KR20220146334A - Substrate, optical filter, solid state image pickup device, and camera module - Google Patents

Abstract

Provided is a substrate capable of having transmission characteristics of visible rays and some near-infrared rays, and also, being applied to a ghost-suppressible optical filter. The substrate has a resin layer including resin and pigment, wherein the substrate satisfies the following requirements (a) and (b), and the resin layer comprises a compound (S) having an absorption maximum at a wavelength of 620 to 760 nm, and a compound (Z) having an absorption maximum at a wavelength of 761 to 850 nm, and transmits at least one of a ray in a visible region and a ray in a near-infrared region. As to the requirement (a), in a wavelength area of 600 to 950 nm, a difference between the longest wavelength (Xa), at which the transmittance when measured in a vertical direction of the substrate is from more than 2% to 2% or less, and the shortest wavelength (Xb), at which the transmittance when measured in the vertical direction of the substrate is from less than 2% to 2% or more, is 80 nm or more. As to the requirement (b), in a wavelength area of 450 to 570 nm, an average value of the transmittance when measured in the vertical direction of the substrate is 70% or more.

Description

Substrate, optical filter, solid-state imaging device and camera module {SUBSTRATE, OPTICAL FILTER, SOLID STATE IMAGE PICKUP DEVICE, AND CAMERA MODULE}

The present invention relates to a substrate, an optical filter and an apparatus using the optical filter. Specifically, it relates to a substrate that selectively transmits visible light and a part of near-infrared rays containing a compound having a specific absorption, an optical filter composed of the substrate, and a solid-state imaging device and a camera module using the optical filter.

Solid-state imaging devices such as video cameras, digital still cameras, cellular phones with camera functions, and smartphones use CCD and CMOS image sensors, which are solid-state imaging devices for color images. A silicon photodiode with sensitivity to near-infrared rays, which cannot be detected by conventional methods, is used. In these solid-state imaging devices, it is necessary to perform visibility correction to make a natural color tone seen by the human eye, and an optical substrate that selectively transmits or cuts light in a specific wavelength region (optical filter, for example, a near-infrared cut filter) is often used

On the other hand, in recent years, attempts have been made to provide a camera module with a sensing function such as motion capture and distance recognition (spatial recognition) using near-infrared rays. In such a use, since it is necessary to selectively transmit visible light and a part of near-infrared rays, it is not possible to use a conventional base material that uniformly shields near-infrared rays.

Then, as a base material which selectively transmits visible light and some near-infrared rays, the optical filter which reduced the incident angle dependence of the visible transmission band using the near-infrared absorption dye like patent documents 1 and 2 is reported, for example.

Japanese Patent Publication No. 5884953 Japanese Patent Publication No. 6642578

By using the substrate that selectively transmits visible light and some near-infrared rays, for example, the dependence on the incident angle of the visible transmission band as an optical filter is small, and color shading of a camera image can be reduced compared to an optical filter using only a general dielectric multilayer film, but on the other hand Therefore, there is a problem of image defect called "ghost" that occurs around the light source. Also in mobile devices such as smartphones, the demand for higher image quality of cameras has been increasing, and the appearance of a substrate capable of suppressing ghosting and selectively transmitting visible light and some near-infrared rays has been desired.

As a result of intensive studies to achieve the above object, the present inventors have used a substrate containing two types of dyes having different absorption characteristics and having a broad absorption band in a wavelength region corresponding to the middle of the visible region and the near-infrared transmission band, It was discovered that the optical filter which is excellent in the transmission characteristic of a visible light and some near-infrared rays, and can suppress a ghost is obtained, and came to complete this invention. Aspects of the present invention are shown below.

Aspects of the present invention are as follows.

[1] A substrate having a resin layer comprising a resin and a dye,

The description satisfies the requirements of (a) and (b) below,

The resin layer contains a compound (S) having an absorption maximum at a wavelength of 620 to 760 nm, and a compound (Z) having an absorption maximum at a wavelength of 761 to 850 nm,

A substrate that transmits at least one of light in the visible region and light in the near-infrared region.

(a) In the region of wavelength 600 to 950 nm, the longest wavelength (Xa) at which the transmittance when measured in the vertical direction of the substrate is from more than 2% to 2% or less, and the transmittance when measured in the vertical direction of the substrate The difference of the shortest wavelength (Xb) from less than 2% to 2% or more is 80 nm or more.

(b) The average value of the transmittance|permeability at the time of measuring in the perpendicular|vertical direction of a base material in the area|region of wavelength 450-570 nm is 70 % or more.

[2] The compound (Z) is at least one compound selected from the group consisting of squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, cyanine-based compounds, croconium-based compounds, and polymethine-based compounds, [ 1].

[3] The description of [1], wherein two or more compounds (S) are contained in the resin layer.

[4] The above resin is a cyclic (poly)olefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a fluorene polycarbonate-based resin, a fluorene polyester-based resin, a polycarbonate-based resin, and a polyamide. Resin, polyarylate-based resin, polysulfone-based resin, polyethersulfone-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate-based resin, fluorinated aromatic polymer-based resin, (modified) acrylic resin, epoxy The substrate of [1], which is at least one selected from the group consisting of a resin-based resin, an allyl ester-based curable resin, a silsesquioxane-based UV-curable resin, an acrylic UV-curable resin, and a vinyl-based UV-curable resin.

[5] The substrate of [1], wherein the resin layer is provided on a resin substrate or a glass substrate as a support.

[6] The substrate of [1], further comprising a compound (N) having an absorption maximum in the wavelength region of Xb+50 nm to Xb+250 nm.

[7] An optical filter having the description of [1], and satisfying the following requirement (c).

(c) having a light-blocking band Za, a light-transmitting band Zb, and a light-blocking band Zc in a region having a wavelength of 600 nm or more, the central wavelength of each band being Za<Zb<Zc, measured in the direction perpendicular to the substrate in Za<Zb<Zc The minimum transmittance in one case is 1% or less, respectively, the maximum transmittance (Tb) when measured in the vertical direction of the substrate in Zb is 45% or more, and when measured in the vertical direction of the substrate in Zc The minimum transmittance is 15% or less, respectively.

[8] The optical filter of [7], wherein the optical filter further satisfies the following requirement (d).

(d) On the long wavelength side of the light transmission band Zb, the value (Ye) of the shortest wavelength at which the transmittance measured in the vertical direction of the optical filter is half of the Tb, and 30° with respect to the vertical direction of the optical filter The absolute value |Ye-Yf| of the difference of the value (Yf) of the shortest wavelength at which the transmittance is half of the Tb when measured at an angle of |Ye-Yf| is less than 35 nm.

[9] The optical filter of [7], wherein the substrate has a dielectric multilayer film on at least one surface side thereof.

[10] The optical filter of [9], wherein the dielectric multilayer film is formed by alternately stacking different material layers, and the difference in refractive index of the material layers is 0.8 or less.

[11] A solid-state imaging device comprising the optical filter of [7].

[12] A camera module including the optical filter of [7].

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the transmission characteristic of visible light and some near-infrared rays, and can provide the base material which can be used for the optical filter which can suppress ghost.

1 : (a) is a schematic diagram which shows the method of measuring the transmittance|permeability when measured in the perpendicular direction of a base material. (b) is a schematic diagram showing a method of measuring transmittance when measured at an angle of 30° with respect to the vertical direction of the substrate on which the dielectric multilayer film is provided. (c) is a schematic diagram for demonstrating the color shading evaluation of the camera image performed by the Example and the comparative example.
Fig. 2 is a spectral transmission spectrum of the substrate obtained in Example 1.
3 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 1. FIG.
Fig. 4 is a spectral transmission spectrum of the substrate obtained in Example 2.
5 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 2. FIG.
Fig. 6 is a spectral transmission spectrum of the substrate obtained in Example 4.
7 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 4. FIG.
Fig. 8 is a spectral transmission spectrum of the substrate obtained in Example 5.
Fig. 9 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 5;
Fig. 10 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 6.
Fig. 11 is a spectral transmission spectrum of the substrate obtained in Example 8.
12 is a spectral transmission spectrum of the substrate obtained in Comparative Example 1. FIG.
13 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 1. FIG.
14 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 2. FIG.
Fig. 15 is a spectral transmission spectrum of the substrate obtained in Comparative Example 3.
16 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 3. FIG.
17 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 4. FIG.
18 is a spectral transmission spectrum of the substrate obtained in Comparative Example 5;
19 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 5;
Fig. 20 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 6.
Fig. 21 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 15;
22 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 16. FIG.
23 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 17. FIG.
24 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 18. FIG.

Hereinafter, the present invention will be specifically described.

[write]

The substrate of the present invention includes a resin layer containing, together with a resin, a compound (S) having an absorption maximum at a wavelength of 620 to 760 nm, and a compound (Z) having an absorption maximum at a wavelength of 761 to 850 nm. Such a substrate has high transmittance in the visible region and broad absorption in a wavelength region of 600 to 950 nm, and can function as an optical filter that selectively transmits visible light and some near-infrared rays.

For this reason, when the substrate of the present invention is applied to an optical filter, unlike a conventional filter that selectively transmits visible light and some near-infrared rays, the wavelength region between the transmitted near-infrared rays and the visible region can be cut by a dielectric multilayer film. no need. Thereby, it is possible to suppress the ghost of the camera image originating from the reflected light of the dielectric multilayer film, and it becomes possible to achieve an excellent image quality not previously available.

As described above, the substrate of the present invention can be used as an optical filter as it is, and it is not always necessary to provide a dielectric multilayer film. Moreover, it is also possible to provide a dielectric multilayer film as needed, and to use the base material with a dielectric multilayer film as an optical filter.

When using the base material of this invention as an optical filter for a solid-state image sensor etc., the one with a higher visible light transmittance is preferable. When such a substrate is used as a solid-state imaging device use, excellent imaging sensitivity can be achieved.

The substrate of the present invention has a resin layer containing at least one compound (S) having an absorption maximum at a wavelength of 620 to 760 nm, and a compound (Z) having an absorption maximum at a wavelength of 761 to 850 nm, respectively. ) or a multilayer laminated base material (ii).

In the case of the single-layer substrate (i), for example, a single-layer substrate composed of a resin layer containing the compound (S) and the compound (Z) is mentioned, and such a single-layer substrate is sometimes referred to as a transparent resin substrate.

In the case where the base material is a multilayer laminated base material (ii), the resin layer containing the compound (S) and the compound (Z) should just be laminated on the surface of a support or the like, for example,

Laminated substrate (ii-1) in which a resin layer containing a compound (S) and a compound (Z) is laminated on a glass support;

A laminated substrate (ii-2) in which a resin layer containing the compound (S) and the compound (Z) is laminated on a transparent resin support not containing the compound (S) and the compound (Z);

A laminated base material (ii-3) in which a resin layer containing either compound (S) or (Z) and a resin layer containing the other or both are laminated;

Laminated base material (ii-4) in which a resin layer containing a compound (S) and a compound (Z) is laminated on a single-layer base material (i)

and the like,

Furthermore, the laminated base material in which the overcoat layer etc. were further laminated|stacked on the above single|monolayer base material (i) and the said laminated base material (ii-1) - (ii-4) are mentioned.

In one preferred aspect of the present invention, both the single-layered substrate and the laminated substrate are composed of a resin material. When all the base materials are comprised from the resin material, the laminated base material by which the overcoat layer etc. were laminated|stacked on the surface of a resin layer from points, such as a scratch resistance improvement, is more preferable.

Further, in the present invention, it is also a preferred aspect to have a glass substrate, and in this case, from the viewpoint of manufacturing cost, a substrate having a resin layer containing the compound (S) and the compound (Z) on one side of the transparent glass substrate is more preferable. do.

The description of the present invention satisfies the following requirements (a) and (b).

(a) In the region of wavelength 600 to 950 nm, the longest wavelength (Xa) at which the transmittance when measured in the vertical direction of the substrate is from more than 2% to 2% or less, and the transmittance when measured in the vertical direction of the substrate The difference of the shortest wavelength (Xb) from less than 2% to 2% or more is 80 nm or more.

The difference between Xb and Xa is preferably 90 nm or more, more preferably 100 nm or more, still more preferably 130 nm or more, particularly preferably 150 nm or more. When the difference between Xb and Xa is within the above range, light can be sufficiently cut between the visible wavelength region and the near-infrared transmission band only by absorption of the substrate, and unlike conventional optical filters, light cut in this wavelength region by a dielectric multilayer film is unnecessary. will do For this reason, the ghost resulting from reflection of the dielectric multilayer film inside a camera module can be reduced, and a very favorable camera image can be obtained.

(b) The average value of the transmittance|permeability at the time of measuring in the perpendicular|vertical direction of a base material in the area|region of wavelength 450-570 nm is 70 % or more.

The average transmittance of the substrate at a wavelength of 450 to 570 nm is preferably 72% or more, more preferably 74% or more, and particularly preferably 76% or more. When a substrate having such a transmission characteristic is used, high light transmission characteristic can be achieved in a visible region and the target near-infrared region, and a camera function and a near-infrared sensing function can be made compatible at a good level.

In addition, when the base material is a laminated base material, the average transmittance may be measured from the surface side of the resin layer containing the compound (S) and the compound (Z) or may be measured from the opposite surface side, and the transmittance does not change.

The thickness of the resin layer comprising the compound (S) and the compound (Z) can be appropriately selected depending on the desired use, and is not particularly limited, but is preferably selected appropriately so as to reduce the incident angle dependence of the optical filter to be used. , Preferably it is 10-200 micrometers, More preferably, it is 20-180 micrometers, Especially preferably, it is 30-150 micrometers.

When a base material has a some resin layer, it is preferable that total thickness exists in the said range.

When the thickness of a resin layer exists in the said range, thickness reduction and weight reduction of the optical filter which has this base material can be carried out, and it can use suitably for various uses, such as a solid-state imaging device. In particular, when it is used for lens units, such as a camera module, since height reduction and weight reduction of a lens unit can be implement|achieved, it is preferable.

<Compound (S)>

The compound (S) is not particularly limited as long as it is a compound having an absorption maximum at a wavelength of 620 to 760 nm, but is preferably a solvent-soluble dye compound, a squarylium-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, a polymethine-based compound It is more preferable that it is at least 1 sort(s) chosen from the group which consists of a compound and a cyanine type compound. In the present invention, at least one selected from the group consisting of squarylium compounds, phthalocyanine compounds and polymethine compounds is more preferable from the viewpoint of having excellent visible light transmission characteristics, steep absorption characteristics and high molar extinction coefficient among them. and at least one squarylium-based compound and at least one selected from the group consisting of phthalocyanine-based compounds and polymethine-based compounds are particularly preferred.

In addition, although a squarylium-type compound and a cyanine-type compound are included in a polymethine-type compound in a broad sense, in this specification, polymethine-type compound other than a squarylium-type compound and a cyanine-type compound is defined as a "polymethine-type compound."

In the present invention, the absorption maximum wavelength of the compound may be measured using a spectrophotometer for the obtained solution after dissolving the compound in a suitable solvent such as dichloromethane, for example.

The compound (S) may contain two or more types of several compounds in the resin layer.

In the case of a plurality of compounds, these compounds may be contained in the same resin layer or may be contained in a separate resin layer.

When contained in the same layer, for example, a resin layer in which two or more compounds (S) are all the same, that is, a resin layer containing two or more compounds (S) is laminated on a single-layer substrate or a support such as a glass support. and laminated substrates. In addition, when included in a separate resin layer, for example, a laminated substrate in which a resin layer containing another compound (S) is laminated on a single-layer substrate containing compound (S), or another compound (S) The laminated base material etc. which were laminated|stacked on the support body of 2 or more layers of resin layers contained respectively are mentioned.

It is more preferable that two or more types of compounds (S) are contained in the same resin layer, and in this case, it becomes easier to control content ratio than when contained in another resin layer.

The content of the compound (S) is, for example, in the case of a single-layer substrate or a laminate substrate in which an overcoat layer or the like is laminated on the surface of the substrate, with respect to 100 parts by mass of the resin constituting the resin layer, preferably 0.01 to 2.0 mass part, More preferably, it is 0.02-1.5 mass part, Especially preferably, it is 0.03-1.0 mass part.

In the case of a laminated substrate in which a resin layer containing a resin composition containing the compound (S) is laminated on a support such as a glass support or a resin support, preferably with respect to 100 parts by mass of the resin constituting the resin layer. 0.1-5.0 mass parts, More preferably, it is 0.2-4.0 mass parts, Especially preferably, it is 0.3-3.0 mass parts.

When content of a compound (S) exists in the said range, the optical filter which made favorable near-infrared absorption and transmission characteristic, and high visible light transmittance compatible can be obtained.

<Compound (Z)>

Although the compound (Z) is not particularly limited as long as it is a compound having an absorption maximum at a wavelength of 761 to 850 nm, it is preferably a solvent-soluble dye compound, and a squarylium-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, and a cyanine-based compound , croconium-based compounds, and at least one selected from the group consisting of polymethine-based compounds other than these is more preferable, and from the viewpoint of achieving excellent visible light transmission properties, squarylium-based compounds, croconium-based compounds, poly A methine-based compound is particularly preferred.

The compound (Z) may be contained in the same layer as the compound (S), or may be contained in a separate layer. When contained in the same layer, for example, both compound (Z) and compound (S) are contained on a single-layer substrate in which both compound (Z) and compound (S) are contained in the resin layer, or on a support such as a glass support. and a laminated base material on which a resin layer to be used is laminated, and when contained in a separate layer, for example, a laminate in which a resin layer containing compound (S) and a resin layer containing compound (Z) are laminated. description can be given.

It is more preferable that the compound (Z) and the compound (S) are contained in the same layer, and in this case, it becomes easier to control the content ratio than when contained in a separate layer.

The compound (Z) may contain two or more types of plurality in the resin layer. In the case of a plurality of compounds, these compounds may be contained in the same resin layer or may be contained in a separate resin layer, but preferably contained in the same resin layer.

The content of the compound (Z) is preferably based on 100 parts by mass of the resin constituting the resin layer containing the compound (Z) in the case where the substrate is a single-layer substrate or a laminate substrate in which an overcoat layer or the like is laminated on its surface. 0.05-2.5 mass parts, More preferably, it is 0.08-1.8 mass parts, Especially preferably, it is 0.10-1.5 mass parts.

In the case of a laminated substrate in which a resin layer containing a resin composition containing the compound (Z) is laminated on a support such as a glass support or a resin support, 100 parts by mass of the resin constituting the resin layer containing the compound (Z) To this, Preferably it is 0.5-25.0 mass parts, More preferably, it is 0.8-18.0 mass parts, Especially preferably, it is 1.0-15.0 mass parts.

When content of compound (Z) exists in the said range, since high visible light transmittance and favorable near-infrared absorption and transmission characteristics can be made compatible, and the said difference of Xb and Xa can be enlarged, it is preferable.

<Compound (N)>

The substrate may further contain a compound (N) having an absorption maximum in the wavelength region of Xb+50 nm to Xb+250 nm. The compound (N) is not particularly limited as long as it has an absorption maximum in the above wavelength region, but is preferably a solvent-soluble dye compound, a squarylium-based compound, a cyanine-based compound, a croconium-based compound, a metal dithiolene complex compound, and It is more preferable that it is at least 1 type selected from the group which consists of a polymethine type compound, It is especially preferable that they are a squarylium type compound, a metal dithiolene complex type compound, and a polymethine type compound.

Since Xb does not substantially change even if compound (N) is included or not, compound (N) can be selected from the measurement results on a substrate not containing compound (N).

The compound (N) may be contained in the same layer as the compounds (S) and (Z), or may be contained in a separate layer. When contained in the same layer, for example, the compound (N) and the compound (N) and the compound ( and a laminated substrate in which a resin layer containing both S) and (Z) is laminated, and when contained in a separate layer, for example, on a resin layer containing compounds (S) and (Z) The base material on which the resin layer in which the compound (N) is contained is laminated|stacked is mentioned.

The content of the compound (N) is, for example, in the case of using a single-layer substrate containing the compound (N) or a laminated substrate in which an overcoat layer or the like is laminated on a single-layer substrate, 100 parts by mass of the resin constituting the resin layer. , Preferably it is 0.010-1.5 mass part, More preferably, it is 0.015-1.0 mass part, Especially preferably, it is 0.020-0.8 mass part.

In the case of the laminated base material in which the resin layer containing the compound (N) was laminated|stacked on the glass support body or the resin support body, with respect to 100 mass parts of resin which forms the resin layer containing the compound (N), Preferably 0.10. -10.0 mass parts, More preferably, it is 0.15-8.0 mass parts, Especially preferably, it is 0.20-5.0 mass parts.

When the content of the compound (N) is within the above range, unnecessary near-infrared rays can be efficiently absorbed while maintaining high visible light transmittance. It is preferable because dependence can be made small. Thereby, it becomes possible to significantly reduce the number of layers of the dielectric multilayer film, and it can be used as a visible region-near-infrared selective transmission filter without the dielectric multilayer film depending on the required characteristics.

<Resin>

A transparent resin is included as resin which comprises a resin layer. As transparent resin, 1 type may be sufficient, and 2 or more types may be sufficient as it.

The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, a dielectric multilayer film can be formed by high-temperature deposition performed at a deposition temperature of 100° C. or higher to ensure thermal stability and film formability. In order to set it as the base material which can be formed, resin whose glass transition temperature (Tg) becomes like this. Preferably it is 110-380 degreeC, More preferably, it is 110-370 degreeC, More preferably, it is 120-360 degreeC. Moreover, since the film which can be vapor-deposited that the glass transition temperature of the said resin is 140 degreeC or more which can vapor-deposit a dielectric multilayer film at higher temperature is obtained, it is especially preferable.

Tg can be specifically measured by the method described in the following Example.

As the transparent resin, when a resin support having a thickness of 0.1 mm containing the resin is formed, the total light transmittance (JIS K7375) of the resin support is preferably 75% or more, more preferably 78% or more. , particularly preferably 80% or more of the resin can be used. When resin used as a total light transmittance becomes this range, the base material (i) obtained will show favorable transparency as an optical film.

When a solvent-soluble resin is used as the transparent resin, the mass average molecular weight (Mw) in terms of polystyrene measured by the gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000, preferably 30,000. -250,000, and a number average molecular weight (Mn) is 10,000-150,000 normally, Preferably it is 20,000-100,000.

Mw and Mn can be specifically measured by the method described in the following Example.

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

Specific examples of these resins include resins described in International Publication No. 2019/168090.

In addition, the overcoat layer etc. in a base material say the resin layer which does not contain the compounds (S), (Z), and (N). The resin layer which does not contain the said compound will not restrict|limit especially if resin is included, The said transparent resin etc. are mentioned as this resin. Moreover, the functional film containing other components may be sufficient.

<Support>

A polyester film, a polycarbonate film, a polyimide film, a cyclic olefin resin film etc. are mentioned as a transparent resin support body which does not contain the compound (Z) used in the laminated base material (i-2). As a support body used in the laminated base material (i-3), a glass plate, a steel belt, a steel drum, etc. are mentioned, for example.

As a support body, the support body made from a glass plate, a steel belt, a steel drum, and transparent resin (for example, a polyester film, a cyclic olefin resin film) is mentioned, for example.

<Other ingredients>

The said base material is the range which does not impair the effect of this invention WHEREIN: You may contain additives, such as antioxidant, a near-ultraviolet absorber, and a fluorescence quencher further. Moreover, when manufacturing a base material by the cast molding mentioned later, manufacture of a base material can be made easy by adding a leveling agent and an antifoaming agent. These other components may be used individually by 1 type, and may use 2 or more types together.

These may be contained in a resin layer, and may be contained in an overcoat layer.

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

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

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

<Method for manufacturing base material>

When the substrate is a single-layer substrate containing the compounds (S) and (Z), it can be formed by, for example, melt molding or cast molding, and if necessary, the overcoat layer is formed by melt molding or cast molding. It may be laminated.

When the base material is a glass support or a resin support, or a resin layer containing the compound (S) and the compound (Z), and optionally the compound (N) is laminated on the single-layer substrate, for example, a glass support or A resin solution containing the compound (S), the compound (Z) and, if necessary, the compound (N) is melt-molded or cast-molded on a resin support or a single-layer substrate, or coated by spin coating, slit coating, inkjet, etc. The laminated base material with a resin layer can be manufactured by drying and removing a solvent, and also performing light irradiation and a heating as needed after doing this.

≪Melt molding≫

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

≪Cast molding≫

Examples of the cast molding include a method in which a resin composition containing a compound (S), a compound (Z), a resin, and a solvent is cast on a suitable support to remove the solvent; Alternatively, the resin composition containing the compound (S), the compound (Z) and the transparent resin is cast on a suitable support to remove the solvent, and when the transparent resin is a curable resin, it is cured by an appropriate method such as ultraviolet irradiation or heating. It can also be manufactured by a method etc.

When the substrate is a single-layer substrate containing the compound (S) and the compound (Z), the substrate can be cast-molded and then the coating film is peeled off the support to obtain the coating film itself as a single-layer substrate. In addition, when the said base material is a laminated base material in which the resin layer containing the compound (S) and the compound (Z) is laminated|stacked on a support, such as a glass support body, a resin support body, or a single-layer base material, the base material is cast-molded after , can be obtained without peeling the coating film.

When the compound (S) and (Z) and (N) contained as needed are contained in another resin layer, the said shaping|molding method may be repeated, or what is necessary is just to bond resin layers together.

As said support body, transparent resin support bodies, such as a polyester film, a polycarbonate film, a polyimide film, and a cyclic olefin resin film, glass supports, such as a glass plate, a steel belt, a steel drum, etc. are mentioned.

In addition, the resin layer on the optical component by a method of using an optical component such as a glass plate, quartz, or transparent plastic as a support, coating the resin composition to dry the solvent, or in the case of a curable resin, appropriately curing. may form.

As little as possible the amount of residual solvent in the resin layer obtained by the said method is good. Specifically, the amount of the residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less with respect to the weight of the resin layer. When the amount of residual solvent is within the above range, a resin layer capable of easily exhibiting a desired function, which is hardly deformed or changed in characteristics, is obtained.

<Optical filter>

The optical filter of this invention has the said base material, and satisfy|fills the following requirement (c).

(c) having a light-blocking band Za, a light-transmitting band Zb, and a light-blocking band Zc in a region having a wavelength of 600 nm or more, the central wavelength of each band being Za<Zb<Zc, measured in the direction perpendicular to the substrate in Za<Zb<Zc The minimum transmittance in one case is 1% or less, respectively, the maximum transmittance (Tb) when measured in the vertical direction of the substrate in Zb is 45% or more, and when measured in the vertical direction of the substrate in Zc The minimum transmittance is 15% or less, respectively.

Zb is the longest wavelength at which the transmittance when measured in the vertical direction of the optical filter is 30% or less to 30% or less from the shortest wavelength Zb1 at a wavelength of 750 nm or more and 1050 nm or less, and from more than 30% to 30% or less. It refers to the wavelength band up to Zb2.

Zc is at a wavelength of 850 nm or more and 1200 nm or less, the transmittance when measured in the vertical direction of the optical filter is the longest wavelength from less than 20% to 20% or more from the shortest wavelength Zc1 from more than 20% to 20% or more It refers to the wavelength band up to Zc2.

When the optical filter of the present invention is used in a solid-state imaging device having both a near-infrared sensing function, etc., the maximum transmittance of the light (near-infrared) transmission band Zb when measured in the vertical direction of the optical filter is preferably higher, The minimum transmittance of the stop bands Za and Zc is preferably lower. In this case, it is possible to achieve an excellent near-infrared sensing function and to efficiently cut light of an unnecessary wavelength, thereby improving the color reproducibility of a camera image.

The minimum transmittance when measured in the vertical direction of the optical filter in the light blocking band Za is 1% or less, preferably 0.8% or less, more preferably 0.7% or less, particularly preferably 0.6% or less. The minimum transmittance when measured in the vertical direction of the optical filter in the light blocking band Zc is 15% or less, preferably 12% or less, more preferably 10% or less, particularly preferably 8% or less. The maximum transmittance when measured in the vertical direction of the optical filter in the light transmission band Zb is 45% or more, preferably 48% or more, more preferably 50% or more, and particularly preferably 53% or more. When the maximum transmittance in Zb and the minimum transmittance in Za and Zc are within the above ranges, a camera image with little noise and excellent color reproducibility can be obtained while achieving a high near-infrared sensing function.

Since the optical filter of the present invention has a base material comprising a resin layer containing a compound (S) having an absorption maximum at a wavelength of 620 to 760 nm, and a compound (Z) having an absorption maximum at a wavelength of 761 to 850 nm, spectral properties The dependence of the angle of incidence is small.

It is preferable that the said optical filter further satisfy|fills the following requirement (d).

(d) On the long wavelength side of the light transmission band Zb, the value (Ye) of the shortest wavelength at which the transmittance measured in the vertical direction of the optical filter is half of the Tb, and 30° with respect to the vertical direction of the optical filter The absolute value |Ye-Yf| of the difference of the value (Yf) of the shortest wavelength at which the transmittance is half of the Tb when measured at an angle of |Ye-Yf| is less than 35 nm.

In the optical filter of the present invention, it is more preferable to reduce the incident angle dependence also on the long wavelength side of the light transmission band Zb. Specifically, the value (Ye) of the shortest wavelength at which the transmittance is half of Tb when measured in the vertical direction of the optical filter, and the transmittance when measured at an angle of 30° with respect to the vertical direction of the optical filter The absolute value |Ye-Yf| of the difference of the value (Yf) of the shortest wavelength that is half of the Tb is preferably smaller, preferably less than 35 nm, more preferably less than 30 nm, still more preferably less than 25 nm, It is particularly preferably less than 20 nm. When |Ye-Yf| is within the above range, the difference in the near-infrared S/N ratio between normal and oblique incidence becomes small, particularly when used for applications such as a camera module with a sensing function, further reducing noise during sensing can do.

The optical filter of the present invention on at least one surface side of the substrate has a value (Ya) of the shortest wavelength at which the transmittance is 20% when measured in the vertical direction of the optical filter in a wavelength region of 580 nm or more, and the optical filter The absolute value |Ya-Yb| of the difference between the value (Yb) of the shortest wavelength at which the transmittance is 20% when measured at an angle of 30° with respect to the vertical direction of |Ya-Yb| is preferably smaller, preferably less than 10 nm, More preferably, it is less than 8 nm, Especially preferably, it is less than 5 nm.

In the optical filter of the present invention, in the light transmission band Zb, the value (Yc) of the shortest wavelength at which the transmittance measured in the vertical direction of the optical filter is half of the Tb, and 30 with respect to the vertical direction of the optical filter The absolute value |Yc-Yd| of the difference of the value (Yd) of the shortest wavelength at which the transmittance is half of the Tb when measured at an angle of ° is preferably smaller, preferably less than 15 nm, more preferably less than 12 nm, particularly preferably less than 10 nm.

When |Ya-Yb| or |Yc-Yd| is in the above range, an optical filter with a wide viewing angle can be obtained, and particularly when used in applications such as a camera module with a sensing function, the image quality of the camera with less ghost and the image edge In addition to being able to achieve color reproducibility (lower color shading), a good sensing function with less noise can be obtained.

The thickness of the optical filter of the present invention may be appropriately selected according to a desired application. However, according to recent trends such as thinning and weight reduction of solid-state imaging devices, it is preferable that the optical filter of the present invention also has a thin thickness. Since the optical filter of this invention contains the said base material, thickness reduction is possible.

The thickness of the optical filter of the present invention is, for example, preferably 200 µm or less, more preferably 180 µm or less, still more preferably 150 µm or less, particularly preferably 120 µm or less, and the lower limit is not particularly limited. , for example, it is preferably 20 μm.

The optical filter of the present invention may be composed of only the substrate, may have another functional film, or may have, for example, a dielectric multilayer film shown below on at least one surface side of the substrate.

[Dielectric Multilayer Film]

The dielectric multilayer film may or may not be in direct contact with the substrate. A dielectric multilayer film is a film which cuts unnecessary near-infrared rays by reflection and has the ability to transmit necessary near-infrared rays, or a film|membrane which has a reflection prevention function in a visible region and a part of near-infrared wavelength region. In the present invention, the dielectric multilayer film may be provided on one side of the substrate or on both sides of the substrate. When providing on one surface side, it is excellent in manufacturing cost and manufacturing easiness, and when providing on both sides, it has high intensity|strength and an optical filter which curvature does not produce easily can be obtained.

When the optical filter of the present invention is applied to a solid-state imaging device or the like, it is preferable to provide a dielectric multilayer film on both surfaces of the substrate, since it is preferable that the optical filter has a smaller warpage. These may be the same or different. When the spectral characteristics of the multilayer dielectric films provided on both surfaces are the same, the transmittances of the light-blocking bands Za and Zc in the near-infrared wavelength region can be effectively reduced. It tends to become easier to extend to the longer wavelength side.

In the dielectric multilayer film, two or more types of material layers are laminated.

As a material constituting the multilayer film, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide or indium oxide is a main component, and titanium oxide, tin oxide and/or cerium oxide etc. are contained in a small amount (for example, 0-10 mass % with respect to the main component), silica, alumina, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride, etc. are mentioned.

From these materials, two or more types of materials are selected so that it may become a predetermined|prescribed refractive index difference. In addition, when a predetermined refractive index difference is constituted, when two or more material layers are alternately three or more layers, it is not limited to being regularly stacked, and the same material layers may be stacked so as not to be stacked, and different material layers may be appropriately layered. It may be laminated|stacked.

The refractive index of the material constituting the multilayer film is not particularly limited as long as it is about 1.2 to 2.5.

Since the absolute value |Ye-Yf| can be made small, it is so preferable that the refractive index difference between the materials which comprises a multilayer film is small. The refractive index difference is preferably 0.8 or less, and more preferably 0.5 or less. Moreover, when comprised from 3 or more types of materials, it is preferable that the refractive index difference of adjacent material layers exists in the said range.

As for the method of laminating|stacking the material layer which has a predetermined refractive index difference, there is no restriction|limiting in particular as long as a dielectric multilayer film is formed. For example, a dielectric multilayer film in which material layers having a predetermined refractive index difference are alternately laminated can be formed directly on a substrate by a CVD method, a sputtering method, a vacuum deposition method, an ion assisted deposition method, an ion plating method, or the like.

Although the physical film thickness of each layer of the material layers constituting the multilayer film may vary depending on the refractive index of each layer, it is usually preferably 5 to 500 nm, and the total value of the physical film thickness of the dielectric multilayer film is 1.0 to 8.0 as the entire optical filter. It is preferable that it is micrometer.

The total number of stacked dielectric multilayer films is preferably 2 to 60 layers, more preferably 4 to 56 layers, and particularly preferably 6 to 50 layers as the entire optical filter. When the thickness of each layer, the thickness of the dielectric multilayer film as a whole, and the total number of stacks are within the above ranges, a sufficient manufacturing margin can be ensured, and warpage of the optical filter and cracks in the dielectric multilayer film can be reduced, and a wide light beam An optical filter having a stop band or a light transmission band can be obtained.

[Other Functional Films]

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

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

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

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

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

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

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

In addition, an organic solvent may be added to the said curable composition as a solvent, and a well-known thing can be used as an organic solvent, You may use individually by 1 type, and may use 2 or more types together.

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

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

[Use of optical filter]

The optical filter of the present invention has a wide viewing angle and can selectively transmit visible light and some near-infrared rays. Therefore, it is useful as an object for visibility correction|amendment of solid-state image sensor, such as a CCD and CMOS image sensor which has both a camera function and a near-infrared sensing function. In particular, digital still cameras, cameras for smartphones, cameras for mobile phones, digital video cameras, cameras for wearable devices, PC cameras, surveillance cameras, automotive cameras, dark cameras, motion capture, laser rangefinders , virtual try-on, license plates It is useful for a recognition device, a television, a car navigation system, a portable information terminal, a video game machine, a portable game machine, a fingerprint authentication system, a digital music player, and the like.

[Solid-State Imaging Device]

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

<Example>

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

<Molecular Weight>

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

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

(b) Using a Tosoh Co., Ltd. GPC apparatus (HLC-8220 type, column: TSKgelα-M, developing solvent: tetrahydrofuran), the mass average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene was measured.

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

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

μ={ln(t _s /t ₀ )}/C

t ₀ : solvent flow time

t _s : flow time of the dilute polymer solution

C: 0.5 g/dL

<Glass transition temperature (Tg)>

Using a differential scanning calorimeter (DSC6200) manufactured by SII·Nano Technologies Co., Ltd., the measurement was performed at a rate of temperature increase: 20° C. per minute and a nitrogen stream.

<Spectral transmittance>

The transmittance|permeability in each wavelength range of a base material and an optical filter was measured using the Hitachi High-Technologies Co., Ltd. product spectrophotometer (U-4100).

Here, the transmittance when measured in the vertical direction of the substrate and the optical filter was measured as light transmitted perpendicularly to the filter as shown in FIG. 1A. In addition, as for the transmittance when measured at an angle of 30° with respect to the vertical direction of the optical filter, light transmitted at an angle of 30° with respect to the vertical direction of the filter as shown in FIG. 1B was measured.

In addition, the transmittance is measured using the spectrophotometer under the condition that light is incident perpendicularly to the substrate and the optical filter, except for the case where Yb, Yd, and Yf of the optical filter are measured. In the case of measuring Yb, Yd, and Yf, measurements are made using the spectrophotometer under the condition that light is incident at an angle of 30° with respect to the vertical direction of the optical filter.

<Evaluation of color shading>

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

There is no problem at all and an acceptable level is “○”, a slight difference in color tone is confirmed, but there is no practical problem as a high-definition camera module, and an acceptable level is “△”. It was judged as "x".

In addition, as shown in FIG.1(c), when imaging, the positional relationship between the white board 112 and the camera module so that the white board 112 occupies 90% or more of the area in the camera image 111 was adjusted.

<Ghost Rating>

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

There is no problem at all, the acceptable level is “○”, and a slight ghost is confirmed, but as a high-definition camera module, there is no practical problem. ' was decided.

[Synthesis Example]

Compound (S), compound (Z), and compound (N) used in the following examples can be synthesized by a generally known method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent Publication 2864475, Japanese Patent 3094037, Japanese Patent 3703869, 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 , Japanese Patent Laid-Open No. 63-124054, "Phthalocyanine -Chemistry and Function-" (IPC, 1997), Japanese Patent Application Laid-Open No. 2007-169315, Japanese Patent Laid-Open No. 2009-108267, Japanese Patent Laid-Open No. 2010 -241873, Japanese Patent 3699464, Japanese Patent 4740631, etc. can be referred and it can synthesize|combine with reference to the method.

<Resin Synthesis Example 1>

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

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

<Resin Synthesis Example 2>

35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g (0.300 mol) of potassium carbonate in a 3L four-necked flask ), 443 g of N,N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube, and a cooling tube were installed in the four-neck flask. Next, after the inside of the flask was purged with nitrogen, the resulting solution was reacted at 140 DEG C for 3 hours, and the resulting water was frequently removed from the Dean-Stark tube. When the production of water was no longer confirmed, the temperature was gradually increased to 160°C, and the reaction was carried out at the same temperature for 6 hours. After cooling to room temperature (25° C.), the resulting salt was removed with a filter paper, the filtrate was reprecipitated in methanol, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum-dried at 60 degreeC overnight, and white powder (henceforth "resin B") was obtained (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a mass average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285°C.

<Resin Synthesis Example 3>

1,4-bis(4-amino-α,α-dimethylbenzyl) in a 500 mL 5-neck flask equipped with a thermometer, stirrer, nitrogen inlet tube, side tube-equipped dropping funnel, Dean-Stark tube and cooling tube under a nitrogen stream Benzene 27.66 g (0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl 7.38 g (0.02 mol) were added, γ-butyrolactone 68.65 g and N,N-dimethylacetamide 17.16 g dissolved. The obtained solution was cooled to 5°C using an ice-water bath and maintained at the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and triethylamine as an imidization catalyst. 0.50 g (0.005 mol) was added in batches. After completion of the addition, the temperature was raised to 180° C. and refluxed for 6 hours while distilling off the effluent from time to time. After completion|finish of reaction, after air-cooling until internal temperature became 100 degreeC, 143.6 g of N,N- dimethylacetamide was added and diluted, and it cooled, stirring, and obtained 264.16g of polyimide resin solutions with a solid content concentration of 20 mass %. . A part of this polyimide resin solution was poured into 1 L of methanol to precipitate polyimide. After wash|cleaning the polyimide separated by filtration with methanol, it was made to dry in 100 degreeC vacuum dryer for 24 hours, and white powder (henceforth "resin C") was obtained. When the IR spectrum of the obtained resin C was measured, absorption of 1704 cm ^-1 and 1770 cm ^-1 peculiar to the imide group was observed. Resin C had a glass transition temperature (Tg) of 310°C, and when the logarithmic viscosity was measured, it was 0.87.

[Example 1]

In Example 1, an optical filter was prepared using a single-layer substrate including a transparent resin substrate.

In a container, 100 parts of Resin A obtained in Synthesis Example 1, 0.04 parts by mass of compound (s-1) represented by the following formula (s-1) as compound (S) (maximum absorption wavelength in dichloromethane 711 nm), and the following formula 0.08 parts by mass of the compound (s-2) represented by (s-2) (maximum absorption wavelength in dichloromethane 736 nm), the compound (z-1) represented by the following formula (z-1) as the compound (Z) ( Absorption maximum wavelength 770 nm in dichloromethane) 0.14 mass parts and methylene chloride were added, and the solution whose resin density|concentration is 20 mass % was obtained. Next, the obtained solution was cast on the smooth glass plate, and after drying at 20 degreeC for 8 hours, it peeled from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain a single-layer substrate comprising a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. The results are shown in Fig. 2 and Table 1.

Subsequently, a dielectric multilayer film (I) was formed on one side of the obtained single-layer substrate, and a dielectric multilayer film (II) was formed on the other surface of the substrate, thereby obtaining an optical filter having a thickness of about 0.105 mm.

The dielectric multilayer film (I) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (18 layers in total). The dielectric multilayer film (II) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (18 layers in total). In any of the dielectric multilayer films (I) and (II), the silica layer and the titania layer are formed from a titania layer, a silica layer, a titania layer, ... A silica layer, a titania layer, and a silica layer were alternately laminated in this order, and the outermost layer of the optical filter was a silica layer.

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

Regarding the thickness of each layer and the number of layers, the wavelength-dependent characteristic of the refractive index of the substrate and the compound (S) or compound (Z) used so as to achieve an antireflection effect in the visible region and selective transmission/reflection performance in the near-infrared region. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) according to the absorption characteristics. When optimizing, in Example 1, the input parameters (target values) to the software are shown in Table 1 below.

As a result of film configuration optimization, in Example 1, in both dielectric multilayer films (I) and (II), a silica layer having a film thickness of 40 to 196 nm and a titania layer having a film thickness of 12 to 120 nm were alternately laminated, the laminated number of 18 It became a multilayer vapor deposition film. Table 2 shows an example of the optimized film configuration.

The spectral transmittance measured at an angle of 30° from the vertical direction and the vertical direction of this optical filter was measured, and the optical properties in each wavelength region were evaluated. The results are shown in Fig. 3 and Table 17.

Moreover, the camera module was created using the obtained optical filter, and evaluation of the ghost of a camera image and color shading was performed. A result is shown in Table 17. The obtained camera image was a good result in color shading and ghosting.

[Example 2]

In Example 2, an optical filter having a single-layer substrate including a transparent resin substrate was prepared.

In Example 1, except that 0.02 mass parts of compound (n-1) (maximum absorption wavelength in dichloromethane 882 nm) represented by the following formula (n-1) was further used as compound (N) in Example 1, Under the same procedure and conditions, a single-layer substrate including a transparent resin substrate containing the compound (S) and the compound (Z) was obtained.

The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. The results are shown in Fig. 4 and Table 17.

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Example 1, and in the same manner as in Example 1, a dielectric multilayer film including 18 silica (SiO ₂ ) and titania (TiO ₂ ) layers was formed on both sides of the dielectric multilayer film. formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 5 and Table 17.

[Example 3]

In Example 3, an optical filter having a laminated base material having overcoat layers on both surfaces of a transparent resin substrate was created.

After preparing a transparent resin substrate in the same manner as in Example 2, a resin composition (1) for overcoat of the following composition was applied to one side of the obtained transparent resin substrate with a bar coater, and heated in an oven at 70° C. for 2 minutes, The solvent was removed by volatilization. At this time, the application|coating conditions of the bar coater were adjusted so that the thickness after drying might be set to 2 micrometers. Next, exposure (exposure amount 500 mJ/cm 2 , 200 mW) was performed using a conveyor type exposure machine, the resin composition for overcoat (1) was cured, and an overcoat layer was formed on the transparent resin substrate. Similarly, an overcoat layer containing the resin composition (1) for overcoating is also formed on the other side of the transparent resin substrate, and an overcoat layer is applied on both surfaces of the transparent resin substrate containing the compound (S) and the compound (Z). A laminated base material having

Resin composition for overcoat (1): 60 parts by mass of tricyclodecane dimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexylphenyl ketone, methyl ethyl ketone (solvent, solid content concentration) (TSC): 30%)

The spectral transmittance of this laminated base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. A result is shown in Table 17.

Subsequently, a dielectric multilayer film was designed using the same design parameters as in Example 1, and in the same manner as in Example 1, a dielectric multilayer film including 18 silica (SiO ₂ ) and titania (TiO ₂ ) layers on both surfaces. formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. A result is shown in Table 17.

[Example 4]

In Example 4, an optical filter having a laminated base material comprising a transparent resin substrate having an overcoat layer on both surfaces was created.

In Example 1, as the compound (Z), 0.15 parts by mass of the compound (z-2) represented by the following formula (z-2) (maximum absorption wavelength in dichloromethane: 825 nm) was further used as in Example 1 A transparent resin substrate containing compound (S) and compound (Z) was obtained under the same procedure and conditions.

Then, similarly to Example 3, an overcoat layer using the resin composition (1) was formed, and a laminated base material having an overcoat layer on both surfaces of the transparent resin substrate containing the compound (S) and the compound (Z) was obtained. The spectral transmittance of this laminated base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. The results are shown in Fig. 6 and Table 17.

Subsequently, a dielectric multilayer film (III) was formed on one side of the obtained laminated substrate, and a dielectric multilayer film (IV) was formed on the other side of the substrate to obtain an optical filter having a thickness of about 0.110 mm.

The dielectric multilayer film (III) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (18 layers in total). The dielectric multilayer film (IV) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (18 layers in total).

The dielectric multilayer films (III) and (IV) were designed in the same manner as in Example 1 except that the input parameters (target values) to the software were changed as shown in Table 3 below in Example 1.

As a result of film configuration optimization, in Example 1, in both dielectric multilayer films (III) and (IV), a silica layer having a film thickness of 33 to 213 nm and a titania layer having a film thickness of 24 to 133 nm are alternately laminated, the number of layers being 18 of the multilayer deposition film. Table 4 shows an example of the optimized film configuration.

About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 7 and Table 17.

[Example 5]

In Example 5, an optical filter provided with a laminated base material having overcoat layers on both surfaces of a transparent resin substrate was created.

Example 4, except that in Example 4, 0.02 parts by mass of the compound (n-2) represented by the following formula (n-2) (maximum absorption wavelength in dichloromethane of 1000 nm) was further used as the compound (N). A laminated base material having overcoat layers on both surfaces of a transparent resin substrate containing the compound (S) and the compound (Z) was obtained under the same procedure and conditions as described above.

The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. The results are shown in Fig. 8 and Table 17.

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Example 4, and in the same manner as in Example 4, a dielectric multilayer film including 18 silica (SiO ₂ ) and titania (TiO ₂ ) layers on both surfaces. formed.

About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 9 and Table 17.

[Example 6]

In Example 6, an optical filter provided with a laminated base material having an overcoat layer on both surfaces of a transparent resin substrate was created.

Under the same procedure and conditions as in Example 5, a laminated base material having overcoat layers on both surfaces of a transparent resin substrate containing compound (S), compound (Z) and compound (N) was obtained.

Then, a dielectric multilayer film (V) was formed on one side of the obtained substrate, and a dielectric multilayer film (VI) was formed on the other side of the substrate to obtain an optical filter having a thickness of about 0.105 mm.

The dielectric multilayer film V is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (8 layers in total). The dielectric multilayer film (VI) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (8 layers in total).

The dielectric multilayer films (V) and (VI) were designed in the same manner as in Example 1 except that the input parameters (target values) to the software in Example 1 were changed as shown in Table 5 below.

As a result of film configuration optimization, in Example 1, in both dielectric multilayer films (V) and (VI), a silica layer having a film thickness of 12 to 107 nm and a titania layer having a film thickness of 12 to 78 nm are alternately laminated, the number of layers being 18 of the multilayer deposition film. Table 6 shows an example of the optimized film configuration.

About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 10 and Table 17.

[Example 7]

In Example 7, an optical filter provided with a laminated base material having an overcoat layer on both surfaces of a transparent resin substrate was created.

Under the same procedure and conditions as in Example 5, a base material having overcoat layers on both surfaces of a transparent resin substrate containing compound (S), compound (Z) and compound (N) was obtained. In Example 7, this base material was used as it is as an optical filter, and evaluation of the optical characteristic in each wavelength range and the ghost and color shading of a camera image were performed similarly to Example 1. A result is shown in Table 17.

[Example 8]

In Example 8, an optical filter provided with a laminated base material having an overcoat layer on both surfaces of a transparent resin substrate was created.

0.04 parts by mass of compound (s-3) represented by the following formula (s-3) (maximum absorption wavelength in dichloromethane 739 nm) as compound (S) instead of compound (s-2) as compound (S) as compound (Z) ( In place of z-2), 0.02 parts by mass of compound (z-3) (maximum absorption wavelength in dichloromethane, 825 nm) represented by the following formula (z-3) was used, and the amount of compound (z-1) added was 0.12 parts by mass. A laminated base material having overcoat layers on both surfaces of a transparent resin substrate containing compound (S), compound (Z), and compound (N) was obtained under the same procedure and conditions as in Example 7 except that it was changed. In Example 8, this base material was used as it is as an optical filter, and evaluation of the optical characteristic in each wavelength range and the ghost and color shading of a camera image were performed similarly to Example 1. The results are shown in Fig. 11 and Table 17.

[Example 9]

In Example 9, the optical filter provided with the laminated base material which has the resin layer containing the compound (S) and the compound (Z) on both surfaces of the resin support body was created.

The resin A and methylene chloride obtained by the synthesis example 1 were added to the container, and the solution whose resin concentration is 20 mass % was obtained (namely, compound (S) and compound (Z) are not included). Except having used this solution, it carried out similarly to Example 1, and created the resin support body.

A resin layer containing a resin composition (A) having the following composition was formed on both surfaces of the obtained resin support in the same manner as in Example 3, and a resin layer containing a compound (S) and a compound (Z) on both surfaces. formed to obtain a laminated substrate.

The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. A result is shown in Table 17.

Resin composition (A): 100 parts by mass of tricyclodecanedimethanol acrylate, 4 parts by mass of 1-hydroxycyclohexylphenyl ketone, 1.0 parts by mass of compound (s-1), 2.0 parts by mass of compound (s-2), compound (z-1) 2.75 parts by mass, compound (z-2) 3.75 parts by mass, compound (n-2) 3.75 parts by mass, methyl ethyl ketone (solvent, TSC: 25%)

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Example 6, and in the same manner as in Example 6, a dielectric multilayer film including 8 silica (SiO ₂ ) and titania (TiO ₂ ) layers on both surfaces. formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. A result is shown in Table 17.

[Example 10]

In Example 10, the optical filter provided with the laminated|multilayer base material which has a resin layer containing a compound (S) and a compound (Z) on one side of a glass support body was created.

On a glass support "OA-10G (thickness 200 μm)" (manufactured by Nippon Denki Glass Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width, the resin composition (B) of the following composition was applied with a spin coater, and hot The solvent was removed by volatilization by heating at 80°C for 2 minutes on the plate. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying might be set to 4 micrometers. Next, exposure (exposure amount 500 mJ/cm 2 , 200 mW) is performed using a conveyor type exposure machine, the resin composition (B) is cured, and the single side of a glass support having a resin layer containing the compound (S) and the compound (Z) The laminated base material formed in was obtained.

The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. A result is shown in Table 17.

Resin composition (B): 20 parts by mass of tricyclodecane dimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexylphenyl ketone, 1.0 parts by mass of compound (s-1); 2.0 parts by mass of compound (s-2), 3.5 parts by mass of compound (z-1), 0.50 parts by mass of compound (n-1), methyl ethyl ketone (solvent, TSC: 35%)

Subsequently, a dielectric multilayer film (VII) was formed on one side of the obtained substrate, and a dielectric multilayer film (VIII) was formed on the other side of the substrate to obtain an optical filter having a thickness of about 0.105 mm.

The dielectric multilayer film (VII) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (8 layers in total). The dielectric multilayer film (VIII) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (8 layers in total).

The dielectric multilayer films (VII) and (VIII) were designed in the same manner as in Example 1 except that the input parameters (target values) to the software in Example 1 were changed as shown in Table 7 below.

As a result of film configuration optimization, in Example 10, in both dielectric multilayer films (VII) and (VIII), a silica layer having a film thickness of 12 to 104 nm and a titania layer having a film thickness of 12 to 76 nm are alternately laminated, the number of stacked 8 of the multilayer deposition film. Table 8 shows an example of the optimized film configuration.

About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. A result is shown in Table 17.

[Example 11]

In Example 11, the optical filter provided with the laminated base material which has a resin layer containing a compound (S) and a compound (Z) on one side of a glass support body was created.

A glass support having a resin layer containing the compound (S) and the compound (Z) in the same procedure and conditions as in Example 10, except that the resin composition (A) was used instead of the resin composition (B) in Example 10. A substrate containing

The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. A result is shown in Table 17.

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Example 6, and in the same manner as in Example 6, a dielectric multilayer film including 8 silica (SiO ₂ ) and titania (TiO ₂ ) layers on both surfaces. formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. A result is shown in Table 17.

[Examples 12 to 14]

In Examples 12 to 14, optical filters having a laminated base material having an overcoat layer on both surfaces of the transparent resin substrate were created.

In Example 6, except that the transparent resin species, solvent, and drying conditions were changed as described in Table 17, in the same procedure and conditions as in Example 6, having an overcoat layer on both sides, compound (S), compound ( A base material of a transparent resin substrate containing Z) and compound (N) was obtained.

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Example 6, and in the same manner as in Example 6, a dielectric multilayer film including 8 silica (SiO ₂ ) and titania (TiO ₂ ) layers on both surfaces. formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. A result is shown in Table 17.

[Comparative Example 1]

In Comparative Example 1, an optical filter having a substrate including a transparent resin substrate having an overcoat layer on both surfaces was prepared.

In Example 3, except that the compound (Z) and the compound (N) were not used, a base material including a transparent resin substrate having an overcoat layer on both surfaces was prepared in the same manner as in Example 3. The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. The results are shown in Fig. 12 and Table 17.

Subsequently, a dielectric multilayer film (IX) was formed on one surface of the obtained substrate, and a dielectric multilayer film (X) was formed on the other surface of the substrate, thereby obtaining an optical filter having a thickness of about 0.109 mm.

The dielectric multilayer film IX is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (18 layers in total). The dielectric multilayer film (X) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (28 layers in total).

The dielectric multilayer films (IX) and (X) were designed in the same manner as in Example 1 except that the input parameters (target values) to the software in Example 1 were changed as shown in Table 9 below.

As a result of film configuration optimization, in Comparative Example 1, the dielectric multilayer film (IX) is a multilayer deposited film having a stacking number of 18, in which a silica layer having a film thickness of 40 to 196 nm and a titania layer having a film thickness of 12 to 120 nm are alternately laminated, a dielectric The multilayer film (X) was a multilayer vapor deposition film having a laminate number of 28 in which silica layers having a film thickness of 15 to 534 nm and titania layers having a film thickness of 12 to 111 nm were alternately laminated. Table 10 shows an example of the optimized film configuration.

About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 13 and Table 17. The obtained optical filter was a result of a large incident angle dependence and inferior ghost and color shading.

[Comparative Example 2]

In Comparative Example 2, an optical filter having a substrate including a transparent resin substrate having an overcoat layer on both surfaces was prepared.

Under the same procedure and conditions as those of Comparative Example 1, a substrate including a transparent resin substrate containing the compound (S) having overcoat layers on both surfaces was obtained.

Subsequently, a dielectric multilayer film (XI) was formed on one side of the obtained substrate, and a dielectric multilayer film (XII) was formed on the other side of the substrate, thereby obtaining an optical filter having a thickness of about 0.110 mm.

The dielectric multilayer film XI is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (18 layers in total). The dielectric multilayer film (XII) is formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 100° C. (26 layers in total).

The dielectric multilayer films (XI) and (XII) were designed in the same manner as in Example 1 except that in Example 1, the input parameters (target values) to software were changed as shown in Table 11 below.

As a result of film configuration optimization, in Comparative Example 2, the dielectric multilayer film (XI) was a multilayer deposited film having a laminate number of 18, in which a silica layer having a film thickness of 33 to 213 nm and a titania layer having a film thickness of 24 to 133 nm were alternately laminated, a dielectric The multilayer film (XII) was a multilayer vapor deposition film having a laminate number of 26 in which a silica layer having a film thickness of 12 to 228 nm and a titania layer having a film thickness of 4 to 106 nm were alternately laminated. Table 12 shows an example of the optimized film configuration.

About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 14 and Table 17. The obtained optical filter was a result of a large incident angle dependence and inferior ghost and color shading.

[Comparative Example 3]

In Comparative Example 3, an optical filter having a substrate including a transparent resin substrate having an overcoat layer on both surfaces was prepared.

In Example 3, the addition amount of the compound (z-1) was 0.03 parts by mass, and the same procedure as in Example 3 was carried out except that the compound (N) was not used. A substrate comprising a transparent resin substrate having an overcoat layer on both sides was written. The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. The results are shown in Fig. 15 and Table 17.

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Comparative Example 1, and in the same manner as in Comparative Example 1, 18 silica (SiO ₂ ) layers, titania (TiO ₂ ) layers, and 28 silica (SiO ₂ ) layers ) layer and a dielectric multilayer film including a titania (TiO ₂ ) layer was formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 16 and Table 17.

[Comparative Example 4]

In Comparative Example 4, an optical filter having a substrate including a transparent resin substrate having an overcoat layer on both surfaces was prepared.

Under the same procedure and conditions as those of Comparative Example 3, a substrate including a transparent resin substrate containing a compound (S) and a compound (Z) having overcoat layers on both surfaces was obtained.

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Comparative Example 2, and in the same manner as in Comparative Example 2, 18 silica (SiO ₂ ) layers, titania (TiO ₂ ) layers, and 26 silica (SiO ₂ ) layers ) layer and a dielectric multilayer film including a titania (TiO ₂ ) layer was formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 17 and Table 17.

[Comparative Example 5]

In Comparative Example 5, an optical filter having a substrate including a transparent resin substrate having an overcoat layer on both surfaces was prepared.

In Example 3, except that the compound (S) and the compound (N) were not used, it carried out similarly to Example 3, and created the base material containing the transparent resin board|substrate which has an overcoat layer on both surfaces. The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. The results are shown in Fig. 18 and Table 17.

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Comparative Example 1, and in the same manner as in Comparative Example 1, 18 silica (SiO ₂ ) layers, titania (TiO ₂ ) layers, and 28 silica (SiO ₂ ) layers ) layer and a dielectric multilayer film including a titania (TiO ₂ ) layer was formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 19 and Table 17.

[Comparative Example 6]

In Comparative Example 6, an optical filter having a substrate including a transparent resin substrate having an overcoat layer on both surfaces was prepared.

Under the same procedure and conditions as those of Comparative Example 5, a substrate including a transparent resin substrate containing the compound (Z) having overcoat layers on both surfaces was obtained.

Subsequently, the dielectric multilayer film was designed using the same design parameters as in Comparative Example 2, and in the same manner as in Comparative Example 2, 18 silica (SiO ₂ ) layers, titania (TiO ₂ ) layers, and 26 silica (SiO ₂ ) layers ) layer and a dielectric multilayer film including a titania (TiO ₂ ) layer was formed. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 20 and Table 17.

[Example 15]

In Example 15, an optical filter having a single-layer substrate including a transparent resin substrate was prepared.

A transparent resin substrate containing compound (S) and compound (Z) was obtained under the same procedure and conditions as in Example 1.

The spectral transmittance of this base material was measured, and the average value of the transmittance|permeability in (Xa), (Xb), and a wavelength of 450-570 nm was calculated|required. A result is shown in Table 17.

Subsequently, a dielectric multilayer film was designed using the design parameters shown in Table 13 below, and a silica (SiO ₂ ) layer, a titania (TiO ₂ ) layer, and an Al ₂ O ₃ layer were alternately formed on both surfaces of the obtained substrate. A total of 18 stacked dielectric multilayer films (XIII) and multilayer dielectric films (XIV) were formed under the same deposition conditions as in the above example. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 21 and Table 17.

[Example 16]

In Example 16, an optical filter having a single-layer substrate including a transparent resin substrate was prepared.

A transparent resin substrate containing compound (S) and compound (Z) was obtained under the same procedure and conditions as in Example 15.

Subsequently, a dielectric multilayer film was designed using the design parameters in Table 14 below, and on both sides of the obtained substrate, a silica (SiO ₂ ) layer, and a Ta ₂ O ₅ layer and a layer Al ₂ O ₃ layer were alternately laminated. A total of 22 layers of a dielectric multilayer film (XV) and a dielectric multilayer film (XVI) were formed under the same deposition conditions as in the above example. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 22 and Table 17.

[Example 17]

In Example 17, an optical filter having a single-layer substrate including a transparent resin substrate was prepared.

A transparent resin substrate containing compound (S) and compound (Z) was obtained under the same procedure and conditions as in Example 15.

Subsequently, the dielectric multilayer film is designed using the design parameters in Table 15 below, and each of the 50 silica (SiO ₂ ) layers, Ta ₂ O ₅ layers, and titania (TiO ₂ ) layers shown in Table 15 below are included. A dielectric multilayer film (XVII) and a dielectric multilayer film (XVIII) were formed under the same deposition conditions as in the above example. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 23 and Table 17.

[Example 18]

In Example 18, an optical filter having a single-layer substrate including a transparent resin substrate was prepared.

A transparent resin substrate containing compound (S) and compound (Z) was obtained under the same procedure and conditions as in Example 16.

Subsequently, the dielectric multilayer film was designed using the design parameters in Table 16, and each of the 22 layers shown in Table 16 was a silica (SiO ₂ ) layer, a titania (TiO ₂ ) layer, an Al ₂ O ₃ layer, and a Ta ₂ O ₅ . Dielectric multilayer films (XIX) and (XX) including layers were formed on both surfaces under the same deposition conditions. About this optical filter, similarly to Example 1, evaluation of the optical characteristic in each wavelength range, and the ghost of a camera image, and color shading was performed. The results are shown in Fig. 24 and Table 17.

In the dielectric multilayer film XIX, a silica (SiO ₂ ) layer, a titania (TiO ₂ ) layer, and an Al ₂ O ₃ layer are alternately stacked to make a total of 22 layers. In the dielectric multilayer film XX, a silica (SiO ₂ ) layer, a Ta ₂ O ₅ layer, and an Al ₂ O ₃ layer are alternately stacked to obtain a total of 22 layers.

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

<Form of description>

ㆍAspect (1): Transparent resin substrate containing compound (S) and compound (Z)

-Aspect (2): A resin layer is provided on both surfaces of a transparent resin substrate containing a compound (S) and a compound (Z)

-Aspect (3): has a resin layer containing compound (S) and compound (Z) on both surfaces of a resin support body

-Aspect (4): has a resin layer containing compound (S) and compound (Z) on one surface of a glass support body

-Aspect (5): It has resin layers on both surfaces of the transparent resin board|substrate containing only compound (S) (comparative example)

-Aspect (6): It has resin layers on both surfaces of the transparent resin-made substrate containing only compound (Z) (comparative example)

<Transparent resin>

ㆍResin A: Cyclic olefin resin (resin synthesis example 1)

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

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

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

<Glass Support>

ㆍGlass support (1): Transparent glass support “OA-10G (thickness 200 μm)” cut to a size of 60 mm in length and 60 mm in width (manufactured by Nippon Denki Glass Co., Ltd.)

≪Compound (S)≫

ㆍCompound (s-1): a squarylium-based compound represented by the above formula (s-1) (maximum absorption wavelength in dichloromethane 711 nm)

ㆍCompound (s-2): a phthalocyanine-based compound represented by the formula (s-2) (maximum absorption wavelength in dichloromethane 736 nm)

ㆍCompound (s-3): a polymethine-based compound represented by the above formula (s-3) (maximum absorption wavelength in dichloromethane 739 nm)

≪Compound (Z)≫

ㆍCompound (z-1): a polymethine-based compound represented by the formula (z-1) (maximum absorption wavelength in dichloromethane 770 nm)

ㆍCompound (z-2): a polymethine-based compound represented by the above formula (z-2) (maximum absorption wavelength in dichloromethane: 825 nm)

ㆍCompound (z-3): a polymethine-based compound represented by the above formula (z-3) (maximum absorption wavelength in dichloromethane: 825 nm)

≪Compound (N)≫

ㆍCompound (n-1): a squarylium-based compound represented by the formula (n-1) (maximum absorption wavelength in dichloromethane 882 nm)

ㆍCompound (n-2): a metal dithiolene complex compound represented by the formula (n-2) (maximum absorption wavelength in dichloromethane: 1000 nm)

<solvent>

ㆍSolvent (1): methylene chloride

ㆍSolvent (2): N,N-dimethylacetamide

ㆍSolvent (3): cyclohexane/xylene (mass ratio: 7/3)

<Drying conditions for transparent resin substrate and resin support>

In Table 17, the drying conditions of the transparent resin board|substrate and resin support body of an Example and a comparative example are as follows. In addition, before drying under reduced pressure, the coating film was peeled from the glass plate.

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

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

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

<Composition for forming a resin layer>

The resin composition which forms the resin layer in the Example of Table 17 is as follows.

ㆍResin composition (1): 60 parts by mass of tricyclodecanedimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexylphenyl ketone, methyl ethyl ketone (solvent, TSC: 30 %)

-Resin composition (A): 100 parts by mass of tricyclodecanedimethanol acrylate, 4 parts by mass of 1-hydroxycyclohexylphenyl ketone, 1.0 parts by mass of compound (s-1), 2.0 parts by mass of compound (s-2); Compound (z-1) 2.75 parts by mass, compound (z-2) 3.75 parts by mass, compound (n-2) 3.75 parts by mass, methyl ethyl ketone (solvent, TSC: 25%)

-Resin composition (B): 20 parts by mass of tricyclodecanedimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexylphenyl ketone, 1.0 parts by mass of compound (s-1) , 2.0 parts by mass of compound (s-2), 3.5 parts by mass of compound (z-1), 0.50 parts by mass of compound (n-1), methyl ethyl ketone (solvent, TSC: 35%)

The optical filter of the present invention is a digital still camera, a smartphone camera, a mobile phone camera, a digital video camera, a wearable device camera, a PC camera, a surveillance camera, a car camera, a dark camera, a motion capture, a laser rangefinder, a virtual try-on , license plate recognition devices, televisions, car navigation systems, portable information terminals, personal computers, video game machines, portable game machines, fingerprint authentication systems, digital music players, and the like.

1: Optical filter or substrate
2: Spectrophotometer
3: light
111: camera image
112: white plate
113: Example of the central part of the white plate
114: Example of the end of the white plate

Claims (12)

As a base material having a resin layer comprising a resin and a dye,
The description satisfies the requirements of (a) and (b) below,
The resin layer contains a compound (S) having an absorption maximum at a wavelength of 620 to 760 nm, and a compound (Z) having an absorption maximum at a wavelength of 761 to 850 nm,
A substrate that transmits at least one of light in the visible region and light in the near-infrared region.
(a) In the region of wavelength 600 to 950 nm, the longest wavelength (Xa) at which the transmittance when measured in the vertical direction of the substrate is from more than 2% to 2% or less, and the transmittance when measured in the vertical direction of the substrate The difference of the shortest wavelength (Xb) from less than 2% to 2% or more is 80 nm or more.
(b) The average value of the transmittance|permeability at the time of measuring in the perpendicular|vertical direction of a base material in the area|region of wavelength 450-570 nm is 70 % or more. According to claim 1, wherein the compound (Z) is at least one compound selected from the group consisting of a squarylium-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, a cyanine-based compound, a croconium-based compound, and a polymethine-based compound person listing. The substrate according to claim 1, wherein two or more compounds (S) are contained in the resin layer. The resin according to claim 1, wherein the resin is a cyclic (poly)olefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a fluorene polycarbonate-based resin, a fluorene polyester-based resin, or a polycarbonate-based resin. , polyamide-based resin, polyarylate-based resin, polysulfone-based resin, polyethersulfone-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate-based resin, fluorinated aromatic polymer-based resin, (modified) acrylic resin A base material which is at least one selected from the group consisting of a resin, an epoxy-based resin, an allyl ester-based curable resin, a silsesquioxane-based UV-curable resin, an acrylic-based UV-curable resin, and a vinyl-based UV-curable resin. The base material of Claim 1 which has the said resin layer on a resin substrate or a glass substrate as a support body. The substrate according to claim 1, further comprising a compound (N) having an absorption maximum in a wavelength region of Xb+50nm to Xb+250nm. An optical filter having the substrate according to claim 1 and satisfying the following requirement (c).
(c) having a light-blocking band Za, a light-transmitting band Zb, and a light-blocking band Zc in a region having a wavelength of 600 nm or more, the central wavelength of each band being Za<Zb<Zc, measured in the direction perpendicular to the substrate in Za<Zb<Zc The minimum transmittance in one case is 1% or less, respectively, the maximum transmittance (Tb) when measured in the vertical direction of the substrate in Zb is 45% or more, and when measured in the vertical direction of the substrate in Zc The minimum transmittance is 15% or less, respectively. The optical filter according to claim 7, wherein the optical filter further satisfies the following requirement (d).
(d) On the long wavelength side of the light transmission band Zb, the value (Ye) of the shortest wavelength at which the transmittance measured in the vertical direction of the optical filter is half of the Tb, and 30° with respect to the vertical direction of the optical filter The absolute value |Ye-Yf| of the difference of the value (Yf) of the shortest wavelength at which the transmittance is half of the Tb when measured at an angle of |Ye-Yf| is less than 35 nm. The optical filter according to claim 7, wherein the substrate has a dielectric multilayer film on at least one surface side thereof. The optical filter according to claim 9, wherein the dielectric multilayer film is formed by alternately stacking different material layers, and the difference in refractive index between the material layers is 0.8 or less. A solid-state imaging device comprising the optical filter according to claim 7. A camera module provided with the optical filter of Claim 7.

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