KR20200128009A - Optical filters, camera modules and electronic devices - Google Patents

Abstract

An object of the present invention is to provide an optical filter that can achieve both suppression of color shading and suppression of ghosts in a camera image at a high level. The optical filter of the present invention satisfies the requirements (a) and (b): (a) a minimum value T _b-0 of the transmittance of light incident from the vertical direction in the region of wavelength 430 to 580 nm, and 30 with respect to the vertical direction. The minimum value T _b-30 of the transmittance of the light incident from the oblique direction and the minimum value T _b-60 of the transmittance of the light incident from the 60 degree oblique direction with respect to the vertical direction are both 55% or more and less than 90%; (b) In the region of wavelength 700 to 780 nm, the average value OD _{a -0} of the optical density for light incident from the vertical direction, and the average value OD _a of the optical density for light incident from the direction inclined at 30 degrees with respect to the vertical direction _{Both -30} and the average value OD _a-60 of the optical density for light incident from the oblique direction at 60 degrees with respect to the vertical direction are 1.8 or more.

Description

Optical filters, camera modules and electronic devices

The present invention relates to an optical filter, a camera module, and an electronic device. More specifically, it relates to an optical filter having specific optical properties, a camera module using the optical filter, and an electronic device having the camera module.

In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, CCDs and CMOS image sensors, which are solid-state imaging elements for color images, are used. As for these solid-state imaging devices, a silicon photodiode having sensitivity to near-infrared rays that cannot be detected by the human eye is used in the light receiving portion thereof. In these solid-state imaging devices, it is necessary to perform luminous sensitivity correction to give a natural color tone as seen by the human eye.Therefore, an optical filter (e.g., a near-infrared cut filter) that selectively transmits or cuts light in a specific wavelength range is sometimes used. many.

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

In Patent Document 2, the Applicant uses a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength region, so that even when the incident angle is changed, the change in optical properties is small, and the near-infrared ray having a high visible light transmittance. We are proposing a cut filter. In addition, Patent Document 3 describes the effect of obtaining a near-infrared cut filter in which a conventional problem of excellent visible light transmittance and a long wavelength of the absorption maximum wavelength can be achieved at a high level by using a phthalocyanine-based dye having a specific structure.

However, in the near-infrared cut filter described in Patent Documents 2 and 3, although the applied substrate has an absorption band of sufficient intensity in the vicinity of 700 nm, it hardly has absorption in the near-infrared wavelength region such as 900 to 1200 nm. Therefore, the light in the near-infrared wavelength region is cut almost only by reflection of the dielectric multilayer film, but in such a configuration, a slight stray light due to internal reflection in the optical filter or reflection between the optical filter and the lens is ghosting when shooting in a dark environment. There was a case that caused me flare. In particular, in recent years, even in mobile devices such as smartphones, high-definition cameras are strongly demanded, and there are cases where conventional optical filters cannot be used suitably.

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

In addition, although Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass substrate and a layer containing a near-infrared absorbing dye, the color shading could not be sufficiently improved even with the configuration described in Patent Document 5. For example, in Fig. 5 of Patent Document 5, optical characteristics graphs at 0 degrees and 30 degrees of incidence are shown, but even at 30 degrees of incidence, a large wavelength in the lower region of the visible light transmission band (630 to 700 nm) Shift is being observed.

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

In addition to the above-described problems, in recent years, for the purpose of further enhancing the performance of the camera module, a new module configuration in which the function of a conventional optical filter that combines absorption by a dye and reflection by a dielectric multilayer film is divided into separate members has also been studied. Also, an optical filter capable of coping with such a configuration is required.

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

The inventors of the present invention have studied intensively in order to solve the above problems, as a result of the minimum transmittance of the light incident from the vertical direction of the optical filter, the 30 degree oblique direction to the vertical direction, and the 60 degree oblique direction to the vertical direction in a specific wavelength region. All of these are in a specific range, and in a specific wavelength region, the average value of the optical density (OD value) for light incident from the vertical direction of the optical filter, the 30 degree oblique direction to the vertical direction, and the 60 degree oblique direction to the vertical direction It has been found that the target near-infrared cut characteristics, visible light transmittance, color shading suppression effect, and ghost suppression effect can be achieved by using optical filters in all of these specific ranges, and the present invention has been completed. Examples of aspects of the present invention are shown below.

[1] Optical filter meeting the following requirements (a) and (b):

(a) In a region with a wavelength of 430 to 580 nm, a minimum value T _b-0 of transmittance of light incident from the vertical direction of the optical filter, and a minimum value T _b-30 of transmittance of light incident from a direction inclined at 30 degrees with respect to the vertical direction , The minimum value T _b-60 of the transmittance of light incident from a direction inclined at 60 degrees with respect to the vertical direction is 55% or more and less than 90%;

(b) In the region of wavelength 700 to 780 nm, the average value OD _a-0 of the optical density for light incident from the vertical direction of the optical filter and the optical density for light incident from the direction inclined at 30 degrees with respect to the vertical direction Both the average value OD _a-30 and the average value OD _a-60 of the optical density for the light incident from the oblique direction at 60 degrees with respect to the vertical direction are 1.8 or more.

[2] The optical filter according to item [1], further meeting the following requirement (c):

(c) In a region having a wavelength of 900 to 1200 nm, the average value T _IR of the transmittance of light incident from the vertical direction of the optical filter is 60% or more.

[3] The optical filter according to item [1] or [2], further meeting the following requirement (d):

(d) In a region with a wavelength of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter, T _a-30 and the average value of the transmittance of light incident from the direction inclined at 30 degrees with respect to the vertical direction And the average value T _a-60 of the transmittance of light incident from the oblique direction at 60 degrees with respect to the vertical direction is 65% or more and less than 90%.

[4] The optical filter according to any one of items [1] to [3], comprising a substrate that satisfies the following requirement (e):

(e) It has a layer containing the compound (A) which has an absorption maximum in the range of wavelength 650-800 nm.

[5] The optical filter according to item [4], wherein the substrate further meets the following requirement (f):

(f) at a wavelength of 600 to 900nm, the transmittance of light incident from the perpendicular direction of the substrate, toward the long wavelength side from the short wavelength side wavelength of the long wavelength side is not more than 10% from a 10% excess of X _a and a base The absolute value |X _b -X _a | of the difference between the wavelength X _b on the shortest wavelength side at which the transmittance of the light incident from the vertical direction is from 10% or less to more than 10% from the short wavelength side toward the long wavelength side is 100 nm or more.

[6] Compound (A), characterized in that at least one compound selected from the group consisting of squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, chromium-based compounds, and cyanine-based compounds. The optical filter according to 4] or [5].

[7] The substrate is the compound (A), wherein the compound (Aa) has an absorption maximum in a region of 650 m or more and 715 nm or less, a compound (Ab) having an absorption maximum in a region of 715 nm or more and 750 nm or less, and a wavelength of 750 nm The optical filter according to any one of items [4] to [6], comprising a compound (Ac) having an absorption maximum in a region of more than 800 nm or less.

[8] The optical filter according to any one of items [4] to [7], wherein the layer containing the compound (A) is a transparent resin layer.

[9] The resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin. , Polyamide resin, aramid resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin , Epoxy resin, silsesquioxane UV curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyetheretherketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl The optical filter according to item [8], characterized in that it is at least one resin selected from the group consisting of ultraviolet-curable resins and resins containing as a main component silica formed by a sol-gel method.

[10] The optical filter according to item [8] or [9], wherein the refractive index (n20d) of the resin constituting the transparent resin layer is 1.50 to 1.53.

[11] A camera module comprising the optical filter according to any one of [1] to [10].

[12] The camera module according to item [10], having a cover member that protects the internal mechanism of the camera module from the outside, and the cover member has a near-infrared ray reflection function.

[13] An electronic device comprising the camera module according to item [10].

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

1 is a diagram showing a configuration in which a transmission spectrum is measured from a vertical direction, a direction of 30 degrees inclination, and a direction of 60 degrees inclination.
Fig. 2 is a schematic diagram showing the configuration of a camera module used for color shading evaluation performed in Examples and Comparative Examples.
3 is a schematic diagram for explaining evaluation of color shading of camera images performed in Examples and Comparative Examples.
4 is a schematic view for explaining ghost evaluation of camera images performed in Examples and Comparative Examples.
5 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG.
6 is a spectral transmission spectrum of the optical filter obtained in Example 2.
7 is a spectral transmission spectrum of the optical filter obtained in Example 3.
8 is a spectral transmission spectrum of the optical filter obtained in Example 4.
9 is a spectral transmission spectrum of the optical filter obtained in Example 5. FIG.
10 is a spectral transmission spectrum of the optical filter obtained in Example 6.
11 is a spectral transmission spectrum of the optical filter obtained in Example 7.
12 is a spectral transmission spectrum of the optical filter obtained in Example 8.
13 is a spectral transmission spectrum of the optical filter obtained in Example 9.
14 is a spectral transmission spectrum of the optical filter obtained in Example 10.
15 is a spectral transmission spectrum of the optical filter obtained in Example 11.
16 is a spectral transmission spectrum of the optical filter obtained in Example 15.
17 is a spectral transmission spectrum of the optical filter obtained in Example 16.
18 is a spectral transmission spectrum of an optical filter obtained in Comparative Example 1. FIG.
19 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 2.
20 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 3.
21 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 4.

Hereinafter, the optical filter according to the present invention, a camera module using the optical filter, and an electronic device having the camera module will be described in detail.

[Optical filter]

The optical filter of the present invention is characterized in that it satisfies the following requirements (a) and (b), and further preferably satisfies the following requirements (c) and/or (d).

(a) In a region with a wavelength of 430 to 580 nm, a minimum value T _b-0 of transmittance of light incident from the vertical direction of the optical filter, and a minimum value T _b-30 of transmittance of light incident from a direction inclined at 30 degrees with respect to the vertical direction And the minimum value T _b-60 of the transmittance of light incident from a direction inclined at 60 degrees with respect to the vertical direction is 55% or more and less than 90%.

(b) In the region of wavelength 700 to 780 nm, the average value OD _a-0 of the optical density for light incident from the vertical direction of the optical filter and the optical density for light incident from the direction inclined at 30 degrees with respect to the vertical direction Both the average value OD _a-30 and the average value OD _a-60 of the optical density for the light incident from the oblique direction at 60 degrees with respect to the vertical direction are 1.8 or more.

(c) In a region having a wavelength of 900 to 1200 nm, the average value T _IR of the transmittance of light incident from the vertical direction of the optical filter is 60% or more.

(d) In a region with a wavelength of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter, T _a-30 and the average value of the transmittance of light incident from the direction inclined at 30 degrees with respect to the vertical direction And the average value T _a-60 of the transmittance of light incident from the oblique direction at 60 degrees with respect to the vertical direction is 65% or more and less than 90%.

Each of the requirements will be described below.

<Requirement (a)>

The T _b-0 and T _b-30 are preferably 63% or more and 86% or less, more preferably 67% or more and 82% or less, and the T _b-60 is preferably 58% or more and 80% or less, More preferably, they are 60% or more and 75% or less.

As a method that satisfies the requirement (a), that is, a method of adjusting the minimum value of each transmittance, for example, a method of appropriately selecting and adjusting the type and amount of compound (A) described later so that the minimum value of the transmittance in the specified range is obtained. Can be lifted.

By satisfying the requirement (a), since the change in the RGB balance is small even at the time of incidence at a high angle of 30 degrees or 60 degrees of incidence, a high-quality camera image can be obtained.

<Requirement (b)>

The OD _a-0 and the OD _a-30 are preferably 1.8 or more and 4.0 or less, more preferably 1.9 or more and 3.5 or less, and the OD _a-60 is preferably 2.1 or more and 4.5 or less, more preferably 2.2 or more Less than 4.0

As a method that satisfies the requirement (b), that is, as a method of adjusting the average value of the optical density (OD value), for example, the type and amount of the compound (A) described later are appropriately selected so that the average value of the transmittance in the specified range is obtained, and How to adjust is mentioned.

By satisfying the requirement (b), the optical filter can sufficiently cut not only the near infrared rays transmitted in the vertical direction but also the near infrared rays transmitted at a high angle of incidence, so that a camera image with no or reduced color shading can be obtained.

Here, the OD value is a common logarithmic value of the transmittance, and can be calculated by the following formula (1). When the average OD value in the specified wavelength range is high, the optical filter indicates that the optical filter has high light cutting characteristics in the wavelength range.

Average OD value in a certain wavelength range = -Log ₁₀ (average transmittance in a certain wavelength range (%)/100)... Equation (1)

<Requirement (c)>

The T _IR is preferably 70% to 98%, more preferably 80% to 95%, still more preferably 85% to 94%, particularly preferably 89% to 93%.

As a method of satisfying the requirement (c), i.e., a method of adjusting the average value of the transmittance of light, for example, a method of appropriately selecting and adjusting the type and amount of compound (A) described below so that the transmittance in the specified range is obtained. .

By satisfying the requirement (c), since the transmittance in the near-infrared region is high and reflected light in the near-infrared region can be reduced, a camera image with reduced ghost can be obtained.

<Requirement (d)>

The T _a-0 is preferably 73% or more and 88% or less, more preferably 76% or more and 86% or less, and the T _a-30 is preferably 72% or more and 87% or less, more preferably 75% It is more than 85%, and said T _a-60 becomes like this. Preferably it is 68% or more and 85% or less, More preferably, it is 70% or more and 80% or less.

As a method that satisfies the requirement (d), that is, how to adjust the average value of each transmittance, for example, a method of appropriately selecting and adjusting the type and amount of compound (A) described below so that the average value of the transmittance in the specified range is obtained. Can be lifted.

By satisfying the requirement (d), a high-quality camera image can be obtained because the change in the RGB balance is small even at a high angle incident of 30 degrees or 60 degrees of incidence.

<The thickness of the optical filter>

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

[materials]

The configuration of the optical filter of the present invention is not particularly limited as long as an optical filter exhibiting the above-described optical properties is obtained, but it is preferable to include a substrate that satisfies the following requirement (e), and the substrate further includes the following requirement (f) It is desirable to meet.

(e) It has a layer containing the compound (A) which has an absorption maximum in the range of wavelength 650-800 nm.

(f) at a wavelength of 600 to 900nm, the transmittance of light incident from the perpendicular direction of the substrate, toward the long wavelength side from the short wavelength side wavelength of the long wavelength side is not more than 10% from a 10% excess of X _a and a base The absolute value |X _b -X _a | of the difference between the wavelength X _b on the shortest wavelength side at which the transmittance of the light incident from the vertical direction is from 10% or less to more than 10% from the short wavelength side toward the long wavelength side is 100 nm or more.

Each of the requirements will be described below.

<Requirement (e)>

In the requirement (e), the component constituting the layer containing the compound (A) is not particularly limited, and examples thereof include a transparent resin, a sol-gel material, a low-temperature curing glass material, etc., but are easy to handle or a compound It is preferable that it is a transparent resin from a viewpoint of compatibility with (A).

As long as the substrate has a layer containing the compound (A), it may be a single layer or a multilayer.

<Requirement (f)>

The difference |X _b -X _a | between the wavelengths X _a and X _b is preferably 110 nm or more, more preferably 115 nm or more, still more preferably 120 nm or more, and particularly preferably 125 nm or more. The upper limit is not particularly limited, but depending on the properties of the compound (A) and other near-infrared absorbers, if the value is too large, the visible light transmittance may decrease, so it is preferably 300 nm or less, for example. If the difference |X _b -X _a | is in the above range, the absorption band of sufficient intensity (width) in the near-infrared wavelength region close to the visible region is obtained, for example, an incident angle such as 30 degrees or 60 degrees of incidence. This is preferable because color shading can be suppressed even under a large condition.

The value of the wavelength between X _a and X _b (X _a +X _b )/2 can be said to be the center wavelength of the absorption band in the near-infrared wavelength region close to the visible region, preferably 650 nm or more and 850 nm or less, More preferably, it is 680 nm or more and 820 nm or less, More preferably, it is 700 nm or more and 800 nm or less. When the value of the wavelength represented by (X _a +X _b )/2 is in the above range, light in the wavelength region near the long wavelength end of the visible region can be more efficiently cut, which is preferable.

The X _a is preferably a wavelength of 610 nm or more and 720 nm or less, more preferably a wavelength of 625 nm or more and 710 nm or less, and still more preferably a wavelength of 630 nm or more and 700 nm or less. When X _a is in such a range, it is preferable because there is little noise and a camera image having excellent color reproducibility tends to be obtained.

<Substrate thickness>

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

≪Compound (A)≫

Compound (A) is not particularly limited as long as it has an absorption maximum in the range of wavelength 650 to 800 nm, but at least selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, chromonium compounds and cyanine compounds. It is preferable that it is one type of compound, and especially a squarylium type compound, a phthalocyanine type compound, and a cyanine type compound are preferable. In addition, compound (A) may be used individually by 1 type, and may be used in combination of 2 or more types.

Although the squarylium-based compound has excellent visible light transmittance, a sharp absorption property, and a high molar extinction coefficient, when absorbing light, it may generate fluorescence, which causes scattered light. In such a case, by using a squarylium-based compound and other compounds (A) in combination, it is possible to obtain an optical filter with less scattered light and better camera image quality.

The maximum absorption wavelength of the compound (A) is preferably 660 nm or more and 795 nm or less, and more preferably 680 nm or more and 790 nm or less.

Compound (A) is not particularly limited as long as it has an absorption maximum in a region of 650 to 800 nm, but from the viewpoint of heat resistance of an optical filter, a compound (Aa) having an absorption maximum in a region of 650 nm or more and 715 nm or less, with a wavelength of more than 715 nm and 750 nm It is more preferable to each contain at least one compound (Ab) having an absorption maximum in the following region and a compound (Ac) having an absorption maximum in a region of more than 750 nm and not more than 800 nm in wavelength. When compound (A) has such a configuration, it is possible to effectively widen the near-infrared absorption band while keeping the decrease in visible light transmittance to a minimum, and to improve heat resistance and weather resistance by the intermolecular interaction of compounds (A). It tends to exist, so it is preferable.

When the compound (A) is a combination of two or more compounds, the difference between the maximum absorption wavelength between the shortest absorption maximum wavelength and the longest absorption maximum wavelength among the applied compounds (A) is preferably 20 to 100 nm, more preferably Is 30 to 90 nm, more preferably 40 to 80 nm. When the difference in the maximum absorption wavelength is within the above range, it is preferable because it is possible to sufficiently reduce the scattered light by fluorescence, and to achieve both a wide absorption band near 700 nm and excellent visible light transmittance.

The content of the entire compound (A) includes, for example, a substrate including a transparent resin substrate containing the compound (A) or a curable resin on a transparent resin substrate containing the compound (A). In the case of using a substrate on which a resin layer such as an overcoat layer is laminated, preferably 0.04 to 2.0 parts by mass, more preferably 0.06 to 1.5 parts by mass, even more preferably 0.08 to 1.0 parts by mass, based on 100 parts by mass of the transparent resin. When using a substrate in which a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) or the like is laminated on a support such as a glass support or a resin support serving as the base as the substrate. To, with respect to 100 parts by mass of the resin forming the transparent resin layer containing the compound (A), preferably 0.4 to 5.0 parts by mass, more preferably 0.6 to 4.0 parts by mass, still more preferably 0.8 to 3.5 parts by mass. .

(Squararylium compound)

The squarylium-based compound is not particularly limited, but at least one compound selected from the group consisting of a squarylium-based compound represented by the following formula (I) and a squarylium-based compound represented by the following formula (II) is preferred. Do. Hereinafter, they are also referred to as "Compound (I)" and "Compound (II)", respectively.

In formula (I), R ^a , R ^b and Ya satisfy the following condition (α) or (β).

Condition (α):

A plurality of R ^a each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or -NR ^e R ^f group;

A plurality of R ^b each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or -NR ^g R ^h group;

A plurality of Ya each independently represents a -NR ^j R ^k group;

L ¹ represents L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h ;

R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;

R ^g and R ^h are each independently a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or a -C(O)R ⁱ group (R ⁱ is -L ^a , -L ^b , -L ^c , -L ^d or -L ^e are represented);

R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;

L ^a represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L;

L ^b represents a halogen-substituted alkyl group having 1 to 12 carbon atoms which may have a substituent L;

L ^c represents an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L;

L ^d represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L;

L ^e represents a heterocyclic group having 3 to 14 carbon atoms which may have a substituent L;

L ^f represents an alkoxy group having 1 to 9 carbon atoms which may have a substituent L;

L ^g represents an acyl group having 1 to 9 carbon atoms which may have a substituent L;

L ^h represents an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L;

L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, It represents at least one substituent selected from the group consisting of a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group and an amino group.

Condition (β):

At least one of two R ^a on one benzene ring is bonded to each other with Y on the same benzene ring to form a 5 or 6 heterocycle including at least one nitrogen atom;

The heterocycle may have a substituent, and R ^b and R ^a not involved in the formation of the heterocycle each independently have the same meaning as R ^b and R ^a in the condition (α).

The total number of carbon atoms including the substituents for L ^a to L ^h is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the number of carbon atoms is more than this range, synthesis of the compound may be difficult, and the absorption intensity of light per unit mass tends to decrease.

Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms in L ^a and L include methyl group (Me), ethyl group (Et), n-propyl group (n-Pr), isopropyl group (i-Pr), Alkyl groups such as n-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, decyl group and dodecyl group ; Alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group and octenyl group; And alkynyl groups, such as an ethynyl group, a propynyl group, a butynyl group, a 2-methyl-1-propynyl group, a hexynyl group, and an octinyl group, are mentioned.

Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms in L ^b and L include trichloromethyl group, trifluoromethyl group, 1,1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group, and heptachloropropyl group. And a heptafluoropropyl group.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in L ^c and L include cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; And polycyclic alicyclic groups such as norbornane group and adamantane group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L ^d and L include phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, A phenanthryl group, an acenaphthyl group, a phenalenyl group, a tetrahydronaphthyl group, an indanyl group, and a biphenylyl group are mentioned.

Examples of the heterocyclic group having 3 to 14 carbon atoms in L ^e and L include furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, Indole, indoline, indolenine, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, acridine, morpholine and phena Groups containing heterocycles, such as gin, are mentioned.

Examples of the alkoxy group having 1 to 12 carbon atoms in L ^f include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, and octyloxy group. I can.

Examples of the acyl group having 1 to 9 carbon atoms in L ^g include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

Examples of the alkoxycarbonyl group having 1 to 9 carbon atoms in L ^h include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group and octyloxycarbonyl group. Can be mentioned.

The L ^a is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 4-phenylbutyl group, 2-cyclohexylethyl, more preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

The L ^b is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, and more preferably a trichloroethyl group. These are lomethyl group, pentachloroethyl group, trifluoromethyl group, and pentafluoroethyl group.

The L ^c is preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group, and a 4-phenylcycloheptyl group, more preferably a cyclopentyl group, a cyclohexyl group, It is a 4-ethylcyclohexyl group.

The L ^d is preferably a phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 3,5-di-tert-butylphenyl group, 4-cyclopentylphenyl group, 2 ,3,6-triphenylphenyl group, 2,3,4,5,6-pentaphenylphenyl group, more preferably phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,3,4,5 ,6-pentaphenylphenyl group.

The L ^e is preferably a group containing furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, and morpholine, and more preferably furan, thiophene, pyrrole, morpholine. It is a group containing.

The L ^f is preferably a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, methoxymethyl group, methoxyethyl group, 2-phenylethoxy group, 3-cyclohexylpropoxy group, pentyloxy group It is a group, a hexyloxy group, and an octyloxy group, More preferably, they are a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

The L ^g is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, and a trifluoromethylcarbonyl group, more preferably an acetyl group, a propionyl group, or a benzoyl group. to be.

The L ^h is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, and a 2-phenylethoxycarbonyl group, and more preferably It is a methoxycarbonyl group and an ethoxycarbonyl group.

The L ^a to L ^h may further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group and an amino group. Such examples include 4-sulfobutyl group, 4-cyanobutyl group, 5-carboxypentyl group, 5-aminopentyl group, 3-hydroxypropyl group, 2-phosphorylethyl group, 6-amino-2,2-dichlorohex Sil group, 2-chloro-4-hydroxybutyl group, 2-cyanocyclobutyl group, 3-hydroxycyclopentyl group, 3-carboxycyclopentyl group, 4-aminocyclohexyl group, 4-hydroxycyclohexyl group , 4-hydroxyphenyl group, pentafluorophenyl group, 2-hydroxynaphthyl group, 4-aminophenyl group, 4-nitrophenyl group, group containing 3-methylpyrrole, 2-hydroxyethoxy group, 3-cyanop A lopoxy group, a 4-fluorobenzoyl group, a 2-hydroxyethoxycarbonyl group, and a 4-cyanobutoxycarbonyl group are mentioned.

R ^a in the above condition (α) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. , A cyclohexyl group, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, and a nitro group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a hydroxyl group.

R ^b in the above condition (α) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. , Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t- Butanoylamino group, cyclohexinoylamino group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group, dimethylamino group, nitro group, acetylamino group, propionyl They are an amino group, a trifluoromethanoylamino group, a pentafluoroethanoylamino group, a t-butanoylamino group, and a cyclohexinoylamino group.

As the Ya, preferably, an amino group, methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-t-butylamino group, N-ethyl-N- Methylamino group, N-cyclohexyl-N-methylamino group, more preferably dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-t-butylamino group to be.

The number of constituent atoms including at least one nitrogen atom 5 formed by bonding of at least one of two R ^a on one benzene ring to Y on the same benzene ring in condition (β) of the above formula (I) Alternatively, examples of the 6 heterocycle include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, and pyrazine. Among these heterocycles, a heterocycle constituting the heterocycle and in which one adjacent carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

In formula (II), X independently represents O, S, Se, NR ^c or C(R ^d R ^d ); A plurality of R ^c each independently represents a hydrogen atom, L ^a , L ^b , L ^c , L ^d or L ^e ; Each of a plurality of R ^d independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or -NR ^e R ^f group, and adjacent R ^d groups are connected to each other to form a substituent. You may form a ring which you may have; L ^a to L ^e , L ¹ , R ^e and R ^f have the same meaning as L ^a to L ^e , L ¹ , R ^e and R ^f defined in the above formula (I).

R ^c in the formula (II) is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n- They are a hexyl group, a cyclohexyl group, a phenyl group, a trifluoromethyl group, and a pentafluoroethyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

R ^d in the formula (II) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and n -Pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, 4-aminocyclohexyl group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group , Ethyl group, n-propyl group, isopropyl group, trifluoromethyl group, and pentafluoroethyl group.

The X is preferably O, S, Se, N-Me, N-Et, CH ₂ , C-Me ₂ , C-Et ₂ , more preferably S, C-Me ₂ , C-Et ₂ .

In the above formula (II), adjacent R ^{d may be} connected to each other to form a ring. Examples of such rings include benzoindolenine ring, α-naphthoimidazole ring, β-naphthoimidazole ring, α-naphthooxazole ring, β-naphthooxazole ring, α-naphthothiazole ring, β-naph Tothiadiazole ring, α-naphthoselenazole ring, and β-naphthoselenazole ring are mentioned.

Compound (I) and compound (II) resonate as in the following formula (I-2) and the following formula (II-2) in addition to the description method such as the following formula (I-1) and the following formula (II-1) The structure can also be represented by the method of describing the structure. That is, the difference between the following formula (I-1) and the following formula (I-2) and the difference between the following formula (II-1) and the following formula (II-2) are only the description method of the structure, and both represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium-based compound is represented by a method described in the following formula (I-1) and the following formula (II-1).

In addition, for example, the compound represented by the following formula (I-3) and the compound represented by the following formula (I-4) can be regarded as the same compound.

The structures of the compounds (I) and (II) are not particularly limited as long as they satisfy the requirements of the formulas (I) and (II), respectively. For example, in the case of showing the structure as in the above formulas (I-1) and (II-1), the left and right substituents bonded to the central 4-membered ring may be the same or different, but the same is easier for synthesis. desirable.

As specific examples of the compounds (I) and (II), compounds (a-1) to (a-36) shown in Tables 1 to 3 below having a basic skeleton represented by the following formulas (IA) to (IH) Can be lifted.

[표 1]

[Table 1]

[Table 2]

[Table 3]

The compounds (I) and (II) may be synthesized by a generally known method, for example, Japanese Patent Laid-Open No. 1-228960, Japanese Patent Laid-Open No. 2001-40234, Japanese Patent No. 3196383, etc. It can be synthesized with reference to the described method or the like.

(Phthalocyanine compound)

The phthalocyanine-based compound is not particularly limited, but is preferably a compound represented by the following formula (III) (hereinafter also referred to as "compound (III)").

In formula (III), M represents a substituted metal atom including two hydrogen atoms, two monovalent metal atoms, divalent metal atoms, or trivalent or tetravalent metal atoms, and a plurality of R _a , R _b , R _c and R _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , or _a combination of at least one of R _a and R _b , R _b and R _c and R _c and R _d is combined, represented by the following formulas (A) to (H) It represents at least one group selected from the group consisting of However, at least one of R _a , R _b , R _c and R _d bonded to the same aromatic ring is not a hydrogen atom.

The amino group, amide group, imide group and silyl group may have a substituent L defined in the formula (I),

L ¹ has the same meaning as L ¹ defined in the formula (I),

L ² represents a hydrogen atom or any of L ^a to L ^e defined in the formula (I),

L ³ represents a hydroxyl group or any of the above L ^a to L ^e ,

L ⁴ represents any of the above L ^a to L ^e .

In formulas (A) to (H), R _x and R _y represent a carbon atom, and a plurality of R _A to R _L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, an imide group , Cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , and the amino group, amide group, imide group and silyl group are represented by the above formula ( You may have the substituent L defined in I), and L ¹ to L ⁴ have the same meaning as L ¹ to L ⁴ defined in the formula (III).

Examples of the amino group which may have a substituent L in R _a to R _d and R _A to R _L include an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group, and a diisopropylamino group.

Examples of the amide group which may have a substituent L in R _a to R _d and R _A to R _L include an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, and a diisopropylamide group. , A dibutylamide group, an α-lactam group, a β-lactam group, a γ-lactam group, and a δ-lactam group.

Examples of the imide group which may have a substituent L in R _a to R _d and R _A to R _L include an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, and a di An isopropylimide group, a dibutylimide group, etc. are mentioned.

Examples of the silyl group which may have a substituent L in R _a to R _d and R _A to R _L include trimethylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, triethylsilyl group, and the like.

In the above R _a to R _d and R _A to R _L , -SL ^{2 is a} thiol group, methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, isobutyl sulfide group, sec- Butyl sulfide group, tert-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butylphenyl sulfide group, 2,6-diphenylphenyl sulfide group, 4-cumylphenyl sulfide group, etc. Can be mentioned.

In the above R _a to R _d and R _A to R _L , -SS-L ^{2 is a} disulfide group, a methyl disulfide group, an ethyl disulfide group, a propyl disulfide group, a butyl disulfide group, an isobutyl disulfide group , sec-butyldisulfide group, tert-butyldisulfide group, phenyldisulfide group, 2,6-di-tert-butylphenyldisulfide group, 2,6-diphenylphenyldisulfide group, 4-cumylphenyldisulfide group Feeder, etc. are mentioned.

Examples of -SO ₂ -L ^{3 in} R _a to R _d and R _A to R _L include a sulfo group, a mesyl group, an ethylsulfonyl group, an n-butylsulfonyl group, and a p-toluenesulfonyl group.

Examples of -N=NL ^{4 in} R _a to R _d and R _A to R _L include a methylazo group, a phenylazo group, a p-methylphenylazo group, and a p-dimethylaminophenylazo group.

Examples of the monovalent metal atom for M include Li, Na, K, Rb, Cs, and the like.

Examples of the divalent metal atoms in M include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, Hg, Sn, Pb, etc. Can be mentioned.

Examples of the substituted metal atoms containing a trivalent metal atom in M include Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga-I, In- F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH, and the like.

As the substituted metal atom containing a tetravalent metal atom in M, TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , ZrCl ₂ , HfCl ₂ , CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , SnI ₂ , Zr(OH) ₂ , Hf(OH) ₂ , Mn(OH) ₂ , Si(OH) ₂ , Ge(OH ) ₂ , Sn(OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , GeR ₂ , SnR ₂ , Ti(OR) ₂ , Cr(OR) ₂ , Si(OR) ₂ , Ge(OR) ₂ , Sn( OR) ₂ (R represents an aliphatic group or an aromatic group), TiO, VO, MnO, etc. are mentioned.

The M is preferably a divalent transition metal, a trivalent or tetravalent metal halide, or a tetravalent metal oxide belonging to groups 5 to 11 of the periodic table, and period 4 to 5, and among them, high visible light transmittance or In view of achieving stability, Cu, Ni, Co and VO are particularly preferred.

The method of synthesizing the phthalocyanine-based compound by cyclization reaction of a phthalonitrile derivative as shown in the following formula (V) is generally known, but the phthalocyanine-based compound obtained is as shown in the following formulas (VI-1) to (VI-4). It is a mixture of four isomers. In the present invention, unless otherwise specified, only one isomer is exemplified for one phthalocyanine compound, but the other three isomers can also be used in the same manner. In addition, although these isomers may be used separately as necessary, in the present invention, isomer mixtures are collectively handled.

Specific examples of the compound (III) include (b-1) to (b-56) shown in Tables 4 to 7 below, which have a basic skeleton represented by the following formulas (III-A) to (III-J). Can be lifted.

[Table 4]

[Table 5]

[Table 6]

[Table 7]

Compound (III) can be synthesized by a generally known method, and for example, it can be synthesized by referring to the method described in Japanese Patent No. 4081149 or ``phthalocyanine-chemistry and function -'' (IPC, 1997). have.

(Cyanine compound)

The cyanine compound is not particularly limited, but is a compound represented by any one of the following formulas (IV-1) to (IV-3) (hereinafter also referred to as ``compounds (IV-1) to (IV-3)'') It is desirable.

In formulas (IV-1) to (IV-3), X _a ^- represents a monovalent anion, a plurality of D independently represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and a plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, Silyl group, -L ¹ , -SL ² , -SS-L ³ , -SO ₂ -L ³ , -N=NL ⁴ , or R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h, and at least one group selected from the group consisting of groups represented by the formulas (A) to (H) in which at least one combination of R _h and R _i is bonded, and the The amino group, amide group, imide group and silyl group may have a substituent L defined in the above formula (I),

L ¹ has the same meaning as L ¹ defined in the formula (I),

L ² represents a hydrogen atom or any of L ^a to L ^e defined in the formula (I),

L ³ represents a hydrogen atom or any of the above L ^a to L ^e ,

L ⁴ represents any of the above L ^a to L ^e ,

Z _a to Z _c and Y _a to Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , _{^{-SS-L 2, -SO 2 -L}} 3, -N = NL 4 (L 1 to L ⁴ are as defined above R _a to R _i in the L ¹ to L ^4), or two adjacent of which An aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding of Z or Y selected from each other; 5-6 membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, oxygen atom, or sulfur atom; Or a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms containing at least one nitrogen atom, an oxygen atom or a sulfur atom, and these aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic hydrocarbon groups are aliphatic hydrocarbon groups having 1 to 9 carbon atoms or halogen You may have an atom.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding of Z or Y to each other in Z _a to Z _c and Y _a to Y _d include, for example, in the aromatic hydrocarbon group in the substituent L The exemplified compound is mentioned.

_A 5-6 membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, an oxygen atom, or a sulfur atom formed by bonding of Z or Y to each other in the above Z _a to Z _c and Y _a to Y _d Examples of examples include the alicyclic hydrocarbon group in the substituent L and the compound (excluding the heteroaromatic hydrocarbon group) exemplified by the heterocycle.

Examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding of Z or Y to each other in Z _a to Z _c and Y _a to Y _d include, for example, as a heterocyclic group in the substituent L The exemplified compounds (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom, or sulfur atom) are mentioned.

In the formulas (IV-1) to (IV-3), -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , an amino group, an amide group which may have a substituent L, Examples of the imide group and silyl group include groups similar to the groups exemplified by the above formula (III).

X _a ^- is when a monovalent anion is not particularly ^{limited, I -, Br -, PF} 6 -, N (SO 2 CF 3) 2 -, B (C 6 F 5) 4 -, a nickel dithiol-rate-based complex, Copper dithiolate-based complexes, etc. are mentioned.

Specific examples of the compounds (IV-1) to (IV-3) include (c-1) to (c-24) shown in Table 8 below.

[Table 8]

The compounds (IV-1) to (IV-3) may be synthesized by a generally known method, and can be synthesized, for example, by a method described in Japanese Patent Laid-Open No. 2009-108267.

<Transparent resin>

The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, in order to ensure thermal stability and moldability into a film, the glass transition temperature (Tg) is preferably 110 to 380 C, more preferably 110 to 370°C, and still more preferably 120 to 360°C. Further, in order to be suitable for a reflow step, the glass transition temperature of the resin is preferably 140°C or higher, and more preferably 230°C or higher.

It is particularly preferable that the refractive index (n20d) of the transparent resin is 1.53 or less. Transparent resins with a refractive index (n20d) of more than 1.53 tend to have many aromatic rings in the molecule, but in the resin of this structure, the interaction with the π conjugated system in the compound (A) molecule is too strong to deteriorate the weather resistance. have.

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

The 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 to 250,000, and the number average molecular weight (Mn) is usually 10,000 to 150,000, It is preferably 20,000 to 100,000.

As transparent resin, for example, cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin , Aramid resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, Silsesquioxane-based UV-curable resin, maleimide-based resin, alicyclic epoxy thermosetting resin, polyetheretherketone-based resin, polyarylate-based resin, allyl ester-based curable resin, acrylic UV-curable resin, vinyl-based UV-curable resin, and Resins containing as a main component silica formed by the sol-gel method are mentioned. Among these, cyclic polyolefin resins, aromatic polyether resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polyarylate resins are used for transparency (optical properties) and heat resistance. It is preferable from the viewpoint of obtaining an optical filter excellent in balance such as reflow resistance and the like, and a cyclic polyolefin resin is particularly preferable from the viewpoint of the refractive index of the resin. The transparent resin may be used individually by 1 type, and may be used in combination of 2 or more types.

≪Cycle polyolefin resin≫

As the cyclic polyolefin resin, a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ), and a resin obtained by hydrogenating the resin Resin is preferred.

In formula (X ₀ ), R ^x1 to R ^x4 each independently represent an atom or group selected from the following (i') to (ix'), and k ^x , m ^x and p ^x are each independently of 0 to 4 Represents an integer.

(i') hydrogen atom

(ii') halogen atom

(iii') trialkylsilyl group

(iv') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom

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

(vi') polar group (except (ii') and (iv'))

(vii') an alkylidene group formed by bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other (however, R ^x1 to R ^x4 not involved in the bond are each independently of the above (i') to (vi' ) Represents an atom or group selected from)

(viii') A monocyclic or polycyclic hydrocarbon ring or heterocycle formed by bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other (however, R ^x1 to R ^x4 not involved in the bond are each independently of the above (i Represents an atom or group selected from') to (vi'))

(ix') a monocyclic hydrocarbon ring or heterocycle formed by bonding of R ^x2 and R ^x3 to each other (however, R ^x1 and R ^x4 not involved in the bond are each independently from (i') to (vi') above Represents the selected atom or group)

In formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i') to (vi'), or a monocyclic or polycyclic alicyclic ring formed by bonding of R ^y1 and R ^y2 to each other Represents a hydrocarbon, an aromatic hydrocarbon or a heterocycle, and k ^y and p ^y each independently represent an integer of 0 to 4.

≪Aromatic polyether resin≫

It is preferable that the aromatic polyether resin has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

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

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

In addition, it is preferable that the aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). .

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

Expression (4) ^{of, R 7, R 8, Y} , m, g , and h is the same meanings as ^{R 7, R 8, Y,} m, g , and h of each independently represents the formula (2), R ^5, R ⁶ , Z, n, e and f each independently have the same meaning as R ⁵ , R ⁶ , Z, n, e and f in the above formula (3).

≪Polyimide resin≫

The polyimide resin is not particularly limited, and may be a polymer compound containing an imide bond in the repeating unit, for example, as described in Japanese Patent Laid-Open No. 2006-199945 or Japanese Patent Laid-Open No. 2008-163107. It can be synthesized by the method.

≪Fluorene polycarbonate resin≫

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

≪Fluorene polyester resin≫

The fluorene polyester resin is not particularly limited, and may be a polyester resin containing a fluorene moiety, and is described in Japanese Patent Laid-Open No. 2010-285505 or Japanese Patent Laid-Open No. 2011-197450, for example. It can be synthesized by the method.

≪Fluorinated aromatic polymer resin≫

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

≪Acrylic UV-curable resin≫

Although it does not specifically limit as an acrylic ultraviolet curable resin, What is synthesize|combined from a resin composition containing a compound which has one or more acrylic groups or methacrylic groups in a molecule|numerator, and a compound which decomposes by ultraviolet rays to generate an active radical is mentioned. The acrylic ultraviolet-curable resin is a substrate in which a transparent resin layer containing a compound (A) and a curable resin is laminated on a glass support or on a resin support serving as a base, or a transparent resin substrate containing compound (A) When using a base material in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated thereon, it can be particularly suitably used as the curable resin.

≪Epoxy clock resin≫

Although it does not specifically limit as an epoxy resin, It can be classified largely into an ultraviolet curing type and a thermosetting type. Examples of the ultraviolet-curable epoxy resin include those synthesized from a composition containing a compound having at least one epoxy group in a molecule and a compound that generates an acid by ultraviolet rays (hereinafter, also referred to as a ``photoacid generator''), Examples of the thermosetting epoxy resin include those synthesized from a composition containing a compound having one or more epoxy groups in a molecule and an acid anhydride. Epoxy-based ultraviolet-curable resin is the substrate, on which a transparent resin layer containing compound (A) is laminated on a glass support or on a resin support to be a base, or on a transparent resin substrate containing compound (A). When a base material on which a resin layer such as an overcoat layer containing a curable resin or the like is laminated is used, it can be particularly suitably used as the curable resin.

≪Resin mainly composed of silica formed by the sol-gel method≫

Examples of resins containing silica as a main component by the sol-gel method include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, and methoxytriethoxysilane, phenyltrimethoxysilane, and phenyltrie. A compound obtained by a sol-gel reaction by hydrolysis of one or more silanes selected from phenylalkoxysilanes such as oxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane can be used as the resin.

≪Commercial product≫

As a commercial item of a transparent resin, the following commercial item etc. are mentioned. Commercially available products of the cyclic polyolefin resin include JSR Corporation Aton, Nippon Xeon Corporation Zeonoa, Mitsui Chemical Corporation APEL, Polyplastics Corporation TOPAS, and the like. As a commercial item of a polyether sulfone resin, Sumitomo Chemical Co., Ltd. Sumika Excel PES etc. are mentioned. As a commercial item of a polyimide-type resin, Mitsubishi Gas Chemical Co., Ltd. Neopulim L etc. are mentioned. As a commercial item of a polycarbonate-type resin, Teijin Co., Ltd. pure Ace etc. are mentioned. As a commercial item of a fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. Upzeta EP-5000 etc. are mentioned. As a commercial item of a fluorene polyester-type resin, the OKP4HT etc. made by Osaka Gas Chemicals are mentioned. As a commercial item of an acrylic resin, Nippon Shokubai Co., Ltd. Acreia etc. are mentioned. As a commercial item of a silsesquioxane type ultraviolet-curable resin, Shinnittetsu Chemical Co., Ltd. Silplus etc. are mentioned.

<Other pigments (X)>

The substrate may further contain other dyes (X) which do not correspond to the compound (A).

Other dyes (X) are not particularly limited as long as the absorption maximum wavelength is less than 650 nm or more than 800 nm and less than 1250 nm, for example, squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, naphthalocyanine-based At least selected from the group consisting of compounds, chromonium compounds, octapyrine compounds, dimonium compounds, pyrrolopyrrole compounds, borondipyrromethene (BODIPY) compounds, perylene compounds and metal dithiolate compounds One kind of compound is mentioned. By using such a dye, it is possible to achieve absorption characteristics and excellent visible light transmittance in a wide near-infrared wavelength range.

The absorption maximum wavelength of the other dye (X) is preferably 805 nm or more and 1200 nm or less, more preferably 810 nm or more and 1150 nm or less, still more preferably 815 nm or more and 1100 nm or less, and particularly preferably 820 nm or more and 1050 nm or less. When the absorption maximum wavelength of the other dye (X) is in such a range, unnecessary near-infrared rays can be efficiently cut, and the dependence of the incident angle of incident light can be reduced.

The content of the other dye (X) is preferably 0.005 to 100 parts by mass of the transparent resin when a substrate including a transparent resin substrate containing the other dye (X) is used as the substrate. 1.0 parts by mass, more preferably 0.01 to 0.9 parts by mass, particularly preferably 0.02 to 0.8 parts by mass, and as the base material, other dyes (X) are contained on a support such as a glass support or a resin support serving as a base A substrate on which a transparent resin layer such as an overcoat layer containing a curable resin or the like is laminated, or an overcoat layer containing a curable resin containing other dyes (X) on a transparent resin substrate containing the compound (A), etc. In the case of using a substrate in which the resin layer of is laminated, preferably 0.05 to 4.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, based on 100 parts by mass of the resin forming the transparent resin layer containing the other dye (X). Parts, particularly preferably 0.2 to 2.0 parts by mass.

<Other ingredients>

The substrate may further contain an antioxidant, a near-ultraviolet absorber, a fluorescence quenching agent, and the like as other components, as long as the effect of the present invention is not impaired. These other components may be used individually by 1 type, and may use 2 or more types together.

Examples of the near ultraviolet absorber include an azomethine compound, an indole compound, a benzotriazole compound, a triazine compound, and a cyanoacrylate compound.

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

In addition, these other components may be mixed together with a resin or the like when producing a substrate, or added when synthesizing a resin. In addition, although the addition amount is appropriately selected according to the desired properties, it is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass per 100 parts by mass of the resin.

<Method of manufacturing base material>

When the substrate is a substrate including a transparent resin substrate containing the compound (A), the transparent resin substrate may be formed by, for example, melt molding or cast molding, and if necessary, after molding By coating a coating agent such as an antireflection agent, a hard coating agent, and/or an antistatic agent, a substrate on which an overcoat layer is laminated can be manufactured.

The substrate is transparent, such as an overcoat layer containing a curable resin containing the compound (A), etc. on a support such as a glass support or a resin support to be a base or a transparent resin substrate not containing the compound (A) In the case of a substrate on which a resin layer is laminated, for example, by melt molding or cast molding a resin solution containing the compound (A) on the support or the transparent resin substrate, preferably spin coating, slit coating, ink jet, etc. After coating by the method of drying and removing the solvent, and additionally performing light irradiation or heating as necessary, to prepare a substrate having a transparent resin layer containing the compound (A) on the support or the transparent resin substrate can do.

≪Melt molding≫

Specifically as the melt molding, a method of melt-molding a pellet obtained by melt-kneading a resin, a compound (A), and other components as necessary; A method of melt-molding a resin composition containing a resin, a compound (A) and other components as necessary; Alternatively, a method of melt-molding a pellet obtained by removing a solvent from a resin composition containing a compound (A), a resin, a solvent and, if necessary, other components may be mentioned. Examples of the melt-molding method include injection molding, melt extrusion molding, or blow molding.

≪Cast molding≫

As the cast molding, a method of casting a resin composition containing a compound (A), a resin, a solvent, and other components as necessary on a suitable support to remove the solvent; Alternatively, a curable composition containing the compound (A), a photocurable resin and/or a thermosetting resin, and, if necessary, other components, is cast on a suitable support and the solvent is removed, and then cured by an appropriate method such as ultraviolet irradiation or heating. It can also be manufactured by a method of making.

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

As the support, for example, a near-infrared absorption glass plate (e.g., a phosphate-based glass plate containing a copper component such as ``BS-11'' manufactured by Matsunami Glass High School or ``NF-50T'' manufactured by AGC Techno Glass), a transparent glass plate (For example, an alkali-free glass plate such as ``OA-10G'' by Nippon Denki Glass Co., ``AN100'' by Asahi Glass Co., etc.), steel belt, steel drum and transparent resin (e.g., polyester film, cyclic olefin system Resin film) a support body is mentioned.

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

The amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the above method is preferably as small as possible. Specifically, the residual solvent amount is preferably 3 parts by mass or less, more preferably 1 part by mass or less, further preferably 0.5 parts by mass or less based on 100 parts by mass of the weight of the transparent resin layer (transparent resin substrate). to be. When the residual solvent amount is in the above range, deformation and characteristics are hardly changed, and a transparent resin layer (transparent resin substrate) capable of easily exerting a desired function is obtained.

[Dielectric multilayer film]

Although it is preferable that the optical filter of the present invention does not have a multilayer dielectric film, the multilayer dielectric film may be provided on at least one side of the substrate as long as the effect of the present invention is not impaired. The dielectric multilayer film in the present invention is a film having an antireflection effect in a visible light region.

The dielectric multilayer film preferably has anti-reflection properties over the entire range of a wavelength of 400 to 610 nm, more preferably 410 to 600 nm, and even more preferably 420 to 590 nm.

As a form in which a multilayer dielectric film is provided on both sides of the base material, when measured from the vertical direction of the optical filter, a form in which a dielectric multilayer film having antireflection properties of a wavelength around 400 to 610 nm is mainly provided on both sides of the base material.

The thickness of the dielectric multilayer film having an antireflection effect in the visible light region is not particularly limited unless the effect of the present invention is impaired, but is preferably 0.01 to 1.0 µm, more preferably 0.05 to 0.5 µm. By setting the thickness in the above range, an optical filter with little warpage or deformation can be obtained.

Examples of the dielectric multilayer film include those obtained by alternately stacking high refractive index material layers and low refractive index material layers. As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of generally 1.7 to 2.5 is selected. Such materials include, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide or indium oxide, etc., and a small amount of tin oxide and/or cerium oxide ( For example, 0 to 10 parts by mass) containing 100 parts by mass of the main component is mentioned.

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

There is no particular limitation on the method of laminating the high refractive index material layer and the low refractive index material layer as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately stacked can be formed on a substrate by a CVD method, sputtering method, vacuum vapor deposition method, ion assist vapor deposition method, ion plating method, or the like.

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

The total number of stacked layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is preferably 1 to 20 layers, and more preferably 2 to 12 layers as the whole optical filter. By setting the number of layers in the above range, an optical filter with little warpage or deformation can be obtained.

In the present invention, the material species constituting the high refractive index material layer and the low refractive index material layer, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, according to the absorption characteristics of the compound (A) or other dye (X), By appropriately selecting the order of lamination and the number of laminations, not only a sufficient transmittance is ensured in the visible region, but also has sufficient light-cutting characteristics in the near-infrared wavelength region, and the reflectance when near-infrared rays enter from the oblique direction can be reduced.

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

[Other functional films]

The optical filter of the present invention includes at least one side of the base material, between the base material and the dielectric multilayer film, the side opposite to the side where the dielectric multilayer film of the base material is provided, or the surface where the base material of the dielectric multilayer film is provided as long as the effect of the present invention is not impaired. On the side opposite to the surface, for the purpose of improving the surface hardness of the substrate or the dielectric multilayer film, improving chemical resistance, preventing static electricity, and removing scratches, a functional film such as an antireflection film, a hard coating film, or an antistatic film can be appropriately provided.

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

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

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

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins or thermosetting resins, and specifically, vinyl compounds, urethane, urethane acrylate, acrylate, epoxy and epoxy acrylate Resin, etc. are mentioned. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.

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

The blending ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 1 to 5 parts by mass when the total amount of the curable composition is 100 parts by mass. to be. When the blending ratio of the polymerization initiator is in the above range, it is possible to obtain a functional film such as an antireflection film, a hard coat film, or an antistatic film, which is excellent in curing properties and handling properties of the curable composition and has a desired hardness.

In addition, an organic solvent may be added as a solvent to the curable composition, and a known organic solvent may be used. As specific examples of the organic solvent, alcohols such as methanol, ethanol, isopropanol, butanol and octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene, and xylene; Amides, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, are mentioned. Solvents may be used alone or in combination of two or more.

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

In addition, in order to increase the adhesion between the substrate and the functional film and/or the dielectric multilayer film, or to increase the adhesion between the functional film and the dielectric multilayer film, the surface of the substrate, the functional film or the dielectric multilayer film may be subjected to 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 excellent near-infrared cutting ability. Therefore, it is useful for correcting the visibility of a solid-state image sensor such as a CCD of a camera module or a CMOS image sensor. In particular, digital still cameras, cameras for smartphones, cameras for mobile phones, digital video cameras, cameras for wearable devices, PC cameras, surveillance cameras, car cameras, televisions, car navigation systems, portable information terminals, video game machines, portable game machines, fingerprints It is useful for authentication systems and digital music players. In addition, it is useful also as a heat ray cut filter or the like attached to a glass plate such as an automobile or a building.

Here, the solid-state imaging device is an image sensor equipped with a solid-state imaging device such as a CCD or CMOS image sensor, and specifically, uses such as digital still cameras, smartphone cameras, mobile phone cameras, wearable device cameras, and digital video cameras. Can be used for For example, the camera module of the present invention includes the optical filter of the present invention. Here, the camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, and the like, and outputs an image or distance information as an electric signal.

It is particularly preferable that the camera module has a cover member that protects the internal mechanism from the outside, and the cover member has a near-infrared reflecting function. The cover member is a near-infrared wavelength band having a reflective function for light incident from the vertical direction of the cover member, preferably 900 to 1100 nm, more preferably 850 to 1150 nm, and particularly preferably 800 to 1200 nm. The means for imparting the near-infrared reflection function to the cover member is not particularly limited, but a dielectric multilayer film in which a high refractive index material and a low refractive index material are alternately stacked is formed on the cover member by CVT method, sputtering method, vacuum evaporation method, ion assist vapor deposition method, etc. The method of forming is preferred.

When the camera module is configured as described above, since light is incident into the camera module while part of the near-infrared ray is cut by the cover member, between the lens and the lens, between the lens and the optical filter, and between the optical filter and the solid image pickup device It is preferable because there is a tendency that unnecessary near-infrared reflection can be reduced, and noise and ghost of a camera image can be reduced. Further, since the camera module of the present invention has an optical filter that efficiently cuts near-infrared rays having a wavelength of 700 to 780 nm by absorption of the compound (A), it is possible to achieve high image quality, which is difficult to realize in a conventional camera module.

Further, the electronic device of the present invention has the camera module of the present invention. Although it does not specifically limit as an electronic device, For example, a smartphone, a mobile phone, a personal computer etc. in the above-mentioned use are mentioned.

Example

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

<molecular weight>

The molecular weight of the resin was measured by the method of the following (a) or (b) in consideration of the solubility of each resin in the solvent.

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

(b) Using the Tosoh Corporation GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF), the mass average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured.

In addition, about the resin synthesized in Resin Synthesis Example 3 described later, the logarithmic viscosity was measured by the following method (c), not the molecular weight by the above method.

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

μ={ln(t _s /t ₀ )}/C

t ₀ : Falling time of the solvent

t _s : Falling time of lean polymer solution

C: 0.5g/dL

<Glass transition temperature (Tg)>

Using a differential scanning calorimeter (DSC6200) manufactured by SI Nanotechnology Co., Ltd., the temperature increase rate was measured at 20°C per minute under a nitrogen stream.

<Spectral transmittance>

The transmittance at each wavelength of the substrate and the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High Technologies.

Here, in the transmittance when measured from the vertical direction of the optical filter, the light (1) transmitted perpendicularly to the optical filter (2) as shown in Fig. 1 (A) is measured with a spectrophotometer (3), and the optical filter In the transmittance when measured from an angle of 30 degrees with respect to the vertical direction of, as shown in Fig. 1(B), the light 1'transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 is measured using a spectrophotometer 3 ) And measured from an angle of 60 degrees with respect to the vertical direction of the optical filter, as shown in Fig. 1(C), light transmitted at an angle of 60 degrees with respect to the vertical direction of the optical filter 2 (1 '') was measured with a spectrophotometer (3).

<Color shading evaluation of camera images>

Color shading evaluation when the optical filter was incorporated in the camera module was performed by the following method. In the same manner as in Japanese Patent Laid-Open No. 2016-110067, a camera module as shown in Fig. 2 was produced, and a white plate having a size of 300 mm x 400 mm was applied using the obtained camera module as a D65 light source (standard light source manufactured by X-Rite). It photographed under the apparatus "Macbeth Jersey II"), and the difference in color tone at the center part and the edge part of a white plate in a camera image was evaluated based on the following criteria.

There is no problem at all, the acceptable level is A, the slight difference in hue is confirmed, but as a high-definition camera module, there is no practical problem, so the acceptable level is B, there is a difference in hue, and the level is not acceptable for high-definition camera module use, C, clear hue. Due to the difference of, it was determined that D was an unacceptable level even for general camera module use.

In addition, as shown in Fig. 3, when photographing, the positional relationship between the white plate 112 and the camera module was adjusted so that the white plate 112 occupies 90% or more of the area of the camera image 111. In addition, as the cover member 210 in FIG. 2, a cover member having a film configuration shown in Table 9 was used, and as the optical filter 240, an optical filter manufactured in the following Examples and Comparative Examples was used.

[Table 9]

<Ghost evaluation of camera image>

Ghost evaluation when the optical filter was incorporated in the camera module was performed by the following method. A camera module was produced in the same way as the color shading evaluation of the camera image, and the camera module was used to shoot in a dark room under a halogen lamp light source (``Lumina Ace LA-150TX'' manufactured by Hayashitokei Kogyo Co., Ltd.). The ghost generation state around the light source was evaluated based on the following criteria.

There is no problem at all, the acceptable level is A, and a little ghost is confirmed, but there is no practical problem as a high-definition camera module, so the acceptable level is B, and the level of ghost is C, which is unacceptable for high-definition camera module applications. It was judged as D as a level that was not acceptable even for general camera module use.

In addition, as shown in FIG. 4, when photographing is performed, the light source 122 is adjusted to be the upper right portion of the camera image 121.

[Synthesis Example]

Compound (A) and near-infrared absorbing dye (X) used in the following examples were synthesized by a generally known method. As a general synthesis method, for example, Japanese Unexamined Patent Publication No. 60-228448, Japanese Unexamined Patent Publication No. Hei1-146846, Japanese Unexamined Patent Publication No. 1-228960, Japanese Patent Unexamined Patent Publication No. 4081149, and Japanese Unexamined Patent Publication 63 -124054, ``phthalocyanine -chemistry and function-'' (IPC, 1997), Japanese Patent Application Publication No. 2007-169315, Japanese Patent Application Publication No. 2009-108267, Japanese Patent Application Publication No. 2010-241873, etc. The described method is mentioned.

<Resin Synthesis Example 1>

100 parts of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene (hereinafter also referred to as "DNM") represented by the following formula (a); 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were put into a nitrogen-substituted reaction vessel, and the solution was heated to 80°C. Subsequently, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.9 parts of a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol/liter) were added to the solution in the reaction vessel as a polymerization catalyst. By heating and stirring at 80°C for 3 hours, a ring-opening polymerization reaction was carried out to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained 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 the hydrogen gas pressure was 100 kg/cm ² , and the reaction temperature. Under the conditions of 165 degreeC, it heated and stirred for 3 hours, and performed hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released from pressure. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, 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, a glass transition temperature (Tg) of 165°C, and a refractive index (n20d) of 1.51.

<Resin Synthesis Example 2>

In a 3L 4-neck flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, and 41.46 g (0.300 mol) of potassium carbonate ), 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 introduction tube, a Dean Stark tube, and a cooling tube were installed in the 4-neck flask. Subsequently, after nitrogen substitution in the flask, the resulting solution was reacted at 140° C. for 3 hours, and the generated water was removed from the Dean Stark tube from time to time. When the generation of water was not confirmed, the temperature was gradually increased to 160° C., and the reaction was performed at the same temperature for 6 hours. After cooling to room temperature (25°C), the resulting salt was removed with a filter paper, and the filtrate was put in methanol to reprecipitate, and the filtrate (residue) was isolated by filtration separation. The obtained filtrate was vacuum-dried at 60°C overnight to obtain a white powder (hereinafter, also referred to as “Resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a mass average molecular weight (Mw) of 188,000, a glass transition temperature (Tg) of 285°C, and a refractive index (n20d) of 1.66.

<Resin Synthesis Example 3>

In a 500 mL 5-neck flask equipped with a thermometer, agitator, a nitrogen inlet tube, a dropping funnel with a side pipe, a Dean Stark tube, and a cooling tube, 1,4-bis(4-amino-α,α-dimethylbenzyl) under a flow of nitrogen Benzene 27.66 g (0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl 7.38 g (0.02 mol) were added, and 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 while maintaining at the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.50 g of triethylamine as an imidization catalyst ( 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 distillate from time to time. After completion of the reaction, after air cooling until the internal temperature reached 100°C, 143.6 g of N,N-dimethylacetamide was added, diluted, and cooled while stirring to obtain 264.16 g of a polyimide resin solution having a solid content concentration of 20% by mass. . A part of this polyimide resin solution was poured into 1 L of methanol to precipitate polyimide. The polyimide fractionated by filtration was washed with methanol, and then dried in a vacuum dryer at 100°C for 24 hours to obtain a white powder (hereinafter also referred to as “Resin C”). As a result of measuring an IR spectrum of the obtained resin C, already distinctive 1704cm ^-1 groups DE, showed the absorption of 1770cm ^-1. Resin C had a glass transition temperature (Tg) of 310°C, a refractive index (n20d) of 1.68, and a logarithmic viscosity measurement of 0.87.

[Example 1]

In a container, 100 parts of resin A obtained in Resin Synthesis Example 1, 0.05 parts of compound (Aa-1) represented by the following formula (Aa-1) as compound (Aa) (maximum absorption wavelength 712 nm in dichloromethane), compound ( 0.12 parts of a compound (Ab-1) (maximum absorption wavelength in dichloromethane 738 nm) represented by the following formula (Ab-1) as Ab), and a compound represented by the following formula (Ac-1) as the compound (Ac) ( Ac-1) (maximum absorption wavelength in dichloromethane: 776 nm) 0.05 part and methylene chloride were added to prepare a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100° C. for 8 hours under reduced pressure to obtain a substrate including a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 5 and Table 15.

[Example 2]

In Example 1, 0.03 parts of compound (Aa-2) represented by the following formula (Aa-2) (maximum absorption wavelength 686 nm in dichloromethane) was used as compound (Aa), and compound (Ab) was not used. And 0.04 parts of compound (Ac-1) and 0.06 parts of compound (Ac-2) represented by the following formula (Ac-2) (maximum absorption wavelength 760 nm in dichloromethane) were used as the compound (Ac). A transparent resin substrate was obtained in the same procedure and conditions as in Example 1.

The resin composition (1) 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 to volatilize and remove the solvent. At this time, the application conditions of the bar coater were adjusted so that the thickness after drying was 2 µm. Next, exposure (exposure amount: 500 mJ/cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1) to form a resin layer on a transparent resin substrate. Similarly, a resin layer containing the resin composition (1) was formed on the other side of the transparent resin substrate to obtain a substrate having a resin layer on both surfaces of the transparent resin substrate. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 6 and Table 15.

Resin composition (1): tricyclodecanedimethanol diacrylate 60 parts, dipentaerythritol hexaacrylate 40 parts, 1-hydroxycyclohexylphenyl ketone 5 parts, methyl ethyl ketone (solvent, solid content concentration (TSC): 30% by mass)

[Example 3]

In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), 0.10 parts of compound (Ab-1) were used as compound (Ab), and compound ( As Ac), except having used 0.04 parts of compound (Ac-1) and 0.05 part of compound (Ac-2), a substrate including a transparent resin substrate was obtained in the same procedure and conditions as in Example 1. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 7 and Table 15.

[Example 4]

In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), and 0.01 parts of compound (Ab-1) were used as compound (Ab), and compound (Ac ) As the compound (Ac-1) 0.03 parts and the compound (Ac-2) 0.04 parts, and other near-infrared absorption dyes (X) represented by the following formula (X-1) (X-1) ( A substrate comprising a transparent resin substrate containing a compound (A) and a near-infrared absorbing dye (X) was obtained in the same procedure and conditions as in Example 1, except that 0.04 part of absorption maximum wavelength in dichloromethane) was used. . The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 8 and Table 15.

[Example 5]

The resin composition (2) of the following composition was applied with a spin coater on a transparent glass substrate ``OA-10G (thickness 150 um)'' (made by Nippon Denki Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width, and hot The solvent was volatilized off by heating on the plate at 80° C. for 2 minutes. At this time, the application conditions of the spin coater were adjusted so that the thickness after drying was 2 µm. Subsequently, exposure (exposure amount: 500 mJ/cm ² , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (2), and a substrate comprising a transparent glass substrate having a transparent resin layer containing the compound (A) was prepared. Got it. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 9 and Table 15.

Resin composition (2): tricyclodecanedimethanol diacrylate 20 parts, dipentaerythritol hexaacrylate 80 parts, 1-hydroxycyclohexylphenyl ketone 4 parts, compound (Aa-1) 3.00 parts, compound (Aa -2) 1.00 parts, compound (Ab-1) 7.00 parts, compound (Ac-1) 4.00 parts, methyl ethyl ketone (solvent, TSC: 35%)

[Example 6]

In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), 0.34 parts of compound (Ab-1) were used as compound (Ab), and compound (Ac ), except that 0.04 part of the compound (Ac-1) was used, and the thickness of the transparent resin substrate was set to 0.08 mm, to obtain a substrate including a transparent resin substrate in the same procedure and conditions as in Example 1. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 10 and Table 15.

[Example 7]

In Example 1, 0.05 parts of compound (Aa-1) was used as compound (Aa), 0.85 parts of compound (Ab-1) was used as compound (Ab), and compound (Ac-1) 0.05 as compound (Ac) A substrate including a transparent resin substrate was obtained in the same procedure and conditions as in Example 1 except that a portion was used and the thickness of the transparent resin substrate was set to 0.04 mm. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 11 and Table 15.

[Example 8]

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

On both surfaces of the obtained resin support, a resin layer containing the resin composition (3) of the following composition was formed in the same manner as in Example 2, and the compound (A) and a near-infrared absorbing dye (X) were included on both surfaces of the resin support. A substrate having a transparent resin layer was obtained. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 12 and Table 15.

Resin composition (3): tricyclodecanedimethanol diacrylate 100 parts, 1-hydroxycyclohexylphenyl ketone 4 parts, compound (Aa-1) 0.50 parts, compound (Ac-1) 0.50 parts, compound (Ac- 2) 2.50 parts, near-infrared absorbing dye (X-1) 1.40 parts, methyl ethyl ketone (solvent, TSC: 25%)

[Example 9]

A resin composition (4) of the following composition was applied on a near-infrared absorption glass substrate ``BS-11 (thickness 120 um)'' (manufactured by Matsunami Glass Kogyo Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width with a spin coater. , The solvent was volatilized off by heating at 80° C. for 2 minutes on a hot plate. At this time, the application conditions of the spin coater were adjusted so that the thickness after drying was 2 µm. Subsequently, exposure (exposure amount: 500 mJ/cm ² , 200 mW) is performed using a conveyor type exposure machine to cure the resin composition (4), and a substrate comprising a near-infrared absorbing glass substrate having a transparent resin layer containing the compound (A) Got it. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 13 and Table 15.

Resin composition (4): tricyclodecanedimethanol diacrylate 20 parts, dipentaerythritol hexaacrylate 80 parts, 1-hydroxycyclohexylphenyl ketone 4 parts, compound (Aa-1) 1.00 parts, compound (Ac -1) 1.00 parts, compound (Ac-2) 5.00 parts, methyl ethyl ketone (solvent, TSC: 35% by mass)

[Example 10]

In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), 0.14 parts of compound (Ab-1) were used as compound (Ab), and compound (Ac ) As the compound (A) and the near-infrared absorbing dye (X) in the same procedure and conditions as in Example 1, except that 0.04 part of the compound (Ac-1) was used, and 0.04 part of the near-infrared absorbing dye (X-1) was used. A substrate including a transparent resin substrate containing a was obtained. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 14 and Table 15.

[Example 11]

In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), 0.34 parts of compound (Ab-1) were used as compound (Ab), and compound ( Except having used 0.04 part of compound (Ac-1) as Ac), it is the same procedure and conditions as Example 1, and obtained the base material containing the transparent resin board|substrate.

A dielectric multilayer film (I) was formed as a first optical layer on one side of the obtained substrate, and a similar dielectric multilayer film (I) was further formed on the other side of the substrate to obtain an optical filter.

As the dielectric multilayer film (I), a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer were alternately stacked at a deposition temperature of 120°C (4 layers in total). The silica layer and the titania layer of the dielectric multilayer film (I) were alternately laminated in the order of a titania layer, a silica layer, a titania layer, and a silica layer from the substrate side, and the outermost layer of the optical filter was a silica layer.

Here, the dielectric multilayer film (I) was a multilayer vapor-deposited film having 4 stacks, in which a silica layer having a thickness of 33 to 88 nm and a titania layer having a thickness of 13 to 111 nm are alternately stacked. The membrane configuration is shown in Table 10 below.

[Table 10]

The optical properties were evaluated by measuring the spectral transmittance of the obtained substrate and the optical filter. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 15 and Table 15.

[Examples 12 to 14]

A substrate was produced in the same manner as in Example 1 except that the resin, the solvent, the drying conditions of the resin substrate, and the compound (A) were changed as shown in Table 15. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. Table 15 shows the results.

[Examples 15 and 16]

A substrate was produced in the same manner as in Example 2, except that the resin, the solvent, the drying conditions of the resin substrate, the compound (A), and the near-infrared absorbing dye (X) were changed as shown in Table 15. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Figs. 16, 17 and 15.

[Comparative Example 1]

In Example 1, except that 0.07 parts of compound (Aa-1) was used as compound (Aa), and 0.08 parts of compound (Ab-1) was used as compound (Ab), in the same procedure and conditions as in Example 1 A substrate containing a transparent resin substrate was obtained. The |X _b -X _a | of the obtained substrate was 61 nm and was less than 100 nm.

Subsequently, a dielectric multilayer film (II) formed by alternately stacking a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a first optical layer on one side of the obtained substrate (total 26 layers) was formed, and further On the other side, as a second optical layer, a dielectric multilayer film (III) formed by alternately stacking a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer (total of 20 layers) was formed, and an optical filter having a thickness of about 0.105 mm was formed. Got it.

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

Regarding the thickness and number of layers of each layer, an optical thin film according to the wavelength-dependent characteristics of the refractive index of the substrate or the absorption characteristics of the applied compound (A) to achieve the antireflection effect in the visible light region and the selective transmission and reflection performance in the near infrared region. Optimization was performed using design software (Essential Macleod, manufactured by Thin Film Center). When optimizing, in this comparative example, input parameters (target values) to the software were as shown in Table 11 below.

[Table 11]

As a result of optimizing the film configuration, the dielectric multilayer film (II) in Comparative Example 1 became a multilayer deposited film having a number of layers of 26 in which a silica layer having a thickness of 31 to 155 nm and a titania layer having a thickness of 10 to 94 nm are alternately stacked. The multilayer film (III) became a multilayer vapor-deposited film having 20 stacks, in which a silica layer having a thickness of 38 to 189 nm and a titania layer having a thickness of 11 to 109 nm are alternately stacked. An example of the optimized film configuration is shown in Table 12 below.

[Table 12]

The optical properties were evaluated by measuring the spectral transmittance of the obtained optical filter. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 18 and Table 15. Although the optical filter obtained in Comparative Example 1 exhibits a relatively good optical density, the decrease in transmittance at high angle incidence is large, the generation of ghosts thought to be caused by near-infrared reflection by the dielectric multilayer film was confirmed, and further, color shading was suppressed. It was confirmed that the effect was inferior.

[Comparative Example 2]

A substrate including a transparent resin substrate was obtained in the same procedure and conditions as in Comparative Example 1. On one side of the obtained substrate, a dielectric multilayer film (IV) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately stacked as a first optical layer (30 layers in total) was formed, and further, the other side of the substrate As a second optical layer, a dielectric multilayer film (V) formed by alternately stacking a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer (20 layers in total) was formed to obtain an optical filter having a thickness of about 0.105 mm.

When optimizing, in this comparative example, input parameters (target values) to the software were as shown in Table 13 below.

[Table 13]

As a result of optimizing the film configuration, the dielectric multilayer film (IV) in Comparative Example 2 became a multilayer deposited film having a stacking number of 30 in which a silica layer having a thickness of 22 to 467 nm and a titania layer having a thickness of 6 to 130 nm were alternately stacked. The multilayer film (V) became a multilayer vapor-deposited film having 20 stacks, in which a silica layer having a thickness of 84 to 206 nm and a titania layer having a thickness of 8 to 109 nm are alternately stacked. An example of an optimized film configuration is shown in Table 14 below.

[Table 14]

The optical properties were evaluated by measuring the spectral transmittance of the obtained optical filter. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 19 and Table 15. It was confirmed that the optical filter obtained in Comparative Example 2 had a large decrease in transmittance at high angle incidence, and was not sufficiently absorbed in the near-infrared wavelength region, so that the color shading suppression effect and the ghost suppression effect were inferior.

[Comparative Example 3]

A substrate including a transparent resin substrate was obtained in the same procedure and conditions as in Comparative Example 1. Subsequently, in the same procedure and conditions as in Example 11, a dielectric multilayer film (I) was formed as a first optical layer on one side of the obtained substrate, and a similar dielectric multilayer film (I) was formed on the other side of the substrate. Thus, an optical filter having a thickness of about 0.101 mm was obtained.

The optical properties were evaluated by measuring the spectral transmittance of the obtained optical filter. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 20 and Table 15. It was confirmed that the optical filter obtained in Comparative Example 3 was not sufficiently absorbed in the near-infrared wavelength region, and the ghost suppressing effect was inferior.

[Comparative Example 4]

A substrate including a transparent resin substrate was obtained in the same procedure and conditions as in Comparative Example 1. The optical properties were evaluated by measuring the spectral transmittance of the optical filter containing this substrate. Further, a camera module was produced using the obtained optical filter, and color shading and ghost evaluation of the camera image were performed. The results are shown in Fig. 21 and Table 15. It was confirmed that the optical filter obtained in Comparative Example 4 had insufficient absorption in the near-infrared wavelength region, and the ghost suppression effect was inferior.

[Comparative Example 5]

A camera module was produced using only a cover member without using an optical filter, and color shading and ghost evaluation of the camera image were performed. Table 15 shows the results. Since the camera module obtained in Comparative Example 5 did not have an optical filter that absorbs the near-infrared region, the degree of both color shading and ghosting was severe, and it was confirmed that the level was unacceptable even for general camera module use.

[Table 15-1]

[Table 15-2]

The constitution of the substrate in Table 15, symbols such as various compounds, and drying conditions of the film [(transparent) resin substrate or resin support] are as follows.

<Type of description>

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

Form (2): Having a resin layer on both sides of a transparent resin substrate containing compound (A)

Form (3): Having a transparent resin layer containing compound (A) on both sides of a resin support

Form (4): Having a transparent resin layer containing compound (A) on one side of a transparent glass substrate

Form (5): having a transparent resin layer containing compound (A) on one side of a near-infrared absorption glass substrate

Form (6): having antireflection layers on both surfaces of a transparent resin substrate containing compound (A)

Form (7): Transparent resin substrate containing compound (A) and near-infrared absorbing dye (X)

Form (8): A near-infrared reflective layer is provided on both surfaces of a transparent resin substrate having _a |X _b -X _a | of less than 100 nm containing the compound (A) (Comparative Example)

Form (9): Has an antireflection layer on both sides of a transparent resin substrate having _a |X _b -X _a | of less than 100 nm containing the compound (A) (comparative example)

Form (10): A transparent resin substrate containing compound (A), wherein |X _b -X _a | is less than 100 nm (Comparative Example)

<Transparent resin>

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

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

Resin C: polyimide resin (resin synthesis example 3)

Resin D: Cyclic olefin resin "Zeonoa 1420R" (manufactured by Nippon Xeon Corporation)

<Glass substrate>

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

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

<Resin support>

Resin-made support (1): a transparent resin substrate containing Resin A having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm

<Near-infrared absorption pigment>

≪Compound (A)≫

Compound (A-a-1): Compound represented by formula (A-a-1) (maximum absorption wavelength in dichloromethane 712 nm)

Compound (A-a-2): Compound represented by formula (A-a-2) (maximum absorption wavelength 686 nm in dichloromethane)

Compound (A-b-1): Compound represented by formula (A-b-1) (maximum absorption wavelength 738 nm in dichloromethane)

Compound (A-c-1): Compound represented by formula (A-c-1) (maximum absorption wavelength in dichloromethane: 776 nm)

Compound (A-c-2): Compound represented by formula (A-c-2) (maximum absorption wavelength in dichloromethane: 760 nm)

Compound (A-c-3): a compound represented by the following formula (A-c-3) (maximum absorption wavelength 773 nm in dichloromethane)

≪Other pigments (X)≫

Near-infrared absorbing dye (X-1): Compound represented by formula (X-1) (maximum absorption wavelength 813 nm in dichloromethane)

Near-infrared absorbing dye (X-2): Compound represented by the following formula (X-2) (maximum absorption wavelength in dichloromethane: 870 nm)

<solvent>

Solvent (1): methylene chloride

Solvent (2): N,N-dimethylacetamide

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

<Film drying conditions>

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

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

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

Moreover, before drying under reduced pressure, the coating film was peeled from the glass plate.

Condition (4): 80℃/2min

Condition (5): 70℃/2min

1, 1', 1'': optical
2: optical filter
3: spectrophotometer
111: camera image
112: white plate
113: Example of the central part of the white plate
114: Example of the end of the white plate
121: camera image
122: light source
123: Example of ghost around light source
200: imaging device
210: cover member
220: lens group
230: aperture
240: optical filter
250: solid-state image sensor
260: housing

Claims (13)

Optical filters that meet the following requirements (a) and (b):
(a) In a region with a wavelength of 430 to 580 nm, a minimum value T _b-0 of transmittance of light incident from the vertical direction of the optical filter, and a minimum value T _b-30 of transmittance of light incident from a direction inclined at 30 degrees with respect to the vertical direction , The minimum value T _b-60 of the transmittance of light incident from a direction inclined at 60 degrees with respect to the vertical direction is 55% or more and less than 90%;
(b) In the region of wavelength 700 to 780 nm, the average value OD _a-0 of the optical density for light incident from the vertical direction of the optical filter and the optical density for light incident from the direction inclined at 30 degrees with respect to the vertical direction Both the average value OD _a-30 and the average value OD _a-60 of the optical density for the light incident from the oblique direction at 60 degrees with respect to the vertical direction are 1.8 or more. The optical filter according to claim 1, further meeting the following requirement (c):
(c) In a region having a wavelength of 900 to 1200 nm, the average value T _IR of the transmittance of light incident from the vertical direction of the optical filter is 60% or more. The optical filter according to claim 1 or 2, further meeting the following requirement (d):
(d) In a region with a wavelength of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident from the vertical direction of the optical filter, T _a-30 and the average value of the transmittance of light incident from the direction inclined at 30 degrees with respect to the vertical direction And the average value T _a-60 of the transmittance of light incident from the oblique direction at 60 degrees with respect to the vertical direction is 65% or more and less than 90%. The optical filter according to any one of claims 1 to 3, comprising a substrate meeting the following requirement (e):
(e) It has a layer containing a compound (A) having an absorption maximum in a region of a wavelength of 650 to 800 nm. The optical filter of claim 4, wherein the substrate further meets the following requirement (f):
(f) at a wavelength of 600 to 900nm, the transmittance of light incident from the perpendicular direction of the substrate, toward the long wavelength side from the short wavelength side wavelength of the long wavelength side is not more than 10% from a 10% excess of X _a and a base The absolute value |X _b -X _a | of the difference between the wavelength X _b on the shortest wavelength side at which the transmittance of the light incident from the vertical direction is from 10% or less to more than 10% from the short wavelength side toward the long wavelength side is 100 nm or more. The compound according to claim 4 or 5, wherein the compound (A) is at least one compound selected from the group consisting of a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a chromonium compound and a cyanine compound. Optical filter, characterized in that. The compound according to any one of claims 4 to 6, wherein the substrate is the compound (A), wherein the compound (Aa) has an absorption maximum in a region of 650 m or more and 715 nm or less, and is absorbed in a region of more than 715 nm and 750 nm or less. An optical filter comprising a compound (Ab) having a maximum and a compound (Ac) having an absorption maximum in a region of more than 750 nm and not more than 800 nm in wavelength. The optical filter according to any one of claims 4 to 7, wherein the layer containing the compound (A) is a transparent resin layer. The resin of claim 8, wherein the resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, and a polycarbohydrate. Nate resin, polyamide resin, aramid resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified ) Acrylic resin, epoxy resin, silsesquioxane UV curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyetheretherketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin , At least one resin selected from the group consisting of a vinyl-based ultraviolet curable resin, and a resin mainly containing silica formed by a sol-gel method. The optical filter according to claim 8 or 9, wherein the resin constituting the transparent resin layer has a refractive index (n20d) of 1.50 to 1.53. A camera module comprising the optical filter according to any one of claims 1 to 10. The camera module according to claim 10, comprising a cover member that protects an internal mechanism of the camera module from the outside, and the cover member has a near-infrared ray reflection function. An electronic device comprising the camera module according to claim 11 or 12.

Images