WO2019168090A1 - Filtre optique, module de caméra et dispositif électronique - Google Patents

Filtre optique, module de caméra et dispositif électronique Download PDF

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Publication number
WO2019168090A1
WO2019168090A1 PCT/JP2019/007777 JP2019007777W WO2019168090A1 WO 2019168090 A1 WO2019168090 A1 WO 2019168090A1 JP 2019007777 W JP2019007777 W JP 2019007777W WO 2019168090 A1 WO2019168090 A1 WO 2019168090A1
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WIPO (PCT)
Prior art keywords
group
resin
optical filter
compound
transmittance
Prior art date
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PCT/JP2019/007777
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English (en)
Japanese (ja)
Inventor
幸恵 田中
勝也 長屋
寛之 岸田
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Jsr株式会社
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Application filed by Jsr株式会社 filed Critical Jsr株式会社
Priority to JP2020503608A priority Critical patent/JP7200985B2/ja
Priority to KR1020207024916A priority patent/KR20200128009A/ko
Priority to CN201980016421.4A priority patent/CN111801606B/zh
Publication of WO2019168090A1 publication Critical patent/WO2019168090A1/fr
Priority to JP2022204178A priority patent/JP7405228B2/ja

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    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B11/00—Filters or other obturators specially adapted for photographic purposes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B17/00—Details of cameras or camera bodies; Accessories therefor
    • G03B17/02—Bodies
    • G03B17/12—Bodies with means for supporting objectives, supplementary lenses, filters, masks, or turrets
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H04N23/50—Constructional details
    • H04N23/55—Optical parts specially adapted for electronic image sensors; Mounting thereof

Definitions

  • the present invention relates to an optical filter, a camera module, and an electronic device. More specifically, the present invention relates to an optical filter having specific optical characteristics, a camera module using the optical filter, and an electronic apparatus having the camera module.
  • a solid-state imaging device such as a video camera, a digital still camera, or a mobile phone with a camera function uses a CCD or CMOS image sensor, which is a solid-state imaging device for color images.
  • CCD or CMOS image sensor silicon photodiodes having sensitivity to near infrared rays that cannot be sensed by human eyes at the light receiving portion are used.
  • These solid-state image sensors need to be corrected for visibility so that they appear natural to the human eye.
  • Optical filters that selectively transmit or cut light in a specific wavelength region (for example, near-infrared cut) Filter) is often used.
  • a near-infrared cut filter those manufactured by various methods are conventionally used.
  • a near-infrared cut filter in which a transparent resin is used as a substrate and a near-infrared absorbing pigment is contained in the transparent resin is known (see, for example, Patent Document 1).
  • the near-infrared cut filter described in Patent Document 1 may not always have sufficient near-infrared absorption characteristics.
  • Patent Document 2 the present applicant uses a transparent resin substrate containing a near-infrared absorbing dye having an absorption maximum in a specific wavelength region, so that there is little change in optical characteristics even when the incident angle is changed, and A near-infrared cut filter having a high visible light transmittance is proposed.
  • Patent Document 3 discloses a near-infrared ray that uses a phthalocyanine dye having a specific structure to achieve both a high visible light transmittance and a long absorption maximum wavelength, both of which are conventional problems. It is described that a cut filter can be obtained.
  • the applied base material has a sufficiently strong absorption band in the vicinity of 700 nm, but in the near-infrared wavelength region of, for example, 900 to 1200 nm. Has almost no absorption. Therefore, light in the near-infrared wavelength region is cut almost only by the reflection of the dielectric multilayer film, but with such a configuration, slight stray light due to internal reflection in the optical filter and reflection between the optical filter and the lens is generated. When shooting in a dark environment, it may cause ghost and flare. In particular, in recent years, there has been a strong demand for high-quality cameras even for mobile devices such as smartphones, and conventional optical filters may not be used favorably.
  • an infrared shielding filter as in Patent Document 4 has been proposed as an optical filter using a base material having a wide absorption in the near infrared wavelength region.
  • a broad absorption in the near-infrared wavelength region is achieved mainly by applying a compound having a dithiolene structure, but the absorption intensity near 700 nm is not sufficient.
  • image degradation may occur due to color shading.
  • Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass base material and a layer containing a near-infrared absorbing dye, but the color shading is sufficiently improved even with the configuration described in Patent Document 5. There was a case that could not be done.
  • FIG. 5 of Patent Document 5 shows an optical characteristic graph at 0 ° incidence and at 30 ° incidence, but the region of the skirt portion of the visible light transmission band (630 to 700 nm) even at 30 ° incidence. ) A large wavelength shift is observed.
  • the optical filter in a specific wavelength region, is perpendicular to the vertical direction, 30 degrees oblique to the vertical direction, and 60 degrees oblique to the vertical direction.
  • the minimum value of the transmittance of incident light is in a specific range, and in a specific wavelength region, the optical filter is perpendicular to the vertical direction, 30 degrees oblique to the vertical direction, and 60 degrees oblique to the vertical direction.
  • the value T b-30 and the minimum value T b-60 of the transmittance of light incident from a direction oblique to the vertical direction by 60 degrees are both 55% or more and less than 90%
  • Both of the value OD a-30 and the average value OD a-60 of the optical density with respect to light incident from a direction oblique by 60 degrees with respect to the vertical direction are 1.8 or more.
  • optical filter according to any one of items [1] to [3], including a substrate that satisfies the following requirement (e): (E) having a layer containing the compound (A) having an absorption maximum in a wavelength region of 650 to 800 nm.
  • the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds.
  • the base material has a compound (Aa) having an absorption maximum in a wavelength region of 650 m or more and 715 nm or less, and a compound having a absorption maximum in a region of wavelength 715 nm or more and 750 nm or less (A- Item 6.
  • the resin constituting the transparent resin layer is a cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, or aramid resin.
  • a camera module comprising the optical filter according to any one of items [1] to [10].
  • an optical filter that has excellent near-infrared cut characteristics, little incident angle dependency, and excellent transmittance characteristics in the visible light wavelength region, color shading suppression effect, and ghost suppression effect.
  • 6 is a spectral transmission spectrum of the optical filter obtained in Example 5.
  • 7 is a spectral transmission spectrum of the optical filter obtained in Example 6.
  • 7 is a spectral transmission spectrum of the optical filter obtained in Example 7.
  • 10 is a spectral transmission spectrum of the optical filter obtained in Example 8.
  • 10 is a spectral transmission spectrum of the optical filter obtained in Example 9.
  • 10 is a spectral transmission spectrum of the optical filter obtained in Example 10.
  • 10 is a spectral transmission spectrum of the optical filter obtained in Example 11.
  • 18 is a spectral transmission spectrum of the optical filter obtained in Example 15.
  • 14 is a spectral transmission spectrum of the optical filter obtained in Example 16.
  • 2 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 1.
  • 3 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 2.
  • 6 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 3.
  • 6 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 4.
  • the optical filter of the present invention is characterized by satisfying the following requirements (a) and (b), and further preferably satisfying the following requirements (C) and / or (D).
  • the value T b-30 and the minimum value T b-60 of the transmittance of light incident from an oblique direction of 60 degrees with respect to the vertical direction are both 55% or more and less than 90%.
  • the average optical density OD a-0 for light incident from the vertical direction of the optical filter and the average optical density for light incident from an oblique direction of 30 degrees with respect to the vertical direction are 1.8 or more.
  • the average value T IR of the transmittance of light incident from the vertical direction of the optical filter is 60% or more.
  • the average value T a-0 of the transmittance of light incident from the vertical direction of the optical filter and the average of the transmittance of light incident from an oblique direction of 30 degrees with respect to the vertical direction are both 65% or more and less than 90%.
  • the T b-0 and the T b-30 are preferably 63% or more and 86% or less, more preferably 67% or more and 82% or less, and the T b-60 is preferably 58% or more and 80% or less. More preferably, it is 60% or more and 75% or less.
  • a method of satisfying the requirement (a) that is, a method of adjusting the minimum value of each transmittance, for example, the type and amount of the compound (A) described later are set so that the minimum value of the transmittance within a specified range is obtained.
  • the method of selecting and adjusting suitably is mentioned.
  • the OD a-0 and the OD a-30 are preferably 1.8 or more and 4.0 or less, more preferably 1.9 or more and 3.5 or less, and the OD a-60 is preferably 2.1. It is 4.5 or more and more preferably 2.2 or more and 4.0 or less.
  • a method of satisfying the requirement (b), that is, a method of adjusting the average value of the optical density (OD value), for example, the type of the compound (A) described later and the average value of the transmittance within a specified range are obtained.
  • a method of appropriately selecting and adjusting the addition amount can be mentioned.
  • the optical filter can sufficiently cut not only near-infrared rays transmitted in the vertical direction but also near-infrared rays transmitted at a high incident angle, so that there was no or reduced color shading. A camera image can be obtained.
  • the OD value is a common logarithm of transmittance, and can be calculated by the following formula (1).
  • the average OD value in the specified wavelength range is high, it indicates that the optical filter has high light cut characteristics in the wavelength region.
  • the TIR is preferably 70% to 98%, more preferably 80% to 95%, still more preferably 85% to 94%, and particularly preferably 89% to 93%.
  • a method of satisfying the requirement (c) that is, a method of adjusting the average value of the light transmittance, for example, the kind and the amount of addition of the compound (A) described later are appropriately selected so that the transmittance in a specified range can be obtained.
  • the method of adjusting is mentioned.
  • T a-0 is preferably 88% or more 73% or less, and more preferably not more than 86% or more 76%
  • the T a-30 is preferably 87% or more 72% or less, more preferably 75% or more
  • the Ta -60 is preferably 68% or more and 85% or less, more preferably 70% or more and 80% or less.
  • a method of satisfying the requirement (d) that is, a method of adjusting the average value of each transmittance, for example, the type and amount of the compound (A) described later are set so that an average value of transmittance within a specified range is obtained.
  • the method of selecting and adjusting suitably is mentioned.
  • the thickness of the optical filter of the present invention is preferably 210 ⁇ m or less, more preferably 190 ⁇ m or less, still more preferably 160 ⁇ m or less, and particularly preferably 130 ⁇ m or less.
  • the lower limit is not particularly limited, but is preferably 20 ⁇ m or more.
  • the configuration of the optical filter of the present invention is not particularly limited as long as the optical filter exhibiting the optical characteristics described above can be obtained, but preferably includes a substrate that satisfies the following requirement (e). It is preferable to satisfy f).
  • is 100 nm or more.
  • the component constituting the layer containing the compound (A) is not particularly limited, and examples thereof include a transparent resin, a sol-gel material, a low-temperature-cured glass material, and the like.
  • a transparent resin is preferable from the viewpoint of compatibility with A).
  • the substrate may be a single layer or a multilayer as long as it has a layer containing the compound (A).
  • between the wavelengths X a and X b is preferably 110 nm or more, more preferably 115 nm or more, still more preferably 120 nm or more, and particularly preferably 125 nm or more.
  • an upper limit is not specifically limited, Since a visible light transmittance
  • is in the above range, it has an absorption band with sufficient intensity (width) in the near-infrared wavelength region close to the visible light region.
  • the incident angle is 30 degrees or 60 degrees. It is preferable because color shading can be suppressed even under a large incident angle such as a degree.
  • the wavelength value (X a + X b ) / 2 between X a and X b can be said to be the center wavelength of the absorption band in the near-infrared wavelength region close to the visible light region, preferably 650 nm or more and 850 nm or less, more preferably Is from 680 nm to 820 nm, more preferably from 700 nm to 800 nm.
  • the value of the wavelength represented by (X a + X b ) / 2 is in the above range, it is preferable because light in the wavelength region near the long wavelength end of the visible light region can be cut more efficiently.
  • X a is preferably from 610 nm to 720 nm, more preferably from 625 nm to 710 nm, and even more preferably from 630 nm to 700 nm.
  • X a is in the above range is preferable because there is a tendency to obtain a camera image noise and excellent little color reproducibility.
  • the thickness of the substrate can be appropriately selected according to the desired application and is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 20 to 180 ⁇ m, and further preferably 25 to 150 ⁇ m.
  • an optical filter using the substrate can be reduced in thickness and weight, and can be suitably used for various applications such as a solid-state imaging device.
  • a base material made of the transparent resin substrate is used in a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height and weight.
  • the compound (A) is not particularly limited as long as it has an absorption maximum in the wavelength region of 650 to 800 nm, but at least selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds.
  • One type of compound is preferable, and squarylium compounds, phthalocyanine compounds, and cyanine compounds are particularly preferable.
  • a compound (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the squarylium-based compound has excellent visible light permeability, steep absorption characteristics, and a high molar extinction coefficient, but may generate fluorescence that causes scattered light during light absorption. In such a case, an optical filter with less scattered light and better camera image quality can be obtained by using a combination of the squarylium compound and the other compound (A).
  • the absorption maximum wavelength of the compound (A) is preferably 660 nm to 795 nm, more preferably 680 nm to 790 nm.
  • the compound (A) is not particularly limited as long as it has an absorption maximum in the wavelength region of 650 to 800 nm. From the viewpoint of heat resistance of the optical filter, the compound (Aa) has an absorption maximum in the wavelength region of 650 to 715 nm. ), A compound (Ab) having an absorption maximum in a region of wavelengths from 715 nm to 750 nm or less, and a compound (Ac) having an absorption maximum in a region of wavelengths from 750 nm to 800 nm or less are more preferable. .
  • the compound (A) has such a configuration, the near-infrared absorption band can be efficiently widened while minimizing the decrease in visible light transmittance, and heat resistance and the like can be increased by the intermolecular interaction between the compounds (A). This tends to improve the weather resistance, which is preferable.
  • the difference between the absorption maximum wavelengths of the compound (A) to be applied having the shortest absorption maximum wavelength and the longest absorption maximum wavelength is preferably 20 to The thickness is 100 nm, more preferably 30 to 90 nm, still more preferably 40 to 80 nm. It is preferable that the difference in absorption maximum wavelength is in the above-mentioned range because scattered light due to fluorescence can be sufficiently reduced and a wide absorption band near 700 nm and an excellent visible light transmittance can be compatible.
  • the total content of the compound (A) is, for example, a base material made of a transparent resin substrate containing the compound (A) or a curable resin on the transparent resin substrate containing the compound (A).
  • a base material on which a resin layer such as an overcoat layer made of, etc. is used it is preferably 0.04 to 2.0 parts by mass, more preferably 0.06 to 2.0 parts by mass with respect to 100 parts by mass of the transparent resin. 1.5 parts by mass, more preferably 0.08 to 1.0 part by mass, and the compound (A) is contained as a substrate on a support such as a glass support or a resin support as a base.
  • a base material on which a transparent resin layer such as an overcoat layer made of a curable resin or the like is used it is preferably 0.1% with respect to 100 parts by mass of the resin forming the transparent resin layer containing the compound (A). 4 to 5.0 parts by weight, more preferably 0 6 to 4.0 parts by weight, more preferably 0.8 to 3.5 mass parts.
  • the squarylium compound is not particularly limited, but is at least one selected from the group consisting of a squarylium compound represented by the following formula (I) and a squarylium compound represented by the following formula (II). Are preferred. Hereinafter, they are also referred to as “compound (I)” and “compound (II)”, respectively.
  • R a , R b and Ya satisfy the following condition ( ⁇ ) or ( ⁇ ).
  • a plurality of R a each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L 1 or —NR e R f group;
  • a plurality of R b s each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L 1 or —NR g R h group;
  • a plurality of Ya each independently represents a —NR j R k group;
  • L 1 represents L a, L b, L c , L d, L e, L f, L g or L h;
  • R e and R f each independently represents a hydrogen atom, -L a ,
  • At least one of two R a on one benzene ring is bonded to Y on the same benzene ring to form a heterocycle having 5 or 6 member atoms containing at least one nitrogen atom;
  • the heterocyclic ring may have a substituent, and R b and R a that is not involved in the formation of the heterocyclic ring are independently synonymous with R b and R a in the condition ( ⁇ ).
  • the total number of carbon atoms including the substituents of L a to L h is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the number of carbon atoms exceeds this range, it may be difficult to synthesize the compound, and the light absorption intensity per unit mass tends to be small.
  • the aliphatic hydrocarbon group L a and 1 to 12 carbon atoms in L such as a methyl group (Me), ethyl (Et), n-propyl group (n-Pr), isopropyl (i-Pr ), N-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.
  • Me methyl group
  • Et ethyl
  • i-Pr isopropyl
  • n-Bu N-butyl group
  • s-Bu sec-butyl group
  • t-Bu tert-butyl group
  • pentyl group hexyl group
  • octyl group nonyl group
  • decyl group dodecyl
  • Alkyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group and octenyl group
  • alkynyl groups such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group and octynyl group.
  • Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms in L b and L include, for example, a trichloromethyl group, a trifluoromethyl group, a 1,1-dichloroethyl group, a pentachloroethyl group, a pentafluoroethyl group, a heptachloro group. Mention may be made of propyl and heptafluoropropyl groups.
  • Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in L c and L include, for example, a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a norbornane group and an adamantane group And polycyclic alicyclic groups such as
  • Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L d and L include, for example, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, Mention may be made of phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl and biphenylyl groups.
  • heterocyclic group having 3 to 14 carbon atoms in Le and L examples include, for example, furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, indole, indoline, indolenine, and benzofuran.
  • Examples of the alkoxy group having 1 to 12 carbon atoms in L f include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group. it can.
  • Examples of the acyl group having 1 to 9 carbon atoms in L g include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.
  • alkoxycarbonyl group having 1 to 9 carbon atoms in L h examples include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, and an octyl group.
  • An oxycarbonyl group can be mentioned.
  • L a preferably a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- butyl group, a pentyl group, a hexyl group, an octyl group, 4-phenylbutyl 2-cyclohexylethyl, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.
  • L b is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, or a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, more preferably a trichloromethyl group.
  • L c is preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group, or a 4-phenylcycloheptyl group, and more preferably a cyclopentyl group, a cyclohexyl group, or a 4-ethylcyclohexyl group. It is.
  • the L d is preferably a phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 3,5-di-tert-butylphenyl group, 4-cyclopentylphenyl group. 2,3,6-triphenylphenyl group, 2,3,4,5,6-pentaphenylphenyl group, more preferably phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,3 , 4,5,6-pentaphenylphenyl group.
  • L e preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, consisting morpholine group, more preferably furan, thiophene, pyrrole, consisting morpholine group.
  • the L f is preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, methoxymethyl group, methoxyethyl group, 2-phenylethoxy group, 3-cyclohexylpropoxy group, pentyloxy group, hexyloxy Group, octyloxy group, more preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group.
  • L g is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, or a trifluoromethylcarbonyl group, and more preferably an acetyl group, a propionyl group, or a benzoyl group.
  • the L h is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group, more preferably A methoxycarbonyl group and an ethoxycarbonyl group;
  • the L a to L h further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, and an amino group. May be. Examples include 4-sulfobutyl, 4-cyanobutyl, 5-carboxypentyl, 5-aminopentyl, 3-hydroxypropyl, 2-phosphorylethyl, 6-amino-2,2-dichloro.
  • R a in the above condition ( ⁇ ) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.
  • R b in the above condition ( ⁇ ) is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group T-butanoylamino group, cyclohexinoylamino group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group, dimethylamino group, nitro group Acet
  • the Ya is preferably an amino group, methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-t-butylamino group, N -Ethyl-N-methylamino group, N-cyclohexyl-N-methylamino group, more preferably dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group , A di-t-butylamino group.
  • At least one of two R a on one benzene ring is bonded to Y on the same benzene ring, and at least 1 nitrogen atom is formed.
  • the heterocyclic ring containing 5 or 6 atoms include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine.
  • a heterocyclic ring that constitutes the heterocyclic ring and in which one atom adjacent to the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.
  • X independently represents O, S, Se, N—R c or C (R d R d ); a plurality of R c s independently represent a hydrogen atom, L a , L b , L c, represents L d or L e; each independently plurality of R d, a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L 1 or -NR e R f group, and adjacent R d groups may be linked to form an optionally substituted ring; L a to L e , L 1 , R e and R f are It is synonymous with L a -L e , L 1 , R e and R f defined in formula (I).
  • R c in the formula (II) is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group.
  • R d in the formula (II) is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl.
  • n-pentyl group n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, 4-aminocyclohexyl group, more preferably hydrogen atom, chlorine atom, fluorine atom Methyl group, ethyl group, n-propyl group, isopropyl group, trifluoromethyl group and pentafluoroethyl group.
  • X is preferably O, S, Se, N-Me, N-Et, CH 2 , C-Me 2 , C-Et 2 , and more preferably S, C-Me 2 , C-Et 2. It is.
  • adjacent R ds may be linked to form a ring.
  • rings include benzoindolenin ring, ⁇ -naphthimidazole ring, ⁇ -naphthimidazole ring, ⁇ -naphthoxazole ring, ⁇ -naphthoxazole ring, ⁇ -naphthothiazole ring, ⁇ -naphthothiadiazole ring,
  • An ⁇ -naphthoselenazole ring and a ⁇ -naphthoselenazole ring can be exemplified.
  • Compound (I) and Compound (II) are represented by the following formulas (I-2) and (II-2) in addition to the description methods such as the following formula (I-1) and the following formula (II-1).
  • the structure can also be expressed by a description method that takes a resonance structure. That is, the difference between the following formula (I-1) and the following formula (I-2), and the difference between the following formula (II-1) and the following formula (II-2) is only the structure description method. Represents the same compound.
  • the structure of the squarylium compound is represented by a description method such as the following formula (I-1) and the following formula (II-1).
  • a compound represented by the following formula (I-3) and a compound represented by the following formula (I-4) can be regarded as the same compound.
  • the structures of the compounds (I) and (II) are not particularly limited as long as they satisfy the requirements of the formulas (I) and (II), respectively.
  • the left and right substituents bonded to the central four-membered ring may be the same or different, It is preferable that they are the same because synthesis is easy.
  • compounds (I) and (II) include compounds (a-1) shown in the following Tables 1 to 3 having basic skeletons represented by the following formulas (IA) to (IH): ) To (a-36).
  • the compounds (I) and (II) may be synthesized by a generally known method.
  • JP-A-1-228960, JP-A-2001-40234, JP-A-3196383, etc. It can be synthesized with reference to the method described.
  • the phthalocyanine compound is not particularly limited, but is preferably a compound represented by the following formula (III) (hereinafter also referred to as “compound (III)”).
  • M represents a substituted metal atom including two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom
  • the amino group, amide group, imide group and silyl group may have the substituent L defined in the formula (I), L 1 has the same meaning as L 1 defined in Formula (I), L 2 represents one of L a ⁇ L e as defined in the hydrogen atom or the formula (I), the L 3 represents either a hydroxyl group or the L a ⁇ L e, L 4 represents represents any of the L a ⁇ L e.
  • the group and the silyl group may have the substituent L defined in the formula (I), and L 1 to L 4 have the same meanings as L 1 to L 4 defined in the formula (III).
  • the amino group which may have a substituent L is an amino group, ethylamino group, dimethylamino group, methylethylamino group, dibutylamino group, diisopropylamino Group and the like.
  • R a to R d and R A to R L as an amide group which may have a substituent L, an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, a diisopropylamide group, Examples thereof include a dibutylamide group, an ⁇ -lactam group, a ⁇ -lactam group, a ⁇ -lactam group, and a ⁇ -lactam group.
  • the imide group that may have a substituent L is an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, a diisopropylimide group, A dibutylimide group etc. are mentioned.
  • Examples of the silyl group that may have a substituent L in R a to R d and R A to R L include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a triethylsilyl group.
  • —SL 2 includes thiol group, methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, isobutyl sulfide group, sec-butyl sulfide group Tert-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butylphenyl sulfide group, 2,6-diphenylphenyl sulfide group, 4-cumylphenyl sulfide group and the like.
  • —SS-L 2 is a disulfide group, methyl disulfide group, ethyl disulfide group, propyl disulfide group, butyl disulfide group, isobutyl disulfide group, sec-butyl disulfide group Tert-butyl disulfide group, phenyl disulfide group, 2,6-di-tert-butylphenyl disulfide group, 2,6-diphenylphenyl disulfide group, 4-cumylphenyl disulfide group and the like.
  • examples of —SO 2 -L 3 include a sulfo group, a mesyl group, an ethylsulfonyl group, an n-butylsulfonyl group, a p-toluenesulfonyl group, and the like.
  • —N ⁇ N—L 4 includes a methylazo group, a phenylazo group, a p-methylphenylazo group, a p-dimethylaminophenylazo group, and the like.
  • examples of monovalent metal atoms include Li, Na, K, Rb, and Cs.
  • the divalent metal atoms include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, Hg, Sn, Pb etc. are mentioned.
  • the substituted metal atom containing a trivalent metal atom includes Al—F, Al—Cl, Al—Br, Al—I, Ga—F, Ga—Cl, Ga—Br, Ga—I, In -F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH and the like.
  • the substituted metal atom containing a tetravalent metal atom includes TiF 2 , TiCl 2 , TiBr 2 , TiI 2 , ZrCl 2 , HfCl 2 , CrCl 2 , SiF 2 , SiCl 2 , SiBr 2 , SiI 2 , GeF 2 , GeCl 2 , GeBr 2 , GeI 2 , SnF 2 , SnCl 2 , SnBr 2 , SnI 2 , Zr (OH) 2 , Hf (OH) 2 , Mn (OH) 2 , Si (OH) 2 , Ge ( OH) 2 , Sn (OH) 2 , TiR 2 , CrR 2 , SiR 2 , GeR 2 , SnR 2 , Ti (OR) 2 , Cr (OR) 2 , Si (OR) 2 , Ge (OR) 2 , Sn (OR) 2 (R represents an aliphatic group or an aromatic group),
  • the M is a divalent transition metal, trivalent or tetravalent metal halide or tetravalent metal oxide belonging to Groups 5 to 11 of the periodic table and belonging to the 4th to 5th periods.
  • Cu, Ni, Co, and VO are particularly preferable because high visible light transmittance and stability can be achieved.
  • a method of synthesizing the phthalocyanine-based compound by a cyclization reaction of a phthalonitrile derivative such as the following formula (V) is generally known.
  • the obtained phthalocyanine-based compounds are represented by the following formulas (VI-1) to (VI) It is a mixture of four isomers such as VI-4).
  • VI-1 a phthalonitrile derivative
  • VI-4 a phthalonitrile derivative
  • the compound (III) include the basic skeletons represented by the following formulas (III-A) to (III-J) and (b-1) to (b-61) shown in Tables 4 to 7 below. ) And the like.
  • Compound (III) may be synthesized by a generally known method. For example, a method described in Japanese Patent No. 4081149 or “phthalocyanine -chemistry and function” (IPC, 1997) is used. It can be synthesized by reference.
  • the cyanine compound is not particularly limited, but is a compound represented by any of the following formulas (IV-1) to (IV-3) (hereinafter referred to as “compounds (IV-1) to (IV-3)”. ) ").) Is preferred.
  • X a - represents a monovalent anion
  • a plurality of D are independently represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom
  • L 1 has the same meaning as L 1 defined in Formula (I)
  • L 2 represents one of L a ⁇ L e as defined in the hydrogen atom or the formula (I)
  • the L 3 represents either a hydrogen atom or the L a ⁇ L e
  • L 4 are, represents any of the L a ⁇ L e
  • the hydrogenation group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.
  • Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z or Y in Z a to Z c and Y a to Y d include, for example, the substituent L
  • the compound illustrated by the aromatic hydrocarbon group is mentioned.
  • the alicyclic hydrocarbon group include compounds exemplified by the alicyclic hydrocarbon group and the heterocyclic ring in the substituent L (excluding the heteroaromatic hydrocarbon group).
  • heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding Z or Y in Z a to Z c and Y a to Y d include, for example, the substituent L And the compounds exemplified as the heterocyclic group (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom or sulfur atom).
  • X a ⁇ is not particularly limited as long as it is a monovalent anion, but I ⁇ , Br ⁇ , PF 6 ⁇ , N (SO 2 CF 3 ) 2 ⁇ , B (C 6 F 5 ) 4 ⁇ , nickel dithiolate. And the like, and copper dithiolate complex.
  • the compounds (IV-1) to (IV-3) may be synthesized by a generally known method, for example, by the method described in JP-A-2009-108267.
  • the transparent resin is not particularly limited as long as it does not impair the effects of the present invention.
  • the glass transition temperature (Tg) is preferably from 110 to 110 in order to ensure thermal stability and film formability. Examples thereof include resins having a temperature of 380 ° C., more preferably 110 to 370 ° C., and still more preferably 120 to 360 ° C.
  • the glass transition temperature of the resin is preferably 140 ° C. or higher, and more preferably 230 ° C. or higher.
  • the refractive index (n20d) of the transparent resin is particularly preferably 1.53 or less.
  • Transparent resins with a refractive index (n20d) exceeding 1.53 tend to have many aromatic rings in the molecule, but the resin with this structure has a strong interaction with the ⁇ -conjugated system in the compound (A) molecule. In some cases, the weather resistance may deteriorate.
  • the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, Particularly preferably 80 to 95% of the resin can be used. If a resin having a total light transmittance in such a range is used, the resulting substrate exhibits good transparency as an optical film.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by a gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000, preferably 30,000 to 250,000.
  • the average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.
  • Transparent resins include, for example, cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, poly Ether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane UV curable Resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin and sol-gel method Formed Silica may be mentioned a resin as a main component was.
  • cyclic polyolefin resins aromatic polyether resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polyarylate resins can be used for transparency (optical properties), heat resistance, and reflow resistance.
  • a cyclic polyolefin resin is particularly preferable from the viewpoint of the refractive index of the resin.
  • Transparent resin may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the cyclic polyolefin-based resin is obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X 0 ) and a monomer represented by the following formula (Y 0 ).
  • a resin and a resin obtained by hydrogenating the resin are preferable.
  • R x1 to R x4 each independently represents an atom or group selected from the following (i ′) to (ix ′), and k x , mx and p x are each independently 0 Represents an integer of ⁇ 4.
  • R x1 and R x2 or R x3 and R x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring (provided that R x1 to R which are not involved in the bond) x4 each independently represents an atom or group selected from (i ′) to (vi ′).
  • Ix ′ A monocyclic hydrocarbon ring or heterocycle formed by bonding R x2 and R x3 to each other (provided that R x1 and R x4 not involved in the bonding are each independently the above (i Represents an atom or group selected from ') to (vi').
  • R y1 and R y2 each independently represent an atom or group selected from the above (i ′) to (vi ′), or R y1 and R y2 are bonded to each other formed monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or heterocyclic, k y and p y are each independently an integer of 0-4.
  • the aromatic polyether-based resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
  • R 1 to R 4 each independently represents a monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represents an integer of 0 to 4.
  • R 1 ⁇ R 4 and a ⁇ d independently has the same meaning as R 1 ⁇ R 4 and a ⁇ d of the formula (1)
  • Y represents a single bond
  • R 7 and R 8 each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group
  • g and h each independently represents 0 to 4 Represents an integer
  • m represents 0 or 1.
  • R 7 is not a cyano group.
  • the aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). Is preferred.
  • R 5 and R 6 each independently represent a monovalent organic group having 1 to 12 carbon atoms
  • Z represents a single bond, —O—, —S—, —SO 2 —, — CO—, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms
  • e and f each independently represents an integer of 0 to 4, and n represents 0 or 1.
  • R 7 , R 8 , Y, m, g and h are each independently synonymous with R 7 , R 8 , Y, m, g and h in formula (2), and R 5 , R 6 , Z, n, e and f are each independently synonymous with R 5 , R 6 , Z, n, e and f in the formula (3).
  • the polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in a repeating unit.
  • the method described in JP-A-2006-199945 and JP-A-2008-163107 is used. Can be synthesized.
  • the fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in JP-A-2008-163194.
  • the fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety.
  • the fluorene polyester resin can be synthesized by the method described in JP 2010-285505 A or JP 2011-197450 A. Can do.
  • the fluorinated aromatic polymer resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond.
  • the polymer preferably contains a repeating unit containing at least one bond, and can be synthesized, for example, by the method described in JP-A-2008-181121.
  • the acrylic ultraviolet curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic or methacrylic groups in the molecule and a compound that decomposes by ultraviolet rays to generate active radicals. Can be mentioned.
  • the acrylic ultraviolet curable resin is a base material in which a transparent resin layer containing a compound (A) and a curable resin is laminated on a glass support or a resin support as a base, or a compound ( When using a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is used on a transparent resin substrate containing A), it can be particularly preferably used as the curable resin.
  • Epoxy resin Although it does not restrict
  • the ultraviolet curable epoxy resin for example, synthesized from a composition containing a compound having one or more epoxy groups in the molecule and a compound that generates an acid by ultraviolet rays (hereinafter also referred to as “photo acid generator”).
  • thermosetting epoxy resins include those synthesized from a composition containing one or more epoxy groups in the molecule and an acid anhydride. Can do.
  • the epoxy ultraviolet curable resin contains, as the base material, a base material obtained by laminating a transparent resin layer containing the compound (A) on a glass support or a base resin support, and the compound (A). In the case of using a base material in which a resin layer such as an overcoat layer made of a curable resin is laminated on a transparent resin substrate to be used, it can be particularly suitably used as the curable resin.
  • Resin mainly composed of silica formed by sol-gel process examples include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxylane, and methoxytriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, A compound obtained by a sol-gel reaction by hydrolysis of one or more silanes selected from phenylalkoxysilanes such as diphenyldiethoxysilane can be used as the resin.
  • cyclic polyolefin resins examples include Arton manufactured by JSR Corporation, ZEONOR manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Corporation.
  • polyethersulfone resins examples include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd.
  • polyimide resins examples include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • commercially available polycarbonate resins include Pure Ace manufactured by Teijin Limited.
  • Examples of commercially available fluorene polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd.
  • Examples of commercially available acrylic resins include NIPPON CATALYST ACRYVIEWER.
  • Examples of commercially available silsesquioxane-based ultraviolet curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd.
  • the base material may further contain other dye (X) that does not correspond to the compound (A).
  • the other dye (X) is not particularly limited as long as it has a maximum absorption wavelength of less than 650 nm or more than 800 nm and not more than 1250 nm.
  • BODIPY boron dipyrromethene
  • the absorption maximum wavelength of the other dye (X) is preferably 805 nm to 1200 nm, more preferably 810 nm to 1150 nm, further preferably 815 nm to 1100 nm, and particularly preferably 820 nm to 1050 nm.
  • the absorption maximum wavelength of the other dye (X) is in such a range, unnecessary near-infrared rays can be efficiently cut and the incident angle dependency of incident light can be reduced.
  • the content of the other dye (X) is, for example, when a base material made of a transparent resin substrate containing the other dye (X) is used as the base material, with respect to 100 parts by mass of the transparent resin.
  • the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.9 part by mass, particularly preferably 0.02 to 0.8 part by mass.
  • It contains a base material in which a transparent resin layer such as an overcoat layer made of a curable resin containing other dye (X) is laminated on a support such as a resin support, or a compound (A).
  • a transparent resin containing other pigment (X) When using a base material in which a resin layer such as an overcoat layer made of a curable resin containing other pigment (X) is laminated on a transparent resin substrate, a transparent resin containing other pigment (X) For 100 parts by mass of the resin forming the layer, 0.05 to 4.0 parts by weight preferred, and more preferably 0.1 to 3.0 mass parts, and particularly preferably 0.2 to 2.0 parts by mass.
  • the base material may further contain an antioxidant, a near-ultraviolet absorber, a fluorescence quencher, and the like as other components as long as the effects of the present invention are not impaired. These other components may be used alone or in combination of two or more.
  • Examples of the near-ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, triazine compounds, and cyanoacrylate compounds.
  • antioxidants examples include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (2,4-di-t-butylphenyl) phosphite and the like.
  • these other components may be mixed with a resin or the like when producing a substrate, or may be added when a resin is synthesized.
  • 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 with respect to 100 parts by weight of the resin. Part.
  • the transparent resin substrate can be formed by, for example, melt molding or cast molding, and further, if necessary, After molding, a substrate on which an overcoat layer is laminated can be produced by coating a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent.
  • a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent.
  • the base material is an overcoat comprising a curable resin containing the compound (A) on a support such as a glass support or a base resin support or a transparent resin substrate containing no compound (A).
  • a support such as a glass support or a base resin support or a transparent resin substrate containing no compound (A).
  • the resin solution containing the compound (A) is melt-molded or cast-molded on the support or the transparent resin substrate, preferably spin After coating by a method such as coating, slit coating or ink jetting, the solvent is dried and removed, and if necessary, further irradiation with light or heating is performed, whereby the compound (A) is formed on the support or the transparent resin substrate.
  • the base material in which the transparent resin layer containing this was formed can be manufactured.
  • melt molding a method of melt molding a pellet obtained by melt-kneading a resin, a compound (A) and other components as necessary; a resin, a compound (A) and a necessary
  • Examples include a method of melt-molding pellets.
  • the melt molding method include injection molding, melt extrusion molding, and blow molding.
  • ⁇ Cast molding As the cast molding, a method of removing a solvent by casting a resin composition containing a compound (A), a resin, a solvent and other components as required on a suitable support; or a compound (A) and After removing a solvent by casting a curable composition containing a photocurable resin and / or a thermosetting resin and other components as necessary on an appropriate support, ultraviolet irradiation, heating, etc. It can also be produced by a method of curing by an appropriate method.
  • the base material is a base material made of a transparent resin substrate containing the compound (A)
  • the base material can be obtained by peeling the coating film from the support after cast molding
  • the base material is made of a curable resin containing the compound (A) on a support such as a glass support or a base resin support or a transparent resin substrate containing no compound (A).
  • the substrate can be obtained by not peeling the coating film after cast molding.
  • a near-infrared absorbing glass plate for example, a phosphate system containing a copper component such as “BS-11” manufactured by Matsunami Glass Industrial Co., Ltd. or “NF-50T” manufactured by AGC Sakai Techno Glass Co., Ltd.) Glass plate
  • transparent glass plate for example, non-alkali glass plate such as “OA-10G” manufactured by Nippon Electric Glass Co., Ltd., “AN100” manufactured by Asahi Glass Co., Ltd.
  • steel belt for example, steel drum, and transparent resin (for example, polyester film) , Cyclic olefin resin film) support.
  • the optical component such as glass plate, quartz or transparent plastic is coated with the resin composition and the solvent is dried, or the curable composition is coated and cured and dried.
  • a transparent resin layer can also be formed on the component.
  • the amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the above method should be as small as possible.
  • the amount of the residual solvent is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.8 parts by mass with respect to 100 parts by mass of the weight of the transparent resin layer (transparent resin substrate). 5 parts by mass or less.
  • the amount of residual solvent is in the above range, a transparent resin layer (transparent resin substrate) that can easily exhibit a desired function, in which deformation and characteristics hardly change can be obtained.
  • the optical filter of the present invention preferably does not have a dielectric multilayer film, but may have a dielectric multilayer film on at least one surface of the substrate as long as the effects of the present invention are not impaired.
  • the dielectric multilayer film in the present invention is a film having an antireflection effect in the visible light region.
  • the dielectric multilayer film preferably has an antireflection property over the entire range of a wavelength of 400 to 610 nm, more preferably a wavelength of 410 to 600 nm, and even more preferably 420 to 590 nm.
  • a form having a dielectric multilayer film on both surfaces of the base material a form having a dielectric multilayer film on both surfaces of the base material mainly having an antireflection characteristic in the vicinity of a wavelength of 400 to 610 nm when measured from the vertical direction of the optical filter Etc.
  • the thickness of the dielectric multilayer film having an antireflection effect in the visible light region is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.01 to 1.0 ⁇ m, more preferably 0.05 to 0.00. 5 ⁇ m. By setting the thickness within the above range, an optical filter with less warpage and distortion can be obtained.
  • Examples of the dielectric multilayer film include those in which a high refractive index material layer and a low refractive index material layer are alternately laminated.
  • a material constituting the high refractive index material layer a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected.
  • Such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as the main components, and titanium oxide, tin oxide, and / or Alternatively, a material containing a small amount of cerium oxide or the like (eg, 0 to 10 parts by mass with respect to 100 parts by mass of the main component) can be used.
  • a material having a refractive index of 1.6 or less can be used, and a material having a refractive index of usually 1.2 to 1.6 is selected.
  • examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium hexafluoride sodium.
  • the method for laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed.
  • a multilayer film can be formed.
  • each of the high refractive index material layer and the low refractive index material layer is usually preferably from 0.1 ⁇ to 0.5 ⁇ , where ⁇ (nm) is the near infrared wavelength to be blocked.
  • the value of ⁇ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm.
  • the optical thickness obtained by multiplying the refractive index (n) by the thickness (d) (n ⁇ d) by ⁇ / 4 the high refractive index material layer, and the low refractive index.
  • the thicknesses of the respective layers of the refractive index material layer are almost the same value, and there is a tendency that the blocking / transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection / refraction.
  • the total number of high refractive index material layers and low refractive index material layers in the dielectric multilayer film is preferably 1 to 20 layers, more preferably 2 to 12 layers as a whole.
  • the material types constituting the high refractive index material layer and the low refractive index material layer, the high refractive index material layer, and the low refractive index material layer in accordance with the absorption characteristics of the compound (A) and other dyes (X) By appropriately selecting the thickness of each layer, the order of lamination, and the number of laminations, it has sufficient light-cutting characteristics in the near-infrared wavelength region while ensuring sufficient transmittance in the visible light region, and diagonally The reflectance when near infrared rays are incident from the direction can be reduced.
  • optical thin film design software for example, Essential Macleod, Thin Film Center
  • both the antireflection effect in the visible light region and the light cut effect in the near infrared region are compatible.
  • the target transmittance at a wavelength of 400 to 700 nm is set to 100%
  • the target Tolerance value is set to 1
  • the target transmittance at a wavelength of 705 to 950 nm is set to 0%.
  • Parameter setting method such as setting Target Tolerance value to 0.5 can be mentioned.
  • the optical filter of the present invention is within the range not impairing the effects of the present invention, at least one surface of the substrate, between the substrate and the dielectric multilayer film, and opposite to the surface on which the dielectric multilayer film is provided.
  • the surface hardness of the substrate or dielectric multilayer film is improved, the chemical resistance is improved, the antistatic and scratch-removing, etc.
  • a functional film such as an antireflection film, a hard coat film or an antistatic film can be appropriately provided.
  • the optical filter of the present invention may include one layer made of the functional film or two or more layers.
  • the optical filter of the present invention may include two or more similar layers or two or more different layers.
  • the method of laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded or cast in the same manner as described above on a base material or a dielectric multilayer film. Examples of the method include molding.
  • it can also be produced by applying a curable composition containing the coating agent or the like on a substrate or a dielectric multilayer film with a bar coater or the like and then curing it by ultraviolet irradiation or the like.
  • the coating agent examples include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethanes, urethane acrylates, acrylates, epoxy And epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.
  • UV ultraviolet
  • EB electron beam
  • the curable composition may contain a polymerization initiator.
  • a polymerization initiator a known photopolymerization initiator or a thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination.
  • a polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
  • the mixing ratio of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, when the total amount of the curable composition is 100 parts by mass. More preferably, it is 1 to 5 parts by mass.
  • the blending ratio of the polymerization initiator is within the above range, it is possible to obtain a functional film such as an antireflective film, a hard coat film or an antistatic film having excellent curing characteristics and handleability of the curable composition and having a desired hardness. it can.
  • an organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used.
  • the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Examples include amides such as methylpyrrolidone.
  • a solvent may be used individually by 1 type and
  • the thickness of the functional film is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, and particularly preferably 0.7 to 5 ⁇ m.
  • the corona is applied to the surface of the base material, the functional film or the dielectric multilayer film.
  • Surface treatment such as treatment or plasma treatment may be performed.
  • the optical filter of the present invention has a wide viewing angle and has excellent near-infrared cutting ability and the like. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS image sensor of a camera module.
  • a solid-state imaging device such as a CCD or CMOS image sensor of a camera module.
  • digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automotive cameras, TVs, car navigation systems, personal digital assistants, video game machines, and portable game machines It is useful for fingerprint authentication system, digital music player, etc. Furthermore, it is also useful as a heat ray cut filter attached to a glass plate of an automobile or a building.
  • the solid-state imaging device is an image sensor including a solid-state imaging device such as a CCD or a CMOS image sensor.
  • a digital still camera a smartphone camera, a mobile phone camera, a wearable device camera, a digital camera It can be used for applications such as video cameras.
  • the camera module of the present invention includes the optical filter of the present invention.
  • the camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, and the like, and outputs images and distance information as electrical signals.
  • the camera module has a cover member that protects the internal mechanism from the outside, and the cover member has a near-infrared reflecting function.
  • the near infrared wavelength band in which the cover member has a function of reflecting light incident from the vertical direction of the cover member is preferably 900 to 1100 nm, more preferably 850 to 1150 nm, and particularly preferably 800 to 1200 nm.
  • the means for providing the near infrared reflection function to the cover member is not particularly limited, but a CVT method, a sputtering method, a vacuum deposition method, an ion-assisted deposition method using a dielectric multilayer film in which a high refractive index material and a low refractive index material are alternately laminated.
  • the method of forming on a cover member by the method etc. is preferable.
  • the camera module When the camera module is configured as described above, light enters the camera module with a portion of the near infrared ray cut by the cover member, so that the lens-lens, the lens-optical filter, This is preferable because unnecessary near-infrared reflection between the optical filter and the solid-state imaging device can be reduced, and noise and ghost of the camera image tend to be reduced. Furthermore, since the camera module of the present invention includes an optical filter that efficiently cuts near infrared rays having a wavelength of 700 to 780 nm by absorption of the compound (A), high image quality that is difficult to achieve with conventional camera modules is achieved. be able to.
  • the electronic device of the present invention has the camera module of the present invention. Although it does not specifically limit as an electronic device, For example, the smart phone in the use mentioned above, a mobile telephone, PC etc. are mentioned.
  • Part means “part by mass” unless otherwise specified.
  • measurement method of each physical property value and the evaluation method of the physical property are as follows.
  • the molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
  • GPC gel permeation chromatography
  • the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the said method.
  • (C) A part of the polyimide resin solution was added to anhydrous methanol to precipitate the polyimide resin, and filtered to separate from the unreacted monomer.
  • 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity ( ⁇ ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. Asked.
  • ⁇ ⁇ ln (t s / t 0) ⁇ / C t 0 : Flowing time of solvent t s : Flowing time of dilute polymer solution C: 0.5 g / dL ⁇ Glass transition temperature (Tg)> Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.
  • ⁇ Spectral transmittance> The transmittance at each wavelength of the substrate and the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.
  • the spectrophotometer 3 transmits light 1 ′ transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG.
  • the transmittance when measured and measured from an angle of 60 degrees with respect to the vertical direction of the optical filter light 1 transmitted at an angle of 60 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. ′′ was measured with a spectrophotometer 3.
  • ⁇ Camera image color shading evaluation> The color shading evaluation when the optical filter was incorporated in the camera module was performed by the following method.
  • a camera module as shown in FIG. 2 is produced in the same manner as in Japanese Patent Application Laid-Open No. 2016-110067, and a white plate having a size of 300 mm ⁇ 400 mm is used as a D65 light source (standard manufactured by X-Rite) using the obtained camera module.
  • the image was taken under the light source device “Macbeth Judge II”), and the difference in color between the center and the edge of the white plate in the camera image was evaluated according to the following criteria.
  • the positional relationship between the white plate 112 and the camera module was adjusted so that the white plate 112 occupied 90% or more of the area in the camera image 111 when shooting.
  • the cover member 210 in FIG. 2 a cover member having a film configuration shown in Table 9 below was used, and as the optical filter 240, an optical filter produced in the following examples and comparative examples was used.
  • Ghost evaluation when the optical filter was incorporated in the camera module was performed by the following method.
  • a camera module is created in the same way as the color shading evaluation of the camera image.
  • the camera module is used to shoot under a halogen lamp light source (“Luminer Ace LA-150TX” manufactured by Hayashi Clock Industry Co., Ltd.) in the dark room.
  • the degree of ghosting around the light source was evaluated according to the following criteria.
  • Dodec-3-ene hereinafter also referred to as “DNM”) 100 parts, 1-hexene (molecular weight regulator) 18 parts, and toluene (ring-opening polymerization solvent) 300 parts nitrogen-substituted reaction The vessel was charged and the solution was heated to 80 ° C.
  • the obtained resin A has a number average molecular weight (Mn) of 32,000, a mass average molecular weight (Mw) of 137,000, a glass transition temperature (Tg) of 165 ° C., and a refractive index (n20d) of 1.51. Met.
  • the obtained resin B has a number average molecular weight (Mn) of 75,000, a mass average molecular weight (Mw) of 188,000, a glass transition temperature (Tg) of 285 ° C., and a refractive index (n20d) of 1.66. Met.
  • Resin C a white powder (hereinafter also referred to as “resin C”).
  • the IR spectrum of the obtained resin C was measured, 1704 cm -1 characteristic of imido group, absorption of 1770 cm -1 were observed.
  • Resin C had a glass transition temperature (Tg) of 310 ° C., a refractive index (n20d) of 1.68, and a logarithmic viscosity of 0.87.
  • Example 1 In a container, 100 parts of resin A obtained in Resin Synthesis Example 1, compound (Aa-1) represented by the following formula (Aa-1) as compound (Aa) (absorption maximum in dichloromethane) 0.05 part of a wavelength 712 nm) 0.12 parts of the compound (Ab-1) represented by the following formula (Ab-1) (absorption maximum wavelength 738 nm in dichloromethane) as the compound (Ab) And 0.05 part of a compound (Ac-1) (absorption maximum wavelength 776 nm in dichloromethane) represented by the following formula (Ac-1) as a compound (Ac) and methylene chloride A solution having a resin concentration of 20% by mass was prepared.
  • compound (Aa-1) represented by the following formula (Aa-1) as compound (Aa) (absorption maximum in dichloromethane) 0.05 part of a wavelength 712 nm) 0.12 parts of the compound (Ab-1) represented by the following formula (Ab-1) (absorption maximum wavelength 7
  • the obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate.
  • the peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a base material composed of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
  • the optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG.
  • Example 2 In Example 1, 0.03 part of the compound (Aa-2) (maximum absorption wavelength 686 nm in dichloromethane) represented by the following formula (Aa-2) was used as the compound (Aa). Compound (Ab) was not used, and 0.04 part of compound (Ac-1) as compound (Ac) and compound (Ac-2) represented by the following formula (Ac-2) -C-2) A transparent resin substrate was obtained by the same procedure and conditions as in Example 1 except that 0.06 part (absorption maximum wavelength in dichloromethane: 760 nm) was used.
  • a resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, exposure (exposure amount: 500 mJ / cm 2 , 200 mW) was performed using a conveyor type exposure machine to cure the resin composition (1), and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate to obtain a base material having resin layers on both surfaces of the transparent resin substrate. The optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG.
  • Resin composition (1) 60 parts of tricyclodecane dimethanol diacrylate, 40 parts of dipentaerythritol hexaacrylate, 5 parts of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30% by mass)
  • TSC solid content concentration
  • Example 3 In Example 1, 0.04 part of Compound (Aa-1) and 0.03 part of Compound (Aa-2) were used as Compound (Aa), and Compound as Compound (Ab) 0.10 parts of (Ab-1) was used, and 0.04 part of compound (Ac-1) and 0.05 part of compound (Ac-2) as compound (Ac)
  • a base material made of a transparent resin substrate was obtained in the same procedure and conditions as in Example 1 except that was used. The optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera
  • Example 4 In Example 1, 0.04 part of Compound (Aa-1) and 0.03 part of Compound (Aa-2) were used as Compound (Aa), and Compound as Compound (Ab) Using 0.01 part of (Ab-1), 0.03 part of compound (Ac-1) and 0.04 part of compound (Ac-2) were used as compound (Ac). In addition, 0.04 parts of near-infrared absorbing dye (X-1) (absorption maximum wavelength 813 nm in dichloromethane) represented by the following formula (X-1) is used as the other near-infrared absorbing dye (X).
  • X-1 near-infrared absorbing dye represented by the following formula (X-1) is used as the other near-infrared absorbing dye (X).
  • the base material which consists of a transparent resin board
  • the optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG.
  • Example 5 On a transparent glass substrate “OA-10G (thickness 150 ⁇ m)” (manufactured by Nippon Electric Glass Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width, a resin composition (2) having the following composition was applied by a spin coater. The solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes. Under the present circumstances, the application
  • the resin composition (2) is cured by exposure (exposure amount: 500 mJ / cm 2 , 200 mW) using a conveyor type exposure machine.
  • exposure amount: 500 mJ / cm 2 , 200 mW Exposure amount: 500 mJ / cm 2 , 200 mW
  • a base material was obtained.
  • the optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG.
  • Resin composition (2) 20 parts of tricyclodecane dimethanol diacrylate, 80 parts of dipentaerythritol hexaacrylate, 4 parts of 1-hydroxycyclohexyl phenyl ketone, 3.00 parts of compound (Aa-1), compound (A -A-2) 1.00 part, Compound (Ab-1) 7.00 part, Compound (Ac-1) 4.00 part, Methyl ethyl ketone (solvent, TSC: 35%) [Example 6]
  • 0.04 part of Compound (Aa-1) and 0.03 part of Compound (Aa-2) were used as Compound (Aa), and Compound as Compound (Ab)
  • the use of 0.34 parts of (Ab-1), the use of 0.04 parts of compound (Ac-1) as compound (Ac), and the thickness of the transparent resin substrate A base material made of a transparent resin substrate was obtained in the same procedure and conditions as in Example 1 except that the thickness was 0.08 mm.
  • the optical transmittance was evaluated by measuring the
  • Example 7 In Example 1, 0.05 part of compound (Aa-1) was used as compound (Aa), and 0.85 part of compound (Ab-1) was used as compound (Ab). Except that 0.05 part of the compound (Ac-1) was used as the compound (Ac) and that the thickness of the transparent resin substrate was 0.04 mm, A base material made of a transparent resin substrate was obtained in the same procedure and conditions. The optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG.
  • Example 8 Resin A and methylene chloride obtained in Resin Synthesis Example 1 were added to a container to prepare a solution having a resin concentration of 20% by mass, and the resin was obtained in the same manner as in Example 1 except that the obtained solution was used. A support was made.
  • Example 2 In the same manner as in Example 2, a resin layer made of the resin composition (3) having the following composition was formed on both surfaces of the obtained resin support, and the compound (A) and near infrared rays were formed on both surfaces of the resin support. A substrate having a transparent resin layer containing the absorbing dye (X) was obtained. The optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG.
  • Resin composition (3) 100 parts of tricyclodecane dimethanol diacrylate, 4 parts of 1-hydroxycyclohexyl phenyl ketone, 0.50 part of compound (Aa-1), 0.50 of compound (Ac-1) Parts, compound (Ac-2) 2.50 parts, near infrared absorbing dye (X-1) 1.40 parts, methyl ethyl ketone (solvent, TSC: 25%)
  • a resin composition (4) having the following composition was applied on a near infrared absorbing glass substrate “BS-11 (thickness 120 ⁇ m)” (manufactured by Matsunami Glass Industry Co., Ltd.) cut to a size of 60 mm in length and 60 mm in width with a spin coater.
  • the solvent was volatilized and removed by heating at 80 ° C. for 2 minutes on a hot plate.
  • coating conditions of the spin coater were adjusted so that the thickness after drying might be set to 2 micrometers.
  • exposure exposure amount: 500 mJ / cm 2 , 200 mW
  • a base material consisting of a substrate was obtained.
  • the optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 13 and Table 15.
  • Resin composition (4) 20 parts of tricyclodecane dimethanol diacrylate, 80 parts of dipentaerythritol hexaacrylate, 4 parts of 1-hydroxycyclohexyl phenyl ketone, 1.00 part of compound (Aa-1), compound (A -C-1) 1.00 parts, Compound (Ac-2) 5.00 parts, methyl ethyl ketone (solvent, TSC: 35% by mass) [Example 10]
  • 0.04 part of Compound (Aa-1) and 0.03 part of Compound (Aa-2) were used as Compound (Aa), and Compound as Compound (Ab)
  • a base material made of a transparent resin substrate containing the compound (A) and the near-infrared absorbing dye (X) was obtained in the same procedure and conditions as in Example 1
  • Example 11 In Example 1, 0.04 part of Compound (Aa-1) and 0.03 part of Compound (Aa-2) were used as Compound (Aa), and Compound as Compound (Ab) The same as Example 1 except that 0.34 parts of (Ab-1) was used and 0.04 part of compound (Ac-1) was used as compound (Ac).
  • substrate was obtained in the procedure and conditions.
  • a dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained base material, and a similar dielectric multilayer film (I) is further formed on the other side of the base material to form an optical filter. Obtained.
  • a silica (SiO 2 ) layer and a titania (TiO 2 ) layer were alternately laminated at a deposition temperature of 120 ° C. (total of 4 layers).
  • the silica layer and the titania layer of the dielectric multilayer film (I) were alternately laminated in the order of the titania layer, the silica layer, the titania layer, and the silica layer from the substrate side, and the outermost layer of the optical filter was a silica layer.
  • the dielectric multilayer film (I) was a multilayer vapor deposition film having a stacking number of 4 in which a silica layer having a thickness of 33 to 88 nm and a titania layer having a thickness of 13 to 111 nm were alternately stacked.
  • the film configuration is shown in Table 10 below.
  • Optical characteristics were evaluated by measuring the spectral transmittance of the obtained substrate and optical filter.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG.
  • Example 12 to 14 A substrate was prepared in the same manner as in Example 1 except that the resin, the solvent, the drying conditions for the resin substrate, and the compound (A) were changed as shown in Table 15.
  • the optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 15.
  • Example 15 and 16 A substrate was prepared in the same manner as in Example 2 except that the resin, the solvent, the drying conditions of the resin substrate, the compound (A), and the near-infrared absorbing dye (X) were changed as shown in Table 15.
  • the optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIGS. 16 and 17 and Table 15.
  • Example 1 In Example 1, 0.07 part of the compound (Aa-1) was used as the compound (Aa), and 0.08 part of the compound (Ab-1) was used as the compound (Ab). A base material made of a transparent resin substrate was obtained in the same procedure and conditions as in Example 1 except that was used.
  • a dielectric multilayer film (II) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated as a first optical layer on one side of the obtained base material (26 layers in total).
  • a dielectric multilayer film (III) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated as a second optical layer on the other surface of the substrate (total 20 layers).
  • an optical filter having a thickness of about 0.105 mm was obtained.
  • the dielectric multilayer films (II) and (III) were designed as follows.
  • optical thin film design software Essential Macleod, Thin Film Center
  • the input parameters (Target values) to the software were as shown in Table 11 below.
  • the dielectric multilayer film (II) is formed by alternately laminating a silica layer having a film thickness of 31 to 155 nm and a titania layer having a film thickness of 10 to 94 nm.
  • the dielectric multi-layer film (III) is a multi-layer vapor-deposited film having 20 layers, in which a silica layer having a thickness of 38 to 189 nm and a titania layer having a thickness of 11 to 109 nm are alternately stacked. It was.
  • An example of the optimized film configuration is shown in Table 12 below.
  • Optical characteristics were evaluated by measuring the spectral transmittance of the obtained optical filter.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated.
  • the results are shown in FIG.
  • the optical filter obtained in Comparative Example 1 shows a relatively good optical density, it has a large decrease in transmittance when incident at a high angle, and ghosting that is considered to be caused by near-infrared reflection by the dielectric multilayer film is generated. It was confirmed that the effect of suppressing color shading was inferior.
  • Comparative Example 2 A base material made of a transparent resin substrate was obtained in the same procedure and conditions as in Comparative Example 1.
  • a dielectric multilayer film (IV) formed by alternately laminating a silica (SiO 2 ) layer and a titania (TiO 2 ) layer as a first optical layer on one side of the obtained substrate (total 30 layers), Furthermore, a dielectric multilayer film (V) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers as the second optical layer on the other surface of the substrate (20 layers in total). An optical filter having a thickness of about 0.105 mm was obtained.
  • the input parameters (Target values) to the software are as shown in Table 13 below.
  • the dielectric multilayer film (IV) is formed by alternately laminating a silica layer having a film thickness of 22 to 467 nm and a titania layer having a film thickness of 6 to 130 nm.
  • the dielectric multi-layer film (V) is a multi-layer vapor-deposited film having 20 layers, in which a silica layer having a thickness of 84 to 206 nm and a titania layer having a thickness of 8 to 109 nm are alternately stacked. It was.
  • An example of the optimized film configuration is shown in Table 14 below.
  • Optical characteristics were evaluated by measuring the spectral transmittance of the obtained optical filter.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. It is confirmed that the optical filter obtained in Comparative Example 2 is inferior in the color shading suppressing effect and the ghost suppressing effect because the transmittance at the high angle incidence is greatly decreased and the absorption in the near infrared wavelength region is not sufficient. It was.
  • Comparative Example 3 A base material made of a transparent resin substrate was obtained in the same procedure and conditions as in Comparative Example 1. Subsequently, a dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained base material in the same procedure and conditions as in Example 11, and the same applies to the other side of the base material. A dielectric multilayer film (I) was formed to obtain an optical filter having a thickness of about 0.101 mm.
  • the optical characteristics were evaluated by measuring the spectral transmittance of the obtained optical filter.
  • a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. It was confirmed that the optical filter obtained in Comparative Example 3 was not sufficiently absorbed in the near infrared wavelength region and was inferior in the ghost suppression effect.
  • Comparative Example 4 A base material made of a transparent resin substrate was obtained in the same procedure and conditions as in Comparative Example 1. The optical transmittance was evaluated by measuring the spectral transmittance of the optical filter comprising this substrate. In addition, a camera module was created using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. It was confirmed that the optical filter obtained in Comparative Example 4 was not sufficiently absorbed in the near infrared wavelength region and was inferior in the ghost suppression effect.
  • Comparative Example 5 A camera module was created using only the cover member without using an optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Table 15. Since the camera module obtained in Comparative Example 5 does not have an optical filter that absorbs the near-infrared region, both the color shading and the ghost are severe, and the level is unacceptable for general camera module applications. confirmed.
  • Optical filter 3 Spectrophotometer 111: Camera image 112: White plate 113: Example of white plate central portion 114: Example of white plate end portion 121: Camera image 122 : Light source 123: Example of ghost around light source 200: Imaging device 210: Cover member 220: Lens group 230: Diaphragm 240: Optical filter 250: Solid-state imaging device 260: Housing

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Abstract

La présente invention aborde le problème visant à fournir un filtre optique apte à obtenir à la fois une suppression d'ombrage de couleur et une suppression d'image fantôme d'une image de caméra à un niveau élevé. Le filtre optique satisfait les exigences (a) et (b) : (a) dans une région de longueur d'onde de 430 à 580 nm, une valeur minimale Tb-0 de transmittance d'une lumière incidente provenant d'une direction verticale, une valeur minimale Tb- 3 0 de transmittance d'une lumière incidente provenant d'une direction inclinée à 30 degrés par rapport à la direction verticale, et une valeur minimale Tb-60 de transmittance d'une lumière incidente provenant d'une direction inclinée à 60 degrés par rapport à la direction verticale sont toutes d'au mons 55 % et de moins de 90 % ; et (b) dans une région de longueur d'onde de 700 à 780 nm, une valeur moyenne ODa-0 de densité optique sur la lumière incidente provenant de la direction verticale, une valeur moyenne ODa -30 de densité optique à la lumière incidente provenant de la direction inclinée à 30 degrés par rapport à la direction verticale, une valeur moyenne ODa -60 de densité optique par rapport à la lumière incidente provenant de la direction inclinée à 60 degrés par rapport à la direction verticale sont toutes d'au moins 1,8.
PCT/JP2019/007777 2018-03-02 2019-02-28 Filtre optique, module de caméra et dispositif électronique WO2019168090A1 (fr)

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KR1020207024916A KR20200128009A (ko) 2018-03-02 2019-02-28 광학 필터, 카메라 모듈 및 전자 기기
CN201980016421.4A CN111801606B (zh) 2018-03-02 2019-02-28 光学滤波器、照相机模块及电子设备
JP2022204178A JP7405228B2 (ja) 2018-03-02 2022-12-21 光学フィルター用樹脂組成物、光学フィルター、カメラモジュールおよび電子機器

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019164269A (ja) * 2018-03-20 2019-09-26 Ａｇｃ株式会社 光学フィルタ、近赤外線吸収色素および撮像装置
JPWO2021049441A1 (fr) * 2019-09-11 2021-03-18
WO2021085372A1 (fr) * 2019-11-01 2021-05-06 Jsr株式会社 Composition de résine, composé (z), filtre optique et utilisation correspondante
JPWO2021095613A1 (fr) * 2019-11-15 2021-05-20
JP2021081520A (ja) * 2019-11-15 2021-05-27 Ａｇｃ株式会社 光学フィルタ、並びにこれを用いた光学装置及び指紋検出装置
CN113292807A (zh) * 2020-02-21 2021-08-24 Jsr株式会社 树脂组合物、化合物、基材、光学滤波器、固体摄像装置及光学传感器装置
WO2022024942A1 (fr) * 2020-07-29 2022-02-03 Ａｇｃ株式会社 Filtre optique
WO2022024941A1 (fr) * 2020-07-29 2022-02-03 Ａｇｃ株式会社 Filtre optique
WO2022075037A1 (fr) * 2020-10-09 2022-04-14 コニカミノルタ株式会社 Composition absorbant le proche infrarouge, film absorbant le proche infrarouge, filtre absorbant le proche infrarouge et capteur d'image pour éléments d'imagerie à semi-conducteur
JP7459709B2 (ja) 2020-07-29 2024-04-02 Ａｇｃ株式会社 光学フィルタ

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012169447A1 (fr) * 2011-06-06 2012-12-13 旭硝子株式会社 Filtre optique, élément d'imagerie à semi-conducteurs, lentilles de dispositif d'imagerie et dispositif d'imagerie
JP2013156460A (ja) * 2012-01-31 2013-08-15 Konica Minolta Inc 携帯情報端末用カバー部材
JP2014052431A (ja) * 2012-09-05 2014-03-20 Asahi Glass Co Ltd 近赤外線吸収フィルタおよび固体撮像装置
JP2016146619A (ja) * 2015-01-30 2016-08-12 Jsr株式会社 固体撮像装置及び光学フィルタ
WO2016171219A1 (fr) * 2015-04-23 2016-10-27 旭硝子株式会社 Filtre optique et dispositif d'imagerie

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5262549A (en) 1991-05-30 1993-11-16 Polaroid Corporation Benzpyrylium dyes, and processes for their preparation and use
JP3163813B2 (ja) 1992-12-28 2001-05-08 日本ゼオン株式会社 近赤外線吸収樹脂組成物、および成形品
JP5489669B2 (ja) 2008-11-28 2014-05-14 Ｊｓｒ株式会社 近赤外線カットフィルターおよび近赤外線カットフィルターを用いた装置
CN108761612B (zh) 2012-08-23 2021-04-06 Ａｇｃ株式会社 近红外线截止滤波器和固体摄像装置
JP6269657B2 (ja) 2013-04-10 2018-01-31 旭硝子株式会社 赤外線遮蔽フィルタ、固体撮像素子、および撮像・表示装置
CN105531608B (zh) 2013-08-20 2020-03-06 Jsr株式会社 滤光器、固体摄像装置以及照相机模块
JP6210180B2 (ja) * 2015-07-28 2017-10-11 Jsr株式会社 光学フィルター及び光学フィルターを具備する環境光センサー

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012169447A1 (fr) * 2011-06-06 2012-12-13 旭硝子株式会社 Filtre optique, élément d'imagerie à semi-conducteurs, lentilles de dispositif d'imagerie et dispositif d'imagerie
JP2013156460A (ja) * 2012-01-31 2013-08-15 Konica Minolta Inc 携帯情報端末用カバー部材
JP2014052431A (ja) * 2012-09-05 2014-03-20 Asahi Glass Co Ltd 近赤外線吸収フィルタおよび固体撮像装置
JP2016146619A (ja) * 2015-01-30 2016-08-12 Jsr株式会社 固体撮像装置及び光学フィルタ
WO2016171219A1 (fr) * 2015-04-23 2016-10-27 旭硝子株式会社 Filtre optique et dispositif d'imagerie

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019164269A (ja) * 2018-03-20 2019-09-26 Ａｇｃ株式会社 光学フィルタ、近赤外線吸収色素および撮像装置
JP7059729B2 (ja) 2018-03-20 2022-04-26 Ａｇｃ株式会社 光学フィルタ、近赤外線吸収色素および撮像装置
JPWO2021049441A1 (fr) * 2019-09-11 2021-03-18
JP7342958B2 (ja) 2019-09-11 2023-09-12 Ａｇｃ株式会社 光学フィルタおよび撮像装置
WO2021085372A1 (fr) * 2019-11-01 2021-05-06 Jsr株式会社 Composition de résine, composé (z), filtre optique et utilisation correspondante
CN114616291A (zh) * 2019-11-01 2022-06-10 Jsr株式会社 树脂组合物、化合物(z)、光学滤波器及光学滤波器的用途
JPWO2021095613A1 (fr) * 2019-11-15 2021-05-20
JP2021081520A (ja) * 2019-11-15 2021-05-27 Ａｇｃ株式会社 光学フィルタ、並びにこれを用いた光学装置及び指紋検出装置
CN114730028A (zh) * 2019-11-15 2022-07-08 Ａｇｃ株式会社 滤光片和使用了该滤光片的指纹检测装置
JP7392412B2 (ja) 2019-11-15 2023-12-06 Ａｇｃ株式会社 光学フィルタ、並びにこれを用いた光学装置及び指紋検出装置
CN113292807A (zh) * 2020-02-21 2021-08-24 Jsr株式会社 树脂组合物、化合物、基材、光学滤波器、固体摄像装置及光学传感器装置
WO2022024941A1 (fr) * 2020-07-29 2022-02-03 Ａｇｃ株式会社 Filtre optique
WO2022024942A1 (fr) * 2020-07-29 2022-02-03 Ａｇｃ株式会社 Filtre optique
JP7459709B2 (ja) 2020-07-29 2024-04-02 Ａｇｃ株式会社 光学フィルタ
WO2022075037A1 (fr) * 2020-10-09 2022-04-14 コニカミノルタ株式会社 Composition absorbant le proche infrarouge, film absorbant le proche infrarouge, filtre absorbant le proche infrarouge et capteur d'image pour éléments d'imagerie à semi-conducteur
CN116348555A (zh) * 2020-10-09 2023-06-27 柯尼卡美能达株式会社 近红外线吸收组合物、近红外线吸收膜、近红外线吸收滤光器和固体摄像元件用图像传感器

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