TW201506461A - Optical filter and apparatus using the optical filter - Google Patents

Abstract

An optical filter is provided, which improves problems in former optical filters such as a near-infrared cut-off optical filter, has a wide view angle and high visible light transmittance, and also has high infrared cut-off property in longer wavelength region such as 1100 to 1200 nm of wavelength. The optical filter has a substrate made of a transparent resin containing a near-infrared absorption dye, and a near-infrared reflection film formed on at least one surface of the substrate. The optical filter satisfies conditions (A) to (D).

Description

Filter and device using the same filter

The present invention relates to a filter and an apparatus using the same.

A solid-state imaging device such as a camera, a digital still camera, or a mobile phone with a camera function uses a CCD image sensor or a CMOS image sensor as a solid-state imaging element of a color image. These solid-state imaging elements use a silicon photodiode having sensitivity to near-infrared rays in the light receiving portion. In these solid-state imaging elements, it is necessary to perform visibility correction that exhibits a natural color in a human eye, and a filter that selectively transmits or cuts light of a specific wavelength region (for example, a near-infrared cut filter) is often used. ).

As such a near-infrared cut filter, those manufactured by various methods have been used since. For example, Patent Document 1 discloses a near-infrared cut filter that uses a substrate containing a transparent resin and contains a near-infrared absorbing dye in a transparent resin. However, the near-infrared cut filter described in Patent Document 1 may not necessarily have sufficient near-infrared absorption characteristics.

Further, in Patent Document 2, the applicant proposes a near-infrared cut filter having a norbornene-based resin substrate and a near-infrared reflective film. Patent The near-infrared cut filter described in the second aspect is excellent in near-infrared cut-off characteristics, moisture absorption resistance, and impact resistance, but cannot obtain a wide viewing angle value.

As a result of an effort by the present inventors, it has been found that by using a transparent resin substrate containing a near-infrared absorbing dye having a maximum absorption at a specific wavelength, it is possible to obtain a near-infrared light having little change in optical characteristics even when the incident angle is changed. A cut-off filter and a near-infrared cut filter having a wide viewing angle and a high visible light transmittance are proposed in Patent Document 3.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-200113

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-338395

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-100084

In recent years, in mobile devices and the like, the image quality required for camera images has also become very high. According to the study by the inventors of the present invention, in order to satisfy the demand for high image quality, in the filter, in addition to the wide viewing angle and the high visible light transmittance, high light cutoff characteristics are required in a region having a relatively long wavelength. Previous filters did not satisfactorily meet this characteristic. An object of the present invention is to provide a filter having the light cutoff characteristic.

The inventors of the present invention conducted diligent research and found that by satisfying the following The above problem can be solved by the filter of the requirements of (A) to (D) below, and the present invention has been completed. An example of the form of the present invention is shown below.

[1] A filter comprising: a substrate made of a transparent resin, comprising a near-infrared absorbing pigment; and a near-infrared reflecting film formed on at least one surface of the substrate; and satisfying the following (A) to the following ( D) requirements:

(A) In the region having a wavelength of 430 nm to 580 nm, the average value of the transmittance when measured from the vertical direction of the filter is 75% or more.

(B) When the wavelength is from 800 nm to 1000 nm, the average value of the reflectance measured from at least one surface is 80% or more when measured from an angle of 5° with respect to the vertical direction of the filter.

(C) When the wavelength is from 1100 nm to 1200 nm, the average value of the reflectance measured from at least one surface is 70% or more when measured from an angle of 5° with respect to the vertical direction of the filter.

(D) In the region of the wavelength of 560 nm to 800 nm, the value (Xa) of the longest wavelength at which the transmittance is 50% measured from the vertical direction of the filter, and the vertical direction with respect to the filter are The absolute value of the difference (Xb) of the value (Xb) of the longest wavelength at which the transmittance at the time of measurement at an angle of 30° is 50% is less than 15 nm.

[2] The filter according to [1], which further satisfies the requirements of (E): (E) a haze value measured by a method according to JIS K7105, 2.0% or less.

[3] The optical filter according to [1] or [2] wherein the near-infrared reflective film is a high refractive index material having a refractive index of more than 1.7 and not more than 2.5 in light having a wavelength of 550 nm. a dielectric multilayer film in which a material layer and a low refractive index layer having a refractive index of 1.2 or more and 1.7 or less in light having a wavelength of 550 nm are alternately laminated, and the layer having the highest refractive index and the refractive index in the dielectric multilayer film The refractive index ratio of the layer having the lowest rate is 1.3 or more, and the ratio of the optical film thickness (physical film thickness × refractive index) of the adjacent high refractive index material layer and the low refractive index material layer continuously becomes 0.8~. Part of 1.2.

[4] The optical filter according to any one of [1] to [3] wherein the transparent resin constituting the transparent resin substrate is selected from the group consisting of a cyclic olefin resin and an aromatic polyether resin. Polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamine resin, polyarylate resin, polyfluorene resin, polyether oxime resin, Polyparaphenylene resin, polyamidoximine resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester At least one resin selected from the group consisting of a resin and a silsesquioxane resin.

[5] The optical filter according to any one of [1] to [4] wherein the transparent resin substrate contains a compound selected from the group consisting of a squarylium compound, a cyanine compound, At least one of a group consisting of a phthalocyanine compound, a naphthalocyanine compound, a croconium compound, a dithiol compound, a diimonium compound, and a porphyrin compound Infrared absorption of pigments.

[6] The optical filter according to any one of [1] to [5] wherein the near-infrared absorbing pigment contains a succinic acid ylide salt selected from the formula (I) described later. At least one of a group consisting of a compound and a squarylium ylide compound represented by the formula (II).

[7] The optical filter according to any one of [1] to [6], comprising: the transparent resin substrate; and the near-infrared reflective film formed on both sides of the substrate .

[8] The optical filter according to [7], wherein the near-infrared reflective film is a dielectric multilayer film, and a difference in the number of layers of the dielectric multilayer film formed on both sides of the substrate is 12 Hereinafter, the difference in physical film thickness is 500 nm or less.

[9] The optical filter according to [7] or [8] wherein the near-infrared reflective film is a dielectric multilayer film, and each of the dielectric multilayer films formed on both sides of the substrate In the case where the average optical film thickness of any of the "10 consecutive layers satisfying the following (h)" is compared with each other, the average optical film thickness of the dielectric multilayer film having a relatively large average optical film thickness is another The average optical film thickness of the electric multilayer film is 1.05 times to 1.60 times: (h) the ratio of the optical film thickness (physical film thickness x refractive index) of the adjacent high refractive index material layer to the low refractive index material layer is 0.8~ 1.2.

[10] The filter according to any one of [1] to [9], which is used for a solid-state imaging device.

[11] A solid-state imaging device, comprising the filter according to any one of [1] to [9].

[12] A camera module comprising the filter according to any one of [1] to [9].

According to the present invention, it is possible to provide a wide viewing angle and a high visible light transmittance, and also have a long wavelength in a wavelength range of 1100 nm to 1200 nm. A filter with high light cutoff characteristics. When such a filter is used for a solid-state imaging device, a camera image with good image quality can be obtained in a small camera module such as a mobile device.

1‧‧‧ Filter

2‧‧‧Spectrophotometer

3‧‧‧Light

4‧‧‧Mirror

(a) of FIG. 1 is a schematic view showing a method of measuring the transmittance at the time of measurement from the vertical direction of the optical filter. (b) of FIG. 1 is a schematic view showing a method of measuring the transmittance when measuring from an angle of 30° with respect to the vertical direction of the filter. (c) of FIG. 1 is a schematic view showing a method of measuring the reflectance when measuring from an angle of 5° with respect to the vertical direction of the filter.

Fig. 2 is a schematic view showing cracks which may occur when the filter is processed into a wafer shape.

3 is a schematic view showing a cross-sectional shape of a press die used when the filter is processed into a wafer shape.

Hereinafter, the present invention will be specifically described.

[filter]

The optical filter of the present invention includes a transparent resin substrate and a near-infrared reflective film formed on at least one surface of the substrate. When the near-infrared reflective film is provided on both surfaces of the transparent resin substrate, the warpage of the filter can be further reduced as compared with the case where the near-infrared reflecting film is provided on only one surface.

The filter of the present invention satisfies the requirements of the following (A) to (D) below.

(A) In the region having a wavelength of 430 nm to 580 nm, the average value of the transmittance when measured from the vertical direction of the filter is 75% or more. The average value is preferably 78% or more, more preferably 80% or more.

In the present invention, for example, by using a transparent resin to be described later and an absorbent having no maximum absorption wavelength in the wavelength region, it is possible to obtain a filter having a high transmittance in a region having a wavelength of 430 nm to 580 nm. Device.

(B) When the wavelength is from 800 nm to 1000 nm, the average value of the reflectance measured from at least one surface is 80% or more when measured from an angle of 5° with respect to the vertical direction of the filter. The average value is preferably 85% or more, more preferably 90% or more.

In the present invention, by providing a predetermined near-infrared reflective film having high near-infrared reflection performance on a transparent resin substrate, it is possible to obtain a filter having sufficient reflection characteristics in such a region having a wavelength of 800 nm to 1000 nm. Light.

(C) When the wavelength is from 1100 nm to 1200 nm, the average value of the reflectance measured from at least one surface is 70% or more when measured from an angle of 5° with respect to the vertical direction of the filter. The average value is preferably 80% or more, more preferably 90% or more.

In the present invention, by forming a near-infrared reflective film having a high average reflectance in a region of a wavelength of 1100 nm to 1200 nm on a transparent resin substrate, it is possible to effectively cut off light in the near-infrared region and reduce the wavelength to Infrared transmittance in a region of 1100 nm to 1200 nm. Thereby, in particular, ghosting when shooting a light source or a heat source can be reduced, and the image quality of the obtained camera image is improved.

In the present invention, a near-infrared reflective film can be provided on a transparent resin substrate, and the near-infrared reflective film can coexist with an anti-reflection effect in a visible region and a light-off effect in a near-infrared region. For example, a high refractive index material, a low refractive index material, a sequence in which each high refractive index material and a low refractive index material are laminated, and a thickness and a number of layers of each layer are optimized. Thereby, a filter having sufficient reflection characteristics in a region having a wavelength of 1100 nm to 1200 nm can be obtained. From the viewpoint of calculation accuracy or shortening of time, an optical film design software (for example, Essential Macleod, manufactured by Thin Film Center Co., Ltd.) can be used for optimization of a near-infrared reflective film.

In addition, in order to reduce the transmittance in the wavelength of 1100 nm to 1200 nm, the near-infrared reflective film may be further added to the transparent resin substrate in a range that does not adversely affect the transmittance of the visible region or the like. An absorption pigment or a metal-containing fine particle or the like is present in a region having a wavelength of from 1100 nm to 1200 nm.

In the present invention, it is possible to design the near-infrared reflective film in such a manner that the reflectance measured from one surface of the filter satisfies the requirement (B) and the reflectance measured from the other surface satisfies the requirement (C). The near-infrared reflective film is designed in such a manner that the reflectance measured from one surface of the filter satisfies both the requirements (B) and the requirements (C).

(D) In the region of the wavelength of 560 nm to 800 nm, the value (Xa) of the longest wavelength at which the transmittance is 50% measured from the vertical direction of the filter, and the vertical direction with respect to the filter are The absolute value of the difference (Xb) of the longest wavelength at which the transmittance at 50° is measured at an angle of 30° | Xa-Xb | 15nm. The absolute value |Xa-Xb| is preferably less than 13 nm, more preferably less than 10 nm.

In the present invention, by combining the light absorption by the near-infrared absorbing pigment with the light reflection by the near-infrared reflecting film, the absolute value of the difference in wavelength at which the predetermined transmittance is obtained becomes the range. Filter. As described above, when the absolute value |Xa-Xb| is in the range of 560 nm to 800 nm in the wavelength range, a filter having a small incident angle dependence of optical characteristics and a wide viewing angle can be obtained, in particular, when When the filter is used for a lens unit such as a camera module, a low profile of the lens unit can be achieved.

In the present invention, as described above, for example, a transparent resin substrate containing a near-infrared absorbing dye having absorption in a specific wavelength region is used, and the characteristics of the near-infrared reflective film are controlled, whereby a balance can be satisfactorily satisfied. (A) ~ Filter for all the requirements of the requirement (D). Since the filter of the present invention satisfies all the requirements of the element (A) to the element (D), satisfactory high image quality can be obtained as compared with the prior filter, especially when used for a solid-state imaging element.

The filter of the present invention preferably further satisfies the requirements of the following (E).

(E) The haze value (JIS K7105 method) is 2.0% or less. The haze value is more preferably 1.5% or less, and particularly preferably 1.0% or less. If the haze value is within this range, a clear camera image can be obtained not only when the filter of the present invention is used for a solid-state imaging device, but also particularly to reduce glare or ghosting when shooting a light source in dark conditions. Therefore, it is better.

[Transparent resin substrate]

A transparent resin substrate constituting the optical filter of the present invention (hereinafter also referred to as "resin The substrate ") has a transparent resin and a near-infrared absorbing dye, and preferably has a maximum absorption in a wavelength range of 600 nm to 800 nm. If the maximum absorption wavelength of the substrate is within the range, the substrate can selectively and efficiently cut off near infrared rays.

When such a resin substrate is used for a filter such as a near-infrared cut filter, the absolute value |Xa-Xb| becomes small. Therefore, it is possible to obtain a filter having a small incident angle dependence of the absorption wavelength and a wide viewing angle.

The resin substrate may be a single layer or a plurality of layers.

The thickness of the resin substrate can be appropriately selected depending on the intended use, and is not particularly limited. However, it is preferably adjusted so that the substrate has an improvement in the incidence angle as described above, and more preferably 30 μm to 250 μm. More preferably, it is 40 μm to 200 μm, and particularly preferably 50 μm to 150 μm.

When the thickness of the resin substrate is within the above range, the filter using the substrate can be reduced in size and weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when the filter is used for a lens unit of a camera module or the like, low-profile of the lens unit can be achieved.

<Transparent Resin>

The resin substrate can be formed using a transparent resin.

The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, in order to ensure thermal stability and mold formability, high-temperature steaming can be performed at a vapor deposition temperature of 100 ° C or higher. The film which is plated to form the dielectric multilayer film may, for example, be a resin having a glass transition temperature (Tg) of preferably from 110 ° C to 380 ° C, more preferably from 110 ° C to 370 ° C, still more preferably from 120 ° C to 360 ° C. In addition, if the resin is glassy When the glass transition temperature is 140 ° C or higher, a film capable of forming a dielectric multilayer film at a higher temperature can be obtained, which is particularly preferable.

When a resin plate having a thickness of 0.1 mm containing the resin is formed as the transparent resin, the total light transmittance (JIS K7105) of the resin sheet can be preferably changed to 75% to 95%, more preferably 78%. 95%, especially good to become 80% ~ 95% resin. When a resin having a total light transmittance of such a range is used, the obtained substrate exhibits excellent transparency as an optical film.

The polystyrene-equivalent weight average molecular weight (Mw) of the transparent resin 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 20,000 to 100,000.

Examples of the transparent resin include a cyclic olefin resin, an aromatic polyether resin, a polyamidene resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, and a polyamine. (Aromatic polyamine) resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyparaphenylene resin, polyamidoximine resin, polyethylene naphthalate ( Polyethylene naphthalate, PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin, and sesquiterpene oxide resin.

(1) Cyclic olefin resin

The cyclic olefin-based resin is preferably at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ). The obtained resin and the resin obtained by hydrogenating the resin.

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

(i') hydrogen atom

(ii') halogen atom

(iii') trialkyldecylalkyl

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

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

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

(vii') an alkylene group formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^{x4 to} each other (wherein R ^x1 to R ^x4 not participating in the bonding are independently represented from the above (i ')~ the atom or base in (vi')

(viii') a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^{x4 to} each other (wherein R ^x1 to R ^x4 not participating in the bonding are respectively independent Ground represents an atom or a base selected from the above (i') to (vi')

(ix') a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding R ^x2 and R ^{x3 to} each other (wherein R ^x1 and R ^x4 which do not participate in the bonding are independently represented from the above (i') ~ the atom or base in (vi')

In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or a group selected from the above (i') to (vi'), or a relationship in which R ^y1 and R ^y2 are bonded to each other. A monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring, k ^y and p ^y each independently represent 0 or a positive integer.

(2) Aromatic polyether resin

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 (1) and a structural unit represented by the following formula (2).

[Chemical 3]

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

Moreover, it is preferable that the aromatic polyether-based resin further has at least 1 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). a structural unit.

[Chemical 5]

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

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

(3) Polyimine resin

The polyimine-based resin is not particularly limited as long as it is a polymer compound containing a quinone bond in a repeating unit, and can be, for example, Japanese Patent Laid-Open No. 2006-199945 or Japanese Patent Laid-Open Publication No. 2008 Documented in -163107 The way to synthesize.

(4) 茀 polycarbonate resin

The fluorene-based polycarbonate 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 JP-A-2008-163194.

(5) 茀 polyester resin

The ruthenium-based polyester resin is not particularly limited as long as it is a polyester resin containing a ruthenium portion, and can be, for example, described in JP-A-2010-285505 or JP-A-2011-197450. The way to synthesize.

(6) Fluorinated aromatic polymer resin

The fluorinated aromatic polymer-based resin is not particularly limited as long as it contains an aromatic ring having at least one fluorine, and contains an ether bond, a ketone bond, a hydrazone bond, a guanamine bond, and a quinone bond. The polymer of the repeating unit of at least one of the groups of the ester bond may be synthesized, for example, by the method described in JP-A-2008-181121.

(7) Commercial products

As a commercial item of a transparent resin, the following commercial item etc. are mentioned. Commercial products of the cyclic olefin resin include Arton manufactured by JSR Co., Ltd., Zeonor manufactured by Japan Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals Co., Ltd., and Polyplastics. TOPAS manufactured by a company limited by shares. As a commercial item of the polyether oxime resin, Sumikaexcel PES manufactured by Sumitomo Chemical Co., Ltd., etc. are mentioned. Commercially available as a polyimide resin For the product, Neopulim L manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like can be cited. As a commercial item of a polycarbonate resin, the Pureace etc. by Teijin Co., Ltd. are mentioned. As a commercial item of the fluorene polycarbonate resin, Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. are mentioned. As a commercial item of the oxime polyester resin, OKP4HT manufactured by Osaka Gas Chemical Co., Ltd., etc. are mentioned. As a commercial item of the acrylic resin, Acryviewa manufactured by Nippon Shokubai Co., Ltd., etc. are mentioned. As a commercial item of a sesquioxane-based resin, Silplus manufactured by Nippon Steel Chemical Co., Ltd. can be cited.

<Near infrared absorbing pigment>

The resin substrate contains a near-infrared absorbing pigment.

The near-infrared absorbing pigment is preferably selected from the group consisting of a squarylium ylide compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a ketone oxime compound, a dithiol compound, and a diimonium compound. At least one of the group consisting of the porphyrin compound. More preferably, the near-infrared absorbing pigment contains at least a squaraine ylide compound. The near-infrared absorbing pigment further preferably contains a squarylium ylide compound and other near-infrared absorbing pigments.

The maximum absorption wavelength of the squarylium ylide compound is preferably 600 nm or more, more preferably 620 nm or more, particularly preferably 650 nm or more, and preferably less than 800 nm, more preferably 760 nm or less, and particularly preferably 740 nm or less. When the maximum absorption wavelength is within such a wavelength range, sufficient near-infrared absorption characteristics and visible light transmittance can be coexisted.

When the squaraine ylide compound is combined with other near infrared absorbing pigments When used, the maximum absorption wavelength of at least one of the other near-infrared absorbing dyes is preferably more than 600 nm, more preferably 640 nm or more, particularly preferably 670 nm or more, and preferably 800 nm or less, more preferably 780 nm or less, particularly preferably Below 760nm. When the maximum absorption wavelength of other near-infrared absorbing pigments is in such a wavelength range, sufficient near-infrared absorption characteristics and visible light transmittance can be coexisted, and when the squarylium ylide compound is used together with other near-infrared absorbing pigments The other near-infrared absorbing pigment can effectively absorb the fluorescence generated by the samarium sulphate salt compound, and can suppress the scattered light intensity of the filter.

Specifically, the other near-infrared absorbing pigment preferably contains at least one selected from the group consisting of a cyanine-based compound and a phthalocyanine-based compound, and particularly preferably a phthalocyanine-based compound. By using a squarylium ylide salt compound in combination with the above compound, a filter having less scattered light and better camera image quality can be obtained.

When the total near-infrared absorbing pigment is 100% by weight, the content of the squarylium ylide compound is preferably 20% by weight to 95% by weight, more preferably 25% by weight to 85% by weight, particularly preferably 30% by weight. 80wt%. When the content ratio of the squarylium ylide compound is within the above range, good visible light transmittance, incident angle dependency improvement, and scattered light reduction effect can be coexisted. Further, two or more kinds of compounds can be used for the squarylium ylide compound and other near-infrared absorbing dyes.

In the resin substrate, the content of the near-infrared absorbing pigment is preferably from 0.01 part by weight to 5.0 parts by weight, more preferably from 0.02 part by weight to 3.5 parts by weight, per 100 parts by weight of the transparent resin used for producing the resin substrate. It is particularly preferably from 0.03 parts by weight to 2.5 parts by weight. If the content of the near infrared absorbing pigment is within the range, then Good near-infrared absorption characteristics and high visible light transmittance can be coexisted.

<<Squaric acid ylide salt compound>>

It is preferable that at least one selected from the group consisting of a squarylium ylide compound represented by the formula (I) and a squarylium ylide compound represented by the formula (II) is used as a group. An acid ylide compound. Hereinafter, they are also referred to as "compound (I)" and "compound (II)", respectively.

In the formula (I), R ^a , R ^b and Y satisfy the conditions of the following (i) or the following (ii).

Condition (i)

The plurality of R ^a each independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or a -NR ^e R ^f group. R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e .

The plurality of R ^b each independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or a -NR ^g R ^h group. R ^g and R ^h each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C(O)R ⁱ group (R ⁱ represents -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ).

A plurality of Y independently represent the -NR ^j R ^k basis. R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e . L ¹ is L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h .

The L ^a ~ L ^h represents (L ^a ) an aliphatic hydrocarbon group having 1 to 9 carbon atoms, (L ^b ) a halogen-substituted alkyl group having 1 to 9 carbon atoms, and (L ^c ) a carbon number of 3~ 14 alicyclic hydrocarbon group, (L ^d ) aromatic hydrocarbon group having 6 to 14 carbon atoms, (L ^e ) heterocyclic group having 3 to 14 carbon atoms, (L ^f ) alkoxy group having 1 to 9 carbon atoms The group (L ^g ) is a fluorenyl group having 1 to 9 carbon atoms or (L ^h ) an alkoxycarbonyl group having 1 to 9 carbon atoms, and the L ^a to the L ^h may have a substituent L.

The substituent L is an aromatic hydrocarbon group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and an aromatic group having 6 to 14 carbon atoms. At least one of a group consisting of a hydrocarbon group and a heterocyclic group having 3 to 14 carbon atoms.

The L ^a to the L ^h may further have at least one atom or group selected from the group consisting of a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, and an amine group.

The total number of carbon atoms including the substituents of L ^a to L ^h is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the number of carbon atoms is larger than this range, it may be difficult to synthesize a dye, and the absorption strength per unit weight tends to be small.

Condition (ii)

At least one of the two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a hetero ring containing at least one nitrogen atom and constituting 5 or 6 atoms. The ring may have a substituent, and R ^b and R ^a not participating in the formation of the hetero ring are independently the same as R ^b and R ^a of the above (i).

R ^a in the condition (i) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group or a third butyl group. The group, the cyclohexyl group, the phenyl group, the hydroxyl group, the amine group, the dimethylamino group, and the nitro group are more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a hydroxyl group.

R ^b in the condition (i) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group or a third butyl group. Base, cyclohexyl, phenyl, hydroxy, amine, dimethylamino, cyano, nitro, ethyl hydrazino, propyl decyl, N-methylethyl decyl, trifluoromethyl hydrazine Amino group, pentafluoroacetamido group, tert-butylamino group, cyclohexylamino group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group , hydroxy, dimethylamino, nitro, ethionylamino, propyl decylamino, trifluoromethyl decylamino, pentafluoroacetamidoamine, tert-butylamino, cyclohexylamine base.

As the Y, an amine group, a methylamino group, a dimethylamino group, and a diethylamine are preferred. , bis-n-propylamino, diisopropylamino, di-n-butylamino, di-tert-butylamino, N-ethyl-N-methylamino, N-cyclohexyl-N-methylamino, More preferred are dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino and di-t-butylamino.

At least one of the two R ^a on one benzene ring in the condition (ii) of the formula (I) and the Y on the same benzene ring are bonded to each other to form at least one nitrogen atom. Examples of the heterocyclic ring having 5 or 6 atoms include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, and pyrazine. Among these heterocyclic rings, a heterocyclic ring constituting the heterocyclic ring and having one atom beside the carbon atom of the benzene ring is preferably a nitrogen atom, and more preferably a pyrrolidine. The substituent which the heterocyclic ring may have is, for example, a substituent L, and preferably an aliphatic hydrocarbon group having 1 to 9 carbon atoms.

In the formula (II), X represents -O-, -S-, -Se-, >NR ^c or >CR ^d ₂ ; and a plurality of R ^c independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ; a plurality of R ^d independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -L ¹ or -NR ^e R ^f a group, adjacent R ^d may be bonded to each other to form a ring which may have a substituent; L ^a ~L ^e , L ¹ , R ^e and R ^f and L ^a ~L ^e as defined in the formula (I), L ¹ , R ^e and R ^{f have} the same meaning.

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

R ^d in the formula (II) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group or a third butyl group. Base, n-pentyl, n-hexyl, cyclohexyl, phenyl, methoxy, trifluoromethyl, pentafluoroethyl, 4-aminocyclohexyl, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group , ethyl, n-propyl, isopropyl, trifluoromethyl, pentafluoroethyl.

As the X, preferably -O-, -S-, -Se-, >N-Me, >N-Et, >CH ₂ , >C(Me) ₂ , >C(Et) ₂ , more preferably Is -S-, >C(Me) ₂ , >C(Et) ₂ . Me and Et represent a methyl group and an ethyl group, respectively.

In the formula (II), adjacent R ^d may be bonded to each other to form a ring. In the above formula (II), a ring in which R ^c and R ^{d are} bonded to each other and a ring in which adjacent R ^{d is} bonded to each other is added, and examples thereof include a benzoindolenine. --naphthyridazole ring, β-naphthyridazole ring, α-naphthoxazole ring, β-naphthoxazole ring, α-naphthylthiazole ring, β-naphthothiadiazole ring, α-naphthyl Selenazole ring, β-naphthoxazole ring.

In addition to the methods described in the following formula (I-1) and the following formula (II-1), the compound (I) and the compound (II) may be represented by the following description methods. In the description, the resonance method is employed as in the following formula (I-2) and the following formula (II-2). In other words, the difference between the following formula (I-1) and the following formula (I-2) and the difference between the following formula (II-1) and the following formula (II-2) are only the description methods of the structure, and The compounds all represent the same compound. In the present invention, the structure of the squaraine indole salt compound is represented by a method as described in the following formula (I-1) and the following formula (II-1), unless otherwise specified.

The compound (I) and the compound (II) are not particularly limited as long as they satisfy the requirements of the formula (I) and the formula (II), respectively, for example, as in the formula (I-1) and the formula. (II-1) When the structure is generally shown, the left and right substituents bonded to the central four-membered ring may be the same or different, but the same is preferable because it is easy to synthesize. Further, for example, a compound represented by the following formula (I-3) and the following formula (I-4) can be used. The compounds represented are considered to be the same compound.

The compound (I) and the compound (II) can be synthesized by a generally known method. For example, Japanese Patent Laid-Open No. Hei 1-228960, Japanese Patent Laid-Open No. 2001-40234, and Japanese Patent No. It is synthesized by the method and the like described in Japanese Patent No. 3196383.

<near UV absorber>

In addition to the near-infrared absorbing pigment, the resin substrate may further contain a near-ultraviolet absorber. The near ultraviolet ray absorbing agent is, for example, at least one selected from the group consisting of a carbamide compound, an anthraquinone compound, a benzotriazole compound, and a triazine compound. The near ultraviolet absorber preferably has at least one maximum absorption at a wavelength of from 300 nm to 420 nm. By using such a resin substrate, it is possible to obtain a filter having a small incident angle dependency in a near-ultraviolet wavelength region and a wide viewing angle.

The above squarylium sulfonium salt compound, phthalocyanine compound, and cyclaline The compound, the near-ultraviolet absorber, and other pigments can be synthesized by a generally known method. For example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, and Japanese Patent No. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2007-169315, Japanese Patent Laid-Open No. 2009-108267, Japanese Patent Laid-Open No. 2010-241873, and Japanese Patent Publication No. 2010-241873 It is synthesized by the method described in Japanese Patent No. 3699464, Japanese Patent No. 4,746,631, and the like.

<Other ingredients>

The resin substrate may further contain an additive such as an antioxidant, an ultraviolet absorber other than the near ultraviolet absorber, a fluorescent matting agent, and a metal complex compound, insofar as the effect of the present invention is not impaired. In addition, when a resin substrate is produced by casting molding to be described later, the production of a resin substrate can be facilitated by adding a leveling agent or an antifoaming agent. These other components may be used alone or in combination of two or more.

As the antioxidant, for example, 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5' can be mentioned. - dimethyldiphenylmethane, and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane.

Further, these additives may be mixed together with a transparent resin or the like in the production of a resin substrate, or may be added at the time of producing a transparent resin. Further, the amount of the additive to be added is appropriately selected in accordance with the desired characteristics, but it is 100 parts by weight with respect to the transparent resin. It is usually from 0.01 part by weight to 5.0 parts by weight, preferably from 0.05 part by weight to 2.0 parts by weight.

<Method for Producing Resin Substrate>

The resin substrate can be formed, for example, by melt molding or cast molding, and if necessary, can be applied by coating one or two or more kinds of antireflection agents, hard coating agents, antistatic agents, and the like after molding. The method of the agent is manufactured.

(1) Melt forming

The resin substrate can be produced, for example, by a method of melt-molding particles obtained by melt-kneading a transparent resin and a near-infrared absorbing dye, and melting a resin composition containing a transparent resin and a near-infrared absorbing dye. A method of forming a method of melt-molding particles obtained by removing a solvent from a resin composition containing a transparent resin, a near-infrared absorbing dye, and a solvent. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

(2) Casting and forming

The resin substrate can be produced, for example, by a method in which a resin composition containing a transparent resin, a near-infrared absorbing dye, and a solvent is applied onto a suitable substrate to remove a solvent, and a near-infrared absorbing pigment is contained. A method in which a curable resin composition is applied onto a suitable substrate and then dried and cured.

Examples of the substrate include a glass plate, a steel strip, a steel drum, and a transparent resin film (for example, a polyester film or a cyclic olefin resin film).

The resin substrate can be obtained by peeling off from the substrate, and the laminate of the substrate and the coating film can be used as a resin substrate without peeling off from the substrate as long as the effect of the present invention is not impaired.

Further, a resin substrate may be directly formed on the optical component by applying the resin composition to an optical component such as a glass plate, a quartz component, or a transparent plastic component, and then drying the solvent. a method; or a method of drying and hardening after coating the curable resin composition.

The solvent is not particularly limited as long as it is used in organic synthesis or the like, and examples thereof include hydrocarbons such as hexane and cyclohexane; methanol, ethanol, isopropanol, butanol, and octanol. Alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate Esters such as esters, 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; dichloromethane, chloroform and tetrachloro Halogenated hydrocarbons such as carbon; guanamines such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The amount of residual solvent in the resin substrate obtained by the above method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight or less based on the weight of the resin substrate. When the amount of the residual solvent is within the above range, a resin substrate which is hard to be deformed or whose characteristics are hard to change and which can easily exhibit a desired function can be obtained.

[Near Infrared Reflective Film]

The near-infrared reflecting film constituting the optical filter of the present invention is a film having the ability to reflect near-infrared rays. In the present invention, the near-infrared reflective film may be provided on one surface of the resin substrate or on both surfaces. When set on one side, the manufacturing cost or It is excellent in ease of manufacture, and when it is provided on both surfaces, it is possible to obtain a filter having high strength and being difficult to warp. When the filter is used for a solid-state imaging device, it is preferable that the warpage of the filter is small from the viewpoint of easiness of mounting steps of the camera module, etc., and therefore it is more preferable to use two of the resin substrates. The side has a near-infrared reflective film.

Examples of the near-infrared reflective film include an aluminum deposited film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and containing a small amount of tin oxide are dispersed, and a high refractive index material layer and a low refractive index material. A dielectric multilayer film in which layers are alternately laminated. Among the near-infrared reflective films, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated is more preferable.

As the material constituting the high refractive index material layer, a material having a refractive index of more than 1.7 can be used, and a material having a refractive index of usually more than 1.7 and not more than 2.5 is selected. Examples of such a material include titanium oxide, zirconium oxide, antimony pentoxide, antimony pentoxide, antimony oxide, antimony oxide, zinc oxide, zinc sulfide, or indium oxide, and the like, and a small amount (for example, relative to The main component is 0% by weight to 10% by weight of titanium oxide, tin oxide and/or cerium oxide.

As a material constituting the low refractive index material layer, a material having a refractive index of 1.7 or less can be used, and a material having a refractive index of usually 1.2 or more and 1.7 or less can be selected. Examples of such a material include cerium oxide, aluminum oxide, cerium fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The refractive index is a refractive index in light having a wavelength of 550 nm.

The dielectric multilayer film preferably has a high refractive index material layer having a refractive index of more than 1.7 and not more than 2.5 and a low refractive material layer having a refractive index of 1.2 or more and 1.7 or less. A multilayer film made of layers.

In the dielectric multilayer film, the refractive index of the layer having the highest refractive index and the layer having the lowest refractive index is preferably 1.3 or more, more preferably 1.4 or more, and particularly preferably 1.5 or more.

Further, in the layer of the high refractive index material and the low refractive index material which are alternately laminated, it is preferable that the optical film thickness of the adjacent high refractive index material layer and the low refractive index material layer of 10 or more layers continuously (physical film) The ratio of the thickness x the refractive index becomes a portion of 0.8 to 1.2, more preferably 12 or more.

If the refractive index ratio of the high refractive index material layer and the low refractive index material layer or the film design of the dielectric multilayer film is in the range as described above, there is a tendency that the reflection characteristics of near-infrared rays are improved and the near-infrared cutoff characteristics are improved. Therefore, it is better.

When the filter has a dielectric multilayer film on both surfaces of the resin substrate, in each of the dielectric multilayer films formed on both surfaces of the substrate, any of the "satisfying 10th (h) below is satisfied" When the average optical film thickness of the layers is compared with each other, that is, when the average optical film thickness on one face is compared with the average optical film thickness on the other face, the average optical film thickness is thicker. The average optical film thickness of the bulk multilayer film is preferably from 1.05 to 1.60 times, and particularly preferably from 1.10 to 1.55 times, of the average dielectric film thickness of the other dielectric multilayer film.

(h) The ratio of the optical film thickness (physical film thickness x refractive index) of the adjacent high refractive index material layer to the low refractive index material layer is 0.8 to 1.2.

When the film configuration of the dielectric multilayer film formed on both surfaces of the substrate satisfies the above conditions, for example, there is a tendency to more effectively reflect near-infrared rays in a wide wavelength range of 700 nm to 1200 nm, and the near-infrared cutoff characteristics are improved. Therefore, it is better.

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

When the near-infrared wavelength to be blocked is λ (nm), the thickness of each layer of the high refractive index material layer and the low refractive index material layer is usually preferably 0.1 λ to 0.5 λ. The value of λ (nm) is, for example, 700 nm to 1400 nm, preferably 750 nm to 1300 nm. When the thickness is in this range, the product (n×d) of the refractive index (n) and the physical film thickness (d) becomes the optical film thickness calculated by λ/4, and the high refractive index material layer and the low refractive index. The thickness of each layer of the material layer is approximately the same value, according to the reflection. The relationship between the optical properties of refraction and the ability to easily control the blocking of specific wavelengths. The tendency to pass.

As a whole of the filter, 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 5 to 60 layers, more preferably 10 to 50 layers, and thus more preferably It is 12 to 50 layers. When the filter has a dielectric multilayer film on both sides of the resin substrate, the number of layers of the dielectric multilayer film formed on both sides of the substrate is poor (that is, the number of layers of one multilayer film and the number of layers of another multilayer film) The difference is 12 or less, particularly preferably 10 or less, and the difference in physical film thickness (that is, the difference between the physical film thickness of one multilayer film and the physical film thickness of the other multilayer film) is 500 nm or less, and more preferably 450 nm or less. Particularly preferred is 400 nm or less. If the dielectric formed on both sides of the substrate When the difference in the number of layers of the multilayer film or the difference in the physical film thickness is within the above range, there is a tendency that the warpage of the filter can be further reduced, which is preferable.

In the present invention, for example, by appropriately selecting the material 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, the order of the layers, and the number of layers, For example, a filter having sufficient reflection characteristics in a region having a wavelength of 1100 nm to 1200 nm can be obtained.

Here, in order to optimize the conditions, as described above, for example, an optical film design software (for example, Core MacLeod, manufactured by Film Center Co., Ltd.) is used to preferentially reduce the transmittance of a region having a wavelength of 1100 nm to 1200 nm. The way to set the parameters can be. In the case of the soft body, for example, after the target transmittance of the wavelength of 1100 nm to 1200 nm is set to 0% or the like, the value of the target tolerance (target Tolerance) is set to 0.5 or less.

[Other functional films]

In the filter of the present invention, in order to increase the surface hardness of the resin substrate or the near-infrared reflective film, improve chemical resistance, antistatic property, and eliminate ruthenium, etc., it is possible to make resin in the range which does not impair the effect of the present invention. A functional film such as an antireflection film, a hard coat film, and an antistatic film is preferably disposed between the substrate and the near-infrared reflective film such as the dielectric multilayer film.

In order to improve the adhesion between the resin substrate and the functional film and/or the near-infrared reflective film, or the adhesion between the functional film and the near-infrared reflective film, the surface of the resin substrate or the functional film may be subjected to corona treatment or plasma treatment. Wait for surface treatment.

[The characteristics of the filter, etc.]

The optical filter of the present invention includes the transparent resin substrate and the near-infrared reflective film formed on at least one surface of the transparent resin substrate. Therefore, the transmittance of the optical filter of the present invention is excellent in the near-infrared cut-off characteristics, particularly in the region of the wavelength of 1100 nm to 1200 nm. When such a filter is used for a solid-state imaging device, high image quality can be achieved, and specifically, a good camera image with few ghost images or the like can be obtained.

In addition, by using, for example, at least one of the near-infrared absorbing dyes contained in the resin substrate, the dye having the maximum absorption at a wavelength of 600 nm to 800 nm can efficiently absorb near-infrared light. Therefore, by combining such a transparent resin substrate and a near-infrared reflective film, a filter having a small incident angle dependency can be obtained.

[Use of filter]

The optical filter of the present invention has a wide viewing angle and excellent near-infrared cut-off performance and the like. Therefore, it is useful as a filter for visibility correction of a solid-state imaging device such as a CCD image sensor or a CMOS image sensor of a camera module. In particular, digital still cameras, mobile phone cameras, digital cameras, personal computer cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, personal digital assistants, video game consoles, portable game consoles It is useful for devices for fingerprint authentication systems, digital music players, and the like. Further, it is also useful as an infrared cut filter or the like attached to a glass plate or the like of an automobile or a building.

[Solid Photographic Device]

The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the so-called solid The body imaging device refers to an image sensor having a solid-state imaging device such as a CCD image sensor or a CMOS image sensor, and is specifically a digital still camera, a mobile phone camera, a digital camera, or the like. For example, the camera module of the present invention is provided with the filter of the present invention.

[Examples]

Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited by the examples. In addition, "parts" means "parts by weight" unless otherwise specified. Moreover, the measuring method of each physical property value and the evaluation method of physical property are as follows.

<molecular weight>

The molecular weight of the resin is measured by the following method (a) or the following (b) in consideration of the solubility of each resin in a solvent. Further, regarding the resin synthesized in Resin Synthesis Example 3 to be described later, the molecular weight was not measured by these methods, and the logarithmic viscosity was measured by the following method (c).

(a) Using a GPC apparatus manufactured by WATERS (150C type, column: H-type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene), measuring standard polystyrene conversion The weight average molecular weight (Mw) and the number average molecular weight (Mn).

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

(c) Putting a part of the polyimine resin solution into anhydrous methanol to polymerize The quinone imine resin was precipitated, and after filtration, it was separated from the unreacted monomer. 0.1 g of polyimine obtained by vacuum drying at 80 ° C for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone using a Cannon-Fenske viscometer. The logarithmic viscosity (μ) at 30 ° C was determined by the following formula.

μ={ln(ts/t0)}/C

T0: the flow time of the solvent

Ts: the flow time of the thin polymer solution

C: 0.5g/dL

<glass transition temperature (Tg)>

The glass transition temperature (Tg) of the resin was measured under a nitrogen gas stream using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies Co., Ltd. at a temperature increase rate of 20 ° C/min.

<Spectral transmittance and reflectance>

The maximum absorption wavelength of the resin substrate, the transmittance and the reflectance in each wavelength region of the filter, and the (Xa) and the (Xb) are manufactured using Hitachi High-Technologies Co., Ltd. A spectrophotometer (U-4100) was used for the measurement.

Here, when the transmittance is measured from the vertical direction of the filter, the light that is transmitted perpendicularly to the filter surface is measured as shown in FIG. 1( a ). In addition, when the transmittance is measured from an angle of 30° with respect to the vertical direction of the filter, the angle is 30° with respect to the vertical direction of the filter surface as shown in FIG. 1( b ). Light transmitted through.

In addition, this transmittance is a case where the measurement (Xb) is excluded, and the measurement is performed using the spectrophotometer under the condition that the light is incident perpendicularly to the filter surface. When the measurement (Xb) is carried out, the transmittance is measured by using the spectrophotometer under the condition that light is incident at an angle of 30° with respect to the vertical direction of the filter surface.

In addition, when the reflectance is measured at an angle of 5° from the vertical direction of the filter, a filter is attached to the jig attached to the apparatus as shown in FIG. 1(c) to perform measurement.

<Haze value>

The haze value of the filter was measured by a method of JIS K7105 using a haze meter (HZ-2) manufactured by Suga Test Instruments Co., Ltd.

<refractive index>

A target layer (a cerium oxide layer or a titanium oxide layer) having a refractive index was deposited on a glass substrate by a single layer to form a sample, and then a spectrophotometer manufactured by Hitachi Advanced Technology Co., Ltd. (U- 4100) The transmittance and reflectance of the prepared sample were measured (the transmittance was measured from the vertical direction of the sample surface, and the reflectance was measured from an angle of 5° with respect to the vertical direction of the sample surface). The obtained transmittance data and reflectance data were input into an optical film design software (core McLeod, manufactured by Membrane Center Co., Ltd.), and function fitting was performed to obtain refractive index of each target layer for light having a wavelength of 550 nm. rate.

<Resin Synthesis Example 1>

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]dodecene (hereinafter also referred to as "DNM") represented by the following formula (a) 100 parts, 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene (solvent for ring-opening polymerization) were added to a reaction vessel substituted with nitrogen, and the solution was heated to 80 °C. Then, 0.2 parts of a toluene solution (concentration: 0.6 mol/l) of triethylaluminum as a polymerization catalyst, and a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol) were added to the solution in the reaction vessel. / l) 0.9 parts, and the solution was heated and stirred at 80 ° C for 3 hours, thereby performing ring-opening polymerization to obtain a ring-opening polymer solution. The polymerization conversion ratio in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution obtained in the manner described above was added to the autoclave, and 0.12 parts of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution, and then The hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen pressure of 100 kg/cm ² and a reaction temperature of 165 °C.

After the obtained reaction solution (hydrogenated polymer solution) was cooled, hydrogen gas was pressure-released. The reaction solution was poured into a large amount of methanol, and the coagulum was separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The 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>

2,6-difluorobenzonitrile 35.12 g (0.253 mol), 9,9-bis(4-hydroxyphenyl)phosphonium 87.60 g (0.250 mol), potassium carbonate 41.46 g (0.300 mol) were added to a 3 L four-necked flask. ), N,N-dimethylacetamide (hereinafter also referred to as "DMAc") 443 g and toluene 111 g. Then, a four-necked flask was equipped with a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube, and a cooling tube.

Then, after the inside of the flask was purged with nitrogen, the obtained solution was reacted at 140 ° C for 3 hours, and the generated water was removed from the Dean-Stark tube at any time. At the time when the formation of water was not observed, the temperature was slowly raised to 160 ° C, and the reaction was carried out at this temperature for 6 hours.

After cooling to room temperature (25 ° C), the formed salt was removed by a filter paper, and the filtrate was poured into methanol to be reprecipitated, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum dried at 60 ° C overnight to obtain a white powder (hereinafter also referred to as "resin B") (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 °C.

<Resin Synthesis Example 3>

1,4-double (4) was placed in a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a dropping funnel with a side tube, a Dean-Stark tube, and a cooling tube under a nitrogen stream. -amino-α,α-dimethylbenzyl)benzene 27.66g (0.08 mol), and 4,4'-bis(4-aminophenoxy)biphenyl 7.38 g (0.02 mol), and It was dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide. The obtained solution was cooled to 5 ° C using an ice water bath, and 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in one portion while maintaining isothermal temperature, and Aminating catalyst triethylamine 0.50 g (0.005 mol). After the completion of the addition, the temperature was raised to 180 ° C, and the distillate was distilled off at any time, and refluxed for 6 hours. After completion of the reaction, air cooling was performed until the internal temperature became 100° C., and then 143.6 g of N,N-dimethylacetamide was added for dilution, and then cooled while stirring to obtain a solid content concentration of 20% by weight. The polyimide resin solution was 264.16 g. A part of the polyimine resin solution was poured into 1 L of methanol to precipitate polyimine. The collected polyimine was washed with methanol, and dried in a vacuum dryer at 100 ° C for 24 hours to obtain a white powder (hereinafter also referred to as "resin C"). The infrared (Infrared, IR) spectrum of the obtained resin C was measured, and as a result, absorption of 1704 cm ^-1 and 1770 cm ^-1 peculiar to the quinone imine group was observed. The obtained resin C had a glass transition temperature (Tg) of 310 ° C and a logarithmic viscosity of 0.87.

<Resin Synthesis Example 4>

9.67 kg (20.90 mol) of 9,9-bis{4-(2-hydroxyethoxy)phenyl}anthracene, 4.585 kg (20.084 mol) of bisphenol A, 9.000 kg of diphenyl carbonate (42.01 mol) 0.02066 kg (2.459 × 10 ^-4 mol) of sodium hydrogencarbonate was added to a 50 L reactor equipped with a stirrer and a distillation apparatus, and the mixture was heated to 215 ° C for 1 hour under a nitrogen atmosphere at 760 Torr and stirred. Thereafter, the degree of pressure reduction was adjusted to 150 Torr over 15 minutes, and the mixture was kept at 215 ° C and 150 Torr for 20 minutes to carry out a transesterification reaction. Further, the temperature was raised to 240 ° C at a rate of 37.5 ° C / Hr, and held at 240 ° C and 150 Torr for 10 minutes. Thereafter, it was adjusted to 120 Torr over 10 minutes, and kept at 240 ° C and 120 Torr for 70 minutes. Thereafter, it was adjusted to 100 Torr over 10 minutes, and kept at 240 ° C and 100 Torr for 10 minutes. Further, the polymerization reaction was carried out by stirring for 10 minutes under conditions of 240 ° C and 1 Torr or less for 10 minutes or less. After the completion of the reaction, nitrogen gas was introduced into the reactor and pressurized, and the produced polycarbonate resin (hereinafter also referred to as "resin D") was pelletized while being granulated. The obtained resin D had a weight average molecular weight (Mw) of 41,000 and a glass transition temperature (Tg) of 152 °C.

<Resin Synthesis Example 5>

Add 9,9-bis{4-(2-hydroxyethoxy)-3,5-dimethylphenyl}fluorene 0.8 mol, ethylene glycol 2.2 mol and isophthalic acid to the reactor. The ester was 1.0 mol, and was slowly heated and melted while stirring to carry out a transesterification reaction, and after adding cerium oxide 20 × 10 ^-4 mol, the temperature was gradually raised to 290 ° C and the pressure was gradually reduced to 1 Torr or less. Remove glycol from one side. Thereafter, the contents were taken out from the reactor to obtain pellets of a polyester resin (hereinafter also referred to as "resin E"). The obtained resin E had a number average molecular weight (Mn) of 40,000 and a glass transition temperature (Tg) of 145 °C.

<Resin Synthesis Example 6>

Adding 16.74 parts of 4,4'-bis(2,3,4,5,6-pentafluorobenzhydryl)diphenyl ether (BPDE) to a reactor equipped with a thermometer, a cooling tube, a gas introduction tube, and a stirrer, 1,9-bis(4-hydroxyphenyl)fluorene (HF) 10.5 parts, potassium carbonate 4.34 parts and DMAc 90 parts. The mixture was warmed to 80 ° C and allowed to react for 8 hours. After the reaction is over, The reaction solution was vigorously stirred by a blender and added to a 1% aqueous acetic acid solution. The precipitated reactant was collected by filtration, washed with distilled water and methanol, and dried under reduced pressure to obtain a fluorinated polyether ketone (hereinafter also referred to as "resin F"). The obtained resin F had a number average molecular weight (Mn) of 71,000 and a glass transition temperature (Tg) of 242 °C.

[Example 1]

100 parts of the resin A obtained in the synthesis example 1 and the squarylium ylide compound represented by the following formula (a-1) (hereinafter also referred to as "compound (a-1)") 0.03 are added to the container. 0.01 parts of a phthalocyanine-based compound (hereinafter also referred to as "compound (b-1)") represented by the following formula (b-1), and further adding dichloromethane, thereby obtaining a resin concentration of 20% by weight. Solution.

Then, the obtained solution was cast onto a smooth glass plate, and after drying at 20 ° C for 8 hours, the coating film was peeled off from the glass plate. Further, the peeled coating film was dried at 100 ° C for 8 hours under reduced pressure to obtain a resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. The spectral transmittance of the resin substrate was measured, and the maximum absorption wavelength was determined. The results are shown in Table 4. The maximum absorption wavelength is 698 nm.

Then, a near-infrared reflective film (I) was formed on one surface of the obtained resin substrate, and a near-infrared reflective film (II) was formed on the other surface of the resin substrate to obtain a filter having a thickness of 0.106 mm.

The near-infrared reflective film (I) is formed by alternately laminating a layer of cerium (SiO ₂ ) and a layer of titanium oxide (TiO ₂ ) at a vapor deposition temperature of 100 ° C (total of 20 layers). The near-infrared reflective film (II) is formed by alternately laminating a layer of cerium (SiO ₂ ) and a layer of titanium oxide (TiO ₂ ) at a vapor deposition temperature of 100 ° C (total of 26 layers). In either of the near-infrared reflective film (I) and the near-infrared reflective film (II), the ceria layer and the titanium oxide layer each have a titanium oxide layer, a ceria layer, and a titanium oxide layer from the resin substrate side. The order of the cerium oxide layer, the titanium oxide layer, and the cerium oxide layer is alternately laminated, and the outermost layer of the filter is a cerium oxide layer.

The design of the near-infrared reflecting film (I) and the near-infrared reflecting film (II) is carried out in the following manner.

Regarding the thickness and the number of layers of each layer, the optical film design software (core McLaugh) is used in combination with the anti-reflection effect of the visible region and the light-off effect of the near-infrared region in combination with the characteristics of the resin substrate or the near-infrared absorbing pigment. De, manufactured by Membrane Center, Inc.). When optimization is performed, in the present embodiment, the input parameters (target values) input to the software are set as in Table 1 below.

As a result of optimization, in Example 1, the near-infrared reflective film (I) was changed to a ceria layer having a film thickness of 88 nm to 185 nm and a film thickness of 98 nm to 108 nm. The titanium oxide layer is alternately laminated to form a multilayer vapor deposition film having a number of layers of 20, and the near-infrared reflective film (II) is changed to a ceria layer having a thickness of 78 nm to 156 nm and a titanium oxide layer having a film thickness of 82 nm to 90 nm. A multilayer vapor deposited film having a buildup number of 26 layers. The ruthenium dioxide layer has a refractive index of 1.445 and the titanium oxide layer has a refractive index of 2.479. The film (I) has a continuous portion of 19 layers, that is, a ratio of an optical film thickness (physical film thickness x refractive index) of an adjacent high refractive index material layer to a low refractive index material layer becomes a portion of 0.8 to 1.2. The film (II) continuously has 25 layers of the portion. An example of the film structure optimized is shown in Table 2.

The spectral transmittance and reflectance of the filter were measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 4. The average value of the transmittance at a wavelength of 430 nm to 580 nm is 91%, the average value of the reflectance at a wavelength of 800 nm to 1000 nm is 99%, and the average value of the reflectance at a wavelength of 1100 nm to 1200 nm is 99%, and the absolute value | Xa- Xb | is 3nm. Further, in the present embodiment, the reflectance in the wavelength of 800 nm to 1000 nm is measured from the side of the near-infrared reflecting film (II) of the filter, and the reflectance in the wavelength of 1100 nm to 1200 nm is near infrared rays from the filter. The measurement was performed on the side of the reflective film (I). As a result of evaluating the haze value of the filter, the haze value was 0.8. The results are shown in Table 4.

[Embodiment 2]

A near-infrared reflective film (III) was formed on one surface of a resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm obtained in Example 1, and a near-infrared reflective film was formed on the other surface of the resin substrate. (IV), and a filter having a thickness of 0.105 mm was obtained.

The near-infrared reflective film (III) is formed by alternately laminating a layer of cerium (SiO ₂ ) and a layer of titanium oxide (TiO ₂ ) at a vapor deposition temperature of 100 ° C (total of 18 layers). The near-infrared reflective film (IV) is formed by alternately laminating a layer of cerium (SiO ₂ ) and a layer of titanium oxide (TiO ₂ ) at a vapor deposition temperature of 100 ° C (total of 18 layers). In either of the near-infrared reflective film (III) and the near-infrared reflective film (IV), the ceria layer and the titanium oxide layer each have a titanium oxide layer, a ceria layer, and a titanium oxide layer from the resin substrate side. The order of the cerium oxide layer, the titanium oxide layer, and the cerium oxide layer is alternately laminated, and the outermost layer of the filter is a cerium oxide layer.

The design of the near-infrared reflective film (III) and the near-infrared reflective film (IV) is carried out in the following manner.

As a result of optimization in the same manner as in the first embodiment, in the second embodiment, the near-infrared reflective film (III) was changed to a ceria layer having a film thickness of 36 nm to 186 nm and a titanium oxide layer having a film thickness of 11 nm to 109 nm. A multilayer vapor deposited film having a laminated layer of 18, and a near-infrared reflective film (IV) having a thickness of 31 nm to 156 nm and a titanium oxide layer having a thickness of 10 nm to 94 nm are alternately laminated. A multilayer vapor deposited film having a laminate number of 18. The ruthenium dioxide layer has a refractive index of 1.445 and the titanium oxide layer has a refractive index of 2.479. The film (III) has a continuous portion of 15 layers, that is, a ratio of an optical film thickness (physical film thickness x refractive index) of an adjacent high refractive index material layer to a low refractive index material layer becomes a portion of 0.8 to 1.2. The film (IV) has 15 layers of the portion in succession. An example of the film structure optimized is shown in Table 3.

The evaluation results of the optical characteristics and the haze value are shown in Table 4. Further, in the present embodiment, the reflectance at a wavelength of 800 nm to 1000 nm is measured from the side of the near-infrared reflecting film (IV) of the filter, and the reflectance at a wavelength of 1100 nm to 1200 nm is near-infrared rays from the filter. The measurement was performed on the side of the reflective film (III).

[Example 3] to [Example 14] and [Comparative Example 1] to [Comparative Example 2] In Example 1, the transparent resin, the near-infrared absorbing dye, the solvent, and the film drying conditions shown in Table 4 were used. A filter having a thickness of 0.106 mm was obtained in the same manner as in Example 1 except that the thickness of each layer of the multilayer vapor-deposited film and the number of layers were optimized. The results are shown in Table 4. Further, in Table 4, the resin concentration of the solution was 20% by weight.

The various compounds used in the examples and comparative examples are as follows.

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

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

Resin C: Polyimine resin (Resin Synthesis Example 3)

Resin D: 茀 polycarbonate resin (Resin Synthesis Example 4)

Resin E: 茀 polyester resin (Resin Synthesis Example 5)

Resin F: fluorinated polyether ketone (Resin Synthesis Example 6)

Resin G: cyclic olefin resin "Zeonor 1420R"

(made by Japan Rui Weng (share))

Resin H: cyclic olefin resin "APEL #6015"

(Mitsui Chemical (share) manufacturing)

Resin I: polycarbonate resin "Pureace" (manufactured by Teijin Co., Ltd.)

Resin J: Polyether oxime resin "Sumilite FS-1300"

(Sumitomo Bakelite (share) manufacturing)

Resin K: Heat-resistant acrylic resin "Acryviewa" (manufactured by Nippon Shokubai Co., Ltd.)

Compound (a-1): a squarylium ylide compound represented by the following formula (a-1)

Compound (a-2): a squarylium ylide compound represented by the following formula (a-2)

Compound (b-1): a phthalocyanine compound represented by the following formula (b-1)

Compound (b-2): a phthalocyanine compound represented by the following formula (b-2)

Compound (c-1): a cyanine compound represented by the following formula (c-1)

[Chemistry 16]

Solvent (1): dichloromethane

Solvent (2): N,N-dimethylacetamide

Solvent (3): ethyl acetate / toluene (weight ratio: 5/5)

Solvent (4): cyclohexane / xylene (weight ratio: 7/3)

Solvent (5): cyclohexane / dichloromethane (weight ratio: 99/1)

Solvent (6): N-methyl-2-pyrrolidone

Further, the film drying conditions of the examples and comparative examples in Table 4 are as follows.

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

Condition (2): 60 ° C / 8 hr → 80 ° C / 8 hr

→140 ° C / 8 hr under reduced pressure

Condition (3): 60 ° C / 8 hr → 80 ° C / 8 hr

→100 ° C / 24 hr under reduced pressure

Condition (4): 40 ° C / 4 hr → 60 ° C / 4 hr

→100 ° C / 8 hr under reduced pressure

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

[Example 15]

The filter fabricated in Example 1 was cut and wafer-formed into a size of 4.5 mm × 4.5 mm using a fully automatic cutter DFD 6340 manufactured by DISCO. The cutting blade was made of SD5000-Y1-60 (51 mm in diameter and 0.04 mm in thickness) manufactured by Disco, and the rotation speed was set to 50,000 rpm, and the feed speed was set to 10 mm/sec. The dicing tape used was UHP-110BZ (thickness: 110 μm) manufactured by DENKA ADTECS. The presence or absence of the crack shown in Fig. 2 was evaluated by visual observation of the wafer after the cutting process, and as a result, no crack was generated.

[Example 16]

The both sides of the filter fabricated in Example 1 were covered with a protective film made of polyethylene having a thickness of 50 μm, and a polyester film having a thickness of 250 μm was used as a mat, and was punched into 4.5 using the punching die shown in FIG. The size of mm × 4.5mm. The inner cone angle of the punching die was set to 0 degrees, and the cutting edge angle was set to 50 degrees. The presence or absence of the crack shown in Fig. 2 was visually evaluated by the presence of the stamped wafer, and as a result, no crack was generated.

As is clear from the results of the respective embodiments, the filter that satisfies the requirements of the present invention has less variation in optical characteristics caused by the incident angle, and is excellent in visible light transmittance or near-infrared cutoff characteristics, and has good balance. The ground simultaneously satisfies various characteristics required for use as a solid-state imaging element. Therefore, the filter of the present invention can be particularly suitably used for solid-state imaging elements as compared to previous filters.

1‧‧‧ Filter

2‧‧‧Spectrophotometer

3‧‧‧Light

4‧‧‧Mirror

Claims (12)

A filter comprising: a substrate made of a transparent resin, comprising a near-infrared absorbing pigment; and a near-infrared reflecting film formed on at least one surface of the substrate; and satisfying the following (A) to (D) below Requirements: (A) In the region with a wavelength of 430 nm to 580 nm, the average value of the transmittance when measured from the vertical direction of the filter is 75% or more; (B) in the region of the wavelength of 800 nm to 1000 nm, when When measured at an angle of 5° with respect to the vertical direction of the filter, the average value of the reflectance measured from at least one surface is 80% or more; (C) in the region of the wavelength of 1100 nm to 1200 nm, when When the angle is 5° with respect to the vertical direction of the filter, the average value of the reflectance measured from at least one surface is 70% or more; (D) in the region of the wavelength of 560 nm to 800 nm, self-filtering The longest wavelength (Xa) at which the transmittance at the time of measurement in the vertical direction of the device is 50%, and the transmittance at the angle of 30° from the vertical direction of the filter is 50%. The absolute value of the difference in the value of the wavelength (Xb) | Xa-Xb | is less than 15 nm. The filter according to claim 1, further satisfying the requirements of the following (E): (E) a haze value measured by a method according to JIS K7105 is 2.0% or less. The filter of claim 1 or 2, wherein the The near-infrared reflective film is a layer of a high refractive index material having a refractive index of more than 1.7 and a wavelength of 550 nm or more and a low refractive index layer having a refractive index of 1.2 or more and 1.7 or less in light having a wavelength of 550 nm alternately laminated. a dielectric multilayer film in which a refractive index ratio of a layer having the highest refractive index and a layer having the lowest refractive index is 1.3 or more, and continuously having 10 or more adjacent high refractive index materials The ratio of the optical film thickness (physical film thickness x refractive index) of the layer to the low refractive index material layer becomes a portion of 0.8 to 1.2. The filter according to the first or second aspect of the invention, wherein the transparent resin constituting the transparent resin substrate is selected from the group consisting of a cyclic olefin resin, an aromatic polyether resin, and a polyamidene. Resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamine resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyparaphenyl resin, Polyamidoximine resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin, and sesquiterpene At least one resin selected from the group consisting of oxyalkylene resins. The filter according to the first or second aspect of the invention, wherein the transparent resin substrate contains a samarium sulphate-based compound, a cyanine compound, a phthalocyanine compound, and a naphthalocyanine system. At least one near-infrared absorbing dye in the group consisting of a compound, a ketone oxime compound, a dithiol compound, a diimonium compound, and a porphyrin compound. The filter according to claim 1 or 2, wherein the near-infrared absorbing pigment contains a compound selected from the group consisting of squarylium sulphate compounds represented by formula (I), and formula (II) At least one of the group consisting of the squarylium sulfonium salt compounds represented: In the formula (I), R ^a , R ^b and Y satisfy the following conditions (i) or (ii): (i) a plurality of R ^a independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group or a cyanogen. a base, a nitro group, a carboxyl group, a phosphate group, a -L ¹ or a -NR ^e R ^f group, wherein R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ; a plurality of R ^b independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or a -NR ^g R ^h group, here , R ^g and R ^h each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C(O)R ⁱ group, and R ⁱ represents -L ^a ,- L ^b , -L ^c , -L ^d or -L ^e ; a plurality of Y independently represent a -NR ^j R ^k group, where R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ; L ¹ is L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h ; said L ^a ~L ^h means L ^a ) aliphatic hydrocarbon group having 1 to 9 carbon atoms, (L ^b ) halogen-substituted alkyl group having 1 to 9 carbon atoms, (L ^c ) alicyclic hydrocarbon group having 3 to 14 carbon atoms, (L ^d ) carbon number 6 ~ 14 aromatic hydrocarbon group, (L ^e) a heterocyclic group having a carbon number of 3 to 14, (L ^f) an alkoxy having 1 to 9 carbon atoms in the Group, (L ^G) acyl carbon number of 1 to 9, or (L ^H) of carbon atoms, an alkoxycarbonyl group having 1 to 9, the L ^a ~ L ^h L may have a substituent; L is a substituent selected from the group consisting of An aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 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 ring having 3 to 14 carbon atoms At least one of the group consisting of: the group L ^a ~L ^h may further have a group selected from the group consisting of a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, and an amine group. At least one atom or group in the group; (ii) at least one of two R ^a groups on one benzene ring is bonded to Y on the same benzene ring to form at least one nitrogen atom and constitutes a heterocyclic ring having 5 or 6 atoms, said heterocyclic ring may have a substituent, and R ^b and R ^a not participating in the formation of said heterocyclic ring are independently the same as R ^b and R ^a of said (i) Meaning, [Chemical 2] In the formula (II), X represents -O-, -S-, -Se-, >NR ^c or >CR ^d ₂ ; and a plurality of R ^c independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ; a plurality of R ^d independently represent a hydrogen atom, a halogen atom, a sulfonic acid group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -L ¹ or -NR ^e R ^f a group, adjacent R ^d may be bonded to each other to form a ring which may have a substituent; L ^a ~L ^e , L ¹ , R ^e and R ^f and L ^a ~L ^e as defined in the formula (I), L ¹ , R ^e and R ^{f have} the same meaning. The optical filter according to claim 1, comprising: the transparent resin substrate; and the near-infrared reflective film formed on both surfaces of the substrate. The filter according to claim 7, wherein the near-infrared reflective film is a dielectric multilayer film, and a difference in the number of layers of the dielectric multilayer film formed on both surfaces of the substrate is 12 or less. Further, the difference in physical film thickness is 500 nm or less. The filter according to claim 7 or 8, wherein the near-infrared reflective film is a dielectric multilayer film, and in each of the dielectric multilayer films formed on both sides of the substrate, When the average optical film thickness of any "seven consecutive layers satisfying the following (h)" is compared with each other, the dielectric film having a thicker average optical film thickness is used. The average optical film thickness of the bulk multilayer film is 1.05 to 1.60 times the average optical film thickness of the other dielectric multilayer film: (h) the optical film thickness of the adjacent high refractive index material layer and the low refractive index material layer ( The ratio of the physical film thickness x the refractive index is 0.8 to 1.2. The filter according to claim 1 or 2, which is used for a solid-state imaging device. A solid-state photographic device comprising the filter of any one of the first to ninth aspects of the invention. A camera module comprising the filter of any one of claims 1 to 9.