 10 nm to 95 nm. The multi-layer vapor-deposited film having a multilayer number of 26 is formed by alternately laminating a silicon dioxide layer with a thickness of 37 nm to 194 nm and a titanium dioxide layer with a thickness of 12 nm to 114 nm. A multilayer vapor-deposited film having a number of 20 layers. An example of the optimized film structure is shown in Table 4 below.

[Table 4]
Table 4
* λ = 550 nm

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

Then, a camera module was produced using the obtained optical filter, and the chromatic aberration and ghosting of the camera image were evaluated. The results are shown in Table 5. The obtained camera image has good results in terms of shading and ghosting.

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

Resin composition (2): 50 g of acrylic urethane compound (1) obtained in Synthesis Example 2 (in terms of solid content), 50 g of tricyclodecane dimethanol acrylate, 1-hydroxycyclohexylphenyl 3 g of ketone, 50 g of pigment dispersion liquid (S-1) obtained in Preparation Example 1 (2.5 g in terms of organic pigment (S)), and 117 g of isopropanol.

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

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

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

Resin composition (4): 100 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 50 g of pigment dispersion liquid (S-2) obtained in Preparation Example 2 (using organic pigments (S) is 2.5 g) and 117 g of methyl isobutyl ketone.

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

Resin composition (5): 100 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 50 g of pigment dispersion liquid (S-2) obtained in Preparation Example 2 (using organic pigments (S) is 2.5 g), 0.5 g of compound (a-1), 0.4 g of compound (a-2), and 112 g of methyl isobutyl ketone.

[Example 6]
A transparent resin film "ZEONOR film ZF16 (thickness 100 μm)" cut into a length of 60 mm and a width of 60 mm (manufactured by Zeon Corporation) was used instead. An optical filter was obtained and evaluated in the same manner as in Example 5 except for a glass substrate. The results are shown in Table 5.

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

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

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

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

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

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

[Comparative Example 1]
To the container, 100 parts of the resin A obtained in Synthesis Example 1, 0.07 g of the compound (a-1) (maximum absorption wavelength in 713 nm in methylene chloride) as the compound (A), and the compound ( a-2) 0.06 g (maximum absorption wavelength in methylene chloride) 0.06 g, and compound (s-6) described in Table 2-2 (maximum absorption wavelength in methylene chloride 1093 nm) 0.2 g And dichloromethane to prepare a solution having a resin concentration of 20% by mass. The compound (s-6) was dissolved in methylene chloride and dyed. The obtained solution was cast onto a smooth glass plate and dried at 20 ° C. for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

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

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

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

Resin composition (7): 100 g of tricyclodecane dimethanol acrylate, 3 g of 1-hydroxycyclohexylphenyl ketone, 2.5 g of compound (s-15), 0.5 g of compound (a-1), and compound (a -2) 0.4 g, methylene chloride 155 g.

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

[table 5]
table 5


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

＜ Form of base material ＞
Form (1): A transparent resin layer containing an organic pigment (S) is provided on both sides of a transparent resin substrate containing the compound (A) Form (2): On a transparent glass substrate ("OA" manufactured by Nippon Electric Glass Co., Ltd.) -10G (thickness 150 μm) ") with transparent resin layer containing organic pigment (S) on both sides (3):" Rion Noah "manufactured by resin support (Zeon, Japan) (ZEONOR) ZF16 ") has a transparent resin layer form containing the compound (A) and an organic pigment (S) on both sides (4): a transparent resin layer form containing an organic pigment (S) on both sides of the resin support (5): Forms of resin layers on both sides of a transparent resin substrate containing compound (A) and compound (S) (6): Forms of transparent resin layers containing compound (S) on both sides of a transparent glass substrate ( 7): There are resin layers on both sides of a transparent resin substrate containing the compound (A)

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

＜ Dilution solvent ＞
Dilution solvent (1): isopropanol dilution solvent (2): methyl isobutyl ketone dilution solvent (3): methyl ethyl ketone dilution solvent (4): dichloromethane

10‧‧‧ Substrate

11‧‧‧first optical layer

12‧‧‧second optical layer

13‧‧‧ third optical layer

14‧‧‧ fourth optical layer

111‧‧‧ camera images

112‧‧‧White board

113‧‧‧ center of white plate

114‧‧‧ end of white plate

121‧‧‧ camera image

122‧‧‧light source

123‧‧‧Ghost around the light source

FIG. 1 (a) and FIG. 1 (b) are schematic diagrams showing examples of preferred configurations of the optical filter of the present invention.

FIG. 2 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG.

FIG. 3 is a schematic diagram for explaining color difference evaluation of camera images performed in Examples and Comparative Examples.

FIG. 4 is a schematic diagram for explaining ghost evaluation of camera images performed in Examples and Comparative Examples.

Claims (11)

An optical filter comprising a substrate that satisfies the following required condition a, and a dielectric multilayer film is formed on at least one surface of the substrate: Necessary condition a: A layer having an organic pigment S having a maximum absorption in a region having a wavelength of 900 nm to 1200 nm. The optical filter according to item 1 of the scope of patent application, wherein the substrate further satisfies the following required condition b: Necessary condition b: A layer including Compound A having the maximum absorption in a region having a wavelength of 650 nm or more and 760 nm or less. The optical filter according to item 2 of the scope of patent application, wherein the compound A is at least one compound selected from the group consisting of a squarylium salt compound, a phthalocyanine compound, and a cyanine compound. The optical filter according to any one of claims 1 to 3, wherein the organic pigment S includes a diimmonium compound represented by the following formula (I): In formula (I), R ¹ independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxyl group, a phosphate group, a -SR ⁱ group, a -SO ₂ R ⁱ group, a -OSO ₂ R ⁱ group, or In any one of ^La to L ^h , R ² independently represents a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -NR ^g R ^h group, a -SR ⁱ group, and -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group, or any one 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 the following L ^a to L any one of ^e, R ⁱ represents L ^a ~ L ^e following any of a, L ^a: aliphatic hydrocarbon group having a carbon number of 1 to 12 L ^b: from 1 to 12 carbon atoms, a halogen-substituted alkyl group L ^c: carbon alicyclic having 3 to 14 cyclic hydrocarbon group L ^d: the aromatic hydrocarbon group having a carbon number of 6 to 14 L ^e: number of carbon atoms of the heterocyclic group having 2 to 14 L ^f: carbon atoms, alkoxy having 1 to 12 L ^g: may have The fluorenyl group L ^h having 1 to 12 carbon atoms of the substituent L: the alkoxycarbonyl group L having 1 to 12 carbon atoms that may have the substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms and a carbon number of 1 Halo-substituted alkyl groups of 12 to 12, alicyclic hydrocarbon groups of 3 to 14 carbons, aromatic hydrocarbon groups of 6 to 14 carbons, and heterocyclic groups of 3 to 14 carbons At least one group, n represents an integer of 0 to 4, X represents an anion required for charge neutralization. The optical filter according to any one of claims 1 to 4, wherein the average particle diameter of the organic pigment S is 200 nm or less. The optical filter according to any one of claims 1 to 5, wherein the layer containing the organic pigment S is a transparent resin layer. The optical filter according to item 6 of the scope of patent application, wherein the transparent resin constituting the transparent resin layer is selected from the group consisting of a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, and Polycarbonate resin, polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, polyfluorene resin, polyether resin, polyparaphenylene resin, polyamine醯 imine resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, acrylic resin, modified acrylic resin, epoxy resin, allyl ester hardening resin, half At least one resin selected from the group consisting of a silicone-based UV-curable resin, an acrylic-based UV-curable resin, and a vinyl-based UV-curable resin. The optical filter according to any one of claims 1 to 7, wherein the base material contains a dispersant having an acidic functional group and is 100 parts by mass with respect to the organic pigment S. Therefore, The content of the dispersant is 5 to 300 parts by mass. The optical filter according to any one of claims 1 to 8 of the patent application scope, which is for a solid-state imaging device. A solid-state imaging device includes the optical filter according to any one of claims 1 to 9 in the scope of patent application. A camera module includes the optical filter according to any one of claims 1 to 9 of the scope of patent application.