KR102547262B1 - Optical filters and devices using optical filters - Google Patents

Abstract

An object of the present invention is to provide an optical filter that has little incident angle dependence and can reduce multiple reflections when near-infrared light is incident from an oblique direction. The optical filter of the present invention has a substrate and a dielectric multilayer film formed on at least one surface of the substrate, wherein the substrate has a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm, and an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less. Having a transparent resin layer containing the compound (S), or having a transparent resin layer containing the compound (A) and a transparent resin layer containing the compound (S), and satisfying the following requirement (a) Characterized in: (a) an average value of transmittance measured from the vertical direction of the optical filter in a wavelength range of 800 to 1000 nm is 5% or less;

Description

Optical filters and devices using optical filters

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

Solid-state imaging devices such as video cameras, digital still cameras, and cell phones with camera functions use CCD or CMOS image sensors, which are solid-state imaging elements for color images. Silicon photodiodes with sensitivity to imperceptible near-infrared light are being used. In these solid-state imaging devices, it is necessary to correct the visibility to make the color tone natural when viewed by the human eye, and an optical filter (for example, a near-infrared cut filter) that selectively transmits or blocks light rays in a specific wavelength range is often used. .

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

In Patent Document 2, the present applicant proposes a near-infrared cut filter having a norbornene-based resin substrate and a near-infrared reflective film. The near-infrared cut filter described in Patent Literature 2 was excellent in near-infrared cutoff characteristics, moisture absorption resistance and impact resistance, but could not take a wide viewing angle value.

In addition, as a result of intensive studies, the present applicant found that a near-infrared cutoff filter with little change in optical characteristics was obtained even when the angle of incidence was changed by using a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength region. , Patent Literature 3 proposes a near-infrared cut filter that combines a wide viewing angle and high visible light transmittance.

Japanese Unexamined Patent Publication No. 6-200113 Japanese Unexamined Patent Publication No. 2005-338395 Japanese Unexamined Patent Publication No. 2011-100084

In recent years, even in mobile devices and the like, the level of image quality required for camera images has become very high. According to the study of the present inventors, in order to satisfy the demand for high image quality, in addition to a wide viewing angle and high visible light transmittance, high light blocking properties are required even in a relatively long wavelength region in an optical filter. In addition, along with the miniaturization of the camera module, the angle of incidence of light rays tends to be larger than before, especially at the end of the screen, but in the conventional optical filter, multiple reflection between the optical filter and the lens, multiple reflection inside the optical filter, and optical filter and solid Ghosts caused by multiple reflections between imaging devices have been a problem in some cases (see FIGS. 1A to 1D ).

An object of the present invention is to provide an optical filter capable of reducing multiple reflections when near-infrared light is incident from an oblique direction and has little dependence on an incident angle.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that by applying a combination of two or more types of compounds having an absorption maximum in a specific wavelength region, the target near-infrared ray blocking properties, visible light transmittance, and multiple reflected light reduction in the near-infrared wavelength region are reduced. It was found that an optical filter capable of achieving the above could be obtained, and the present invention was completed. An example of the aspect of the present invention is shown below.

[1] A base material and a dielectric multilayer film formed on at least one side of the base material,

The base material has a transparent resin layer containing a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm and a compound (S) having an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less, or the compound (A) It has a transparent resin layer containing and a transparent resin layer containing the compound (S),

An optical filter characterized in that it satisfies the following requirement (a):

(a) An average value of transmittance measured from the vertical direction of the optical filter in a wavelength range of 800 to 1000 nm is 5% or less.

[2] The optical filter according to item [1], which further satisfies the following requirement (b):

(b) The average value of the transmittance measured from the vertical direction of the optical filter in the wavelength range of 430 to 580 nm is 75% or more.

[3] Item [1] or [characterized in that the compound (S) is at least one selected from the group consisting of squarylium-based compounds, cyanine-based compounds, pyrrolopyrrole-based compounds, and metal dithiolate-based compounds; 2] the optical filter described in.

[4] The optical filter according to any one of items [1] to [3], wherein the compound (S) is a squarylium-based compound represented by the following formula (Z).

In formula (Z), substitution units A and B each independently represent any of the substitution units represented by the following formulas (I) and (II).

In Formulas (I) and (II), the part indicated by the broken line represents the binding site with the central tetrahedral ring,

X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ -;

R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R ⁱ group, - OSO ₂ Represents a R ⁱ group or any of the following La to L ^h , R ^g and R ^h each independently ^represent a hydrogen atom, a -C(O)R ⁱ group or any of the following La to ^{L e ,} and R ⁱ represents any one of the following La to ^{L e ,}

(L ^a ) An aliphatic hydrocarbon group having 1 to 12 carbon atoms

(L ^b ) A halogen-substituted alkyl group having 1 to 12 carbon atoms

(L ^c ) An alicyclic hydrocarbon group having 3 to 14 carbon atoms

(L ^d ) Aromatic hydrocarbon group having 6 to 14 carbon atoms

(L ^e ) Heterocyclic group having 3 to 14 carbon atoms

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

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

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

The substituent L is composed of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. It is at least 1 sort(s) selected from the group.

[5] The optical filter according to any one of items [1] to [4], wherein the substrate has a dielectric multilayer film on both sides.

[6] Any one of [1] to [5], wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. The optical filter described in.

[7] The transparent resin is a cyclic (poly) olefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a fluorene polycarbonate-based resin, a fluorene polyester-based resin, a polycarbonate-based resin, Polyamide-based resin, polyarylate-based resin, polysulfone-based resin, polyethersulfone-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate-based resin, fluorinated aromatic polymer-based resin, (modified) acrylic resin [1] characterized in that it is at least one resin selected from the group consisting of epoxy-based resins, allyl ester-based curable resins, silsesquioxane-based UV-curable resins, acrylic-based UV-curable resins, and vinyl-based UV-curable resins. The optical filter according to any one of [6] to [6].

[8] The optical filter according to any one of items [1] to [7], wherein the substrate contains a transparent resin substrate containing compound (A) and compound (S).

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

[10] A solid-state imaging device provided with the optical filter according to any one of [1] to [8].

[11] A camera module comprising the optical filter according to any one of [1] to [8].

According to the present invention, it is possible to provide an optical filter having excellent near-infrared ray blocking characteristics, low incidence angle dependence, excellent transmittance characteristics in the visible wavelength region, and excellent multi-reflection light reducing effect in the near-infrared wavelength region.

1A is a schematic diagram showing multi-reflected light rays between an optical filter and a lens entering a solid-state imaging device.
Fig. 1B is a schematic diagram showing multiple reflected light rays entering the solid-state imaging device inside the optical filter.
1C is a schematic diagram showing multi-reflected light rays between an optical filter and a solid-state image sensor entering the solid-state image sensor.
1D is a schematic diagram showing multiple reflected light rays between an optical filter and a solid-state imaging device entering the solid-state imaging device.
Fig. 2(a) is a schematic diagram showing a method of measuring the transmittance when measured from the vertical direction of the optical filter. 2(b) is a schematic diagram showing a method of measuring transmittance when measured from an angle of 30° with respect to the vertical direction of the optical filter. Fig. 2(c) is a schematic diagram showing a method of measuring the reflectance when measured from an angle of 30° with respect to the vertical direction of the optical filter. 2(d) is a schematic diagram showing a method of measuring reflectance when measured from an angle of 5° with respect to the vertical direction of the deposition monitor glass.
3(a) and (b) are schematic diagrams showing examples of preferred configurations of the optical filter of the present invention.
4 is a spectral transmission spectrum of the substrate obtained in Example 1.
5(a) is a spectral reflectance spectrum when measured from an angle of 5° with respect to the vertical direction of the dielectric multilayer film (I) prepared in Example 1, and FIG. It is a spectral reflectance spectrum when measured from an angle of 5 degrees with respect to the vertical direction of the dielectric multilayer film (II).
6 is a spectral transmission spectrum of the optical filter obtained in Example 1.
Fig. 7 shows spectral reflection measured from an angle of 30° with respect to the vertical direction of the optical filter obtained in Example 1 when the incident surface of the light beam is on the dielectric multilayer film (II) (second optical layer) side. it's a spectrum
8 is a spectral transmission spectrum of the substrate obtained in Example 2.
9 is a spectral transmission spectrum of the optical filter obtained in Example 2.
Fig. 10 shows spectral reflection measured from an angle of 30° with respect to the vertical direction of the optical filter obtained in Example 2, when the incident surface of the light beam is on the dielectric multilayer film (IV) (second optical layer) side. it's a spectrum

Hereinafter, the present invention will be described in detail.

[Optical filter]

An optical filter according to the present invention is a substrate having a transparent resin layer containing at least one compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm and a compound (S) having an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less, respectively. (i) or a base material (i) having a transparent resin layer containing compound (A) and a transparent resin layer containing compound (S), and a dielectric multilayer film formed on at least one side of the base material (i). . Therefore, the optical filter of the present invention has excellent near-infrared ray blocking characteristics, low incident angle dependence, excellent transmittance characteristics in the visible wavelength region, and excellent multi-reflected light reduction effect in the near-infrared wavelength region.

When the optical filter of the present invention is used for a solid-state imaging device, it is preferable that the transmittance in the near-infrared wavelength region is low. In particular, it is known that the light receiving sensitivity of the solid-state imaging device is relatively high in the wavelength range of 800 to 1000 nm, and by reducing the transmittance in this wavelength range, correction of the visibility of the camera image and the human eye can be effectively performed, and excellent color reproducibility can be achieved. can

The optical filter of the present invention has an average transmittance of 5% or less, preferably 4% or less, more preferably 3% or less, particularly preferably, when measured from the vertical direction of the optical filter in the wavelength range of 800 to 1000 nm less than 2%. When the average transmittance at a wavelength of 800 to 1000 nm is within this range, it is preferable because near infrared rays can be sufficiently blocked and excellent color reproducibility can be achieved.

When the optical filter of the present invention is used for a solid-state imaging device or the like, a higher visible light transmittance is preferable. Specifically, the average transmittance measured from the vertical direction of the optical filter in the wavelength range of 430 to 580 nm is preferably 75% or more, more preferably 80% or more, even more preferably 83% or more, particularly preferably more than 85% When the average transmittance in this wavelength range is within this range, excellent imaging sensitivity can be achieved when the optical filter of the present invention is used for a solid-state imaging device.

The optical filter of the present invention has a value (Xa) of the shortest wavelength at which the transmittance is 50% when measured from the vertical direction of the optical filter in the wavelength range of 560 to 800 nm, and a value of 30° with respect to the vertical direction of the optical filter. The one where the absolute value of the difference of the value (Xb) of the wavelength at which the transmittance|permeability when measured from an angle becomes 50% is small is preferable. The absolute value of the difference between (Xa) and (Xb) is preferably less than 20 nm, more preferably less than 15 nm, and particularly preferably less than 10 nm. Such an optical filter is obtained by forming a dielectric multilayer film on the substrate (i).

The optical filter of the present invention has a dielectric multilayer film on at least one surface of the substrate (i). The dielectric multilayer film of the present invention is a film having an ability to reflect near infrared rays. In the present invention, the near-infrared reflective film may be formed on one side or both sides of the substrate (i). When formed on one side, the manufacturing cost and ease of manufacture are excellent, and when formed on both sides, an optical filter having high strength and hardly warping or twisting can be obtained. When an optical filter is applied to a solid-state imaging device, it is preferable to form a dielectric multilayer film on both surfaces of a resin substrate, since it is preferable that the warpage or twist of the optical filter is small.

The dielectric multilayer film preferably has reflection characteristics over the entire wavelength range of 700 to 1100 nm, more preferably has reflection characteristics over the entire wavelength range of 700 to 1150 nm, and particularly preferably 700 to 1200 nm. In the form of having a dielectric multilayer film on both sides of the substrate (i), a first optical layer having a reflection characteristic mainly in the vicinity of a wavelength of 700 to 950 nm when measured from an angle of 5 ° with respect to the vertical direction of the optical filter of the substrate (i) A form having a second optical layer having on one side and having a reflection characteristic mainly in the vicinity of 900 nm to 1150 nm when measured from an angle of 5 ° with respect to the vertical direction of the optical filter on the other side of the substrate (i) (FIG. 3 (a) of) or, when measured from an angle of 5 ° with respect to the vertical direction of the optical filter, a third optical layer having a reflection characteristic mainly in the vicinity of a wavelength of 700 to 1150 nm is provided on one side of the substrate (i), and (i) a form having a fourth optical layer having an antireflection property in the visible region on the other side (see FIG. 3(b)), and the like.

Since the optical filter of the present invention contains the compound (S) in the base material (i), even if it has a dielectric multilayer film having a near-infrared reflection characteristic, the reflectance when near-infrared rays are incident from an oblique direction on at least one surface of the optical filter can be reduced. can In particular, the optical filter has a first optical layer on one side and a second optical layer on the other side, or a third optical layer on one side of the optical filter and a fourth optical layer on the other side. In the case of having , this tendency becomes remarkable. As a result of intensive studies, the present applicant has found that light in the near-infrared wavelength region incident from an oblique direction with respect to the vertical direction, in particular oblique incident light having a wavelength of 815 to 935 nm, is the main cause of various ghosts during multiple reflections. The lowest value of the reflectance measured from at least one side when measured from an angle of 30° with respect to the vertical direction of the optical filter in the wavelength range of 815 to 935 nm is preferably 80% or less, more preferably 75% or less, particularly Preferably it is 70% or less. If the reflectance is within this range, it is preferable because various ghosts resulting from multiple reflected light tend to be reduced when used for solid-state imaging devices, especially when shooting a scene including a light source in a dark place.

The thickness of the optical filter of the present invention may be appropriately selected according to the desired application, but according to the trend of thinning and weight reduction of solid-state imaging devices in recent years, it is preferable that the thickness of the optical filter of the present invention is also thin. Since the optical filter of the present invention includes the substrate (i), it is possible to reduce the thickness.

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

[Description (i)]

The substrate (i) may be a single layer or a multilayer, and has a transparent resin layer containing at least one compound (A) and at least one compound (S), or a transparent resin layer containing compound (A) and compound (S). ). In the case where the substrate (i) is a single layer, for example, a substrate made of a transparent resin substrate (ii) containing the compound (A) and the compound (S) is exemplified, and this transparent resin substrate (ii) is It becomes the said transparent resin layer. In the case of a multilayer, a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) and the compound (S) is laminated on a support such as a glass support or a base resin support, for example. A base material, a base material in which a resin layer such as an overcoat layer containing a curable resin containing the compound (A) is laminated on a substrate (iii) made of a transparent resin containing the compound (S), and a transparent containing compound (A) A base material on which a resin layer such as an overcoat layer containing a curable resin containing the compound (S) is laminated on a resin substrate (iv), a transparent resin substrate containing the compound (A) and the compound (S) (ii) ) on which a resin layer such as an overcoat layer containing a curable resin or the like is laminated. From the viewpoints of manufacturing cost and ease of adjusting optical properties, and achieving the effect of removing scratches on a resin support or transparent resin substrate (ii) and improving the scratch resistance of the base material (i), the compound (A) A base material in which a resin layer such as an overcoat layer containing a curable resin is laminated on a transparent resin substrate (ii) containing the compound (S) is particularly preferred. Further, when a glass support is used as the support for the substrate (i), a glass support that does not contain a near-infrared absorber is particularly preferable from the viewpoint of strength of the substrate and support for thinning.

Hereinafter, a layer containing at least one kind selected from compounds (A) and compounds (S) and a transparent resin is also referred to as a "transparent resin layer", and other resin layers are simply referred to as a "resin layer".

The lowest transmittance (Ta) measured from the vertical direction of the substrate (i) in the wavelength region of 600 nm or more and less than 750 nm is preferably 40% or less, more preferably 25% or less, particularly preferably 10% or less.

The shortest wavelength (Xc) at which the transmittance measured from the vertical direction of the substrate (i) in the wavelength region of 600 nm or more becomes from more than 50% to 50% or less is preferably 610 to 670 nm, more preferably 620 to 665 nm, Particularly preferably, it is 630 to 660 nm.

When (Ta) and (Xc) of the substrate (i) are within these ranges, unnecessary near-infrared rays can be selectively and efficiently blocked, and when a dielectric multilayer film is formed on the substrate (i), it is near the visible wavelength to near-infrared wavelength range. It is possible to reduce the incident angle dependence of the optical properties of .

The lowest transmittance (Tb) measured from the vertical direction of the substrate (i) in the wavelength region of 800 nm or more and 1050 nm or less is preferably 80% or less, more preferably 70% or less, particularly preferably 60% or less.

When the (Tb) of the substrate (i) is within this range, the reflectance when near-infrared rays are incident from an oblique direction when the dielectric multilayer film is formed on the substrate (i) after maintaining high visible light transmittance can be reduced.

The average transmittance of the substrate (i) at a wavelength of 430 to 580 nm is preferably 75% or more, more preferably 78% or more, and particularly preferably 80% or more. If a substrate having such transmission characteristics is used, it is possible to achieve high light transmission characteristics in the visible region and to achieve a high-sensitivity camera function.

The thickness of the substrate (i) can be appropriately selected depending on the intended use and is not particularly limited, but is preferably appropriately selected so as to reduce the incident angle dependence of the obtained optical filter, preferably 10 to 200 μm, more preferably 15 to 180 μm, particularly preferably 20 to 150 μm.

When the thickness of the substrate (i) is within the above range, an optical filter using the substrate (i) can be reduced in thickness and weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when the base material (i) including the transparent resin substrate (ii) is used for a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height and weight.

<Compound (A)>

The compound (A) is not particularly limited as long as it has an absorption maximum at a wavelength of 600 nm or more and less than 750 nm, but is preferably a solvent-soluble dye compound, and is selected from the group consisting of squarylium compounds, phthalocyanine compounds and cyanine compounds. It is more preferable that it is 1 type, and it is still more preferable that it contains a squarylium-type compound, and it is still more preferable that it contains at least one type of each of a squarylium-type compound and the other compound (A), and as the other compound (A), phthalocyanine A type compound and a cyanine type compound are particularly preferable.

Although squarylium-based compounds have excellent visible light transmittance, steep absorption characteristics, and high molar extinction coefficient, they sometimes generate fluorescence that causes scattered light upon absorption of light. In such a case, by using a squarylium-based compound in combination with the other compound (A), an optical filter with less scattered light and better camera image quality can be obtained.

The absorption maximum wavelength of the compound (A) is preferably 620 nm or more and 748 nm or less, more preferably 650 nm or more and 745 nm or less, and particularly preferably 660 nm or more and 740 nm or less.

The content of the compound (A) is determined as the base material (i), for example, a base material containing a transparent resin substrate (ii) containing the compound (A) and the compound (S) or a base material containing the compound (A). In the case of using a base material in which a resin layer such as an overcoat layer containing a curable resin containing the compound (S) is laminated on a transparent resin substrate (iv), the amount is preferably 0.01 to 2.0 weight relative to 100 parts by weight of the transparent resin. part, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight, and as the substrate (i), the compound (A) and the compound (S) are added to a glass support or a base resin support. A base material on which a transparent resin layer such as an overcoat layer containing a curable resin or the like is laminated, or a transparent resin substrate (iii) containing a compound (S) containing a curable resin or the like containing a compound (A) In the case of using a substrate laminated with a resin layer such as an overcoat layer, the amount is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.0 parts by weight, based on 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). part, particularly preferably 0.3 to 3.0 parts by weight.

<Compound (S)>

The compound (S) is not particularly limited as long as it has an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less, but it is preferably a solvent-soluble dye compound, and squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, naphthalocyanine-based compounds, It is more preferably at least one selected from the group consisting of a rolopyrrole compound, a croconium compound, a hexapyrine compound, a metal dithiolate compound, and a ring-extended BODIPY (borondipyrromethene) compound, and is a squarylium-based compound. It is more preferably at least one selected from the group consisting of compounds, cyanine-based compounds, pyrrolopyrrole-based compounds, and metal dithiolate-based compounds, and is particularly preferably a squarylium-based compound represented by the following formula (Z). By using such a compound (S), high near-infrared ray blocking properties near the absorption maximum and good visible light transmittance can be simultaneously achieved.

In formula (Z), substitution units A and B each independently represent any of the substitution units represented by the following formulas (I) and (II).

In Formulas (I) and (II), the part indicated by the broken line represents the binding site with the central tetrahedral ring,

X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ -;

R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R ⁱ group, - OSO ₂ Represents a R ⁱ group or any of the following La to L ^h , R ^g and R ^h each independently ^represent a hydrogen atom, a -C(O)R ⁱ group or any of the following La to ^{L e ,} and R ⁱ represents any one of the following La to ^{L e ,}

(L ^a ) An aliphatic hydrocarbon group having 1 to 12 carbon atoms

(L ^b ) A halogen-substituted alkyl group having 1 to 12 carbon atoms

(L ^c ) An alicyclic hydrocarbon group having 3 to 14 carbon atoms

(L ^d ) Aromatic hydrocarbon group having 6 to 14 carbon atoms

(L ^e ) Heterocyclic group having 3 to 14 carbon atoms

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

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

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

The substituent L is composed of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. It is at least 1 sort(s) selected from the group.

Preferably, R ¹ is 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, a cyclohexyl group, a phenyl group, They are a hydroxyl group, an amino group, a dimethylamino group, and a nitro group, More preferably, they are a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, n-propyl group, an isopropyl group, and a hydroxyl group.

As the R ² to R ⁷ , preferably, independently of one another, 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, Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, tri Fluoromethanoylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexanoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group and more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a hydroxyl group, a dimethylamino group, a methoxy group, an ethoxy group, an acetylamino group, and a propionylamino group. , a trifluoromethanoylamino group, a pentafluoroethanoylamino group, a t-butanoylamino group, a cyclohexanoylamino group, a methylthio group, or an ethylthio group.

Preferably, R ⁸ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, n-pentyl group, or n-hexyl group. Pyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, more preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, They are tert-butyl group and n-decyl group.

The X is preferably an oxygen atom, a sulfur atom, or -NR ⁸ -, particularly preferably an oxygen atom or a sulfur atom in the substituted unit of formula (I), and -NR ⁸ in the substituted unit of formula (II). -am.

In addition to the description method such as the following formula (S1), the structure of the squarylium-based compound can also be expressed by the description method taking a resonance structure such as the following formula (S2). That is, the difference between the following formula (S1) and the following formula (S2) is only the method of describing the structure, and all represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium-based compound is shown by a description method such as the following formula (S1).

In addition, for example, a compound represented by the following formula (S1) and a compound represented by the following formula (S3) can be regarded as the same compound.

In the compound represented by formula (Z), the left and right units bonded to the central quaternary ring may be the same or different as long as they are represented by formula (I) or formula (II), respectively. One is preferable because it is synthetically easy. That is, among the compounds represented by the formula (Z), those represented by the following formula (III) or formula (IV) are preferable.

Specific examples of the compound represented by the formula (Z) include compounds (s-1) to (s-58) shown in Tables 1 and 2 below, and compounds (s-59) and compounds represented by the following formulas ( s-60).

As squarylium-based compounds, cyanine-based compounds, pyrrolopyrrole-based compounds, and metal dithiolate-based compounds other than the squarylium-based compound represented by the above formula (Z), it is not particularly limited as long as it has an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less. , For example, the following compounds (s-61) to (s-67) are exemplified.

The absorption maximum wavelength of the compound (S) is 750 nm or more and 1050 nm or less, preferably 770 nm or more and 1000 nm or less, more preferably 780 nm or more and 970 nm or less, still more preferably 790 nm or more and 960 nm or less, particularly preferably 800 nm or more and 950 nm or less. . When the maximum absorption wavelength of the compound (S) is within this range, unnecessary near-infrared rays that cause various ghosts can be effectively blocked.

The compound (S) 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. 3094037, Japanese Patent No. 3196383 It can be synthesized with reference to methods described in publications and the like.

The content of the compound (S) is, as the base material (i), for example, a base material containing a transparent resin substrate (ii) containing the compound (A) and the compound (S) or a base material containing the compound (S). In the case of using a base material in which a resin layer such as an overcoat layer containing a curable resin containing the compound (A) is laminated on a transparent resin substrate (iii), the amount is preferably 0.01 to 2.0 weight relative to 100 parts by weight of the transparent resin. part, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight, and as the substrate (i), the compound (A) and the compound (S) are added to a glass support or a base resin support. A base material on which a transparent resin layer such as an overcoat layer containing a curable resin or the like is laminated, or a transparent resin substrate (iv) containing a compound (A) containing a curable resin or the like containing a compound (S) In the case of using a substrate laminated with a resin layer such as an overcoat layer, the amount is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.0 parts by weight, based on 100 parts by weight of the resin forming the transparent resin layer containing the compound (A). part, particularly preferably 0.3 to 3.0 parts by weight. When the content of the compound (S) is within the above range, an optical filter having both good near-infrared absorption characteristics and high visible light transmittance can be obtained.

<Other pigments (X)>

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

Other dyes (X) are not particularly limited as long as they have an absorption maximum wavelength of less than 600 nm or more than 1050 nm, but those having an absorption maximum wavelength of more than 1050 nm are preferred. Examples of such a dye include squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, octapyrine compounds, dimonium compounds, pyrrolopyrrole compounds, borondipyrromethenes ( BODIPY)-based compounds, perylene-based compounds, and at least one compound selected from the group consisting of metal dithiolate-based compounds.

<transparent resin>

The transparent resin layer and the transparent resin substrates (ii) to (iv) to be laminated on a resin support or a glass support can be formed using a transparent resin.

As the transparent resin used for the base material (i), one type may be used alone, or two or more types may be used.

The transparent resin is not particularly limited as long as the effect of the present invention is not impaired. For example, a dielectric multilayer film is formed by high-temperature vapor deposition at a deposition temperature of 100°C or higher to ensure thermal stability and moldability into a film. In order to obtain a film that can be formed, a resin having a glass transition temperature (Tg) of preferably 110 to 380°C, more preferably 110 to 370°C, still more preferably 120 to 360°C is exemplified. In addition, when the glass transition temperature of the resin is 140° C. or higher, a film capable of depositing and forming a dielectric multilayer film at a higher temperature is obtained, which is particularly preferable.

As the transparent resin, when a resin plate having a thickness of 0.1 mm containing the resin is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95%, particularly A resin that is preferably 80 to 95% can be used. When a resin whose total light transmittance falls within this range is used, the resulting substrate exhibits good transparency as an optical film.

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

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

≪Cyclic (poly)olefin resin≫

As the cyclic (poly)olefin-based 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 the resin is hydrogenated Resin obtained by adding is preferable.

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

(i') hydrogen atom

(ii') halogen atom

(iii') a trialkylsilyl group

(iv') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms and 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') a polar group (except for (iv'))

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

(viii') a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by combining R ^x1 and R ^x2 or R ^x3 and R ^x4 (provided that R ^x1 to R ^x4 not involved in the bond are each independently represents an atom or group selected from ') to (vi'))

(ix') A monocyclic hydrocarbon ring or heterocyclic ring formed by combining R ^x2 and R ^x3 with each other (provided that R ^x1 and R ^x4 not involved in the bonding are each independently from the above (i') to (vi') represent selected atoms or groups)

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

≪Aromatic polyether-based resin≫

It is preferable that the aromatic polyether-based 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 monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represent an integer of 0 to 4.

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

Further, the aromatic polyether-based resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

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

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

≪Polyimide-based resin≫

The polyimide-based resin is not particularly limited, as long as it is a high molecular compound containing an imide bond in a repeating unit. can be synthesized in this way.

<<Fluorene polycarbonate type resin>>

The fluorene polycarbonate-based resin is not particularly limited, as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in Japanese Unexamined Patent Publication No. 2008-163194 .

<<Fluorene polyester type resin>>

The fluorene polyester resin is not particularly limited, as long as it is a polyester resin containing a fluorene moiety. can be synthesized in this way.

<<Fluorinated Aromatic Polymer-Based Resins>>

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

≪Acrylic UV curable resin≫

The acrylic UV-curable resin is not particularly limited, but includes one synthesized from a resin composition containing a compound having at least one acrylic or methacrylic group in a molecule and a compound decomposed by ultraviolet rays to generate active radicals. The acrylic ultraviolet curable resin is a substrate (i) in which a transparent resin layer containing a compound (S) and a curable resin is laminated on a glass support or on a resin support as a base, or a substrate containing the compound (S). When using a base material in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated on a transparent resin substrate (ii), the curable resin can be used particularly suitably.

≪Commercial product≫

Examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic (poly)olefin resins include Artone manufactured by JSR Co., Ltd., Zeonoa manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Co., Ltd. As a commercial item of polyether sulfone type-resin, Sumitomo Chemical Co., Ltd. product Sumica Excel PES etc. are mentioned. As a commercial item of polyimide-type resin, Mitsubishi Gas Chemical Co., Ltd. neoprem L etc. are mentioned. As a commercial item of 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. product Uphizeta EP-5000 grade|etc., is mentioned. As a commercial item of fluorene polyester type resin, Osaka Gas Chemical Co., Ltd. product OKP4HT etc. are mentioned. As a commercial item of acrylic resin, Ac reviewer by Nippon Shokubai Co., Ltd., etc. are mentioned. As a commercial item of a silsesquioxane type|system|group UV curable resin, the Nippon Steel Chemical Co., Ltd. Silplus etc. are mentioned.

<Other ingredients>

The base material (i) may further contain additives such as antioxidants, near-ultraviolet absorbers, and fluorescence quenchers within a range not impairing the effects of the present invention. These other components may be used individually by 1 type, and may use 2 or more types together.

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

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

In addition, these additives may be mixed with a resin or the like when manufacturing the substrate (i), or may be added when synthesizing the resin. The addition amount is appropriately selected depending on the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the resin.

<Method for producing base material (i)>

When the substrate (i) is a substrate comprising the transparent resin substrates (ii) to (iv), the transparent resin substrates (ii) to (iv) may be formed by, for example, melt molding or cast molding. Alternatively, a base material on which an overcoat layer is stacked may be prepared by coating a coating agent such as an antireflection agent, a hard coat agent, and/or an antistatic agent after molding, if necessary.

When the base material (i) is a base material in which a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) and the compound (S) is laminated on a glass support or a base resin support, Example For example, a resin solution containing compound (A) and compound (S) is melt-molded or cast-molded on a glass support or a base resin support, preferably by a method such as spin coating, slit coating, or ink jet coating. After that, the solvent is removed by drying, and a base material having a transparent resin layer formed on a glass support or a base resin support can be manufactured by further irradiating light or heating as necessary.

≪Melt molding≫

As the melt molding, specifically, a method of melt molding a pellet obtained by melt kneading a resin, a compound (A), a compound (S), or the like; a method of melt-molding a resin composition containing a resin, compound (A), and compound (S); or a method of melting and molding pellets obtained by removing the solvent from a resin composition containing the compound (A), the compound (S), the resin, and the solvent. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫

Examples of the cast molding include a method of casting a resin composition containing compound (A), compound (S), resin, and solvent onto a suitable support and removing the solvent; or a method of casting a curable composition containing compound (A), compound (S), photocurable resin and/or thermosetting resin onto an appropriate support, removing the solvent, and then curing by an appropriate method such as ultraviolet irradiation or heating; can also be produced by

When the substrate (i) is a substrate including a transparent resin substrate (ii) containing compound (A) and compound (S), the substrate (i) can be obtained by peeling the coating film from the support after cast molding. In addition, a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) and the compound (S) is formed on a support such as a glass support or a base resin support for the base material (i). In the case of a laminated base material, the base material (i) can be obtained by not peeling off the coating film after cast molding.

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

In addition, a transparent resin layer may be formed on an optical component such as a method of coating an optical component such as a glass plate, quartz or transparent plastic with the resin composition and drying a solvent, or a method of coating the curable composition and curing and drying it. may be

The amount of residual solvent in the transparent resin layer (transparent resin substrate (ii)) obtained by the above method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and even more preferably 0.5% by weight or less relative to the weight of the transparent resin layer (transparent resin substrate (ii)). . When the amount of residual solvent is within the above range, a transparent resin layer (substrate (ii) made of transparent resin) that is hard to deform or change in characteristics and can easily exhibit desired functions is obtained.

[dielectric multilayer film]

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

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

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

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, where λ (nm) is the wavelength of the near-infrared rays to be blocked. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is within this range, the optical film thickness calculated by the product of the refractive index (n) and the film thickness (d) (n × d) as λ/4, and the thickness of each layer of the high refractive index material layer and the low refractive index material layer are approximately It tends to be the same value, and the blocking/transmission of a specific wavelength can be easily controlled from the relation of the optical characteristics of reflection/refraction.

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

In the present invention, the material type 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, and the order of lamination according to the absorption characteristics of the compound (A) or compound (S) , By appropriately selecting the number of layers, after ensuring sufficient transmittance in the visible region, it is possible to have sufficient light blocking properties in the near-infrared wavelength region and reduce the reflectance when near-infrared rays are incident from an oblique direction.

In order to optimize the above conditions, for example, optical thin film design software (e.g., Essential Macleod, manufactured by Thin Film Center) is used, so that the antireflection effect in the visible region and the light blocking effect in the near infrared region can be compatible. Just set the parameters. In the case of the above software, for example, when designing the first optical layer, the target transmittance of wavelengths of 400 to 700 nm is set to 100% and the value of Target Tolerance is set to 1, and then the target transmittance of wavelengths of 705 to 950 nm is set to 0. Parameter setting methods such as setting the value of % and Target Tolerance to 0.5 can be mentioned. These parameters may change the value of Target Tolerance by dividing the wavelength range more finely according to various characteristics of the substrate (i).

[Other Functional Films]

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

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

The method for laminating the functional film is not particularly limited, but examples thereof include a method in which a coating agent such as an antireflection agent, a hard coat agent, and/or an antistatic agent is melt-molded or cast-molded to the substrate (i) or the dielectric multilayer film in the same manner as described above. .

In addition, it can also be produced by applying the curable composition containing the coating agent or the like onto the substrate (i) or the dielectric multilayer film with a bar coater or the like and then curing it by irradiation with ultraviolet light or the like.

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

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

The compounding ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, still more preferably 1 to 5% by weight, based on 100% by weight of the total amount of the curable composition. am. When the blending ratio of the polymerization initiator is within the above range, the curable composition has excellent curing properties and handling properties, and functional films such as antireflection films, hard coat films, and antistatic films having desired hardness can be obtained.

In addition, an organic solvent may be added to the curable composition as a solvent, and a known organic solvent can be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons, such as benzene, toluene, and xylene; Amides, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, are mentioned.

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

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

In addition, for the purpose of improving the adhesion between the substrate (i) and the functional film and/or the dielectric multilayer film or the adhesion between the functional film and the dielectric multilayer film, the surface of the substrate (i), the functional film, or the dielectric multilayer film is subjected to corona treatment or plasma treatment. can be processed

[Usage of optical filter]

The optical filter of the present invention has a wide viewing angle, excellent near-infrared ray blocking ability, and the like. Therefore, it is useful for correcting the visibility of solid-state imaging devices such as CCD and CMOS image sensors of camera modules. In particular, digital still cameras, smart phone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, portable information terminals, video game consoles, portable game consoles, fingerprint authentication Useful for systems, digital music players, etc. In addition, it is also useful as a heat ray cut filter mounted on a glass plate or the like of automobiles, buildings, or the like.

[Solid-state imaging device]

The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device is an image sensor having a solid-state imaging device such as a CCD or CMOS image sensor, and specifically, it is used for applications such as digital still cameras, smart phone cameras, mobile phone cameras, wearable device cameras, and digital video cameras. available. For example, the camera module of the present invention includes the optical filter of the present invention.

[Example]

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

<molecular weight>

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

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

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

In addition, for the resin synthesized in Resin Synthesis Example 3 described later, the logarithmic viscosity was measured by the following method (c) instead of measuring the molecular weight by the above method.

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

μ={ln(t _s /t ₀ )}/C

t ₀ : solvent flow time

t _s : flow time of lean polymer solution

C: 0.5 g/dL

<Glass transition temperature (Tg)>

The temperature increase rate was measured at 20°C per minute under a nitrogen stream using a differential scanning calorimeter (DSC6200) manufactured by SII·Technology Co., Ltd.

<Spectral transmittance>

(Ta), (Xc) and (Tb) of the substrate and the transmittance in each wavelength region of the optical filter, (Xa) and (Xb) were measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Co., Ltd. was measured using

Here, in the case of transmittance measured from the vertical direction of the optical filter, as shown in FIG. In (b) of FIG. 2, light transmitted at an angle of 30° with respect to the vertical direction of the filter was measured. In addition, for the reflectance measured at an angle of 30° with respect to the vertical direction of the optical filter, as shown in FIG. In the case of the reflectance measured from an angle of 5°, the measurement was performed by setting an optical filter on a jig attached to the apparatus as shown in FIG. 2(d).

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

[Synthesis Example]

Compound (A) and Compound (S) used in the following Examples were synthesized by generally known methods. As a general synthesis method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open No. 1 -146846, Japanese Patent Laid-Open No. 1-228960, Japanese Patent No. 4081149, Japanese Patent Laid-Open No. 63-124054, "Phthalocyanine -Chemistry and Function-" (IPC, 1997), Japanese Patent Laid-Open The methods described in Japanese Patent Laid-open No. 2007-169315, Japanese Unexamined Patent Publication No. 2009-108267, Japanese Unexamined Patent Publication No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631 and the like are exemplified.

<Resin Synthesis Example 1>

100 parts of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^{2,5.1 7,10} ]dodeca-3-ene represented by the following formula (a) (hereinafter also referred to as "DNM"); 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene (a solvent for ring-opening polymerization reaction) were introduced into a nitrogen-purged reaction vessel, and the solution was heated to 80°C. Subsequently, 0.2 part of a toluene solution of triethylaluminum (0.6 mol/liter) as a polymerization catalyst and 0.9 part of a toluene solution of tungsten hexachloride (concentration: 0.025 mol/liter) modified with methanol were added to the solution in the reaction vessel, and this solution was A ring-opening polymerization reaction was carried out by heating and stirring at 80°C for 3 hours 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 obtained in this way was put into an autoclave, 0.12 part of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution, and the hydrogen gas pressure was 100 kg/cm ² , and the reaction temperature was The hydrogenation reaction was performed by heating and stirring under conditions of 165°C for 3 hours. 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, the coagulated material was separated and collected, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The obtained Resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165°C.

<Resin Synthesis Example 2>

In a 3L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g (0.300 mol) of potassium carbonate ), 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 coke with a nitrogen inlet tube, a Dean Stark tube, and a cooling tube were installed in the four-necked flask. Subsequently, after purging the inside of the flask with nitrogen, the obtained solution was reacted at 140°C for 3 hours, and the resulting water was removed from the Dean Stark tube at any time. When the production of water was no longer seen, the temperature was gradually raised to 160°C, and the mixture was reacted at the same temperature for 6 hours. After cooling to room temperature (25°C), the produced salt was removed with a filter paper, the filtrate was reprecipitated in methanol, and the filtrate (residue) was isolated by filtration. The resulting 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 weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285°C.

<Resin Synthesis Example 3>

1,4-bis(4-amino-α,α-dimethylbenzyl) was added to a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with bypass tube, Dean Stark tube and cooling tube under a nitrogen stream. 27.66 g (0.08 mol) of benzene and 7.38 g (0.02 mol) of 4,4'-bis(4-aminophenoxy)biphenyl were dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide. made it The resulting solution was cooled to 5° C. using an ice water bath, and while maintaining 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 were added. (0.005 mol) was added in one batch. After completion of the addition, the temperature was raised to 180°C, and the mixture was refluxed for 6 hours while distilling off the distillate from time to time. After completion of the reaction, air cooling was performed until the internal temperature reached 100°C, followed by dilution by adding 143.6 g of N,N-dimethylacetamide and cooling while stirring to obtain 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight. . A portion of this polyimide resin solution was poured into 1 L of methanol to precipitate polyimide. After washing the filtered polyimide with methanol, it was dried for 24 hours in a vacuum dryer at 100°C to obtain a white powder (hereinafter also referred to as "Resin C"). As a result of measuring the IR spectrum of the obtained Resin C, absorptions at 1704 cm ^-1 and 1770 cm ^-1 peculiar to the imide group were observed. Resin C had a glass transition temperature (Tg) of 310°C and a logarithmic viscosity of 0.87.

[Example 1]

In Example 1, an optical filter having a base material comprising a transparent resin substrate was produced in the following procedure and conditions.

In a container, 100 parts of Resin A obtained in Resin Synthesis Example 1, 0.02 part of the compound (s-11) described in Table 1 (maximum absorption wavelength in dichloromethane: 776 nm) as compound (S), and the following formula as compound (A) 0.03 part of compound (a-1) represented by (a-1) (maximum absorption wavelength in dichloromethane) and compound (a-2) represented by the following formula (a-2) (maximum absorption in dichloromethane) wavelength 733 nm) and methylene chloride were added to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, and after drying at 20°C for 8 hours, it was peeled from the glass plate. The peeled coating film was further dried at 100°C for 8 hours under reduced pressure to obtain a base material made of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. The spectral transmittance of this substrate was measured, and (Ta), (Tb) and (Xc) were obtained. Results are shown in Figure 4 and Table 5.

Subsequently, a dielectric multilayer film (I) was formed as a first optical layer on one side of the obtained substrate, and a dielectric multilayer film (II) was formed as a second optical layer on the other side of the substrate to obtain an optical filter having a thickness of about 0.104 mm. .

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

The design of the dielectric multilayer films (I) and (II) was performed as follows.

Regarding the thickness of each layer and the number of layers, the wavelength-dependent characteristics of the refractive index of the substrate or the absorption of the applied compound (S) and compound (A) can be achieved to achieve the antireflection effect in the visible region and the selective transmission/reflection performance in the near infrared region. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) according to the characteristics. When performing the optimization, in this embodiment, the input parameter (Target value) to the software was set as shown in Table 3 below.

As a result of optimizing the film configuration, in Example 1, the dielectric multilayer film (I) is a multilayer deposited film of 26 layers, in which silica layers with a film thickness of 31 to 157 nm and titania layers with a film thickness of 10 to 95 nm are alternately laminated, and the dielectric multilayer film (II) was a multilayer deposited film of 20 layers formed by alternately stacking silica layers with a film thickness of 38 to 199 nm and titania layers with a film thickness of 12 to 117 nm. Table 4 shows an example of an optimized film configuration, and a spectral reflectance spectrum measured from an angle of 5° from the vertical direction of a glass substrate for deposition monitoring in which each dielectric multilayer film is formed on one side as a single film is shown in FIG. 5. In addition, when measuring the reflectance of glass for deposition monitoring, in order to eliminate the influence of backside reflection, the surface on which the dielectric multilayer film is not formed is painted over with black acrylic paint to prevent reflection, and then the surface on which the dielectric multilayer film is formed is measured. It was set as the incident surface of the measurement light.

The spectral transmittance measured from the vertical direction of the obtained optical filter and at an angle of 30° from the vertical direction was measured, and the optical properties in each wavelength range were evaluated. Results are shown in Figure 6 and Table 5. In addition, the spectral reflectance of the optical filter obtained was measured at an angle of 30° from the vertical direction of each surface. It was confirmed that the value of the lowest reflectance in the range of 1 to 935 nm became small. Fig. 7 shows a spectral reflectance spectrum measured at an angle of 30 DEG from the vertical direction of the optical filter when the light incident surface is on the dielectric multilayer film (II) side. The average value of the transmittance at a wavelength of 430 to 580 nm is 88%, the average value of the transmittance at a wavelength of 800 to 1000 nm is 1% or less, and the vertical direction at a wavelength of 815 to 935 nm When measured from an angle of 30 °, The lowest value of the reflectance measured from at least one side was 61%, and the absolute value |Xa-Xb| was 3 nm.

[Example 2]

In Example 1, instead of 0.02 part of compound (s-11), 0.005 part of compound (s-27) (maximum absorption wavelength in dichloromethane) of Table 1 was used and the following formula (a) as compound (A) -3) 0.03 part of compound (a-3) (maximum absorption wavelength in dichloromethane 703 nm) and compound (a-4) represented by the following formula (a-4) (maximum absorption wavelength in dichloromethane 736 nm) ) A base material comprising a transparent resin substrate containing compound (S) and compound (A) was obtained in the same procedure and conditions as in Example 1 except for using 0.07 part. The spectral transmittance of this substrate was measured, and (Ta), (Tb) and (Xc) were obtained. Results are shown in Figure 8 and Table 5.

Subsequently, as in Example 1, a dielectric multilayer film (III) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (a total of 26 layers) as a first optical layer is formed on one side of the obtained base material, Further, as a second optical layer, a dielectric multilayer film (IV) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (a total of 20 layers) is formed on the other side of the base material to have a thickness of about 0.104 mm. I got an optical filter. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the substrate. The spectral transmittance of the obtained optical filter was measured, and the optical properties in each wavelength range were evaluated. Results are shown in Figure 9 and Table 5. In addition, as a result of measuring the spectral reflectance of the obtained optical filter at an angle of 30° from the vertical direction of each surface, when the light incident surface is the dielectric multilayer film (IV) side (second optical layer side), the wavelength It was confirmed that the value of the lowest reflectance in 815 to 935 nm became small. Fig. 10 shows a spectral reflectance spectrum measured at an angle of 30 DEG from the vertical direction of the optical filter when the light incident surface is the dielectric multilayer film (IV) side.

[Example 3]

In Example 3, an optical filter having a base material comprising a transparent resin substrate having resin layers on both sides was fabricated in the following procedure and conditions.

In Example 1, instead of 0.02 part of compound (s-11), 0.02 part of compound (s-25) shown in Table 1 (maximum absorption wavelength in dichloromethane: 781 nm) was used, and as compound (A), compound (a- 1) Transparent resin containing compound (S) and compound (A) in the same procedure and conditions as in Example 1 except for using 0.03 part, 0.01 part of compound (a-3) and 0.08 part of compound (a-4) got the board

A resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater, and heated in an oven at 70° C. for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Subsequently, exposure (exposure amount of 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine to cure the resin composition (1), and a resin layer was formed on the 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 sides of the transparent resin substrate containing the compound (S) and the compound (A). The spectral transmittance of this substrate was measured, and (Ta), (Tb) and (Xc) were obtained. The results are shown in Table 5.

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

Subsequently, as in Example 1, a dielectric multilayer film (V) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (a total of 26 layers) as a first optical layer was formed on one side of the obtained base material, Further, as a second optical layer, a dielectric multilayer film (VI) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (total of 20 layers) was formed on the other side of the base material to have a thickness of about 0.108 mm. I got an optical filter. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the substrate and the like as in Example 1. The spectral transmittance and spectral reflectance of this optical filter were measured, and the optical properties in each wavelength range were evaluated. The results are shown in Table 5.

[Example 4]

In Example 4, an optical filter having a base material comprising a resin substrate having transparent resin layers containing compound (S) and compound (A) on both sides was fabricated in the following procedure and conditions.

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

A resin product having a transparent resin layer containing the compound (S) and the compound (A) on both sides of the obtained resin substrate by forming a resin layer containing the resin composition (2) having the following composition in the same manner as in Example 3 A substrate including a substrate was obtained. The spectral transmittance of this substrate was measured, and (Ta), (Tb) and (Xc) were obtained. The results are shown in Table 5.

Resin composition (2): tricyclodecane dimethanol acrylate 100 parts by weight, 1-hydroxycyclohexylphenyl ketone 4 parts by weight, compound (s-11) 0.50 parts by weight, compound (a-1) 0.75 parts by weight, compound (a-2) 0.75 parts by weight, methyl ethyl ketone (solvent, TSC: 25%)

Subsequently, as in Example 1, a dielectric multilayer film (VII) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (a total of 26 layers) as a first optical layer is formed on one side of the obtained base material, Further, as a second optical layer, a dielectric multilayer film (VIII) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (total of 20 layers) is formed on the other side of the base material to have a thickness of about 0.108 mm. I got an optical filter. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the substrate and the like as in Example 1. The spectral transmittance and spectral reflectance of this optical filter were measured, and the optical properties in each wavelength range were evaluated. The results are shown in Table 5.

[Example 5]

In Example 5, an optical filter having a base material comprising a transparent glass substrate having a transparent resin layer containing compound (S) and compound (A) on one side thereof was manufactured according to the following procedure and conditions.

On a transparent glass substrate "OA-10G (thickness: 200 µm)" (manufactured by Nippon Denki Glass Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width, a resin composition (3) having the following composition was applied by a spin coater, The solvent was volatilized off by heating at 80°C for 2 minutes on a hot plate. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying was 2 μm. Subsequently, exposure (exposure amount of 500 mJ/cm ² , 200 mW) is performed using a conveyor-type exposure machine to cure the resin composition (3) to form a transparent glass substrate having a transparent resin layer containing compound (S) and compound (A). I obtained a document that says The spectral transmittance of this substrate was measured, and (Ta), (Tb) and (Xc) were obtained. The results are shown in Table 5.

Resin composition (3): 20 parts by weight of tricyclodecane dimethanol acrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexylphenyl ketone, 1.0 parts by weight of compound (s-11), 1.5 parts by weight of compound (a-1), 1.5 parts by weight of compound (a-2), methyl ethyl ketone (solvent, TSC: 35%)

Subsequently, as in Example 1, a dielectric multilayer film (IX) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (a total of 26 layers) as a first optical layer was formed on one side of the obtained base material, Further, as a second optical layer, a dielectric multilayer film (X) formed by alternately stacking silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (total of 20 layers) is formed on the other side of the base material to have a thickness of about 0.108 mm. I got an optical filter. The dielectric multilayer film was designed using the same design parameters as in Example 1 after considering the wavelength dependence of the refractive index of the substrate and the like as in Example 1. The spectral transmittance of this optical filter was measured, and the optical properties in each wavelength range were evaluated. The results are shown in Table 5.

[Examples 6 to 15]

A base material and an optical filter were produced in the same manner as in Example 3 except that the resin, solvent, drying conditions for the resin substrate, compound (S) and compound (A) were changed as shown in Table 5. Table 5 shows the optical properties of the obtained substrate and optical filter.

[Comparative Example 1]

A substrate and an optical filter were produced in the same manner as in Example 1, except that Compound (S) and Compound (A) were not used. Table 5 shows the optical properties of the obtained substrate and optical filter.

[Comparative Example 2]

A substrate and an optical filter were produced in the same manner as in Example 3 except that Compound (S) was not used and 0.03 part of Compound (a-1) and 0.03 part of Compound (a-2) were used as Compound (A). Table 5 shows the optical properties of the obtained substrate and optical filter.

[Comparative Example 3]

An optical filter was produced in the same manner as in Example 1, except that a transparent glass substrate "OA-10G (thickness: 200 µm)" (manufactured by Nippon Denki Glass Co., Ltd.) was used as the base material. Table 5 shows the optical properties of the substrate and the obtained optical filter.

The configuration of the base material and various compounds used in Examples and Comparative Examples are as follows.

<Type of description>

Aspect (1): transparent resin substrate containing compound (S) and compound (A)

Aspect (2): having a resin layer on both sides of a transparent resin substrate containing compound (S) and compound (A)

Aspect (3): has a transparent resin layer containing compound (S) and compound (A) on both sides of a resin substrate

Mode (4): having a transparent resin layer containing compound (S) and compound (A) on one side of a glass substrate

Embodiment (5): transparent resin substrate not containing compound (S) and compound (A) (comparative example)

Embodiment (6): having resin layers on both sides of a transparent resin substrate containing compound (A) (comparative example)

Form (7): glass substrate (comparative example)

<transparent resin>

Resin A: cyclic olefin resin (resin synthesis example 1)

Resin B: Aromatic polyether resin (Resin Synthesis Example 2)

Resin C: Polyimide-based resin (Resin Synthesis Example 3)

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

<Glass Substrate>

Glass substrate (1): A transparent glass substrate "OA-10G (thickness: 200 µm)" cut to a size of 60 mm in length and 60 mm in width (manufactured by Nippon Denki Glass Co., Ltd.)

<Near-infrared absorbing dye>

<Compound (A)>

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

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

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

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

Compound (a-5): Cyanine-based compound represented by the following formula (a-5) (maximum absorption wavelength in dichloromethane: 681 nm)

Compound (a-6): squarylium-based compound represented by the following formula (a-6) (maximum absorption wavelength in dichloromethane: 713 nm)

<Solvent>

Solvent (1): Methylene Chloride

Solvent (2): N,N-dimethylacetamide

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

Drying conditions of the (transparent) resin substrates of Examples and Comparative Examples in Table 5 are as follows. In addition, the coating film was peeled from the glass plate before drying under reduced pressure.

<Film Drying Conditions>

Condition (1): 20℃/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

The optical filter of the present invention is widely used in digital still cameras, mobile phone cameras, digital video cameras, personal computer cameras, surveillance cameras, automobile cameras, televisions, vehicle-mounted devices for car navigation systems, portable information terminals, video game consoles, and portable game consoles. , a device for a fingerprint authentication system, a digital music player, and the like. In addition, it can be suitably used as a heat ray cut filter mounted on a glass plate or the like of automobiles, buildings, or the like.

1 : optical filter
2: Spectrophotometer
3: light
4 : Lens
5: solid-state imaging element
6: multi-reflected light
7 : reflection mirror
8: dielectric multilayer film
9: Glass for deposition monitor (rear surface treated with antireflection film)
10: Substrate (i)
11: first optical layer
12: second optical layer
13: third optical layer
14: 4th optical layer

Claims (11)

A substrate and a dielectric multilayer film formed on at least one surface of the substrate,
The base material has a transparent resin layer containing a compound (A) having an absorption maximum at a wavelength of 600 nm or more and less than 750 nm and a compound (S) having an absorption maximum at a wavelength of 750 nm or more and 1050 nm or less, or the compound (A) It has a transparent resin layer containing and a transparent resin layer containing the compound (S),
meets the following requirement (a);
An optical filter characterized in that the compound (S) is a squarylium-based compound represented by the following formula (Z):
(a) An average value of transmittance measured from the vertical direction of the optical filter in a wavelength range of 800 to 1000 nm is 5% or less.

[In formula (Z), substituent units A and B each independently represent any of the substituent units represented by the following formulas (I) and (II)]

[In formulas (I) and (II), the part indicated by the broken line represents the binding site with the central tetracyclic ring,
X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ -;
R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R ⁱ group, - OSO ₂ Represents a R ⁱ group or any of the following La to L ^h , R ^g and R ^h each independently ^represent a hydrogen atom, a -C(O)R ⁱ group or any of the following La to ^{L e ,} and R ⁱ represents any one of the following La to ^{L e ,}
(L ^a ) An aliphatic hydrocarbon group having 1 to 12 carbon atoms
(L ^b ) A halogen-substituted alkyl group having 1 to 12 carbon atoms
(L ^c ) An alicyclic hydrocarbon group having 3 to 14 carbon atoms
(L ^d ) Aromatic hydrocarbon group having 6 to 14 carbon atoms
(L ^e ) Heterocyclic group having 3 to 14 carbon atoms
(L ^f ) An alkoxy group having 1 to 12 carbon atoms
(L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L;
(L ^h ) An alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L
The substituent L is composed of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. At least one species selected from the group] The optical filter according to claim 1, further satisfying the following requirement (b):
(b) The average value of the transmittance measured from the vertical direction of the optical filter in the wavelength range of 430 to 580 nm is 75% or more. The optical filter according to claim 1 or 2, characterized by having dielectric multilayer films on both sides of the substrate. The optical filter according to claim 1 or 2, wherein the compound (A) is at least one compound selected from the group consisting of squarylium-based compounds, phthalocyanine-based compounds, and cyanine-based compounds. The transparent resin according to claim 1 or 2, wherein the transparent resin is a cyclic (poly)olefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, Polycarbonate-based resins, polyamide-based resins, polyarylate-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorinated aromatic polymers At least one resin selected from the group consisting of resin, (modified) acrylic resin, epoxy resin, allyl ester curable resin, silsesquioxane-based UV curable resin, acrylic UV curable resin, and vinyl UV curable resin. characterized optical filters. The optical filter according to claim 1 or 2, wherein the substrate contains a transparent resin substrate containing compound (A) and compound (S). The optical filter according to claim 1 or 2, which is for a solid-state imaging device. A solid-state imaging device comprising the optical filter according to claim 1 or 2. A camera module provided with the optical filter according to claim 1 or 2. delete delete

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