JP2012103340A - Near-infrared cut filter, solid-state imaging sensor and solid-state imager equipped with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a near-infrared cut filter that has a wide view angle, is excellent in the ability to cut near-infrared ray, furthermore, has heat resistance suitable for use in solder re-flow process, and can appropriately be used especially for a solid-state imager such as a CCD and a CMOS.SOLUTION: The near-infrared cut filter includes a lamination plate having a resin layer on at least one side of a glass substrate, and has a transmittance satisfying: a condition (B) in which, in the range of a wavelength of 800 to 1000 nm, the average value of the transmittance measured from the vertical direction of the near-infrared cut filter is 20% or less; and a condition (C) in which an absolute value |Xa-Xb| of the difference between the longest wavelength (Xa) at which the transmittance measured from the vertical direction of the near-infrared cut filter is 70% in the area having a wavelength of 800 nm or less and the shortest wavelength (Xb) at which the transmittance measured from the vertical direction of the near-infrared cut filter is 30% in the area having a wavelength of 580 nm or more is below 75 nm.

Description

  The present invention relates to a near-infrared cut filter. Specifically, the present invention relates to a near-infrared cut filter that has both a sufficient viewing angle and solder reflow heat resistance and can be suitably used as a visibility correction filter for a solid-state imaging device such as a CCD or CMOS.

  Video cameras, digital still cameras, mobile phones with camera functions, etc. use color image solid-state image sensors such as CCD and CMOS image sensors, but these solid-state image sensors have sensitivity to near infrared rays in their light receiving parts. Since a silicon photodiode is used, it is necessary to correct visibility, and a near-infrared cut filter is often used.

  As such a near-infrared cut filter, what was conventionally manufactured by various methods is used. For example, a metal such as silver deposited on the surface of a transparent substrate such as glass to reflect near infrared rays, or a transparent resin such as acrylic resin or polycarbonate resin to which a near infrared absorbing dye is added is practically used. Has been.

  When glass is used as the substrate, the substrate itself has heat resistance, so it can be applied to a process having a so-called solder reflow process, and the optical component and device can be downsized and the manufacturing process can be simplified. It becomes.

  However, the near-infrared cut filter in which metal oxides having different refractive indexes are alternately laminated on a glass substrate has a poor viewing angle such that optical characteristics are different with respect to normal incident light and oblique incident light. This glass substrate can be replaced with thin glass, and can be made thinner, for example, with a thickness of 0.1 mm (Patent Document 1). On the other hand, in a so-called colored glass filter that cuts near-infrared light by light absorption, in order to obtain a predetermined optical density, the glass substrate becomes thick, and it is difficult to reduce the size of the optical component. (Non-Patent Document 1).

  The present applicant has proposed a near-infrared cut filter having a norbornene-based resin substrate and a near-infrared reflective film in Japanese Patent Application Laid-Open No. 2005-338395 (Patent Document 2). The near-infrared cut filter described in Patent Document 2 is excellent in near-infrared cut ability, moisture absorption resistance, and impact resistance, and can be thinned, but cannot take a sufficient viewing angle value. Since a plastic resin is used as a substrate, it has poor heat resistance and may not be used in the solder reflow process.

JP 2007-197280 A JP 2005-338395 A

Sigma Koki Co., Ltd. General Catalog Near Infrared Absorption Filter CCF-50S-500C

  The present invention has a wide viewing angle, excellent near-infrared cutting ability, and heat resistance suitable for use in a solder reflow process, and can be suitably used for a solid-state imaging device such as a CCD or CMOS. The purpose is to obtain an infrared cut filter. Furthermore, it aims at providing the solid-state image sensor and solid-state imaging device which comprise the said near-infrared cut off filter.

The near-infrared cut filter of the present invention includes a laminate having a resin layer on at least one surface of a glass substrate, and the transmittance satisfies the following (A) to (D).
(A) In the wavelength range of 430 to 580 nm, the average value of the transmittance when measured from the vertical direction of the near infrared cut filter is 75% or more.
(B) In the wavelength range of 800 to 1000 nm, the average value of the transmittance when measured from the vertical direction of the near infrared cut filter is 20% or less.
(C) In the wavelength region of 800 nm or less, the longest wavelength (Xa) at which the transmittance when measured from the vertical direction of the near-infrared cut filter is 70%, and in the wavelength region of wavelength 580 nm or more, The absolute value | Xa−Xb | of the difference from the shortest wavelength (Xb) at which the transmittance when measured from the vertical direction is 30% is less than 75 nm.
(D) In the wavelength range of 560 to 800 nm, the wavelength value (Ya) at which the transmittance when measured from the vertical direction of the near-infrared cut filter is 50%, and 30 ° with respect to the vertical direction of the near-infrared cut filter The absolute value | Ya−Yb | of the difference in wavelength value (Yb) at which the transmittance when measured from the angle of 50% is less than 15 nm.

The resin layer preferably contains a near infrared absorber.
The laminated board preferably satisfies the following requirement (i).
(I) It has an absorption maximum wavelength between 600 and 800 (nm).
The laminate preferably satisfies the following formulas (ii) and (iii).
(Ii) 1/700 ≦ (thickness of resin layer / thickness of glass substrate) ≦ 2/5
(Iii) 30 ≦ thickness of glass substrate (μm) ≦ 1000

  The resin layer preferably contains at least one resin selected from the group consisting of polyimide resins, polyethylene naphthalate resins, polyethersulfone resins, polyether resins, and cyclic olefin resins.

The infrared absorber preferably satisfies the following (iv).
(Iv) 5% weight loss temperature measured by thermogravimetric analysis in the atmosphere is 250 ° C. or more. The near-infrared cut filter of the present invention preferably has a dielectric multilayer film on at least one side of the laminate.

  The near-infrared cut filter of the present invention includes (a) a structural unit derived from a (meth) acryloyl group-containing compound, (b) a structural unit derived from a carboxylic acid group-containing compound, between the glass substrate and the resin layer, And (c) it preferably has a cured layer having a structural unit derived from the epoxy group-containing compound.

In the near-infrared cut filter of the present invention, it is preferable that a visible light antireflection layer is formed on the surface of the resin layer opposite to the surface on which the glass substrate is laminated.
The near-infrared cut filter of the present invention can be used for a solid-state imaging element, a solid-state imaging device, and the like.

  The near-infrared cut filter of the present invention has a wide viewing angle, excellent near-infrared cut ability, and sufficient heat resistance to be applied to a production method having a solder reflow process.

FIG. 1 (a) shows a conventional camera module. FIG. 1 (b) shows an example of a camera module in the case of using the near-infrared cut filter 6 ′ obtained by the present invention. FIG. 2 shows a method of measuring the transmittance when measured from the vertical direction of the near-infrared cut filter. FIG. 3 shows a method of measuring the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter.

  Hereinafter, the present invention will be specifically described.

[Near-infrared cut filter]
The near-infrared cut filter of the present invention includes a laminate having a resin layer on at least one surface of a glass substrate, and the light transmittance thereof satisfies the above (A) to (D).

  In the above (A) wavelength range of 430 to 580 nm, the average transmittance when measured from the vertical direction of the near-infrared cut filter is 75% or more, preferably 78% or more, more preferably 80% or more. . When the transmittance in the wavelength range is within the above range, the intensity of light passing through the near-infrared cut filter is sufficiently secured and can be suitably used for a camera module or a lens unit.

  In the above-mentioned (B) wavelength range of 800 to 1000 nm, the average value of the transmittance when measured from the vertical direction of the near infrared cut filter is 20% or less, preferably 15% or less, more preferably 10% or less. . When the transmittance in the wavelength range is within the above range, near infrared rays can be sufficiently cut.

  (C) In the wavelength region of 800 nm or less, the longest wavelength (Xa) having a transmittance of 70% when measured from the vertical direction of the near infrared cut filter, and the near infrared cut filter in the wavelength region of 580 nm or more The absolute value | Xa−Xb | of the difference from the shortest wavelength (Xb) at which the transmittance when measured from the vertical direction is 30% is less than 75 nm, preferably 72 nm or less, more preferably 70 nm or less. It is. If the absolute value of the difference between Xa and Xb is in the above range, the transmittance changes abruptly between Xa and Xb near the near-infrared wavelength region, so that the near-infrared can be efficiently cut.

  In the above (D) wavelength range of 560 to 800 nm, the wavelength value (Ya) at which the transmittance when measured from the vertical direction of the near-infrared cut filter is 50%, and in the wavelength range of 560 to 800 nm, in the vertical direction On the other hand, the absolute value | Ya−Yb | of the difference in wavelength value (Yb) at which the transmittance when measured from an angle of 30 ° is 50% is less than 15 nm, more preferably 13 nm or less, particularly preferably 10 nm. The following is preferable.

  If the absolute value of the difference between Ya and Yb is in the above range, a near-infrared cut filter having a small angle dependency of the light transmission characteristic can be obtained, and as a result, it enters an image sensor such as a CCD or CMOS. The angle dependency of light is reduced, and the color reproducibility of the photographed image is excellent.

  When the laminated board which has the resin layer containing the following specific near-infrared absorber on at least one surface of a glass substrate, the near-infrared cut filter which satisfy | fills said (A)-(D) can be obtained.

<Laminated plate>
The laminate has a resin layer on at least one side of the glass substrate. The resin layer preferably contains a near-infrared absorber, and the laminated plate preferably satisfies the following formula (i), the following formula (ii), and the following formula (iii).
(I) It has an absorption maximum wavelength (hereinafter also referred to as λ _max ) between 600 and 800 (nm).
(Ii) 1/700 ≦ (thickness of resin layer / thickness of glass substrate) ≦ 2/5
(Iii) 30 ≦ (thickness of glass substrate: μm) ≦ 1000
By having a resin layer containing the following specific near-infrared absorber on at least one surface of the glass substrate, a laminate satisfying the above (i) can be obtained.

Λ _max of the laminate is preferably in the range of 640 to 770 (nm), more preferably 660 to 720 (nm). By having the λ _max in the above wavelength range, the wavelength range of light incident on a CMOS or the like that is sensitive to near-infrared light is limited, so that the color of the image captured by the CMOS or the like is actually visually observed. It is closer to the color observed in.
The ratio of the thickness of the resin layer to the thickness of the glass substrate is preferably from 1/700 to 2/5, more preferably from 1/400 to 1/5, particularly preferably from 1/200 to 1/8. It is.

  When the ratio of the thickness of the resin layer to the thickness of the glass substrate is smaller than 1/700, the thickness of the resin layer relative to a certain thickness of the glass substrate is so thin that it becomes difficult to control the thickness of the resin layer. In some cases, it is difficult to stably control the light absorption performance of the near infrared absorber. This tendency becomes remarkable especially when the glass substrate is thin. On the other hand, when the ratio of the thickness of the resin layer to the thickness of the glass substrate is greater than 2/5, when heat is applied in the solder reflow process, due to the difference in the coefficient of thermal expansion between the resin layer and the glass substrate, Curling may occur in the laminate. This tendency becomes remarkable especially when the glass substrate is thin.

≪Glass substrate≫
The glass substrate used in the present invention is not particularly limited as long as it is a substrate containing silicate as a main component, and examples thereof include a quartz glass substrate having a crystal structure. In addition, a borosilicate glass substrate, a soda glass substrate, a color glass substrate, and the like can be used. In particular, glass substrates such as non-alkali glass substrates and low α-ray glass substrates can be used for solid-state imaging devices such as CCDs and CMOSs. Therefore, it is possible to arrange these substrates close to the solid-state imaging device, which is preferable.

  The thickness of the glass substrate is preferably 30 to 1000 μm, more preferably 50 to 750 μm, and particularly preferably 50 to 700 μm. When the thickness of the glass substrate is less than 30 μm, the glass substrate itself is easily broken, and handling may be extremely difficult. Moreover, when the thickness of the glass substrate is thicker than 1000 μm, the original purpose of thinning the near-infrared cut filter may not be achieved.

  When the thickness of the glass substrate is in the above range, the near-infrared cut filter 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 used in a lens unit such as a camera module, it is preferable because a low profile of the lens unit can be realized.

≪Resin layer≫
It is preferable that the resin layer used for this invention contains the resin which has heat resistance applicable to a solder reflow process, and the near-infrared absorber which has an absorption maximum between wavelengths 600-800 nm.

<Resin with heat resistance>
Examples of the heat-resistant resin include polyimide resins, polyethylene naphthalate resins, polyether sulfone resins, polyether resins (polyether ketone resins and polyether nitrile resins), polycarbonates, polyarylates, and cyclic resins. An olefin resin etc. can be mentioned. These resins may be used alone or in combination of two or more.

  The resin having heat resistance preferably has a glass transition temperature (Tg) of 220 to 380 ° C., more preferably 240 to 360 ° C., and particularly preferably 250 to 350 ° C. in terms of resistance to the solder reflow process. .

  The resin layer has a total light transmittance at a thickness of 0.1 mm of preferably 75 to 94%, more preferably 78 to 93%, and particularly preferably 80 to 92%. Is preferably used. When the total light transmittance is within such a range, the resin layer obtained from the resin exhibits good transparency as an optical member.

  The thickness of the resin layer is not particularly limited as long as it satisfies the above (ii), but is preferably 1 to 100 μm, more preferably 2 to 50 μm, and particularly preferably 3 to 30 μm.

  When the thickness of the resin layer is within the above range, the near-infrared cut filter of the present invention 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 used in a lens unit such as a camera module, it is preferable because a low profile of the lens unit can be realized.

<Polyimide resin>
What is necessary is just to synthesize | combine by the method generally known as said polyimide resin, for example, can be synthesize | combined by the method described in Unexamined-Japanese-Patent No. 2008-163107. Commercially available products include transparent polyimide film types TT, TMM, HM (manufactured by Toyobo Co., Ltd.), transparent polyimide films using oxydiphthalic anhydride (manac) and transparent polyimide films (made by IST) Neoprim ( (Mitsubishi Gas Chemical Co., Ltd.) etc. can be used suitably.

<Polyethylene naphthalate resin>
As the polyethylene naphthalate resin, for example, polyethylene naphthalate produced by polycondensation of a lower alkyl ester of naphthalene dicarboxylic acid and ethylene glycol can be suitably used. As a commercially available product, Teonex (manufactured by Teijin Limited) or the like can be suitably used.

<Polyethersulfone resin>
The polyethersulfone resin is produced, for example, by reacting dihalogenodiphenylsulfone and a divalent phenol compound in an organic polar solvent in the presence of anhydrous alkali metal carbonate and / or anhydrous alkali metal bicarbonate. The polyether sulfone resin thus obtained can be suitably used. As commercially available products, SUMIKAEXCEL PES, SUMIKAEXCEL 7600P (manufactured by Sumitomo Chemical Co., Ltd.), PES (manufactured by Mitsui Chemicals), Ultrazone E (manufactured by BASF Japan), Radel A (manufactured by Solvay Advanced Polymers), etc. are preferably used. be able to.

<Polyetherketone resin>
The polyether ketone resin is produced, for example, by reacting a dihalogenobenzophenone and a divalent phenol compound in an organic polar solvent in the presence of anhydrous alkali metal carbonate and / or anhydrous alkali metal hydrogen carbonate. Polyether ketone resins can be suitably used. As commercially available products, VICTREX (manufactured by Victrex) and KetaSpire (manufactured by Solvay) can be suitably used.

<Polyether nitrile resin>
The polyether nitrile resin is produced, for example, by reacting dihalogenobenzonitrile and a divalent phenol compound in an organic polar solvent in the presence of anhydrous alkali metal carbonate and / or anhydrous alkali metal hydrogen carbonate. The polyether nitrile resin thus obtained can be suitably used. Specifically, polymers described in JP-A-2007-246629 and JP-A-2006-199746 can be suitably used.

<Polycarbonate>
Examples of the polycarbonate include melt polycondensation of dihydric phenol and phosgene or carbonate, or presence of an anhydrous alkali metal carbonate and / or an anhydrous alkali metal bicarbonate and an organic base in an organic polar solvent. Polycarbonate produced by reaction under the above can be suitably used. As commercially available products, polycarbonate (Teijin Chemicals, manufactured by Bayer), Teflon Neo (produced by Idemitsu), and the like can be suitably used.

<Polyarylate>
Examples of the polyarylate include melt polycondensation of a divalent aromatic carboxylic acid derivative and a divalent phenol compound, or an anhydrous alkali metal carbonate and / or an anhydrous alkali metal bicarbonate in an organic polar solvent, and Polyarylate produced by reacting in the presence of an organic base can be preferably used. As commercial products, Vectran (manufactured by Kuraray Co., Ltd.), U polymer (manufactured by Unitika Ltd.) and the like can be suitably used.

<Cyclic olefin resin>
As the cyclic olefin-based resin, for example, a monomer represented by the following formula (X ₀ ) or a monomer composition containing a monomer represented by the following formula (Y ₀ ) is polymerized, If necessary, a resin obtained by further hydrogenation can be used.

[In the formula (X ₀ ), R ^{x1 to} R ^x4 each independently represents one selected from the following (i) to (viii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a trialkylsilyl group,
(Iv) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms including a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
(V) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,
(Vi) polar group (except (iv)),
(Vii) R ^x1 and R ^x2 , or R ^x3 and R ^x4 represent an alkylidene group formed by bonding to each other, and R ^{x1 to} R ^x4 not involved in the bonding are the above (i) Represents one selected from (vi),
(Viii) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by bonding to each other, and R ^{x1 to} R ^x4 not participating in the bond are Each independently selected from the above (i) to (v), or R ^x2 and R ^x3 represent a monocyclic saturated hydrocarbon ring or heterocyclic ring formed by bonding to each other, R ^{x1 to} R ^{x4 that} are not involved in the bond are independently selected from the above (i) to (v).
k ^x , ^mx and p ^x each independently represents 0 or a positive integer. ]

[In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represents one selected from the above (i) to (vi) or the following (ix) and (x).
(Ix) R ^y1 and R ^y2 represent a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by bonding to each other;
(X) An aromatic ring formed by combining R ^y1 and R ^y2 with each other.
k ^y and p ^y are each independently, represent 0 or a positive integer. ]

  Among the above resins, polyether resins (polyether ketone resins and polyether nitrile resins) are particularly preferable. By using a polyether-based resin, it is possible to obtain a near-infrared cut filter having sufficient heat resistance for the solder reflow process and sufficiently high visible light transmittance for use as an optical material.

<Near infrared absorber>
The near-infrared absorber that can be used in the near-infrared cut filter of the present invention has (iv) a 5% weight loss temperature measured by thermogravimetric analysis in the air, preferably 250 ° C. or more, and more preferably 260 C. or higher, particularly preferably 270.degree. C. or higher. When the weight reduction temperature satisfies the above-described conditions, it is possible to provide a near-infrared cut filter having a stable quality, ensuring sufficient thermal properties for use in the solder reflow process without being decomposed even under high temperature conditions.

  Further, the near-infrared absorber used in the present invention preferably has an absorption maximum at a wavelength of 600 to 800 nm, more preferably 640 to 770 (nm), particularly preferably 660 to 720 (nm). It is desirable to have.

By using such a near-infrared absorber, the laminated board and near-infrared cut filter which satisfy | fill said (A)-(D) and (i) can be obtained.
Examples of such near infrared absorbers include cyanine dyes, phthalocyanine dyes, aminium dyes, iminium dyes, azo dyes, anthraquinone dyes, diimonium dyes, squarylium dyes, and porphyrin dyes. It is done.

  Since the resin layer containing such a near-infrared absorber has the above-mentioned heat resistance, it can be applied to a solder reflow process.

Specific examples of the commercially available near infrared absorber include Lumogen IR765, Lumogen IR788 (manufactured by BASF); ABS643, ABS654, ABS667, ABS670T, IRA693N, IRA735 (manufactured by Exciton); SDA3598, SDA6075, SDA80, SDA8303, SDA8470, SDA3039, SDA3040, SDA3922, SDA7257 (manufactured by HW SANDS); TAP-15, IR-706 (manufactured by Yamada Chemical Co., Ltd.);
These near infrared absorbers may be used individually by 1 type, and may use 2 or more types together.

In the present invention, the amount of the near-infrared absorber used is appropriately selected according to the desired properties, but is usually 0.01 to 10.0% by weight, preferably 100% by weight, preferably 100% by weight of the resin used in the present invention. It is 0.01 to 8.0 weight%, More preferably, it is 0.01 to 5.0 weight%.
When the amount of the near-infrared absorber used is within the above range, the near-infrared cut filter having a small near-infrared cut ability, a transmittance in the range of 430 to 580 nm and an excellent intensity is obtained. Can do.

  When the amount of the near-infrared absorber used is larger than the above range, a near-infrared cut filter in which the properties of the near-infrared absorber appear more strongly may be obtained, but the transmittance in the range of 430 to 580 nm is a desired value. The near-infrared cut filter having a high transmittance in the range of 430 to 580 nm when the use amount of the near-infrared absorber is less than the above range. However, it may be difficult to obtain a near-infrared cut filter in which the properties of the near-infrared absorber are difficult to appear and the absorption angle dependency of the absorption wavelength is small.

<Optical characteristics of resin layer>
The resin layer of the present invention has (i) an absorption maximum wavelength (hereinafter also referred to as “λ _max ”) between 600 and 800 (nm), preferably 640 to 770 (nm), more preferably 660 to 720. (Nm). By having the λ _max in the above wavelength range, the wavelength range of light incident on the CMOS having sensitivity to near-infrared light is limited. Therefore, the color of the image captured by the CMOS or the like is actually visually observed. It is closer to the observed hue.

<Other ingredients>
In the resin layer, other components such as an antioxidant, an ultraviolet absorber and a surfactant can be further added as long as the effects of the present invention are not impaired.

  Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane and tetrakis [ Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.
When a resin layer is produced by a solution casting method described later, the production of the resin layer can be facilitated by adding a surfactant or an antifoaming agent.

  As said surfactant, the following copolymers (S) obtained by a commercial item or radical polymerization can be used, These can be used individually or in combination of 2 or more types.

The copolymer (S) is a copolymer of a fluorinated alkyl group-containing monomer (M1), a polyoxyethylene chain-containing monomer (M2), and an ethylenically unsaturated monomer (M3) having a silicone chain. Monomers other than the above (M1) to (M3) may be used as necessary.
Examples of the fluorinated alkyl group-containing monomer (M1) include monomers represented by the following formulas (M-1-1) and (M-1-2).

As the polyoxyethylene chain-containing monomer (M2), Shin-Nakamura Chemical Co., Ltd., NK-esters M-40G, M-90G, AM-90G, NOF Corporation Bremer PME-200, PME-400, PME-550, etc. are mentioned.
Examples of the ethylenically unsaturated monomer (M3) having a silicone chain include a monomer containing a structural unit represented by the following general formula (M3 ′).

(In the formula (M3 ′), R ⁴ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ⁵ and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms, phenyl. Represents a group or general formula (2), and m represents an integer of 0 to 200. In formula (2), R ⁷ , R ^8, and R ⁹ each independently represent 1 to 20 carbon atoms. An alkyl group or a phenyl group, and n represents an integer of 0 to 200.)

  Moreover, as a more specific example of the ethylenically unsaturated monomer (M3) having a silicone chain, a monomer represented by the following formula M-3-1 to 3 may be mentioned.

(In formulas M3-1 to 1-3, Me and Ph represent a methyl group and a phenyl group, respectively, and r, s, and t each independently represents an integer of 0 to 200.)

  The production method of the copolymer (S) is not particularly limited, and is based on a known method, that is, a polymerization method such as radical polymerization method, cationic polymerization method, anionic polymerization method, solution polymerization method, bulk polymerization method, and emulsion. Although it can be produced by a polymerization method or the like, the radical polymerization method is particularly convenient and industrially preferable. In the radical polymerization method, a polymerization initiator such as a radical initiator can be used.

  In the production of the copolymer (S), the mixing ratio of each of the monomers (M1), (M2) and (M3) with respect to 100% by mass in total of the monomers as raw materials for the copolymer (S) The monomer (M1) is preferably 20 to 50% by mass, more preferably 25 to 40% by mass, the monomer (M2) is preferably 15 to 40% by mass, more preferably 20 to 35% by mass, A monomer (M3) becomes like this. Preferably it is 10-30 mass%, More preferably, it is 15-25 mass%. The weight average molecular weight of the copolymer (S) is preferably 5,000 to 25,000, more preferably 10,000 to 25,000, and particularly preferably 15,000 to 25,000. is there.

  Examples of the surfactant other than the above-described copolymer (S) include a fluorine-based surfactant and a silicone-based surfactant, and these can also be used in combination.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable.
Examples of commercially available fluorosurfactants include BM-1000 and BM-1100 (manufactured by BM CHEMIE); MegaFuck F142D, F172, F173, F183, F178, F191, F191, F471, F476 (above, Dainippon Ink & Chemicals, Inc.); Florard FC-170C, -171, -430, -431 (above, manufactured by Sumitomo 3M); Surflon S-112,- 113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, manufactured by Asahi Glass Co., Ltd.) Ftop EF301, 303, 352 (above, manufactured by Shin-Akita Kasei Co., Ltd.); FT-100, -110, -140A, -15 0, the same -250, the same -251, the same -300, the same -310, the same -400S, the tergent FTX-218, the same -251 (manufactured by Neos Co., Ltd.).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.); TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

  It should be noted that additives such as antioxidants, ultraviolet absorbers and surfactants may be mixed with the resin components when producing the resin layer, or may be added when synthesizing the resin. The addition amount is appropriately selected according to 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. is there.

≪Resin layer manufacturing method≫
The resin layer containing the near-infrared absorber is, for example, a method of melt-molding pellets obtained by melt-kneading the resin, the near-infrared absorber and, if necessary, the other components, a resin, a near-infrared absorber, Manufacturing by a method of melt-molding pellets obtained by removing the solvent from the liquid resin composition containing the solvent and, if necessary, the other components, or a method of casting (cast molding) the above-mentioned liquid resin composition Can do.

(A) Melt molding Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

(B) Casting As a casting method, the solvent may be removed by casting the liquid resin composition on a suitable base material. For example, on a base material such as a steel belt, a steel drum, or a polyester film. In addition, the above-mentioned liquid resin composition is applied and the solvent is dried to form a coating film, and then the coating film is peeled off from the substrate, whereby the resin layer can be obtained alone.
Alternatively, the resin layer can be directly formed on the glass substrate by coating the glass substrate with the above liquid composition and drying the solvent.

  The amount of residual solvent in the resin layer obtained by the above method should be as small as possible, and is usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. When the amount of residual solvent in the resin layer exceeds 3% by weight, the resin layer may be deformed over time or the characteristics of the resin layer may be changed, and a desired function may not be exhibited.

≪Hardened layer≫
Since the resin layer and the glass substrate have different chemical compositions and thermal expansion coefficients, it is preferable to provide a cured layer between the resin layer and the glass substrate to ensure their sufficient adhesion. Although it will not specifically limit if the hardened layer used for this invention consists of a material which can ensure the adhesiveness between a resin layer and a glass substrate, For example, (a) Structural unit derived from the (meth) acryloyl group containing compound, ( It is preferable to have b) a structural unit derived from a carboxylic acid group-containing compound and (c) a structural unit derived from an epoxy group-containing compound, since the adhesion between the resin layer and the glass substrate is increased.

<(A) Structural unit derived from (meth) acryloyl group-containing compound>
The structural unit (a) is not particularly limited as long as it is a structural unit derived from a (meth) acryloyl group-containing compound. As the (meth) acryloyl group-containing compound, for example, monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters are preferable from the viewpoint of good polymerizability. In the present invention, “(meth) acryl” means “acryl” or “methacryl”.

  Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl). Mention may be made of phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate and ω-carboxypolycaprolactone monoacrylate.

  As these commercial items, for example, Aronix M-101, M-111, M-114, and M-5300 (above, manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S, TC -120S (above, Nippon Kayaku Co., Ltd.); Biscote 158, 2311 (above, Osaka Organic Chemical Industries, Ltd.).

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate and 1,9-nonanediol Mention may be made of dimethacrylate.

  As these commercial items, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.); KAYARAD HDDA, HX-220, R-604 ( As mentioned above, Nippon Kayaku Co., Ltd.); Biscoat 260, 312, 335HP (Osaka Organic Chemical Co., Ltd.); Light acrylate 1,9-NDA (Kyoeisha Chemical Co., Ltd.); be able to.

  Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol. Pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2-acryloyl) Oxyethyl) In addition to phosphate and tri (2-methacryloyloxyethyl) phosphate, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule And the polyfunctional urethane acrylate type compound obtained by making it react with the compound which has 3, 4, or 5 (meth) acryloyloxy group can be mentioned.

Commercially available products of trifunctional or higher functional (meth) acrylic acid esters are trade names such as Aronix M-309, M-315, M-400, M-405, M-450, and M-7100. M-8030, M-8060, TO-1450 (above, manufactured by Toagosei Co., Ltd.); KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA- 120, the same DPEA-12 (above, manufactured by Nippon Kayaku Co., Ltd.); Biscote 295, 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemical Industries, Ltd.); As a commercial product containing a polyfunctional urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.); KAYARAD DPHA-40H (Nippon Kayaku) Co., Ltd.)) can be mentioned.
These (meth) acryloyl group-containing compounds (a) can be used alone or in admixture of two or more in the cured layer.

<(B) Structural unit derived from carboxylic acid group-containing compound>
The structural unit (b) is not particularly limited as long as it is a structural unit derived from a compound containing a carboxylic acid group. Examples of the carboxylic acid group-containing compound include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, and polymers having carboxylic acid groups.

  Examples of monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid and 2-methacryloyloxyethyl hexahydrophthal Mention may be made of acids.

Examples of the dicarboxylic acid include maleic acid, fumaric acid, and citraconic acid.
Examples of the dicarboxylic acid anhydride include the dicarboxylic acid anhydride.

  The polymer having a carboxylic acid group is a compound having a carboxylic acid group, for example, a compound having at least one polymer selected from acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like. A polymer or a copolymer of these compounds and the (meth) acryloyl group-containing compound can be preferably used.

  Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride is preferable from the viewpoint of copolymerization reactivity.

<(C) Structural unit derived from epoxy group-containing compound>
The structural unit (c) is not particularly limited as long as it is a structural unit derived from an epoxy group-containing compound. Examples of the epoxy group (oxiranyl group) -containing compound include oxiranyl groups such as (meth) acrylic acid oxiranyl (cyclo) alkyl ester, α-alkylacrylic acid oxiranyl (cyclo) alkyl ester, and glycidyl ether compound having an unsaturated bond. An unsaturated compound having an oxetanyl group such as a (meth) acrylic acid ester having an oxetanyl group.

  As (meth) acrylic acid oxiranyl (cyclo) alkyl ester, for example, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid 3,4 -Epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) acrylic acid 3,4-epoxycyclohexyl and (meth) acrylic acid 3,4-epoxycyclohexylmethyl. Acid oxiranyl (cyclo) alkyl esters such as glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate and α-ethyl Acrylic acid 3, 4 Examples of the glycidyl ether compound having an unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether, which have an oxetanyl group ( Examples of (meth) acrylic acid esters include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, and 3-((meth) acryloyloxymethyl) -2-methyl. Oxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyloxymethyloxetane Beauty 3-ethyl-3- (meth) acryloyloxy methyl oxetane and the like.

  Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl- 3-Methacryloyloxymethyloxetane or 3-ethyl-3-methyloxetane is preferred from the viewpoint of polymerizability.

<Optional component>
Arbitrary components such as an acid generator, an adhesion assistant, a surfactant, and a polymerization initiator can be added to the cured layer as long as the effects of the present invention are not impaired. These addition amounts are appropriately selected according to the desired properties, and are usually each based on a total of 100 parts by weight of the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound and the epoxy group-containing compound. The content is 0.01 to 15.0 parts by weight, preferably 0.05 to 10.0 parts by weight.

<Polymerization initiator>
The polymerization initiator is a component that generates active species capable of initiating polymerization of monomer components in response to light rays such as ultraviolet rays and electron beams. Such a polymerization initiator is not particularly limited, and examples thereof include an O-acyloxime compound, an acetophenone compound, a biimidazole compound, an alkylphenone compound, and a benzophenone compound. Specific examples thereof include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl- 6-Benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9- Ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4 -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, -Phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl benzophenone, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned. These polymerization initiators can be used alone or in admixture of two or more.

The cured layer is, for example, a pellet obtained by melt-kneading the composition (I) containing the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound, the epoxy group-containing compound and, if necessary, the optional component. , A method of melt-molding pellets obtained by removing the solvent from the liquid composition containing the composition (I) and the solvent, or a method of casting (cast molding) the liquid composition described above Can be manufactured.
Examples of the melt molding method and the cast molding method include the same methods as described above.

  The amount of the (meth) acryloyl group-containing compound is preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight per 100 parts by weight of the composition (I). The amount is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight per 100 parts by weight of the composition (I), and the amount of the epoxy group-containing compound is 100 parts by weight of the composition (I). The amount is preferably 15 to 50 parts by weight, more preferably 20 to 40 parts by weight.

  The amount of the optional component is appropriately selected depending on the desired properties, but is preferably 0.01 to 15.0 parts by weight, more preferably 0.05 to 100 parts by weight per 100 parts by weight of the composition (I). 10.0 parts by weight.

  The thickness of the cured layer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm.

≪Dielectric multilayer film≫
The dielectric multilayer film used in the present invention is a film having the ability to reflect and / or absorb near infrared rays. In the present invention, the dielectric multilayer film may be provided on one side or both sides of the laminated plate. When it is provided on one side, it is excellent in production cost and manufacturability, and when it is provided on both sides, it is possible to obtain a near-infrared cut filter having high strength and less warpage.

  As a material of the dielectric multilayer film, for example, ceramic can be used. In order to form a near-infrared cut filter using the effect of light interference, it is preferable to use two or more ceramics having different refractive indexes.

Alternatively, it is also preferable to use a noble metal film having absorption in the near-infrared region in consideration of the thickness and the number of layers so as not to affect the visible light transmittance of the near-infrared cut filter.
Specifically, a configuration in which high refractive index material layers and low refractive index material layers are alternately stacked can be suitably used as the dielectric multilayer film.

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 range of 1.7 to 2.5 is usually selected.
Examples of the material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as a main component, and titanium oxide, tin oxide, and / or cerium oxide. The thing which contained a small amount is mentioned.

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 range of 1.2 to 1.6 is usually selected.
Examples of this material include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

  The method for forming the dielectric multilayer film on the laminated plate is not particularly limited, but the high refractive index material layer and the low refractive index material layer are alternately formed by, for example, CVD, sputtering, or vacuum deposition. A laminated dielectric multilayer film is formed, and this is laminated to the laminated plate with an adhesive, and directly on the laminated plate by a CVD method, a sputtering method, a vacuum deposition method, etc. A method of forming a dielectric multilayer film in which refractive index material layers are alternately stacked can be exemplified.

  The thicknesses of the high refractive index material layer and the low refractive index material layer are generally 0.1λ to 0.5λ of the infrared wavelength λ (nm) to be blocked. When the thickness is out of the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by λ / 4, and the optical characteristics of reflection and refraction are different. The relationship is broken, and it tends to be difficult to control blocking / transmission of a specific wavelength.

The number of laminated layers in the dielectric multilayer film is preferably 5 to 50 layers, more preferably 10 to 45 layers.
In addition, if the substrate is warped when the dielectric multilayer film is deposited, in order to eliminate this, the dielectric multilayer film is deposited on both sides of the substrate. A method of irradiating with radiation such as ultraviolet rays can be taken. In addition, when irradiating a radiation, you may irradiate while performing the vapor deposition of a dielectric multilayer, and you may irradiate separately after vapor deposition.

≪Visible light antireflection layer≫
The visible light antireflection layer used in the present invention is not particularly limited as long as it prevents or reduces the reflection of visible light at the interface between the resin layer and air. The visible light antireflection layer is preferably formed on the surface of the resin layer opposite to the surface on which the glass substrate is laminated. When providing the dielectric multilayer film on both surfaces of the laminate, it is not necessary to provide a visible light antireflection layer. When providing the dielectric multilayer film on one surface of the laminate, the laminate The plate is preferably formed on the surface opposite to the surface on which the dielectric multilayer film is laminated.

  The visible light antireflection layer is formed, for example, by laminating the high refractive index material and the low refractive index material described in the dielectric multilayer film in the number of laminated layers 1 to 5 by a CVD method, a sputtering method, a vacuum deposition method, or the like. Can be formed. In addition, after applying a heat and / or UV curable material to the surface of the resin layer, a fine shape such as a cone of the order of several tens to several hundreds of nanometers is transferred to this material using a mold or the like. A method of curing this material by heat and / or UV to form a visible light antireflection layer, or a sol-gel material having a different refractive index as described in Preparation Examples 12 and 13 (hydrolysis and polymerization of alkoxide, etc.). A material in which a colloidal material is dispersed in a solution) is applied and laminated to form a visible light antireflection layer (wet coating). In the case of using a sol-gel material, the visible light antireflection layer is usually cured by heat, but is generated by using an energy ray (for example, ultraviolet rays) to generate an acid or the like that becomes a condensation catalyst and is cured. May be formed (JP 2000-109560, JP 2000-1648).

  In particular, since the materials and equipment used for forming the dielectric multilayer film can be used as they are, a method for forming a visible light antireflection layer by the same method as that for forming the dielectric multilayer film, or production. From the viewpoint of improving the property, the method for forming the visible light antireflection layer by wet coating can be suitably used.

  The thickness of the visible light antireflection layer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.5 μm.

[Use of near-infrared cut filter]
These near-infrared cut filters obtained by the present invention have a small incident angle dependency and an excellent near-infrared cut ability. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS of a camera module. In particular, digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, personal digital assistants, personal computers, video games, medical equipment, USB memory, portable game machines, fingerprint authentication systems, digital music Useful for players, toy robots and toys. Furthermore, it is also useful as a heat ray cut filter or the like attached to glass or the like of automobiles and buildings.

  Since the near-infrared cut filter of the present invention has particularly small incident angle dependency, it can be generally incorporated in any position of a camera module composed of a lens, a cover glass, a CMOS, etc., and can cope with a solder reflow process. Due to its heat resistance, the camera module for mobile phones can be fully automatically mounted on the main board of the mobile phone. From the above features, the quality and cost as a near-infrared cut filter for mobile phone camera modules is particularly important. -Significant merit is expected in terms of design.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

Weight average molecular weight The weight average molecular weight (hereinafter referred to as Mw) by GPC in the present invention was measured using the HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation column: Four TSKgelGMH _HR- N manufactured by Tosoh Corporation are used.
Column temperature: 40 ° C
Moving layer: tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min Sample concentration: 1.0% by mass
Sample injection amount: 100 microliters Detector: differential refractometer

Transmittance characteristics by wavelength The light transmittance by wavelength in the range of 350 to 1200 nm was measured using a Hitachi spectrophotometer U-4100 (manufactured by Hitachi, Ltd.).
Here, in the wavelength region of 800 nm or less, the longest wavelength (Xa) at which the transmittance when measured from the vertical direction of the near infrared cut filter is 70% and the wavelength region of 580 nm or more of the near infrared cut filter The shortest wavelength (Xb) at which the transmittance when measured from the vertical direction was 30% was measured.

In the wavelength range of 560 to 800 nm, the near infrared cut filter has a wavelength value (Ya) at which the transmittance when measured from the vertical direction is 50%, and in the wavelength range of 560 to 800 nm, the near infrared cut filter The wavelength value (Yb) at which the transmittance was 50% when measured from an angle of 30 ° with respect to the vertical direction was measured.
Moreover, the average value of the transmittance | permeability in the range of the absorption maximum wavelength, the wavelength of 430-580 nm, and the wavelength of 800-1000 nm was measured.

Reflow test A near-infrared cut filter is fixed on a glass epoxy substrate SL-EP (manufactured by Nitto Shinko Co., Ltd.) with a thickness of 1 mm with Kapton tape, and a JEDEC standard reflow apparatus (STR-2010N2M-III) manufactured by Senju Metal Industry In accordance with J-STD-02D, a solder reflow treatment reaching a maximum temperature of about 270 ° C. is performed, and the wavelength value at which the transmittance is 50% when measured from the vertical direction of the filter in the wavelength range of 560 nm to 800 nm. The change value (half-value change by reflow (nm)) was obtained from the following formula, and the absolute value was defined as reflow resistance.
Half-value change by reflow (nm) = [wavelength value at which transmittance before solder reflow processing is 50% (Ya)] − [wavelength value at which transmittance after solder reflow processing is 50% (Za)]

Adhesion evaluation The adhesion of the resin layer to the glass substrate was evaluated by the adhesive cross-cut tape method described in JIS K-5400-1990, 8.5.3. In addition, [◎] indicates that no peeling is observed, [○] indicates that peeling is not observed but a part of the end of each grid is missing, and [◯] indicates that peeling is observed even in part. [×].

Appearance evaluation Appearance of near-infrared cut filters obtained in the following Examples and Comparative Examples [◎] when there is no warpage or distortion at all, while there is a slight warpage when there is no problem in actual use [ [Circle]], a case where warpage and distortion were severe and actual use was difficult was evaluated as [×].

(Monomer synthesis)
<Synthesis Example 1><< Production of 1,2,4,5-cyclohexanetetracarboxylic dianhydride >>
A 5 liter Hastelloy (HC22) autoclave was charged with 552 g of pyromellitic acid, 200 g of a catalyst with rhodium supported on activated carbon (manufactured by NE Chemcat Corporation) and 1656 g of water, and stirred. Then, the inside of the reactor was replaced with nitrogen gas. Next, the inside of the reactor was replaced with hydrogen gas, and the temperature of the reactor was increased to 60 ° C. with a hydrogen pressure of 5.0 MPa. The reaction was carried out for 2 hours while maintaining the hydrogen pressure at 5.0 MPa. The hydrogen gas in the reactor was replaced with nitrogen gas, the reaction solution was extracted from the autoclave, and the reaction solution was filtered while hot to separate the catalyst. The filtrate was concentrated by evaporating water under reduced pressure using a rotary evaporator to precipitate crystals. The precipitated crystals were separated into solid and liquid at room temperature and dried to obtain 481 g (yield 85.0%) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

<Synthesis Example 2><< Synthesis of Polyether Resin (P-1) >>
In a 1 L three-necked flask equipped with a stirrer, thermometer, Dean-Stark tube, nitrogen inlet tube and condenser tube, 157.68 g (450 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene, 2,2-bis (4 -Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 16.81 g (50 mmol), 2,6-difluorobenzonitrile 69.55 g (500 mmol) and potassium carbonate 76.02 g (550 mmol) I took a scale. After nitrogen substitution, 897 mL of N, N-dimethylacetamide (DMAc) and 448 mL of toluene were added and stirred. The reaction solution was heated to reflux at 130 ° C. in an oil bath. Water produced by the reaction was trapped in a Dean-Stark tube. After 3 hours, when almost no water was observed, toluene was removed out of the system from the Dean-Stark tube. The reaction temperature was gradually raised to 150 ° C. and stirring was continued for 2 hours. Then, the reaction solution was allowed to cool and diluted with 2.3 L of tetrahydrofuran (THF). Inorganic salts insoluble in the reaction solution were filtered, and the filtrate was poured into 3 L of methanol to precipitate the product. The precipitated product was filtered and dried, then dissolved in 3.2 L of THF, and poured into 2 L of methanol for reprecipitation.
The precipitated white powder was filtered and dried to obtain 69 g of a polyether resin (P-1). The number average molecular weight in terms of polystyrene measured by GPC was 53,000, and the weight average molecular weight was 105,000.

<Synthesis Example 3><< Synthesis of Polyimide Resin (P-2) >>
In a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with a side tube, a Dean-Stark tube and a condenser tube, 10.0 g (0. 05 mol) and 85 g of N-methyl-2-pyrrolidone as a solvent were dissolved and then 11.2 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride obtained in Synthesis Example 1 ( 0.05 mol) was charged in a solid state at room temperature over 1 hour and stirred at room temperature for 2 hours. Next, 30.0 g of xylene was added as an azeotropic dehydration solvent, the temperature was raised to 180 ° C., the reaction was performed for 3 hours, and xylene was refluxed in a Dean-Stark tube to separate the azeotropic product water. After 3 hours, it was confirmed that the distillation of water had ended, xylene was distilled off while raising the temperature to 190 ° C. over 1 hour, 29.0 g was recovered, and then air-cooled until the internal temperature reached 60 ° C. As a result, 105.4 g of an N-methyl-2-pyrrolidone solution of polyimide resin (P-2) was obtained.

(Synthesis of other components)
<Synthesis Example 4><< Synthesis of Surfactant (Copolymer (S-1)) >>
In a glass flask equipped with a stirrer, a condenser and a thermometer, 28.4 parts by mass of the fluorinated alkyl group-containing monomer represented by the formula M-1-1 and NK-ester M-90G (new monomer M2) Nakamura Chemical Co., Ltd.) 20.7 parts by mass, 18.1 parts by mass of an ethylenically unsaturated monomer having a silicone chain represented by the following formula M-3-4, a compound in which both ends of tetramethylene glycol are methacrylated 3.4 parts by weight, 5.9 parts by weight of methyl methacrylate, 23.5 parts by weight of 2-ethylhexyl acrylate and 414 parts by weight of isopropyl alcohol (hereinafter abbreviated as IPA) were charged, and polymerization was started under reflux in a nitrogen gas stream After adding 0.7 parts by mass of azobisisobutyronitrile (AIBN) as an agent and 4 parts by mass of lauryl mercaptan as a chain transfer agent Effecting copolymerization was refluxed for 8 hours at 75 ° C., to obtain a copolymer (S-1). Regarding the molecular weight of the obtained copolymer (S-1), the number average molecular weight was 2,800, and the weight average molecular weight was 5,300. The molecular weight distribution (Mw / Mn) was 1.9.

<Synthesis Example 5><< Synthesis of Surfactant (Copolymer (S-2)) >>
In a glass flask equipped with a stirrer, a condenser and a thermometer, 28.4 parts by mass of the fluorinated alkyl group-containing monomer represented by the formula M-1-1 and NK-ester M-90G (new monomer M2) Nakamura Chemical Co., Ltd.) 20.7 parts by mass, 18.1 parts by mass of an ethylenically unsaturated monomer having a silicone chain represented by the formula M-3-4, a compound in which both ends of tetramethylene glycol are methacrylated 3.4 parts by weight, 5.9 parts by weight of methyl methacrylate, 23.5 parts by weight of 2-ethylhexyl acrylate, and 414 parts by weight of IPA were charged, and 0.7 parts by weight of AIBN as a polymerization initiator under reflux in a nitrogen gas stream After adding 1 part by mass of lauryl mercaptan as a transfer agent, the mixture was refluxed at 75 ° C. for 8 hours for copolymerization to obtain a copolymer (S-2). Regarding the molecular weight of the obtained copolymer (S-2), the number average molecular weight was 4,700, and the weight average molecular weight was 11,000. Moreover, molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis Example 6><< Synthesis of Surfactant (Copolymer (S-3)) >>
In a glass flask equipped with a stirrer, a condenser and a thermometer, 28.4 parts by mass of the fluorinated alkyl group-containing monomer represented by the formula M-1-1 and NK-ester M-90G (new monomer M2) Nakamura Chemical Co., Ltd.) 20.7 parts by mass, 18.1 parts by mass of an ethylenically unsaturated monomer having a silicone chain represented by the formula M-3-4, a compound in which both ends of tetramethylene glycol are methacrylated Charge 3.4 parts by weight, 5.9 parts by weight of methyl methacrylate, 23.5 parts by weight of 2-ethylhexyl acrylate and 414 parts by weight of IPA, and add 0.7 parts by weight of AIBN as a polymerization initiator under reflux in a nitrogen gas stream. Then, the mixture was refluxed at 73 ° C. for 10 hours for copolymerization to obtain a copolymer (S-3). Regarding the molecular weight of the obtained copolymer (S-3), the number average molecular weight was 5,600, and the weight average molecular weight was 21,000. The molecular weight distribution (Mw / Mn) was 3.8.

(Preparation of curable composition)
<Preparation Example 1><< Preparation of Curable Composition Solution (G-1) >>
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), 20 parts by weight, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl ] Fluorene 30 parts by weight, methacrylic acid 20 parts by weight, glycidyl methacrylate 30 parts by weight, 3-glycidoxypropyltrimethoxysilane 3 parts by weight, 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, Ciba Specialty Chemicals Co., Ltd. )) 5 parts by weight and 1 part by weight of Sun-Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 50 wt%. Filter with 2μm Millipore filter and hard It was prepared gender composition solution (G-1).

<Preparation Example 2><< Preparation of Curable Composition Solution (G-2) >>
30 parts by weight of isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.), 20 parts by weight of 1,9-nonanediol diacrylate, 20 parts by weight of methacrylic acid, glycidyl methacrylate 30 Parts by weight, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals) and Sun-Aid SI-110 main agent (Sanshin Chemical) (Made by Kogyo Co., Ltd.) 1 part by weight was mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid concentration was 50 wt%, and then filtered through a Millipore filter having a pore size of 0.2 μm to obtain a curable composition solution ( G-2) was prepared.

<Preparation Example 3><< Preparation of Curable Composition Solution (G-3) >>
9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 30 parts by weight, 1,9-nonanediol diacrylate 20 parts by weight, methacrylic acid 20 parts by weight, glycidyl methacrylate 30 parts by weight, 3-glycol Sidoxypropyltrimethoxysilane 5 parts by weight, 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and Sun-Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) 1 part by weight is mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 50 wt%, and then filtered through a Millipore filter with a pore size of 0.2 μm to prepare a curable composition solution (G-3). did.

<Preparation Example 4><< Preparation of Curable Composition Solution (G-4) >>
10 parts by weight of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), 30 parts by weight of 1,9-nonanediol diacrylate, 25 weights of methacrylic acid Parts, glycidyl methacrylate 35 parts by weight, 3-glycidoxypropyltrimethoxysilane 3 parts by weight, 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals) 4 parts by weight, 1, 2 -Octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (trade name: IRGACURE OXE01, manufactured by Ciba Specialty Chemical Co., Ltd.) 3 parts by weight and Sunade SI-110 main agent ( Sanshin Chemical Industry Co., Ltd.) 0.5 parts by weight After mixing the solid content concentration was dissolved in propylene glycol monomethyl ether acetate so that 50 wt%, filtered through a Millipore filter having a pore size 0.2 [mu] m, curable composition solution (G-4) was prepared.

<Preparation Example 5><< Preparation of Curable Composition Solution (G-5) >>
9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 30 parts by weight, 1,9-nonanediol diacrylate 40 parts by weight, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (product) Name: KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 10 parts by weight, 1,9-nonanediol diacrylate 30 parts by weight, 3-glycidoxypropyltrimethoxysilane 5 parts by weight and 1-hydroxycyclohexylbenzophenone (trade name) : IRGACURE184, manufactured by Ciba Specialty Chemical Co., Ltd.) 5 parts by weight are mixed, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 50 wt%, and then filtered through a Millipore filter with a pore size of 0.2 μm. , Curable composition The (G-5) was prepared.

(Preparation of near-infrared absorbent resin solution)
<Preparation Example 6> Preparation of Resin Solution (D-1) Ratio of resin / near infrared absorber to the polyether-based resin (P-1) obtained in Synthesis Example 2 with a near infrared absorber ABS670T (manufactured by Exciton). Was added to 100 parts by weight / 1.00 part by weight and dissolved in dichloromethane so that the solid content concentration was 10 wt%, and then the surfactant (copolymer (S- The 1% DMAc diluted solution of 1)) was added so that the resin / surfactant ratio was 100 parts by weight / 0.10 parts by weight.
These were mixed and then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-1).

<Preparation Example 7> Preparation of Resin Solution (D-2) Ratio of Resin / Near Infrared Absorber with Near Infrared Absorber ABS670T (manufactured by Exciton) to the polyether resin (P-1) obtained in Synthesis Example 2 Was added to 100 parts by weight / 1.10 parts by weight and dissolved in dichloromethane so that the solid content concentration was 10 wt%, and then the surfactant (copolymer) obtained in Synthesis Example 5 was further added. A 1% DMAc diluted solution of S-2)) was added so that the resin / surfactant ratio was 100 parts by weight / 0.10 parts by weight.
These were mixed and then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-2).

<Preparation Example 8> Preparation of Resin Solution (D-3) Ratio of Resin / Near Infrared Absorber with Near Infrared Absorber ABS670T (manufactured by Exciton) to the polyether resin (P-1) obtained in Synthesis Example 2 Was added to 100 parts by weight / 1.10 parts by weight, dissolved in dichloromethane so that the solid content concentration was 10 wt%, and then the surfactant (copolymer (copolymer) obtained in Synthesis Example 6 was used. A 1% DMAc diluted solution of S-3)) was added so that the resin / surfactant ratio was 100 parts by weight / 0.10 parts by weight.
These were mixed and then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-3).

<Preparation Example 9> Preparation of Resin Solution (D-4) Near-infrared absorber Lumogen IR765 (manufactured by BASF) was added to the polyether resin (P-1) obtained in Synthesis Example 2 as a resin / near-infrared absorber. The mixture was added so that the ratio was 100 parts by weight / 1.00 part by weight, dissolved in dichloromethane so that the solid content concentration was 10 wt%, and then the surfactant (copolymer) obtained in Synthesis Example 6 was used. A 1% DMAc diluted solution of (S-3)) was added so that the resin / surfactant ratio was 100 parts by weight / 0.15 parts by weight.
These were mixed and then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-4).

<Preparation Example 10> Preparation of Resin Solution (D-5) Ratio of Resin / Near Infrared Absorber to Polyether Resin (P-1) Obtained in Synthesis Example 2 with Near Infrared Absorber ABS670T (Exciton) Is added to 100 parts by weight / 1.00 part by weight, dissolved in dichloromethane so that the solid content concentration is 10 wt%, and then 1% of the Fantent FTX-218 (manufactured by Neos Co., Ltd.) The DMAc diluted solution was added so that the resin / surfactant ratio was 100 parts by weight / 0.20 parts by weight.
These were mixed and then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-5).

<Preparation Example 11> Preparation of Resin Solution (D-6) To the polyether resin (P-1) obtained in Synthesis Example 2, a near-infrared absorber Lumogen IR765 (manufactured by BASF) was used as a resin / near-infrared absorber. The mixture was added so that the ratio was 100 parts by weight / 0.10 part by weight, dissolved in dichloromethane so that the solid content concentration was 10 wt%, and then the surfactant (copolymer (S -3)) was added so that the resin / surfactant ratio was 100 parts by weight / 0.15 parts by weight.
These were mixed and then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-6).

<Comparative Preparation Example 1> Preparation of Resin Solution (D-7) The polyether resin (P-1) obtained in Synthesis Example 2 was dissolved in dichloromethane so that the solid content concentration would be 10 wt%, and then the surface activity was obtained. A 1% DMAc diluted solution of Footent FTX-218 (manufactured by Neos Co., Ltd.) was added as an agent so that the resin / surfactant ratio was 100 parts by weight / 0.15 parts by weight.
These were mixed and then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-7).

<Comparative Preparation Example 2> Preparation of Resin Solution (D-8) A near-infrared absorber SIR159 (manufactured by Mitsui Chemicals) was added to the polyether resin (P-1) obtained in Synthesis Example 2 as a resin / near-infrared ray. It was added so that the ratio of the absorbent was 100 parts by weight / 1.10 parts by weight, dissolved in dichloromethane so that the solid content concentration was 10 wt%, and then surfactant FTX-218 (Co., Ltd.) as a surfactant. 1% DMAc diluted solution of Neos) was added so that the resin / surfactant ratio was 100 parts by weight / 0.15 parts by weight.
These were mixed and then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-8).

(Preparation of high refractive index composition for wet coating)
<Preparation Example 12> Preparation of High Refractive Index Composition (W-1) In a vessel equipped with a stirrer, phenyltrimethoxysilane (101.2 g, 0.51 mol) and an electric conductivity of 8 × 10 ^-5 S After containing cm ⁻¹ ion-exchanged water (14.8 g, 0.82 mol), phenyltrimethoxysilane was hydrolyzed by heating and stirring under conditions of a temperature of 60 ° C. for 6 hours. Next, methanol by-produced by hydrolysis was distilled off while adding methyl isobutyl ketone (hereinafter abbreviated as MIBK) dropwise. And finally, solid content was adjusted to 22 weight% and the solution (henceforth polysiloxane (1)) containing polysiloxane was obtained. With respect to the obtained polysiloxane (1), the weight average molecular weight in terms of polystyrene was measured using GPC, and it was 1500.

In addition, after containing tetrabutoxy titanium (129.3 g, 0.38 mol) in a container equipped with a stirrer substituted with nitrogen, the electric conductivity was 8 × 10 ⁻⁵ S · under heating and stirring at a temperature of 85 ° C. A solution of cm ⁻¹ ion-exchanged water (13.1 g, 0.73 mol) in 257.5 g of butyl alcohol was added dropwise from a dropping funnel over 1 hour, and then heated and stirred at 85 ° C. for 2 hours.

  Subsequently, 63.4 g of white crystals were obtained by removing the solvent and by-product butyl alcohol by hydrolysis using a rotary evaporator. Then, MIBK was added to finally adjust the solid content to 22% by weight to obtain a solution containing polytitanoxane (hereinafter referred to as polytitanoxane (1)).

  Next, polysiloxane (1) (solid content and solvent) 26 parts by weight, polytitanoxane (1) (solid content and solvent) 74 parts by weight, photoacid generator (Sartomer, CD1012) 0.7 part by weight, and dehydration 3.0 parts by weight of methyl orthoformate as the agent were uniformly mixed to obtain a high refractive index composition (W-1).

The obtained high refractive index composition (W-1) was spin-coated on a silicon wafer under atmospheric conditions to form a coating film having a thickness of 0.15 μm. A conveyor type high-pressure mercury lamp (2 kW) manufactured by Oak Manufacturing Co., Ltd. was used so that the amount of exposure was 300 mJ / cm ² (irradiation time: 3 seconds) at 25 ° C. in the atmosphere. The cured film was formed by irradiating with ultraviolet rays.
When the refractive index at 633 nm in the obtained cured film was measured using an ellipsometer, the refractive index was 1.70.

(Preparation of low refractive index composition for wet coating)
<Preparation Example 13> Preparation of low refractive index composition (W-2) In a vessel equipped with a stirrer, methyltrimethoxysilane (69.4 g, 0.51 mol) and an electric conductivity of 8 × 10 ^-5 S After containing cm ⁻¹ ion-exchanged water (14.8 g, 0.82 mol), methyltrimethoxysilane was hydrolyzed by heating and stirring at a temperature of 60 ° C. for 6 hours. Next, while dropping MIBK, methanol by-produced by hydrolysis was distilled off. And finally, solid content was adjusted to 22 weight% and the solution (henceforth polysiloxane (2)) containing polysiloxane was obtained. It was 2000 when the weight average molecular weight of polystyrene conversion was measured about the obtained polysiloxane (2) using GPC.

  Next, 100 parts by weight of polysiloxane (2) (solid content and solvent), 0.7 parts by weight of a photoacid generator (CD1012 manufactured by Sartomer Co.), and 3.0 parts by weight of methyl orthoformate as a dehydrating agent were each uniform. To obtain a low refractive index composition (W-2).

The obtained low refractive index composition (W-2) was spin-coated on a silicon wafer under atmospheric conditions to form a coating film having a thickness of 0.15 μm.
A conveyor type high-pressure mercury lamp (2 kW) manufactured by Oak Manufacturing Co., Ltd. was used so that the amount of exposure was 300 mJ / cm ² (irradiation time: 3 seconds) at 25 ° C. in the atmosphere. The cured film was formed by irradiating with ultraviolet rays.
When the refractive index at 633 nm of the obtained cured film was measured using an ellipsometer, the refractive index was 1.41.

<Film Production Example 1> Production of Film (F-1) The polyether-based resin (P-1) obtained in Synthesis Example 2 is replaced with a near-infrared absorber ABS670T (manufactured by Exciton) with a resin / infrared absorber ratio. 100 parts by weight / 0.12 parts by weight were added and dissolved in dichloromethane so that the solid content concentration was 8 wt%. After obtaining a solution, the solution was filtered with a Millipore filter having a pore size of 5 μm. . The filtrate was cast on a smooth glass plate and dried at 200 ° C. for 7 hours and further under reduced pressure at 200 ° C. for 8 hours to obtain a film (F-1) having a thickness of 30 μm.

<Film Production Example 2> Production of Film (F-2) Near-infrared absorber ABS670T (manufactured by Exciton) was added to the N-methyl-2-pyrrolidone solution of the polyimide resin (P-2) obtained in Synthesis Example 3. After adding the resin / near-infrared absorber ratio to 100 parts by weight / 0.12 parts by weight and diluting with N-methyl-2-pyrrolidone so that the solid content concentration becomes 5 wt%, It was applied to a plate and heated on a hot plate at 90 ° C. for 1 hour to evaporate the solvent (N-methyl-2-pyrrolidone) and then peeled off from the glass plate to obtain a self-supporting film. This self-supporting film was fixed on a stainless steel fixing jig and vacuum-dried at 200 ° C. for 5 hours, and then heated for 5 hours at a temperature of 220 ° C. in a nitrogen stream to further evaporate the solvent. -2) was obtained.

<Film Production Example 3> Production of Film (F-3) 2,6-Naphthalenedicarboxylic Acid Dimethyl Ester (NDCM) and Ethylene Glycol (EG) were dissolved at EG / NDCM = 2.2 (molar ratio) to obtain an ester. As an exchange catalyst, 1.6 mol of germanium oxide was added to 10 g of NDCM, and a transesterification reaction was performed under a pressure of 3.0 kg / cm ² .

Subsequently, a polycondensation reaction was carried out in a conventional manner under high temperature and high vacuum to obtain pellet-shaped polyethylene naphthalate. This pellet-shaped polyethylene naphthalate is dried at 170 ° C. for 5 hours and then supplied to an extruder hopper. Further, ABS670T (manufactured by Exciton) as an infrared absorber is 0.02 weight with respect to 100 parts by weight of polyethylene naphthalate. The melted temperature is 290 ° C., the polyethylene naphthalate and ABS 670T are melted at a melting temperature of 290 ° C., and the molten polymer containing a near-infrared absorber is passed through a 1 mm slit die and the surface temperature is 50 ° C. The sheet was extruded on a cooling drum to obtain a sheet having a thickness of about 1 mm.
In this sheet, it was visually confirmed that ABS670T was uniformly dissolved in polyethylene naphthalate. Further, the obtained sheet was preheated at 130 ° C., further longitudinally stretched by 3.0 times with an IR heater having a surface temperature of 880 ° C., and then supplied to a tenter, and 3.3 times at 140 ° C. Transversely stretched. The obtained biaxially oriented film was heat-fixed at a temperature of 220 ° C. for 10 seconds to obtain a film (F-3) having a thickness of 90 μm.

<Film Production Example 4> Production of Film (F-4) Polyethersulfone (manufactured by Sumitomo Chemical Co., Ltd., SUMIKAEXCEL 7600P) was dissolved in DMAc with stirring at 85 ° C. so that the solid content concentration was 16%. The solution was once cooled to 25 ° C., and then ABS670T (manufactured by Exciton) was added at room temperature so that the resin / infrared absorbing agent ratio was 100 parts by weight / 0.02 parts by weight, followed by stirring. The obtained liquid material is cast on a glass support, the solvent is evaporated at a set temperature of 100 ° C. for 1 hour by a hot plate, and then heat-treated at a set temperature of 250 ° C. for 1 hour by a hot air dryer. And peeled from the glass plate to obtain a film (F-4) containing an infrared absorber having a thickness of 35 μm.

(Create laminate)
<Laminate Production Example 1> Production of Laminate (K-1) After applying the curable composition solution (G-1) obtained in Preparation Example 1 to a glass substrate having a thickness of 700 μm by spin coating, hot The plate was heated at 80 ° C. for 2 minutes to volatilize and remove the solvent, thereby forming a cured layer. At this time, the application conditions of the spin coater were adjusted so that the thickness of the cured layer was about 0.8 μm. Next, on the hardened layer, the resin solution (D-1) obtained in Preparation Example 6 was applied using a spin coater under conditions such that the half-value on the long wavelength side was 646 nm, and was heated on a hot plate at 80 ° C. Heating was performed for 5 minutes to volatilize and remove the solvent, and a resin layer was formed. Subsequently, it exposed using the conveyor type exposure machine from the glass surface side (exposure amount 1J / cm < ² >, illumination intensity 200mW), and it baked at 230 degreeC for 20 minutes after that in an oven, and obtained the laminated board (K-1).

<Laminate Production Example 2> Production of Laminate (K-2) Laminate Production Example 1 except that the resin solution (D-5) obtained in Preparation Example 10 was used instead of the resin solution (D-1). A laminate (K-2) was prepared in the same manner as described above.

<Laminate Production Example 3> Production of Laminate (K-3) Resin using curable composition solution (G-2) obtained in Preparation Example 2 instead of curable composition solution (G-1) A laminate (K-3) was produced in the same manner as in the laminate production example 1 except that the resin solution (D-2) obtained in Preparation Example 7 was used instead of the solution (D-1).

<Laminate Production Example 4> Production of Laminate (K-4) Resin using curable composition solution (G-2) obtained in Preparation Example 2 instead of curable composition solution (G-1) A laminated board (K-4) was produced in the same manner as in laminated board production example 1 except that the resin solution (D-3) obtained in Preparation Example 8 was used instead of the solution (D-1).

<Laminate Production Example 5> Production of Laminate (K-5) Resin using curable composition solution (G-2) obtained in Preparation Example 2 instead of curable composition solution (G-1) A laminated board (K-5) was produced in the same manner as in laminated board production example 1 except that the resin solution (D-5) obtained in Preparation Example 10 was used instead of the solution (D-1).

<Laminate Production Example 6> Production of Laminate (K-6) Resin using curable composition solution (G-3) obtained in Preparation Example 3 instead of curable composition solution (G-1) A laminated board (K-6) was produced in the same manner as in laminated board production example 1 except that the resin solution (D-3) obtained in Preparation Example 8 was used instead of the solution (D-1).

<Laminate Production Example 7> Production of Laminate (K-7) Resin using curable composition solution (G-3) obtained in Preparation Example 3 instead of curable composition solution (G-1) A laminated board (K-7) was produced in the same manner as in laminated board production example 1 except that the resin solution (D-4) obtained in Preparation Example 9 was used instead of the solution (D-1).

<Laminate Production Example 8> Production of Laminate (K-8) Except for using the curable composition solution (G-4) obtained in Preparation Example 4 instead of the curable composition solution (G-1). Produced a laminate (K-8) in the same manner as in laminate production example 1.

<Laminate Production Example 9> Production of Laminate (K-9) Resin using curable composition solution (G-4) obtained in Preparation Example 4 instead of curable composition solution (G-1) A laminated board (K-9) was produced in the same manner as in laminated board production example 1 except that the resin solution (D-3) obtained in Preparation Example 8 was used instead of the solution (D-1).

<Laminate Production Example 10> Production of Laminate (K-10) Resin using curable composition solution (G-2) obtained in Preparation Example 2 instead of curable composition solution (G-1) A laminate is prepared in the same manner as in Preparation Example 1 of a laminate except that the resin solution (D-5) obtained in Preparation Example 10 is used instead of the solution (D-1), and further on the resin layer Multi-layer vapor deposition film (visible light antireflection layer) that prevents visible light reflection at a deposition temperature of 200 ° C. [Silica (SiO ₂ : film thickness 10 to 100 nm) layers and titania (TiO ₂ : film thickness 10 to 120 nm) layers alternately The number of laminated layers 4] was formed to obtain a laminated plate (K-10).

<Laminated plate production example 11> Production of laminated plate (K-11) A laminated plate was produced in the same manner as in laminated plate production example 8, and the high refractive index obtained in Preparation Example 12 on the resin layer of this laminated plate. The composition (W-1) was spin-coated to form a coating film having a thickness of 0.1 μm. A conveyor type high-pressure mercury lamp (2 kW) manufactured by Oak Manufacturing Co., Ltd. was used so that the amount of exposure was 300 mJ / cm ² (irradiation time: 3 seconds) at 25 ° C. in the atmosphere. The film was irradiated with ultraviolet rays to form a high refractive index film.

Next, the low refractive index composition (W-2) obtained in Preparation Example 13 was spin-coated on the high refractive index film to form a coating film having a thickness of 0.1 μm. A conveyor type high-pressure mercury lamp (2 kW) manufactured by Oak Manufacturing Co., Ltd. was used so that the amount of exposure was 300 mJ / cm ² (irradiation time: 3 seconds) at 25 ° C. in the atmosphere. Then, ultraviolet rays were used to form a low refractive index film, and a laminate (K-11) having a cured layer, a resin layer, a high refractive index film and a low refractive index film in this order from the glass substrate side was obtained.

<Laminate Production Example 12> Production of Laminate K-12 After applying the curable composition solution (G-2) obtained in Preparation Example 2 to a glass substrate having a thickness of 50 μm by slit coating, on a hot plate The mixture was heated at 80 ° C. for 2 minutes to volatilize and remove the solvent to form a cured layer. Under the present circumstances, the application | coating conditions of the slit coater were adjusted so that the film thickness of a hardened layer might be about 1.0 micrometer. Next, the resin solution (D-6) obtained in Preparation Example 11 was applied onto the cured layer of the glass substrate using a slit coater under conditions such that the half wavelength on the long wavelength side was 646 nm. The solvent was removed by volatilization by heating at 0 ° C. for 5 minutes. Subsequently, it exposed using the conveyor type exposure machine from the glass surface side (exposure amount 1J / cm < ² >, illumination intensity 200mW), and it baked at 230 degreeC for 20 minutes after that in an oven, and obtained the laminated board (K-12).

<Laminate Production Example 13> Production of Laminate (K-13) Only the resin solution (D-1) obtained in Preparation Example 6 is applied to a glass substrate having a thickness of 50 [mu] m so that the half wavelength on the long wavelength side is 646 nm. The solution was spin-coated under various conditions and heated on a hot plate at 80 ° C. for 5 minutes to volatilize and remove the solvent. Subsequently, it exposed using the conveyor type exposure machine from the glass surface side (exposure amount 1J / cm < ² >, illumination intensity 200mW), and it baked at 230 degreeC for 20 minutes after that in an oven, and obtained the laminated board (K-13).

<Laminated plate production example 14> Production of laminated plate (K-14) Curable composition solution (G-5) obtained in Preparation Example 5 instead of curable composition solution (G-1) (acrylic only) ) And using the resin solution (D-3) obtained in Preparation Example 8 instead of the resin solution (D-1), the same method as in Laminate Preparation Example 1 was used. )created.

<Laminate Production Example 15> Production of Laminate (K-15) After applying the curable composition solution (G-2) obtained in Preparation Example 2 on a glass substrate having a thickness of 700 μm by spin coating, hot The plate was heated at 80 ° C. for 2 minutes to volatilize and remove the solvent to form a cured layer. At this time, the application conditions of the spin coater were adjusted so that the thickness of the cured layer was about 0.8 μm. Next, after laminating the film (F-1) obtained in Film Production Example 1 on the cured layer using a laminating apparatus, exposure (exposure amount) using a conveyor type exposure machine from the glass surface side. 1 J / cm ² , illuminance 200 mW), and then fired in an oven at 230 ° C. for 20 minutes to obtain a laminate (K-15).

<Laminated plate production example 16> Production of laminated plate (K-16) Laminated plate production example 15 except that the film (F-2) obtained in film production example 2 was used instead of the film (F-1). Similarly, a laminate (K-16) was prepared.

<Laminate Production Example 17> Production of Laminate (K-17) Using the curable composition solution (G-3) obtained in Preparation Example 3 instead of the curable composition solution (G-2), a film A laminated board (K-17) was produced in the same manner as in laminated board production example 15 except that the film (F-3) obtained in film production example 3 was used instead of (F-1).

<Laminate Production Example 18> Production of Laminate (K-18) A film using the curable composition solution (G-4) obtained in Preparation Example 4 instead of the curable composition solution (G-2). A laminated board (K-18) was produced in the same manner as in laminated board production example 15 except that the film (F-4) obtained in film production example 4 was used instead of (F-1).

<Comparative Laminate Production Example 1> Production of Laminate R-1 Resin solution using curable composition solution (G-2) obtained in Preparation Example 2 instead of curable composition solution (G-1) A laminated board (R-1) was produced in the same manner as in laminated board production example 1 except that the resin solution (D-7) obtained in Comparative Preparation Example 1 was used instead of (D-1).

<Comparative Laminate Production Example 2> Production of Laminate (R-2) After applying the curable composition solution (G-1) obtained in Preparation Example 1 to a glass substrate having a thickness of 700 μm by spin coating, The mixture was heated on a hot plate at 80 ° C. for 2 minutes to volatilize and remove the solvent, thereby forming a cured layer. At this time, the application conditions of the spin coater were adjusted so that the thickness of the cured layer was about 0.8 μm. Next, on the cured layer, the resin solution (D-8) obtained in Comparative Preparation Example 2 was applied using a spin coater under conditions such that the light transmittance at the absorption maximum wavelength of the laminate was 2%. And heated on a hot plate at 80 ° C. for 5 minutes to volatilize and remove the solvent. Subsequently, it exposed using the conveyor type exposure machine from the glass surface side (exposure amount 1J / cm < ² >, illumination intensity 200mW), and baked at 230 degreeC for 20 minutes after that, and obtained the laminated sheet (R-2).

The thickness of the resin layer and the adhesion of the resin layer to the glass substrate in the laminates (K-1) to (K-18), laminate (R-1) and laminate (R-2) obtained above. The absorption maximum wavelength of these laminates was measured. The results are shown in the columns of Example K′-1 to K′-18, Example R′-1 and Example R′-2 corresponding to Table 1 below.
In addition, the film thickness of the resin layer was measured using a stylus-type film thickness meter, and the absorption maximum wavelength of the laminate was measured using a spectrophotometer.

<Near infrared cut filter creation example>
A multilayer deposited film (dielectric multilayer film) [silica (SiO ₂ : film thickness 20) reflecting near infrared rays at a deposition temperature of 200 ° C. on the glass substrates of the laminated plates K-1 to 18 and the laminated plates R-1 to R-2. ˜250 nm) and titania (TiO ₂ : film thickness 70 to 130 nm) layers are alternately laminated, and the number of laminations 44] is formed, and the corresponding near infrared cut filters K′-1 to 18 and R '-1 to 2 were obtained. The total thickness of the multilayer deposited films was about 5.5 μm.

<Examples K'-1 to 18 and Comparative Examples R'-1 to 2>
The obtained near-infrared cut filters K′-1 to 18 and R′-1 to 2 were subjected to optical property evaluation, reflow test, adhesion evaluation, and appearance evaluation. The results are summarized in Table 1 below. In the table, Xa is the longest wavelength at which the transmittance is 70% when measured from the vertical direction of the near-infrared cut filter in the wavelength region of 800 nm or less, and Xb is the near-infrared cut filter in the wavelength region of 580 nm or more. The shortest wavelength at which the transmittance is 30% when measured from the vertical direction, Ya is the wavelength value at which the transmittance is 50% in the wavelength range of 560 to 800 nm when measured from the vertical direction, and Yb is the vertical direction. The value of the wavelength at which the transmittance is 50% in the wavelength range of 560 to 800 nm when measured from an angle of 30 ° with respect to the angle, Za is the wavelength range of 560 to 800 nm when measured from the vertical direction after the solder reflow test Is the value of the wavelength at which the transmittance is 50%.

  The near-infrared cut filter of the present invention includes a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, an automobile camera, a personal digital assistant, a personal computer, a video game, a medical device, a USB memory, and a portable game machine. It can be suitably used for fingerprint authentication systems, digital music players, toy robots, toys and the like. Furthermore, it can be suitably used as a heat ray cut filter or the like attached to glass or the like of automobiles and buildings.

1: Camera module 2: Lens barrel 3: Flexible substrate 4: Hollow package 5: Lens 6: Near-infrared cut filter 6 ': Near-infrared cut filter 7 obtained by the present invention: CCD or CMOS image sensor 8: Near-infrared cut Filter 9: Spectrophotometer

Claims (11)

A near-infrared cut filter comprising a laminated plate having a resin layer on at least one side of a glass substrate and having a transmittance satisfying the following (A) to (D).
(A) The average value of the transmittance when measured from the vertical direction of the near-infrared cut filter in the wavelength range of 430 to 580 nm is 75% or more. In the wavelength region where the average transmittance when measured from is 20% or less (C) 800 nm or less, the longest wavelength (Xa) at which the transmittance when measured from the vertical direction of the near-infrared cut filter is 70% The absolute value | Xa−Xb | of the difference from the shortest wavelength (Xb) at which the transmittance is 30% when measured from the vertical direction of the near-infrared cut filter in the wavelength region of 580 nm or more is less than 75 nm (D ) In the wavelength range of 560 to 800 nm, the transmittance when measured from the vertical direction of the near-infrared cut filter is 50%. Absolute value of the difference between the wavelength value (Ya) and the wavelength value (Yb) at which the transmittance is 50% when measured from an angle of 30 ° with respect to the vertical direction of the near-infrared cut filter | Ya−Yb | Is less than 15nm   The near-infrared cut filter according to claim 1, wherein the resin layer contains a near-infrared absorber. The near-infrared cut filter according to claim 1, wherein the laminated plate satisfies the following requirement (i).
(I) It has an absorption maximum wavelength in 600 to 800 (nm). The near-infrared cut filter according to any one of claims 1 to 3, wherein the laminated plate satisfies the following formulas (ii) and (iii).
(Ii) 1/700 ≦ (thickness of resin layer / thickness of glass substrate) ≦ 2/5
(Iii) 30 ≦ thickness of glass substrate (μm) ≦ 1000   The resin layer includes at least one resin selected from the group consisting of a polyimide resin, a polyethylene naphthalate resin, a polyether sulfone resin, a polyether resin, and a cyclic olefin resin. Item 5. The near-infrared cut filter according to any one of Items 1 to 4. The near-infrared cut filter according to claim 1, wherein the infrared absorber satisfies the following (iv).
(Iv) 5% weight loss temperature measured by thermogravimetric analysis in air is 250 ° C. or higher   The near-infrared cut filter according to claim 1, further comprising a dielectric multilayer film on at least one surface of the laminated plate.   Between the glass substrate and the resin layer, (a) a structural unit derived from a (meth) acryloyl group-containing compound, (b) a structural unit derived from a carboxylic acid group-containing compound, and (c) an epoxy group-containing compound. The near-infrared cut filter according to any one of claims 1 to 7, further comprising a cured layer having a derived structural unit.   The near-infrared cut filter according to any one of claims 1 to 8, wherein a visible light antireflection layer is formed on a surface of the resin layer opposite to the surface on which the glass substrate is laminated. .   A solid-state imaging device comprising the near infrared cut filter according to claim 1.   A solid-state imaging device comprising the near-infrared cut filter according to claim 1.

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