[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2019054394A1 - Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging device - Google Patents

Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging device Download PDF

Info

Publication number
WO2019054394A1
WO2019054394A1 PCT/JP2018/033735 JP2018033735W WO2019054394A1 WO 2019054394 A1 WO2019054394 A1 WO 2019054394A1 JP 2018033735 W JP2018033735 W JP 2018033735W WO 2019054394 A1 WO2019054394 A1 WO 2019054394A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
group
infrared
phosphonic acid
composition
Prior art date
Application number
PCT/JP2018/033735
Other languages
French (fr)
Japanese (ja)
Inventor
洋介 水谷
なつみ 板本
大福　幸司
福坂　潔
一成 中原
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2019542077A priority Critical patent/JP7103362B2/en
Publication of WO2019054394A1 publication Critical patent/WO2019054394A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Definitions

  • the present invention relates to a near infrared absorbing composition, a near infrared absorbing film using the same, and an image sensor for a solid-state imaging device, and more specifically, dispersion stability and near infrared cut of constituent materials in storage over a long period of time
  • the present invention relates to a near infrared absorbing composition having excellent stability, a near infrared absorbing film using the composition, and an image sensor for a solid-state imaging device including the near infrared absorbing film.
  • CCD Charge Coupled Device
  • CMOS Complementary Metal-Oxide Semiconductor
  • a near-infrared absorptive composition using a copper phosphonate complex is disclosed (see, for example, Patent Documents 1 to 3).
  • An object of the present invention is to provide an image sensor for a solid-state imaging device, which comprises a near-infrared absorptive film formed using the same and the near-infrared absorptive film.
  • the composition is a near infrared ray absorbing composition containing a copper phosphonate complex and two or more dispersants.
  • a near infrared absorptive composition having improved dispersion stability and near infrared cut stability during storage of copper complex particles over a long period of time, a near infrared absorptive film formed using the composition, and the near infrared absorptive film It has been found that an image sensor for a solid-state imaging device can be realized, and the present invention has been made.
  • It is a near-infrared absorptive composition containing a phosphonic acid copper complex and 2 or more types of dispersing agents, wherein at least one of the dispersing agents has a structure represented by the following general formula (1), and A near-infrared absorptive composition characterized by being a dispersant A having a molecular weight of 190 or less.
  • R 1 represents a hydrogen atom or a monovalent to tetravalent organic group.
  • R 2 represents an alkylene group having 2 to 4 carbon atoms.
  • R 3 represents a hydrogen atom, an alkyl group or an acyl group.
  • a is an integer of 0 to 10.
  • b is an integer of 1 to 4;
  • Functional groups hydroxy group, thiol group, carbonyl group, carboxy group, sulfonic acid group, cyano group, amino group, and pyridyl group.
  • the dispersant other than the dispersant A is a dispersant having no structure represented by the general formula (1).
  • Phosphonic acid group A Ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, 2-ethylhexylphosphonic acid, 2-chloroethylphosphonic acid, 3-bromopropylphosphonic acid, 3 Methoxybutylphosphonic acid, 1,1-dimethylpropylphosphonic acid, 1,1-dimethylethylphosphonic acid, 1-methylpropylphosphonic acid.
  • Phosphonic acid group B phenylphosphonic acid, 4-methoxyphenylphosphonic acid, (4-aminophenyl) phosphonic acid, (4-bromophenyl) phosphonic acid, 3-phosphonobenzoic acid, 4-phosphonobenzoic acid, and (4- Hydroxyphenyl) phosphonic acid.
  • the value of the molar ratio (phosphorus / copper) with respect to copper of the phosphorus which comprises the said phosphonic acid copper complex is 1.5 or less,
  • the said 1 to 6 characterized by the above-mentioned Near infrared absorbing composition.
  • a near-infrared-absorbing film characterized by using the near-infrared-absorbing composition according to any one of the items 1 to 7.
  • the near-infrared absorptive film according to claim 8, comprising a matrix resin having a polysiloxane.
  • An image sensor for a solid-state imaging device comprising the near-infrared absorptive film according to any one of items 8 to 10.
  • two or more dispersants are contained together with the phosphonic acid copper complex particles, and at least one of the dispersants is represented by the general formula (1).
  • a dispersant A having a structure and a molecular weight of 190 or less is applied.
  • the copper phosphonate copper complex has a specific structure with a low molecular weight in the formation step of the copper phosphonate copper complex when examining how stably it is possible to prepare a copper phosphonate copper complex that exhibits absorption characteristics in the near infrared wavelength region
  • dispersant A By mixing dispersant A from the initial state, it becomes easier to act on copper phosphonate, and furthermore, by introducing a site of interaction with copper in one or more other dispersants, copper phosphonate is introduced.
  • the stronger interaction between the complex and the plurality of dispersants enables formation of a copper phosphonate complex particle having an average particle diameter of several hundreds nm, without requiring a large shearing force at the time of particle dispersion. found.
  • dispersant at least one type of dispersant, by applying dispersant A having an oxyalkylene unit represented by the general formula (1) in the main chain and having a molecular weight limited to 190 or less
  • dispersant A having an oxyalkylene unit represented by the general formula (1) in the main chain and having a molecular weight limited to 190 or less In addition to the excellent action of the above, it also acts as a liquid dispersion medium effectively, and from this point as well, it greatly contributes to the stabilization of the copper phosphonate copper complex particles in the near infrared ray absorbing composition. I guess.
  • the near-infrared absorptive composition of the present invention is a near-infrared absorptive composition containing a copper phosphonate complex and two or more dispersants, and at least one of the dispersants has the above-mentioned general formula (1) It is characterized by being a dispersant A having a structure represented by and having a molecular weight of 190 or less. This feature is a technical feature common to the inventions according to the following embodiments.
  • At least one of the two or more kinds of the dispersants constituting the near-infrared-absorbent composition is the above from the viewpoint of being able to further exhibit the effects aimed by the present invention.
  • Storage stability over a longer period of time (dispersion stability and near-infrared cut stability of copper phosphonate copper complex particles) having a dispersant B having at least one functional group selected from the specific functional group of It is preferable at the point which can obtain the near-infrared absorptive composition which has these.
  • one type uses dispersant A having a structure represented by the above general formula (1) and having a molecular weight of 190 or less
  • the further excellent long-term can be achieved by the other dispersing agent used in combination being a dispersing agent not having the structure represented by the general formula (1), that is, by applying two or more kinds of dispersing agents having different structures. It is preferable at the point which can obtain the near-infrared absorptive composition which has storage stability (dispersion stability and near-infrared cut stability of copper phosphonate copper complex particle
  • the alkyl phosphonic acid of a specific structure as a phosphonic acid which comprises a phosphonic acid copper complex from the point which can express the outstanding near-infrared absorptivity which is the objective of this invention more.
  • the ratio of solid content to the total weight of the near-infrared ray absorbing composition within the range of 10 to 34 mass% results in the concentration of an appropriate solid (for example, copper phosphonate copper complex particles), and over a long period of time Even during the storage period, the particle aggregation is suppressed, which is preferable in that long-term storage stability (dispersion stability and near infrared cut stability of copper phosphonate copper complex particles) can be obtained.
  • the value of the molar ratio of phosphorus to copper (phosphorus / copper) is set to 1.5 or less to constitute the phosphonic acid copper complex in that a more excellent near-infrared absorptivity can be obtained.
  • the near-infrared absorptive composition of the present invention contains a copper phosphonate complex and two or more dispersants, and at least one of the dispersants has a structure represented by the general formula (1), and It is characterized by being a dispersant A having a molecular weight of 190 or less.
  • the copper phosphonic acid complex which is a typical component of the near-infrared absorptive composition of this invention, and the dispersing agent to apply are demonstrated.
  • the present invention is not limited to only the configuration exemplified here.
  • the near-infrared absorbing composition of the present invention is characterized by containing a copper phosphonate complex.
  • the near-infrared absorptive composition of this invention contains the phosphonic acid compound which has a structure represented by following General formula (2).
  • R 1 represents a branched, linear or cyclic alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an aryl group or an allyl group, and at least one hydrogen Even if the atom is substituted with a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxyl group, a hydroxyl group or a group having an aromatic ring, It may not be substituted.
  • Examples of phosphonic acid compounds having a structure represented by the general formula (2) include ethylphosphonic acid represented by phosphonic acid group A, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid and octylphosphonic acid Acid, 2-ethylhexylphosphonic acid, 2-chloroethylphosphonic acid, 3-bromopropylphosphonic acid, 3-methoxybutylphosphonic acid, 1,1-dimethylpropylphosphonic acid, 1,1-dimethylethylphosphonic acid, 1-methyl Propylphosphonic acid, phenylphosphonic acid represented by phosphonic acid group B, 4-methoxyphenylphosphonic acid, (4-aminophenyl) phosphonic acid, (4-bromophenyl) phosphonic acid, 3-phosphonobenzoic acid, 4- And phosphonobenzoic acid, (4-hydroxyphenyl) phosphonic acid, etc.
  • the phosphonic acid constituting the phosphonic acid copper complex is preferably at least one alkylphosphonic acid selected from the following phosphonic acid group.
  • the phosphonic acid copper complex according to the present invention has a structure represented by the following general formula (3).
  • R is an alkyl group, a phenyl group or a benzyl group.
  • the copper salt which can supply a bivalent copper ion is used.
  • the phosphonic acid constituting the phosphonic acid copper complex is preferably an alkyl phosphonic acid.
  • alkyl phosphonic acid ethyl phosphonic acid copper complex, propyl phosphonic acid copper complex, butyl phosphonic acid copper complex, pentyl phosphonic acid copper complex Hexylphosphonic acid copper complex, octylphosphonic acid copper complex, 2-ethylhexylphosphonic acid copper complex, 2-chloroethylphosphonic acid copper complex, 3-bromopropylphosphonic acid copper complex, 3-methoxybutylphosphonic acid copper complex, 1, 1-Dimethylpropylphosphonic acid copper complex, 1,1-dimethylethylphosphonic acid copper complex, 1-methylpropylphosphonic acid copper complex, phenylphosphonic acid copper complex, 4-methoxyphenylphosphonic acid copper complex, (4-aminophenyl) Phosphonate copper complex, (4-Bromophenyl) phosphonate copper complex, 3 Phosphon
  • the near-infrared absorptive composition of the present invention is characterized by containing two or more dispersants together with the copper phosphonate complex.
  • At least one dispersant is a dispersant A having a structure represented by the following general formula (1) and having a molecular weight of 190 or less.
  • the other dispersant to be used in combination with the dispersant A is not particularly limited, but one dispersant is preferably a dispersant B having at least one functional group selected from the following functional group group.
  • Functional groups hydroxy group, thiol group, carbonyl group, carboxy group, sulfonic acid group, cyano group, amino group, and pyridyl group.
  • dispersant A Even if two or more dispersants having different structures are used in combination as dispersant A, or the other one is a dispersion not having a structure represented by the general formula (1) defined by dispersant A An agent may be used in combination.
  • At least one of the two or more dispersants has a structure represented by the following general formula (1), and a dispersant A having a molecular weight of 190 or less It is characterized by being.
  • R 1 represents a hydrogen atom or a monovalent to tetravalent organic group.
  • R 2 represents an alkylene group having 2 to 4 carbon atoms.
  • R 3 represents a hydrogen atom, an alkyl group or an acyl group.
  • a is an integer of 0 to 10.
  • b is an integer of 1 to 4; a is preferably an integer of 1 to 10.
  • the structures represented in parentheses may be the same or different.
  • R 1 is a hydrogen atom or, as a monovalent to tetravalent organic group, an acyl group having 2 to 10 carbon atoms, a carbon number within a range that the molecular weight is 190 or less 1 to 10 linear, branched or cyclic alkyl group, aryl group having 6 to 10 carbon atoms or aralkyl group are mentioned, and at least one hydrogen atom bonded to a carbon atom constituting the alkyl group is a halogen It may be substituted by an atom, a hetero atom or an aromatic ring.
  • R 2 represents an alkylene group having 2 to 4 carbon atoms, and n represents 1 to 10.
  • the carbon number of the acyl group is preferably 2 to 10.
  • the carbon number of the alkyl group is preferably 1 to 15.
  • the carbon number of the aryl group or the aralkyl group is preferably 6 to 20.
  • the carbon number of the alkylene group represented by R 2 is preferably 2 to 3, more
  • the acyl group represented by R 1 also includes a divalent acid group derived from a dicarboxylic acid, and, for example, 2-ethylbutanoyl group, (meth) acryloyl group, propionyl group , Butyryl group, valeryl group, isovaleryl group, hexanoyl group, heptanedioyl group.
  • (meth) acryloyl group and 2-ethylhexanoyl group are preferable.
  • examples of the alkyl group represented by R 1 include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group and a nonyl group. Among these, methyl and lauryl are preferable. Furthermore, as the aryl group or aralkyl group represented by R 1 , a phenyl group or 4-nonylphenyl group is preferable. Furthermore, as the alkylene group represented by R 2 , an ethylene group, a propylene group, a butylene group and a tetramethylene group are preferable. By employing such a group, the solubility and dispersibility of the copper-containing phosphorus compound in the resin can be significantly improved.
  • PGMEA Propylene glycol monomethyl ether acetate (molecular weight: 132) 2) PGEEA: Propylene glycol monoethyl ether acetate (molecular weight: 146) 3) PGBEA: Propylene glycol monobutyl ether acetate (molecular weight: 174) 4) Ethylene glycol diacetate (molecular weight: 146) 5) Ethylene glycol diglycidyl ether (molecular weight: 174) 6) Ethylene glycol monomethyl ether acetate (molecular weight: 118) 7) Ethylene glycol monoethyl ether acetate (molecular weight: 132) 8) Ethylene glycol monobutyl ether acetate (molecular weight: 160) 9) Ethylene glycol dibutyl ether (molecular weight: 174) 10) Ethylene glycol monoacetate (molecular weight: 104) 11) Ethylene glycol monoisopropylene
  • At least one of the two or more dispersants has a structure represented by the general formula (1) described above, and a dispersant A having a molecular weight of 190 or less And at least one of the two or more dispersants is preferably a dispersant B having at least one functional group selected from the following functional group groups. It is.
  • the functional group possessed by the dispersant B is at least one selected from a hydroxy group, a thiol group, a carbonyl group, a carboxy group, a sulfonic acid group, a cyano group, an amino group, and a pyridyl group.
  • each dispersing agent can be mentioned as an example of the dispersing agent B which has the said functional group based on this invention.
  • Alkyl imidazoline 2) polyoxyethylene (2) lauryl ether 3) sorbitan monopalmitate 4) polyoxyethylene alkyl (C8) ether phosphate ester 5) styrene-maleic acid 6) polyvinyl pyrrolidone 7) polyoxyethylene styrene Fluorinated phenyl ether 8) polyoxyethylene tridecyl ether 9) 2-ethylhexyl carboxylic acid 10) trimethyl-1-hexanol 11) phenoxyethanol etc.
  • the dispersion liquid B a commercial item can also be used.
  • Kao's Emulgen series for example, 102 KG, 103, 105, 106, 108, 109, etc.
  • Reodore SP-P 10 Ameet series (102, 302), etc. , A208N)
  • DKS Discoat N-14 Pitzcor K-30, Neugen series (EA-157, TDS-100, etc.) and the like.
  • dispersants examples include, for example, dioxyethylene lauryl ether having a molecular weight exceeding 190, trioxyethylene lauryl ether, tetraoxyethylene lauryl ether, pentaoxyethylene lauryl ether, hexaoxyethylene lauryl Ether, heptaoxyethylene lauryl ether, octaoxyethylene lauryl ether, nonaoxyethylene lauryl ether, decaoxyethylene lauryl ether, undecaoxyethylene lauryl ether, dodecaoxyethylene lauryl ether, tridecaoxyethylene lauryl ether, tetradecaoxyethylene Ether compounds such as lauryl ether, diethylene glycol dimethacrylate (NK ester 2G, Shin-Nakamura Chemical Co., Ltd.) Molecular weight: 242), triethylene glycol dimethacrylate (molecular weight: 286), polyethylene glycol # 200
  • copper acetate is used as a copper salt for supplying copper, tetrahydrofuran (abbreviation: THF) as a solvent, and propylene glycol monomethyl ether acetate (abbreviation: PGMEA, molecular weight) as dispersant A according to the present invention Mix and dissolve: 132).
  • THF tetrahydrofuran
  • PGMEA propylene glycol monomethyl ether acetate
  • the insoluble copper salt for example, copper acetate
  • Dispersant B is added to the copper acetate solution and stirred to prepare Solution A.
  • THF is added to the alkylphosphonic acid and stirred to prepare a solution B.
  • the solution B is added while stirring the solution A, and the solution is stirred at room temperature for a fixed time.
  • Near infrared absorbing compositions can be prepared.
  • One feature of the present invention is to form a near-infrared-absorbing film using the near-infrared-absorbing composition of the present invention.
  • a matrix resin is added to the near-infrared absorbing composition containing two or more dispersants of the present invention and a copper phosphonate complex, and fine particles of copper phosphonate are dispersed in the matrix resin. It is formed by putting it in the state of doing.
  • at least one near-infrared dye having an absorption maximum wavelength in a wavelength range of 650 to 800 nm can be added. Examples of near infrared dyes include cyanine dyes, squarylium dyes, croconium dyes, phlocyanine dyes, naphthalocyanine dyes and the like.
  • the coating solution for forming a near infrared ray absorbing film having the above configuration is applied onto a substrate by a spin coating method or a coating method using a dispenser to form a near infrared ray absorbing film. Thereafter, the coating film is subjected to a predetermined heat treatment to cure the coating film, thereby forming a near infrared absorbing film.
  • the matrix resin used to form the near-infrared absorbing film is a resin having light transparency to visible light and near-infrared light and capable of dispersing fine particles of copper phosphonate complex. Copper phosphonate complexes are relatively less polar substances and disperse well in hydrophobic materials. For this reason, as a matrix resin for near-infrared absorptive film formation, resin which has an acryl group, an epoxy group, or a phenyl group can be used. Among them, it is particularly preferable to use a resin having a phenyl group as a matrix resin of the near infrared ray absorbing film. In this case, the matrix resin of the near infrared absorptive film exhibits high heat resistance.
  • polysiloxane silicone resin is difficult to be decomposed by heat, has high light transmittance to visible light and near infrared light, and has high heat resistance, and thus has a characteristic suitable as a material for an image sensor for a solid-state imaging device. .
  • polysiloxane as a matrix resin of a near-infrared absorptive film.
  • Specific examples of the polysiloxane that can be used as a matrix resin of a near infrared absorbing film include KR-255, KR-300, KR-2621-1, KR-211, KR-311, KR-216, KR-212, And KR-251. All of these are silicone resins manufactured by Shin-Etsu Chemical Co., Ltd.
  • silicone resin for example, SS-6203, SS-6309, VS-9301, and VS-9506 can be mentioned, and all of them are silicone resins manufactured by San Yuleck.
  • a matrix resin used for formation of the near-infrared absorptive film of this invention it is a preferable aspect to contain the matrix resin which has an epoxy group from a low gas permeability viewpoint.
  • the matrix resin having an epoxy group constituting the near-infrared absorptive film exhibits high moisture resistance, and thus has a characteristic suitable as a material for an image sensor for a solid-state imaging device.
  • the resin having an epoxy group that can be used as a matrix resin of a near infrared absorbing film include KJC-X5 (manufactured by Shin-Etsu Chemical Co., Ltd.), NLD-L-672 (manufactured by San Yurec Co., Ltd.), LE-1421 (San Yulek) Company) and EpiFine series (made by KISCO company) can be mentioned.
  • resin which has both the polysiloxane mentioned above and an epoxy group is also preferable to use as matrix resin of a near-infrared absorptive film.
  • a matrix resin having both of these polysiloxanes and an epoxy group exhibits high heat resistance and moisture resistance, and thus has properties suitable as a material for an image sensor for a solid-state imaging device.
  • resin having both polysiloxane and epoxy group that can be used as a matrix resin of a near infrared absorbing film
  • resin having both polysiloxane and epoxy group that can be used as a matrix resin of a near infrared absorbing film
  • EpiFine series manufactured by KISCO
  • ILLUMIKA series manufactured by Kaneka
  • additives Various additives known in the prior art can be applied to the near-infrared absorptive film of the present invention as long as the object effects of the present invention are not impaired.
  • sensitizers, crosslinking agents, curing accelerators, fillers, Thermal curing accelerators, thermal polymerization inhibitors, plasticizers, etc. and adhesion promoters to the substrate surface and other auxiliary agents (eg, conductive particles, fillers, antifoaming agents, flame retardants, leveling) Agents, peeling accelerators, antioxidants, perfumes, surface tension regulators, chain transfer agents, etc.) may be used in combination.
  • paragraph numbers (0183) to (0260) of JP 2012-003225 A paragraph numbers (0101) to (0102) of JP 2008-250074 A
  • JP 2008-250074 A JP 2008-250074 A.
  • the description of Paragraph Nos. (0103) to (0104) in Paragraph No. and Paragraph Nos. (0107) to (0109) in JP-A 2008-250074 can be referred to.
  • the near-infrared absorbing composition of the present invention can be in the form of a liquid, so it is easy to form a near-infrared-absorbing film, for example, a near-infrared cut filter, by a simple process of forming a film by spin coating, for example. Can be manufactured.
  • the near-infrared absorptive film of the present invention is, for example, a visibility correction member for CCD, CMOS, or other light receiving element, a member for photometry, a member for heat ray absorption, a composite optical filter, a lens member (for example, glasses, Sunglasses, goggles, optical systems, optical waveguide systems, etc., fiber members (eg, optical fibers), noise cutting members, display covers or display filters such as plasma display front plates, projector front plates, light source heat ray cutting members, color tone
  • the correction member, the illumination luminance adjustment member, the optical element (for example, a light amplification element, a wavelength conversion element, etc.), a Faraday element, an optical communication function device such as an isolator, an optical disc element, etc. are suitable.
  • the application of the near-infrared absorbing composition of the present invention is particularly for a near-infrared cut filter disposed on the light receiving side of a solid-state imaging element substrate (for example, for a near-infrared cut filter for wafer level lens)
  • the present invention is characterized in that it is applied to an image sensor for a solid-state imaging device as a near infrared cut filter or the like on the back surface side (the opposite side to the light receiving side).
  • the near-infrared absorptive film (near-infrared cut filter) of this invention is arrange
  • FIG. 1 is a schematic cross-sectional view showing a configuration of a camera module provided with a solid-state imaging device provided with an infrared cut filter that is a near infrared absorptive film of the present invention.
  • the number described in the parenthesis at the end of a component represents the code
  • the camera module (1) shown in FIG. 1 is connected to a circuit board (12) which is a mounting board via a solder ball (60) which is a connecting member.
  • the camera module (1) comprises a solid-state imaging device substrate (10) including an imaging device portion on a first main surface of a silicone substrate, and a first major surface side of the solid-state imaging device substrate (10) And a near infrared cut filter (9, a near infrared absorptive film) provided on the flattening layer (8), and a near infrared cut filter (9).
  • a glass substrate (3; light transmitting substrate) disposed above, a lens holder (5) disposed above the glass substrate (3) and having an imaging lens (4) in an internal space; And a light shielding and electromagnetic shield (6) disposed to surround the glass substrate (3).
  • Each member is bonded by an adhesive (2, 7).
  • the present invention is a method of manufacturing a camera module having a solid-state imaging device substrate and an infrared cut filter disposed on the light-receiving side of the solid-state imaging device substrate, wherein the light-receiving side of the solid-state imaging device substrate
  • a near infrared absorptive film can be formed by spin coating an infrared absorptive liquid composition.
  • a near infrared absorptive film is formed by spin coating the near infrared absorptive composition of the present invention on the planarizing layer (8) to cut the near infrared radiation. Form a filter (9).
  • the incident light (L) from the outside passes through the imaging lens (4), the glass substrate (3), the near infrared cut filter (9), and the flattening layer (8) sequentially, and then solid It reaches the imaging element portion of the imaging element substrate (10).
  • the camera module (1) is connected to the circuit board (12) via the solder balls (11, connection material) on the second principal surface side of the solid-state imaging element substrate (10).
  • Example 1 Preparation of Near-Infrared Absorbent Composition >> (Preparation of Near-Infrared Absorbent Composition 1) A near infrared absorbing composition 1 was prepared according to the following method.
  • dispersant A1 a copper acetate solution containing dispersant A1
  • a polycarboxylic acid type polymer dispersant having a carboxy group as a functional group as a dispersant B (60 wt% of the copper acetate solution prepared above (Product name: Homogen L 18 by Kao Corporation, hereinafter, “Dispersant”) A) A was obtained by adding 1.0 g of the compound B1) and stirring. On the other hand, 6.0 g of THF was added to 0.63 g of propyl phosphonic acid as the alkyl phosphonic acid and stirred to prepare a solution B.
  • Dispersant C1 Phosphate ether dispersant, Plysurf A 208 F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkyl (C8) ether phosphate, compound having a structure represented by the general formula (1))
  • Phosphate ether dispersant, Plysurf A 208 F manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkyl (C8) ether phosphate, compound having a structure represented by the general formula (1)
  • Preparation of Near Infrared Absorbent Composition 3 A near infrared absorbing composition 3 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that octylphosphonic acid was used as the alkylphosphonic acid in place of propylphosphonic acid.
  • a near infrared absorptive composition 4 was prepared in the same manner as in the preparation of the near infrared absorptive composition 1 except that hexylphosphonic acid was used as the alkylphosphonic acid in place of propylphosphonic acid.
  • a near infrared absorbing composition 5 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that ethylphosphonic acid was used as the alkylphosphonic acid in place of propylphosphonic acid.
  • the near infrared rays of the comparative example are prepared similarly except that the same amount of toluene (molecular weight: 92) is used instead of the dispersant A1 (PGMEA) which is the dispersant A in the preparation of the near infrared radiation absorbing composition 1 described above.
  • Absorbent composition 7 was prepared.
  • a near infrared absorbing composition 11 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the following dispersing agent A2 was used instead of the dispersing agent A (PGMEA) as the dispersing agent A. .
  • Dispersant A2 Propylene glycol monoethyl ether acetate (molecular weight: 146) (Preparation of Near-Infrared Absorbent Composition 12) A near infrared absorptive composition 12 was prepared in the same manner except that the following dispersant A3 was used instead of the dispersant A1 (PGMEA) which is the dispersant A in the preparation of the near infrared absorptive composition 1 described above. .
  • PGMEA dispersant A1
  • Dispersant A3 Propylene glycol monobutyl ether acetate (molecular weight: 174) (Preparation of Near Infrared Absorbent Composition 13)
  • near-infrared ray absorption is carried out in the same manner, except that the following dispersant B2 is used in place of the dispersant B1 (polycarboxylic acid type polymer dispersant) as the dispersant B.
  • Sex composition 13 was prepared.
  • Dispersant B2 Neohytenol L-30 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene sulfosuccinic acid, functional group: sulfone group)
  • Preparation of Near-Infrared Absorbent Composition 14 In the preparation of the above-mentioned near-infrared ray absorbing composition 1, near-infrared ray absorption is carried out in the same manner, except that the following dispersant B3 is used in place of the dispersant B1 (polycarboxylic acid type polymer dispersant) as the dispersant B. Sex composition 14 was prepared.
  • Dispersant B3 Cathogen TML (Daiichi Kogyo Seiyaku Co., Ltd., lauryltrimethylammonium clothide, functional group: amino group) (Preparation of Near Infrared Absorbent Composition 15) 3.29 g of copper acetate monohydrate was added to a solution of 10.0 g of 2-ethylhexyl-2-ethylhexyl phosphonate in 15 g of toluene, and acetic acid was distilled off while the solution was heated to reflux.
  • a near infrared absorptive composition 15 was prepared in which the copper complex of 2-ethylhexyl-2-ethylhexyl phosphonate (represented as * 1 in Table I) is 40% by mass in terms of solid content ratio.
  • a near infrared absorbing composition 16 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1 except that the following dispersing agent A4 was used in place of the dispersing agent A (PGMEA) as the dispersing agent A. .
  • Dispersant A4 1,3-butylene glycol dimethacrylate (molecular weight: 226) (Preparation of Near Infrared Absorbent Composition 17)
  • a near infrared absorbing composition 17 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that 0.63 g of propylphosphonic acid was changed to 0.87 g of phenylphosphonic acid.
  • a near infrared absorbing composition 18 was prepared in the same manner as in the preparation of the near infrared absorbing composition 2 except that 0.63 g of propylphosphonic acid was changed to 0.87 g of phenylphosphonic acid.
  • Table 1 shows the basic composition of the above-prepared near infrared ray absorbing compositions 1 to 18.
  • Dispersant A1 Propylene glycol monomethyl ether acetate (PGMEA, molecular weight: 132)
  • Dispersant A2 Propylene glycol monoethyl ether acetate (molecular weight: 146)
  • Dispersant A3 Propylene glycol monobutyl ether acetate (molecular weight: 174)
  • Dispersant A4 1,3-butylene glycol dimethacrylate (molecular weight: 226)
  • Dispersant B2 Neohytenol L-30 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene sulfosuccinic acid, functional group: sul
  • Sample 1 was prepared by diluting the solvent component of the near infrared absorptive composition such that the particle concentration of the alkylphosphonic acid copper complex which is the particle was 1.0% by mass for the near infrared absorptive composition.
  • the average particle diameter of the sample 1 was measured by a dynamic light scattering method using ELSZ-1000 manufactured by Otsuka Electronics Co., Ltd. as a measurement device.
  • the average particle diameter immediately after preparation measured by the above method was ranked according to the following criteria.
  • Average particle size is in the range of 10 to 300 nm ⁇ : Average particle size is in the range of 301 to 500 nm ⁇ : Average particle size is in the range of 501 to 700 nm ⁇ : Average particle size Is at least 701 nm (measurement of average particle size after storage)
  • a stock solution of a near infrared absorbing composition is housed in a glass container, the container is sealed in a state of being filled with nitrogen gas, and this glass container is stored in the dark at 5 ° C. for 3 days.
  • Sample 2 after storage processing was prepared by diluting with the solvent component of the near-infrared absorptive composition such that the particle concentration of the alkylphosphonic acid copper complex which is the particles was 1.0% by mass.
  • the average particle diameter was measured by the method similar to the above about sample 2, and the same ranking was performed.
  • Sample 1 was prepared by diluting the solvent component of the near infrared absorptive composition such that the particle concentration of the alkylphosphonic acid copper complex which is the particle was 1.0% by mass for the near infrared absorptive composition.
  • the spectral transmittance of the sample 1 in the wavelength range of 380 to 1200 nm was measured using a spectrophotometer V-570 manufactured by JASCO Corporation as a measurement apparatus.
  • the average spectral transmittance in a wavelength range of 750 to 1100 nm was 1.0%
  • the maximum transmittance T max1 in a visible light region was measured.
  • the maximum transmittance T max1 in the visible light region of the near-infrared absorbing composition immediately after preparation measured by the above method was ranked according to the following criteria.
  • a stock solution of a near infrared absorbing composition is housed in a glass container, the container is sealed in a state filled with nitrogen gas, and the glass container is stored in the dark at 5 ° C.
  • the spectral transmittance of the sample 2 in the wavelength range of 380 to 1200 nm is measured by the same method as above, and the average spectral transmittance in the wavelength range of 750 to 1100 nm is 1.0% after storage.
  • the maximum transmittance T max2 in the visible light region (400 to 750 nm) was measured.
  • the decrease width ⁇ T (T max1 -T max2 ) of the visible light transmittance of the maximum transmittance T max2 of the sample 2 after storage with respect to the maximum transmittance T max1 of the sample 1 immediately after the preparation measured above is determined. According to the criteria, the visible light transmittance after storage was ranked.
  • the reduction width ⁇ T of visible light transmittance is less than 1.0%
  • the reduction width ⁇ T of visible light transmittance is 1.0% or more and less than 3.0%
  • visible light transmittance The reduction width ⁇ T of is 3.0% or more and less than 5.0%.
  • ⁇ The reduction width ⁇ T of the visible light transmittance is less than 5.0%.
  • the near-infrared absorbing composition of the present invention is smaller than the comparative example in average particles of alkylphosphonic acid copper complex particles immediately after preparation and after being stored. It can be seen that the deterioration rate of the average particle size is low and the storage stability is excellent. Furthermore, the near-infrared absorbing composition of the present invention is superior to the comparative example in the transmittance in the visible light region with respect to the transmittance in the near-infrared region, and the effect on the visible light transmittance is small. It can be seen that it has the ability to cut ambient light. Furthermore, it can be seen that the characteristics do not change even if storage processing is performed.
  • Example 2 Preparation of near-infrared absorbing film >> A polysiloxane silicone resin (KR-255, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to each of the near infrared absorbing compositions prepared in Example 1 and stirred to prepare a coating solution for forming a near infrared absorbing film. . The prepared coating solution was applied onto a substrate by spin coating to form a near infrared absorptive film.
  • KR-255 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 3 Preparation of near-infrared absorbing film >> A resin (KJC-X5, manufactured by Shin-Etsu Chemical Co., Ltd.) having an epoxy group is added to each of the near infrared absorbing compositions prepared in Example 1 and stirred to prepare a coating solution for forming a near infrared absorbing film. did. The prepared coating solution was applied onto a substrate by spin coating to form a near infrared absorptive film.
  • KJC-X5 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the near-infrared absorptive composition of the present invention is excellent in the dispersion stability and near-infrared cut stability of constituent materials in storage over a long period of time, and the near-infrared absorptive film produced by the near-infrared absorptive composition is a video
  • the present invention can be suitably used as an image sensor for a solid-state imaging device applied to a camera, a digital still camera, a mobile phone with a camera function, and the like.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Optical Filters (AREA)
  • Solid State Image Pick-Up Elements (AREA)

Abstract

The purpose of the present invention is to provide: a near-infrared absorbing composition having excellent dispersion stability of constituent materials and near-infrared cutting stability in long-term storage; a near-infrared absorbing film formed by using the composition; and an image sensor which is for a solid-state imaging device and is equipped with the near-infrared-absorbing film. A near-infrared absorbing composition according to the present invention is characterized by containing a copper phosphonate complex and two or more dispersants, wherein at least one of the dispersants is a dispersant A which has a structure represented by general formula (1) and has a molecular weight of 190 or less.

Description

近赤外線吸収性組成物、近赤外線吸収性膜及び固体撮像素子用イメージセンサーNear infrared absorbing composition, near infrared absorbing film, and image sensor for solid-state imaging device
　本発明は、近赤外線吸収性組成物と、これを用いた近赤外線吸収性膜及び固体撮像素子用イメージセンサーに関し、より詳しくは、長期間にわたる保存における、構成材料の分散安定性及び近赤外線カット安定性に優れた近赤外線吸収性組成物と、これを用いた近赤外線吸収性膜と、当該近赤外線吸収性膜を具備する固体撮像素子用イメージセンサーに関する。 The present invention relates to a near infrared absorbing composition, a near infrared absorbing film using the same, and an image sensor for a solid-state imaging device, and more specifically, dispersion stability and near infrared cut of constituent materials in storage over a long period of time The present invention relates to a near infrared absorbing composition having excellent stability, a near infrared absorbing film using the composition, and an image sensor for a solid-state imaging device including the near infrared absorbing film.
　近年、ビデオカメラ、デジタルスチルカメラ、カメラ機能付き携帯電話などにはカラー画像の固体撮像素子としてＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）やＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ－ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）イメージセンサーが用いられているが、これら固体撮像素子はその受光部において近赤外線波長領域に感度を有するシリコンフォトダイオードを使用しているため、視感度補正を行うことが必要となり、そのため、近赤外線カットフィルターを用いることが多い。 In recent years, CCD (Charge Coupled Device) and CMOS (Complementary Metal-Oxide Semiconductor) image sensors have been used as solid-state imaging devices for color images in video cameras, digital still cameras, mobile phones with cameras, etc. Since the imaging device uses a silicon photodiode having sensitivity in the near infrared wavelength region in its light receiving portion, it is necessary to perform visibility correction, and therefore, a near infrared cut filter is often used.
　このような近赤外線カットフィルターを形成するための材料の一例として、ホスホン酸銅錯体を用いた近赤外線吸収性組成物が開示されている（例えば、特許文献１～３参照。）。 As an example of a material for forming such a near-infrared cut filter, a near-infrared absorptive composition using a copper phosphonate complex is disclosed (see, for example, Patent Documents 1 to 3).
　上記特許文献において、ホスホン酸銅錯体の分散媒体としては、特許文献１では１種の溶媒を適用すること、特許文献２では特定の可溶化剤を１種適用すること、特許文献３では特定の溶媒を１種適用することにより、品質の向上、例えば、保存安定性の向上を図っているが、いずれの特許文献でも、近赤外線吸収性組成物において、ホスホン酸銅塩に対し、バインダーである樹脂成分を添加した後での安定性を問題としているが、バインダー成分を含まない状態での近赤外線吸収性組成物の安定性に関しての言及はなく、本発明者らが検討を行った結果、バインダー樹脂を添加する前の段階での近赤外線吸収性組成物の分散安定性が、最終品質に対し大きく影響を与えることが判明し、早急な改良が必要とされている。 In the above patent documents, as a dispersion medium of the copper phosphonate copper complex, in patent document 1, one solvent is applied, in patent document 2, one specific solubilizer is applied, and in patent document 3, a specific solvent is specified. Although the improvement of quality, for example, the improvement of storage stability is aimed at by applying one kind of solvent, in any patent documents, it is a binder to phosphonic acid copper salt in a near-infrared absorptive composition Although the stability after adding the resin component is a problem, there is no mention of the stability of the near infrared absorbing composition in the state without the binder component, and as a result of investigation by the present inventors, It has been found that the dispersion stability of the near infrared absorbing composition at the stage before adding the binder resin greatly affects the final quality, and urgent improvement is required.
特許第４６８４３９３号公報Patent No. 4684393 特許第４９２６６９９号公報Patent No. 4926699 gazette 特許第５８９０８０５号公報Patent No. 5890805 gazette
　本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、長期間にわたる保存における、構成材料の分散安定性及び近赤外線カット安定性に優れた近赤外線吸収性組成物と、これを用いて形成した近赤外線吸収性膜と、当該近赤外線吸収性膜を具備する固体撮像素子用イメージセンサーを提供することである。 The present invention has been made in view of the above problems and circumstances, and the problem to be solved is a near infrared ray absorbing composition excellent in dispersion stability and near infrared ray cut stability of constituent materials in storage over a long period of time An object of the present invention is to provide an image sensor for a solid-state imaging device, which comprises a near-infrared absorptive film formed using the same and the near-infrared absorptive film.
　本発明者は、上記課題を解決すべく上記問題の原因等について検討した結果、ホスホン酸銅錯体と、２種以上の分散剤を含有する近赤外線吸収性組成物であって、当該分散剤の少なくとも１種が、オキシアルキレン単位を有し、かつ分子量が１９０以下の低分子の分散剤Ａであることを特徴とする近赤外線吸収性組成物により、近赤外線吸収性組成物を構成するホスホン酸銅錯体粒子の長期間にわたる保存における分散安定性及び近赤外カット安定性が向上した近赤外線吸収性組成物と、これを用いて形成した近赤外線吸収性膜と、当該近赤外線吸収性膜を具備する固体撮像素子用イメージセンサーを実現することができることを見いだし、本発明に至った。 As a result of examining the cause of the above problems and the like in order to solve the above problems, the present inventor has found that the composition is a near infrared ray absorbing composition containing a copper phosphonate complex and two or more dispersants. A phosphonic acid constituting a near infrared ray absorbing composition according to a near infrared ray absorbing composition characterized in that at least one type is a low molecular dispersant A having an oxyalkylene unit and having a molecular weight of 190 or less. A near infrared absorptive composition having improved dispersion stability and near infrared cut stability during storage of copper complex particles over a long period of time, a near infrared absorptive film formed using the composition, and the near infrared absorptive film It has been found that an image sensor for a solid-state imaging device can be realized, and the present invention has been made.
　すなわち、本発明に係る上記課題は、以下の手段により解決される。 That is, the above-mentioned subject concerning the present invention is solved by the following means.
　１．ホスホン酸銅錯体と、２種以上の分散剤を含有する近赤外線吸収性組成物であって、当該分散剤の少なくとも１種が、下記一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａであることを特徴とする近赤外線吸収性組成物。 1. It is a near-infrared absorptive composition containing a phosphonic acid copper complex and 2 or more types of dispersing agents, wherein at least one of the dispersing agents has a structure represented by the following general formula (1), and A near-infrared absorptive composition characterized by being a dispersant A having a molecular weight of 190 or less.
Figure JPOXMLDOC01-appb-C000002
 〔式中、Ｒ１は水素原子又は１～４価の有機基を表す。Ｒ２は炭素数２～４のアルキレン基を表す。Ｒ３は、水素原子、アルキル基又はアシル基を表す。ａは０～１０の整数である。ｂは１～４の整数である。〕
　２．前記２種以上の分散剤のうちの少なくとも１種が、下記官能基群から選ばれる少なくとも一つの官能基を有する分散剤Ｂであることを特徴とする第１項に記載の近赤外線吸収性組成物。
Figure JPOXMLDOC01-appb-C000002
 [Wherein, R 1 represents a hydrogen atom or a monovalent to tetravalent organic group. R 2 represents an alkylene group having 2 to 4 carbon atoms. R 3 represents a hydrogen atom, an alkyl group or an acyl group. a is an integer of 0 to 10. b is an integer of 1 to 4; ]
2. The near-infrared-absorbing composition according to claim 1, wherein at least one of the two or more dispersants is a dispersant B having at least one functional group selected from the following functional group group: object.
　官能基群：ヒドロキシ基、チオール基、カルボニル基、カルボキシ基、スルホン酸基、シアノ基、アミノ基、及びピリジル基。 Functional groups: hydroxy group, thiol group, carbonyl group, carboxy group, sulfonic acid group, cyano group, amino group, and pyridyl group.
　３．前記２種以上の分散剤のうち、前記分散剤Ａを除く分散剤が、前記一般式（１）で表される構造を有していない分散剤であることを特徴とする第１項又は第２項に記載の近赤外線吸収性組成物。 3. Among the two or more dispersants, the dispersant other than the dispersant A is a dispersant having no structure represented by the general formula (1). The near-infrared absorptive composition of 2 items.
　４．前記ホスホン酸銅錯体を構成するホスホン酸が、下記ホスホン酸群Ａから選ばれる少なくとも１種のホスホン酸であることを特徴とする第１項から第３項までのいずれか一項に記載の近赤外線吸収性組成物。 4. 4. The phosphonic acid according to any one of items 1 to 3, wherein the phosphonic acid constituting the phosphonic acid copper complex is at least one phosphonic acid selected from the following phosphonic acid group A: Infrared absorbing composition.
　ホスホン酸群Ａ：エチルホスホン酸、プロピルホスホン酸、ブチルホスホン酸、ペンチルホスホン酸、ヘキシルホスホン酸、オクチルホスホン酸、２－エチルヘキシルホスホン酸、２－クロロエチルホスホン酸、３－ブロモプロピルホスホン酸、３－メトキシブチルホスホン酸、１，１－ジメチルプロピルホスホン酸、１，１－ジメチルエチルホスホン酸、１－メチルプロピルホスホン酸。 Phosphonic acid group A: Ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, 2-ethylhexylphosphonic acid, 2-chloroethylphosphonic acid, 3-bromopropylphosphonic acid, 3 Methoxybutylphosphonic acid, 1,1-dimethylpropylphosphonic acid, 1,1-dimethylethylphosphonic acid, 1-methylpropylphosphonic acid.
　５．前記ホスホン酸銅錯体を構成するホスホン酸が、下記ホスホン酸群Ｂから選ばれる少なくとも１種のホスホン酸であることを特徴とする第１項から第３項までのいずれか一項に記載の近赤外線吸収性組成物。 5. 4. The phosphonic acid according to any one of the items 1 to 3, wherein the phosphonic acid constituting the phosphonic acid copper complex is at least one phosphonic acid selected from the following phosphonic acid group B: Infrared absorbing composition.
　ホスホン酸群Ｂ：フェニルホスホン酸、４－メトキシフェニルホスホン酸、（４－アミノフェニル）ホスホン酸、（４－ブロモフェニル）ホスホン酸、３－ホスホノ安息香酸、４－ホスホノ安息香酸、及び（４－ヒドロキシフェニル）ホスホン酸。 Phosphonic acid group B: phenylphosphonic acid, 4-methoxyphenylphosphonic acid, (4-aminophenyl) phosphonic acid, (4-bromophenyl) phosphonic acid, 3-phosphonobenzoic acid, 4-phosphonobenzoic acid, and (4- Hydroxyphenyl) phosphonic acid.
　６．近赤外線吸収性組成物全質量に対する固形分の比率が、１０～３４質量％の範囲内であることを特徴とする第１項から第５項までのいずれか一項に記載の近赤外線吸収性組成物。 6. 6. The near-infrared absorptivity according to any one of the items 1 to 5, wherein the ratio of the solid content to the total mass of the near-infrared absorptive composition is in the range of 10 to 34% by mass. Composition.
　７．前記ホスホン酸銅錯体を構成するリンの銅に対するモル比（リン／銅）の値が、１．５以下であることを特徴とする第１項から第６項までのいずれか一項に記載の近赤外線吸収性組成物。 7. The value of the molar ratio (phosphorus / copper) with respect to copper of the phosphorus which comprises the said phosphonic acid copper complex is 1.5 or less, The said 1 to 6 characterized by the above-mentioned Near infrared absorbing composition.
　８．少なくとも第１項から第７項までのいずれか一項に記載の近赤外線吸収性組成物を用いたことを特徴とする近赤外線吸収性膜。 8. What is claimed is: 1. A near-infrared-absorbing film characterized by using the near-infrared-absorbing composition according to any one of the items 1 to 7.
　９．ポリシロキサンを有するマトリックス樹脂を含有することを特徴とする第８項に記載の近赤外線吸収性膜。 9. 9. The near-infrared absorptive film according to claim 8, comprising a matrix resin having a polysiloxane.
　１０．エポキシ基を有するマトリックス樹脂を含有することを特徴とする第９項に記載の近赤外線吸収性膜。 10. 10. The near-infrared absorptive film according to claim 9, which contains a matrix resin having an epoxy group.
　１１．第８項から第１０項までのいずれか一項に記載の近赤外線吸収性膜を具備していることを特徴とする固体撮像素子用イメージセンサー。 11. An image sensor for a solid-state imaging device, comprising the near-infrared absorptive film according to any one of items 8 to 10.
　本発明の上記手段により、長期間にわたる保存における、構成材料の分散安定性及び近赤外線カット安定性に優れた近赤外線吸収性組成物と、これを用いて形成した近赤外線吸収性膜と、当該近赤外線吸収性膜を具備する固体撮像素子用イメージセンサーを提供することができる。 A near-infrared absorptive composition excellent in dispersion stability and near-infrared cut stability of constituent materials during storage over a long period of time by the above-mentioned means of the present invention, a near-infrared absorptive film formed using the composition, It is possible to provide an image sensor for a solid-state imaging device having a near infrared absorbing film.
　本発明の効果の発現機構・作用機構については明確になっていないが、以下のように推察している。 Although the mechanism for expressing the effects of the present invention and the mechanism of action have not been clarified, they are presumed as follows.
　本発明の近赤外線吸収性組成物においては、ホスホン酸銅錯体粒子とともに、２種以上の分散剤を含有する構成とし、当該分散剤の少なくとも１種を、前記一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａを適用することを特徴とする。 In the near-infrared absorptive composition of the present invention, two or more dispersants are contained together with the phosphonic acid copper complex particles, and at least one of the dispersants is represented by the general formula (1). A dispersant A having a structure and a molecular weight of 190 or less is applied.
　この様に、ホスホン酸銅錯体粒子を含む近赤外線吸収性組成物において、２種以上の分散剤を適用することにより、それぞれ単独の分散剤では予想できなかったシナジー効果が発現し、樹脂成分を添加する前の状態でのホスホン酸銅錯体粒子の微粒子化や、長期保存後の粒径安定性や近赤外線カット安定性に優れた効果を発現することが判明した。 Thus, by applying two or more dispersants to the near-infrared absorptive composition containing copper phosphonate copper complex particles, synergy effects which could not have been predicted with each single dispersant were exhibited, and the resin component It turned out that the fine particle of the phosphonate copper complex particle in the state before adding, and the effect excellent in the particle-diameter stability after a long-term storage and near-infrared cut stability are expressed.
　特に、近赤外線波長領域に吸収特性を発現するホスホン酸銅錯体を、いかに安定して調製することができるかを検討する際に、ホスホン酸銅錯体の形成段階で、低分子量で特定構造を有する分散剤Ａを初期状態から混合しておくことにより、よりホスホン酸銅に作用しやすくなり、更に、もう１種以上の分散剤に、銅との相互作用部位を導入することにより、ホスホン酸銅錯体と複数の分散剤とがより強く相互作用することで、粒子分散時に大きな剪断力を必要とすることなく、平均粒径が数１００ｎｍレベルのホスホン酸銅錯体粒子を形成することができるとこと判明した。 In particular, it has a specific structure with a low molecular weight in the formation step of the copper phosphonate copper complex when examining how stably it is possible to prepare a copper phosphonate copper complex that exhibits absorption characteristics in the near infrared wavelength region By mixing dispersant A from the initial state, it becomes easier to act on copper phosphonate, and furthermore, by introducing a site of interaction with copper in one or more other dispersants, copper phosphonate is introduced. The stronger interaction between the complex and the plurality of dispersants enables formation of a copper phosphonate complex particle having an average particle diameter of several hundreds nm, without requiring a large shearing force at the time of particle dispersion. found.
　加えて、分散剤の少なくとも１種として、一般式（１）で表されるオキシアルキレン単位を主鎖に有し、かつ分子量を１９０以下に限定した分散剤Ａを適用することにより、分散剤としての優れた作用の他に、液状で分散媒としても効果的に作用するため、この点からも、近赤外線吸収性組成物中におけるホスホン酸銅錯体粒子の安定化に大きく貢献しているものと推測している。 In addition, as a dispersant, at least one type of dispersant, by applying dispersant A having an oxyalkylene unit represented by the general formula (1) in the main chain and having a molecular weight limited to 190 or less In addition to the excellent action of the above, it also acts as a liquid dispersion medium effectively, and from this point as well, it greatly contributes to the stabilization of the copper phosphonate copper complex particles in the near infrared ray absorbing composition. I guess.
本発明の近赤外線吸収性膜を具備した固体撮像素子を備えたカメラモジュールの構成の一例を示す概略断面図Schematic sectional drawing which shows an example of a structure of the camera module provided with the solid-state image sensor which comprised the near-infrared absorptive film of this invention
　本発明の近赤外線吸収性組成物は、ホスホン酸銅錯体と、２種以上の分散剤を含有する近赤外線吸収性組成物であって、当該分散剤の少なくとも１種が、前記一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａであることを特徴とする。この特徴は、下記各実施形態に係る発明に共通する技術的特徴である。 The near-infrared absorptive composition of the present invention is a near-infrared absorptive composition containing a copper phosphonate complex and two or more dispersants, and at least one of the dispersants has the above-mentioned general formula (1) It is characterized by being a dispersant A having a structure represented by and having a molecular weight of 190 or less. This feature is a technical feature common to the inventions according to the following embodiments.
　本発明の近赤外線吸収性組成物においては、本発明の目的とする効果をより発現できる観点から、近赤外線吸収性組成物を構成する２種以上の分散剤のうちの少なくとも１種が、前記の特定の官能基群から選ばれる少なくとも一つの官能基を有する分散剤Ｂとすることが、より優れた長期間にわたる保存安定性（ホスホン酸銅錯体粒子の分散安定性と近赤外線カット安定性）を有する近赤外線吸収性組成物を得ることができ点で好ましい。 In the near-infrared absorptive composition of the present invention, at least one of the two or more kinds of the dispersants constituting the near-infrared-absorbent composition is the above from the viewpoint of being able to further exhibit the effects aimed by the present invention. Storage stability over a longer period of time (dispersion stability and near-infrared cut stability of copper phosphonate copper complex particles) having a dispersant B having at least one functional group selected from the specific functional group of It is preferable at the point which can obtain the near-infrared absorptive composition which has these.
　また、近赤外線吸収性組成物を構成する２種以上の分散剤のうち、１種は前記一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａを用い、併用するその他の分散剤が、前記一般式（１）で表される構造を有していない分散剤とすること、すなわち構造の異なる２種以上の分散剤を適用することにより、更に優れた長期保存安定性（ホスホン酸銅錯体粒子の分散安定性と近赤外線カット安定性）を有する近赤外線吸収性組成物を得ることができ点で好ましい。 In addition, among the two or more types of dispersants constituting the near-infrared absorbing composition, one type uses dispersant A having a structure represented by the above general formula (1) and having a molecular weight of 190 or less, The further excellent long-term can be achieved by the other dispersing agent used in combination being a dispersing agent not having the structure represented by the general formula (1), that is, by applying two or more kinds of dispersing agents having different structures. It is preferable at the point which can obtain the near-infrared absorptive composition which has storage stability (dispersion stability and near-infrared cut stability of copper phosphonate copper complex particle | grains).
　また、ホスホン酸銅錯体を構成するホスホン酸として、特定構造のアルキルホスホン酸を適用することが、本願発明の目的である優れた近赤外線吸収能をより発現させることができる点で好ましい。 Moreover, it is preferable to apply the alkyl phosphonic acid of a specific structure as a phosphonic acid which comprises a phosphonic acid copper complex from the point which can express the outstanding near-infrared absorptivity which is the objective of this invention more.
　また、近赤外線吸収性組成物全質量に対する固形分の比率を、１０～３４質量％の範囲内とすることが、適切な固形物（例えば、ホスホン酸銅錯体粒子）の濃度となり、長期間にわたる保存期間中でも粒子凝集性が抑制され、より優れた長期保存安定性（ホスホン酸銅錯体粒子の分散安定性と近赤外線カット安定性）を得ることができる点で好ましい。 In addition, setting the ratio of solid content to the total weight of the near-infrared ray absorbing composition within the range of 10 to 34 mass% results in the concentration of an appropriate solid (for example, copper phosphonate copper complex particles), and over a long period of time Even during the storage period, the particle aggregation is suppressed, which is preferable in that long-term storage stability (dispersion stability and near infrared cut stability of copper phosphonate copper complex particles) can be obtained.
　また、ホスホン酸銅錯体を構成する銅に対するリンのモル比（リン／銅）の値を、１．５以下とすることが、より優れた近赤外線吸収能を得ることができる点で好ましい。 In addition, it is preferable to set the value of the molar ratio of phosphorus to copper (phosphorus / copper) to 1.5 or less to constitute the phosphonic acid copper complex in that a more excellent near-infrared absorptivity can be obtained.
　以下、本発明とその構成要素、及び本発明を実施するための形態・態様について詳細な説明をする。なお、本願において、数値範囲を表す「～」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “to” representing a numerical range is used in the meaning including the numerical values described before and after that as the lower limit value and the upper limit value.
　《近赤外線吸収性組成物の構成》
　本発明の近赤外線吸収性組成物は、ホスホン酸銅錯体と、２種以上の分散剤を含有し、分散剤の少なくとも１種が前記一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａであることを特徴とする。 << Composition of a near-infrared absorptive composition >>
The near-infrared absorptive composition of the present invention contains a copper phosphonate complex and two or more dispersants, and at least one of the dispersants has a structure represented by the general formula (1), and It is characterized by being a dispersant A having a molecular weight of 190 or less.
　以下、本発明の近赤外線吸収性組成物の代表的な構成成分であるホスホン酸銅錯体及び適用する分散剤について説明する。ただし、本発明はここで例示する構成にのみ限定されるものではない。 Hereinafter, the copper phosphonic acid complex which is a typical component of the near-infrared absorptive composition of this invention, and the dispersing agent to apply are demonstrated. However, the present invention is not limited to only the configuration exemplified here.
　〔ホスホン酸銅錯体〕
　本発明の近赤外線吸収性組成物では、ホスホン酸銅錯体を含有することを特徴とする。 [Phosphonic acid copper complex]
The near-infrared absorbing composition of the present invention is characterized by containing a copper phosphonate complex.
　はじめに、本発明に係るホスホン酸銅錯体を構成するホスホン酸化合物について説明する。 First, the phosphonic acid compound which comprises the phosphonic acid copper complex which concerns on this invention is demonstrated.
　〈ホスホン酸化合物〉
　本発明の近赤外線吸収性組成物は、下記一般式（２）で表される構造を有するホスホン酸化合物を含むものである。 <Phosphonic acid compound>
The near-infrared absorptive composition of this invention contains the phosphonic acid compound which has a structure represented by following General formula (2).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記一般式（２）において、Ｒ１は、炭素数が１～３０である分岐状、直鎖状又は環状のアルキル基、アルケニル基、アルキニル基、アリール基又はアリル基を表し、少なくとも一つの水素原子が、ハロゲン原子、オキシアルキル基、ポリオキシアルキル基、オキシアリール基、ポリオキシアリール基、アシル基、アルデヒド基、カルボキシル基、ヒドロキシル基、又は、芳香環を有する基で置換されていても、置換されていなくてもよい。 In the above general formula (2), R 1 represents a branched, linear or cyclic alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an aryl group or an allyl group, and at least one hydrogen Even if the atom is substituted with a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxyl group, a hydroxyl group or a group having an aromatic ring, It may not be substituted.
　一般式（２）で表される構造を有するホスホン酸化合物の例としては、ホスホン酸群Ａで表されるエチルホスホン酸、プロピルホスホン酸、ブチルホスホン酸、ペンチルホスホン酸、ヘキシルホスホン酸、オクチルホスホン酸、２－エチルヘキシルホスホン酸、２－クロロエチルホスホン酸、３－ブロモプロピルホスホン酸、３－メトキシブチルホスホン酸、１，１－ジメチルプロピルホスホン酸、１，１－ジメチルエチルホスホン酸、１－メチルプロピルホスホン酸や、ホスホン酸群Ｂで表されるフェニルホスホン酸、４－メトキシフェニルホスホン酸、（４－アミノフェニル）ホスホン酸、（４－ブロモフェニル）ホスホン酸、３－ホスホノ安息香酸、４－ホスホノ安息香酸、（４－ヒドロキシフェニル）ホスホン酸等が挙げられ、その一例を、下記化合物（Ｈ－１）～（Ｈ－８）として例示する。 Examples of phosphonic acid compounds having a structure represented by the general formula (2) include ethylphosphonic acid represented by phosphonic acid group A, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid and octylphosphonic acid Acid, 2-ethylhexylphosphonic acid, 2-chloroethylphosphonic acid, 3-bromopropylphosphonic acid, 3-methoxybutylphosphonic acid, 1,1-dimethylpropylphosphonic acid, 1,1-dimethylethylphosphonic acid, 1-methyl Propylphosphonic acid, phenylphosphonic acid represented by phosphonic acid group B, 4-methoxyphenylphosphonic acid, (4-aminophenyl) phosphonic acid, (4-bromophenyl) phosphonic acid, 3-phosphonobenzoic acid, 4- And phosphonobenzoic acid, (4-hydroxyphenyl) phosphonic acid, etc. An example, the following compound (H-1) exemplified as ~ (H-8).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　本発明においては、ホスホン酸銅錯体を構成するホスホン酸が、下記ホスホン酸群から選ばれる少なくとも１種のアルキルホスホン酸であることが好ましい。 In the present invention, the phosphonic acid constituting the phosphonic acid copper complex is preferably at least one alkylphosphonic acid selected from the following phosphonic acid group.
　エチルホスホン酸
　プロピルホスホン酸
　ブチルホスホン酸
　ペンチルホスホン酸
　ヘキシルホスホン酸
　オクチルホスホン酸
　２－エチルヘキシルホスホン酸
　２－クロロエチルホスホン酸
　３－ブロモプロピルホスホン酸
　３－メトキシブチルホスホン酸
　１，１－ジメチルプロピルホスホン酸
　１，１－ジメチルエチルホスホン酸
　１－メチルプロピルホスホン酸
　〈ホスホン酸銅錯体〉
　本発明に係るホスホン酸銅錯体は、下記一般式（３）で表される構造を有する。 Ethyl phosphonic acid Propyl phosphonic acid Butyl phosphonic acid pentyl phosphonic acid hexyl phosphonic acid octyl phosphonic acid 2-ethylhexyl phosphonic acid 2-chloroethyl phosphonic acid 3-bromopropyl phosphonic acid 3-methoxybutyl phosphonic acid 1,1-dimethylpropyl phosphonic acid 1 1,1-Dimethylethyl phosphonic acid 1-Methyl propyl phosphonic acid <Phosphonic acid copper complex>
The phosphonic acid copper complex according to the present invention has a structure represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　上記一般式（３）において、Ｒはアルキル基、フェニル基、又はベンジル基である。 In the above general formula (3), R is an alkyl group, a phenyl group or a benzyl group.
　一般式（３）で表される構造を有するホスホン酸銅錯体の形成に用いられる銅塩としては、２価の銅イオンを供給することが可能な銅塩が用いられる。例えば、無水酢酸銅、無水ギ酸銅、無水ステアリン酸銅、無水安息香酸銅、無水アセト酢酸銅、無水エチルアセト酢酸銅、無水メタクリル酸銅、無水ピロリン酸銅、無水ナフテン酸銅、無水クエン酸銅等の有機酸の銅塩、該有機酸の銅塩の水和物若しくは水化物；酸化銅、塩化銅、硫酸銅、硝酸銅、リン酸銅、塩基性硫酸銅、塩基性炭酸銅等の無機酸の銅塩、該無機酸の銅塩の水和物若しくは水化物；水酸化銅が挙げられる。 As a copper salt used for formation of the phosphonic acid copper complex which has a structure represented by General formula (3), the copper salt which can supply a bivalent copper ion is used. For example, anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, copper benzoate anhydrous, copper acetoacetate anhydrous, copper ethylacetoacetate anhydrous, copper methacrylate anhydride, copper anhydrous pyrophosphate, copper naphthenate anhydrous, copper anhydrous citrate etc. Copper salts of organic acids, hydrates or hydrates of copper salts of organic acids; inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, basic copper carbonate, etc. Copper salts, hydrates or hydrates of copper salts of the inorganic acids, and copper hydroxide.
　本発明においては、ホスホン酸銅錯体を構成するホスホン酸が、アルキルホスホン酸であることが好ましく、例えば、エチルホスホン酸銅錯体、プロピルホスホン酸銅錯体、ブチルホスホン酸銅錯体、ペンチルホスホン酸銅錯体、ヘキシルホスホン酸銅錯体、オクチルホスホン酸銅錯体、２－エチルヘキシルホスホン酸銅錯体、２－クロロエチルホスホン酸銅錯体、３－ブロモプロピルホスホン酸銅錯体、３－メトキシブチルホスホン酸銅錯体、１，１－ジメチルプロピルホスホン酸銅錯体、１，１－ジメチルエチルホスホン酸銅錯体、１－メチルプロピルホスホン酸銅錯体、フェニルホスホン酸銅錯体、４－メトキシフェニルホスホン酸銅錯体、（４－アミノフェニル）ホスホン酸銅錯体、（４－ブロモフェニル）ホスホン酸銅錯体、３－ホスホノ安息香酸銅錯体、４－ホスホノ安息香酸銅錯体、（４－ヒドロキシフェニル）ホスホン酸銅錯体等を挙げることができる。 In the present invention, the phosphonic acid constituting the phosphonic acid copper complex is preferably an alkyl phosphonic acid. For example, ethyl phosphonic acid copper complex, propyl phosphonic acid copper complex, butyl phosphonic acid copper complex, pentyl phosphonic acid copper complex Hexylphosphonic acid copper complex, octylphosphonic acid copper complex, 2-ethylhexylphosphonic acid copper complex, 2-chloroethylphosphonic acid copper complex, 3-bromopropylphosphonic acid copper complex, 3-methoxybutylphosphonic acid copper complex, 1, 1-Dimethylpropylphosphonic acid copper complex, 1,1-dimethylethylphosphonic acid copper complex, 1-methylpropylphosphonic acid copper complex, phenylphosphonic acid copper complex, 4-methoxyphenylphosphonic acid copper complex, (4-aminophenyl) Phosphonate copper complex, (4-Bromophenyl) phosphonate copper complex, 3 Phosphono copper benzoate complexes, 4-phosphono copper benzoate complexes, and (4-hydroxyphenyl) copper phosphonate complexes.
　〔分散剤〕
　本発明の近赤外線吸収性組成物においては、ホスホン酸銅錯体とともに、２種以上の分散剤を含有することを特徴とする。 Dispersant
The near-infrared absorptive composition of the present invention is characterized by containing two or more dispersants together with the copper phosphonate complex.
　２種以上の分散剤のうち、少なくとも１種は、下記一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａであることを特徴とする。この分散剤Ａと併用するその他の分散剤としては、特に制限はないが、一つとしては、下記官能基群から選ばれる少なくとも一つの官能基を有する分散剤Ｂであることが好ましい。 Among the two or more dispersants, at least one dispersant is a dispersant A having a structure represented by the following general formula (1) and having a molecular weight of 190 or less. The other dispersant to be used in combination with the dispersant A is not particularly limited, but one dispersant is preferably a dispersant B having at least one functional group selected from the following functional group group.
　官能基群：ヒドロキシ基、チオール基、カルボニル基、カルボキシ基、スルホン酸基、シアノ基、アミノ基、及びピリジル基。 Functional groups: hydroxy group, thiol group, carbonyl group, carboxy group, sulfonic acid group, cyano group, amino group, and pyridyl group.
　また、分散剤Ａで構造の異なる２種以上の分散剤を併用しても、又は他方の１種を、分散剤Ａで規定する一般式（１）で表される構造を有していない分散剤を併用してもよい。 Also, even if two or more dispersants having different structures are used in combination as dispersant A, or the other one is a dispersion not having a structure represented by the general formula (1) defined by dispersant A An agent may be used in combination.
　（分散剤Ａ）
　本発明の近赤外線吸収性組成物においては、２種以上の分散剤のうち、少なくとも１種が、下記一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａであることを特徴とする。 (Dispersant A)
In the near-infrared absorptive composition of the present invention, at least one of the two or more dispersants has a structure represented by the following general formula (1), and a dispersant A having a molecular weight of 190 or less It is characterized by being.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記一般式（１）において、Ｒ１は水素原子又は１～４価の有機基を表す。Ｒ２は炭素数２～４のアルキレン基を表す。Ｒ３は、水素原子、アルキル基又はアシル基を表す。ａは０～１０の整数である。ｂは１～４の整数である。ａは好ましくは１～１０の整数である。ｂが２以上の場合、括弧内で表される構造は、同じであっても異なっていてもよい。 In the above general formula (1), R 1 represents a hydrogen atom or a monovalent to tetravalent organic group. R 2 represents an alkylene group having 2 to 4 carbon atoms. R 3 represents a hydrogen atom, an alkyl group or an acyl group. a is an integer of 0 to 10. b is an integer of 1 to 4; a is preferably an integer of 1 to 10. When b is 2 or more, the structures represented in parentheses may be the same or different.
　上記一般式（１）で表される化合物の中でも、ｂが１である化合物が好ましい。 Among the compounds represented by the above general formula (1), compounds in which b is 1 are preferable.
　更には、一般式（１）において、分子量が１９０以下となる範囲で、Ｒ１は、水素原子又は、１～４価の有機基としては、炭素数が２～１０のアシル基、炭素数が１～１０の直鎖状、分岐状若しくは環状のアルキル基、炭素数が６～１０のアリール基若しくはアラルキル基が挙げられ、アルキル基を構成する炭素原子に結合した少なくとも一つの水素原子が、ハロゲン原子、ヘテロ原子又は芳香環で置換されていてもよい。Ｒ２は炭素数が２～４のアルキレン基を示し、ｎは１～１０を示す。アシル基の炭素数は、好ましくは２～１０である。アルキル基の炭素数は、好ましくは１～１５である。アリール基又はアラルキル基の炭素数は、好ましくは６～２０である。Ｒ２で示されるアルキレン基の炭素数は、好ましくは２～３、更に好ましくは２である。 Furthermore, in the general formula (1), R 1 is a hydrogen atom or, as a monovalent to tetravalent organic group, an acyl group having 2 to 10 carbon atoms, a carbon number within a range that the molecular weight is 190 or less 1 to 10 linear, branched or cyclic alkyl group, aryl group having 6 to 10 carbon atoms or aralkyl group are mentioned, and at least one hydrogen atom bonded to a carbon atom constituting the alkyl group is a halogen It may be substituted by an atom, a hetero atom or an aromatic ring. R 2 represents an alkylene group having 2 to 4 carbon atoms, and n represents 1 to 10. The carbon number of the acyl group is preferably 2 to 10. The carbon number of the alkyl group is preferably 1 to 15. The carbon number of the aryl group or the aralkyl group is preferably 6 to 20. The carbon number of the alkylene group represented by R 2 is preferably 2 to 3, more preferably 2.
　上記一般式（１）において、Ｒ１で表されるアシル基としてはジカルボン酸から誘導される２価の酸基も含まれ、例えば、２－エチルブタノイル基、（メタ）アクリロイル基、プロピオニル基、ブチリル基、バレリル基、イソバレリル基、ヘキサノイル基、ヘプタンジオイル基が挙げられる。これらの中でも、（メタ）アクリロイル基、２－エチルヘキサノイル基が好ましい。また、Ｒ１で表されるアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、アミル基、ヘキシル基、ノニル基が挙げられる。これらの中でも、メチル基、ラウリル基が好ましい。またさらに、Ｒ１で表されるアリール基若しくはアラルキル基としては、フェニル基、４－ノニルフェニル基が好ましい。さらに、Ｒ２で表されるアルキレン基としては、エチレン基、プロピレン基、ブチレン基、テトラメチレン基が好適である。このような基を採用することで、銅を含むリン化合物の樹脂への溶解性及び分散性を顕著に向上させることができる。 In the above general formula (1), the acyl group represented by R 1 also includes a divalent acid group derived from a dicarboxylic acid, and, for example, 2-ethylbutanoyl group, (meth) acryloyl group, propionyl group , Butyryl group, valeryl group, isovaleryl group, hexanoyl group, heptanedioyl group. Among these, (meth) acryloyl group and 2-ethylhexanoyl group are preferable. Also, examples of the alkyl group represented by R 1 include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group and a nonyl group. Among these, methyl and lauryl are preferable. Furthermore, as the aryl group or aralkyl group represented by R 1 , a phenyl group or 4-nonylphenyl group is preferable. Furthermore, as the alkylene group represented by R 2 , an ethylene group, a propylene group, a butylene group and a tetramethylene group are preferable. By employing such a group, the solubility and dispersibility of the copper-containing phosphorus compound in the resin can be significantly improved.
　本発明に係る分散剤Ａで表される化合物例を以下に示す。 Examples of the compound represented by the dispersant A according to the present invention are shown below.
　１）ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート（分子量：１３２）
　２）ＰＧＥＥＡ：プロピレングリコールモノエチルエーテルアセテート（分子量：１４６）
　３）ＰＧＢＥＡ：プロピレングリコールモノブチルエーテルアセテート（分子量：１７４）
　４）エチレングリコールジアセテート（分子量：１４６）
　５）エチレングリコールジグリシジルエーテル（分子量：１７４）
　６）エチレングリコールモノメチルエーテルアセテート（分子量：１１８）
　７）エチレングリコールモノエチルエーテルアセテート（分子量：１３２）
　８）エチレングリコールモノブチルエーテルアセテート（分子量：１６０）
　９）エチレングリコールジブチルエーテル（分子量：１７４）
　１０）エチレングリコールモノアセテート(分子量：１０４)
　１１）エチレングリコールモノイソプロピルエーテル（分子量：１０４）
　１２）エチレングリコールモノエチルエーテル（分子量：９０）
　１３）エチレングリコールモノメトキシメチルエーテル（分子量：１０６）
　１４）グリセリン１，３－ジアセテート（分子量：１７６）
　１５）グリセリン１，２－ジメチルエーテル（分子量：１２０）
　１６）グリセリン１，３－ジメチルエーテル（分子量：１２０）
　１７）グリセリン１，３－ジエチルエーテル（分子量：１４８）
　１８）２－クロロ－１，３－プロパンジオール（分子量１１０）
　１９）３－クロロ－１，２－プロパンジオール（分子量１１０）
　２０）ジエチレングリコールエチルメチルエーテル（分子量：１４８）
　２１）ジエチレングリコールジメチルエーテル（分子量：１３４）
　２２）ジエチレングリコールモノエチルエーテルアセテート(分子量：１７６)
　２３）ジエチレングリコールモノブチルエーテル（分子量：１６２）
　２４）ジエチレングリコールモノメチルエーテル(分子量：１２０)
　２５）ジプロピレングリコール（分子量：１３４）
　２６）ジプロピレングリコールモノプロピルエーテル（分子量：１７６）
　２７）トリエチレングリコール（分子量：１５０）
　２８）トリエチレングリコールジメチルエーテル（分子量：１７８）
　２９）トリエチレングリコールモノエチルエーテル（分子量：１７８）
　３０）トリエチレングリコールモノメチルエーテル（分子量：１６４）
　３１）プロピレングリコール（分子量：７６）
　３２）プロピレングリコールモノエチルエーテル(分子量：１０４)
　上記分散剤の中でも、特に、１）～１７）、２０）～２４）、２６）、２８）～３０）、３２）で示す分散剤が好ましい。 1) PGMEA: Propylene glycol monomethyl ether acetate (molecular weight: 132)
2) PGEEA: Propylene glycol monoethyl ether acetate (molecular weight: 146)
3) PGBEA: Propylene glycol monobutyl ether acetate (molecular weight: 174)
4) Ethylene glycol diacetate (molecular weight: 146)
5) Ethylene glycol diglycidyl ether (molecular weight: 174)
6) Ethylene glycol monomethyl ether acetate (molecular weight: 118)
7) Ethylene glycol monoethyl ether acetate (molecular weight: 132)
8) Ethylene glycol monobutyl ether acetate (molecular weight: 160)
9) Ethylene glycol dibutyl ether (molecular weight: 174)
10) Ethylene glycol monoacetate (molecular weight: 104)
11) Ethylene glycol monoisopropyl ether (molecular weight: 104)
12) Ethylene glycol monoethyl ether (molecular weight: 90)
13) Ethylene glycol monomethoxymethyl ether (molecular weight: 106)
14) Glycerin 1,3-diacetate (molecular weight: 176)
15) Glycerin 1,2-dimethyl ether (molecular weight: 120)
16) Glycerin 1,3-dimethyl ether (molecular weight: 120)
17) Glycerin 1,3-diethyl ether (molecular weight: 148)
18) 2-Chloro-1,3-propanediol (molecular weight 110)
19) 3-Chloro-1,2-propanediol (molecular weight 110)
20) Diethylene glycol ethyl methyl ether (molecular weight: 148)
21) Diethylene glycol dimethyl ether (molecular weight: 134)
22) Diethylene glycol monoethyl ether acetate (molecular weight: 176)
23) Diethylene glycol monobutyl ether (molecular weight: 162)
24) Diethylene glycol monomethyl ether (molecular weight: 120)
25) Dipropylene glycol (molecular weight: 134)
26) Dipropylene glycol monopropyl ether (molecular weight: 176)
27) Triethylene glycol (molecular weight: 150)
28) Triethylene glycol dimethyl ether (molecular weight: 178)
29) Triethylene glycol monoethyl ether (molecular weight: 178)
30) Triethylene glycol monomethyl ether (molecular weight: 164)
31) Propylene glycol (molecular weight: 76)
32) Propylene glycol monoethyl ether (molecular weight: 104)
Among the above-mentioned dispersants, dispersants shown in 1) to 17), 20) to 24), 26), 28) to 30), and 32) are particularly preferable.
　（分散剤Ｂ）
　本発明の近赤外線吸収性組成物においては、２種以上の分散剤の少なくとも１種が、上記説明した一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａであることを特徴の一つとするが、更に、２種以上の分散剤のうちの少なくとも１種が、下記官能基群から選ばれる少なくとも一つの官能基を有する分散剤Ｂであることが好ましい態様である。 (Dispersant B)
In the near-infrared absorptive composition of the present invention, at least one of the two or more dispersants has a structure represented by the general formula (1) described above, and a dispersant A having a molecular weight of 190 or less And at least one of the two or more dispersants is preferably a dispersant B having at least one functional group selected from the following functional group groups. It is.
　分散剤Ｂが有する官能基は、ヒドロキシ基、チオール基、カルボニル基、カルボキシ基、スルホン酸基、シアノ基、アミノ基、及びピリジル基から選ばれる少なくとも１種である。 The functional group possessed by the dispersant B is at least one selected from a hydroxy group, a thiol group, a carbonyl group, a carboxy group, a sulfonic acid group, a cyano group, an amino group, and a pyridyl group.
　本発明に係る上記官能基を有する分散剤Ｂの例として、以下の各分散剤を挙げることができる。 The following each dispersing agent can be mentioned as an example of the dispersing agent B which has the said functional group based on this invention.
　１）アルキルイミダゾリン
　２）ポリオキシエチレン（２）ラウリルエーテル
　３）ソルビタンモノパリミテート
　４）ポリオキシエチレンアルキル（Ｃ８）エーテルリン酸エステル
　５）スチレンーマレイン酸
　６）ポリビニルピロリドン
　７）ポリオキシエチレンスチレン化フェニルエーテル
　８）ポリオキシエチレントリデシルエーテル
　９）２－エチルヘキシルカルボン酸
　１０）トリメチル－１－ヘキサノール
　１１）フェノキシエタノール等。 1) Alkyl imidazoline 2) polyoxyethylene (2) lauryl ether 3) sorbitan monopalmitate 4) polyoxyethylene alkyl (C8) ether phosphate ester 5) styrene-maleic acid 6) polyvinyl pyrrolidone 7) polyoxyethylene styrene Fluorinated phenyl ether 8) polyoxyethylene tridecyl ether 9) 2-ethylhexyl carboxylic acid 10) trimethyl-1-hexanol 11) phenoxyethanol etc.
　また、分散液Ｂとしては市販品も用いることができる。例えば、花王製のエマルゲンシリーズ（例えば、１０２ＫＧ、１０３、１０５、１０６、１０８、１０９等）、レオドールＳＰ－Ｐ１０、アミートシリーズ（１０２、３０２）など、第一工業製薬製のプライサーフシリーズ（Ａ２０８Ｆ、Ａ２０８Ｎ）、ＤＫＳディスコートＮ－１４、ピッツコールＫ－３０、ノイゲンシリーズ（ＥＡ－１５７、ＴＤＳ－１００等）などを挙げることができる。 Moreover, as the dispersion liquid B, a commercial item can also be used. For example, Kao's Emulgen series (for example, 102 KG, 103, 105, 106, 108, 109, etc.), Reodore SP-P 10, Ameet series (102, 302), etc. , A208N), DKS Discoat N-14, Pitzcor K-30, Neugen series (EA-157, TDS-100, etc.) and the like.
　（その他の分散剤）
　上記分散剤Ａと併用可能なその他の分散剤としては、例えば、分子量が１９０を超えるジオキシエチレンラウリルエーテル、トリオキシエチレンラウリルエーテル、テトラオキシエチレンラウリルエーテル、ペンタオキシエチレンラウリルエーテル、ヘキサオキシエチレンラウリルエーテル、ヘプタオキシエチレンラウリルエーテル、オクタオキシエチレンラウリルエーテル、ノナオキシエチレンラウリルエーテル、デカオキシエチレンラウリルエーテル、ウンデカオキシエチレンラウリルエーテル、ドデカオキシエチレンラウリルエーテル、トリデカオキシエチレンラウリルエーテル、テトラデカオキシエチレンラウリルエーテル等のエーテル系化合物や、ジエチレングリコールジメタクリレート（ＮＫエステル２Ｇ、新中村化学工業社製、分子量：２４２）、トリエチレングリコールジメタクリレート（分子量：２８６）、ポリエチレングリコール＃２００ジメタクリレート（ＮＫエステル４Ｇ、新中村化学工業社製、分子量：３３０）、トリプロピレングリコールプロピルエーテル、トリエチレングリコールビス（２－エチルヘキサネート）（アクロス社製）、１，３－ブチレングリコールジメタクリレート等を挙げることができる。 (Other dispersants)
Examples of other dispersants that can be used in combination with the above-mentioned dispersant A include, for example, dioxyethylene lauryl ether having a molecular weight exceeding 190, trioxyethylene lauryl ether, tetraoxyethylene lauryl ether, pentaoxyethylene lauryl ether, hexaoxyethylene lauryl Ether, heptaoxyethylene lauryl ether, octaoxyethylene lauryl ether, nonaoxyethylene lauryl ether, decaoxyethylene lauryl ether, undecaoxyethylene lauryl ether, dodecaoxyethylene lauryl ether, tridecaoxyethylene lauryl ether, tetradecaoxyethylene Ether compounds such as lauryl ether, diethylene glycol dimethacrylate (NK ester 2G, Shin-Nakamura Chemical Co., Ltd.) Molecular weight: 242), triethylene glycol dimethacrylate (molecular weight: 286), polyethylene glycol # 200 dimethacrylate (NK ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 330), tripropylene glycol propyl ether, triethylene glycol bis ( 2-ethylhexanate) (manufactured by Acros), 1,3-butylene glycol dimethacrylate and the like.
　《近赤外線吸収性組成物の調製方法》
　ホスホン酸銅錯体と、２種以上の分散剤を含有する近赤外線吸収性組成物の調製方法としては、特に制限はないが、例えば、下記の方法に従って調製することができる。 << Preparation Method of Near-Infrared Absorbent Composition >>
Although there is no restriction | limiting in particular as a preparation method of the near-infrared absorptive composition containing a phosphonic acid copper complex and 2 or more types of dispersing agents, For example, it can prepare according to the following method.
　銅を供給する銅塩として、例えば、酢酸銅を用い、溶媒として、例えば、テトラヒドロフラン（略称：ＴＨＦ）と、本発明に係る分散剤Ａとして、例えば、プロピレングリコールモノメチルエーテルアセテート（略称：ＰＧＭＥＡ、分子量：１３２）を混合及び溶解する。この際、濾過操作により、不溶解状態の銅塩（例えば、酢酸銅）を除去して、酢酸銅溶液を調製する。次に、この酢酸銅溶液に対して、分散剤Ｂを加えて撹拌し、Ａ液を調製する。また、アルキルホスホン酸にＴＨＦを加えて撹拌し、Ｂ液を調製する。次に、Ａ液を撹拌しながらＢ液を添加し、室温で一定時間撹拌する。次に、高温環境下、例えば、８５℃で３時間を要して、溶媒であるＴＨＦを揮発させて、分散物Ａとその他の分散剤である分散剤Ｂとアルキルホスホン酸銅の微粒子を含む、近赤外線吸収性組成物を調製することができる。 For example, copper acetate is used as a copper salt for supplying copper, tetrahydrofuran (abbreviation: THF) as a solvent, and propylene glycol monomethyl ether acetate (abbreviation: PGMEA, molecular weight) as dispersant A according to the present invention Mix and dissolve: 132). At this time, the insoluble copper salt (for example, copper acetate) is removed by a filtration operation to prepare a copper acetate solution. Next, Dispersant B is added to the copper acetate solution and stirred to prepare Solution A. Further, THF is added to the alkylphosphonic acid and stirred to prepare a solution B. Next, the solution B is added while stirring the solution A, and the solution is stirred at room temperature for a fixed time. Next, in a high temperature environment, for example, it takes 3 hours at 85 ° C. to volatilize the solvent THF to contain the dispersion A and the other dispersant dispersant B and fine particles of copper alkylphosphonate. Near infrared absorbing compositions can be prepared.
　《近赤外線吸収性膜とその適用分野》
　本発明においては、本発明の近赤外線吸収性組成物を用いて、近赤外線吸収性膜を形成することを一つの特徴とする。 «Near-infrared absorbing film and its application field»
One feature of the present invention is to form a near-infrared-absorbing film using the near-infrared-absorbing composition of the present invention.
　本発明の近赤外線吸収性膜は、本発明の２種以上の分散剤とホスホン酸銅錯体を含む近赤外線吸収性組成物に、マトリクス樹脂を添加し、マトリクス樹脂にホスホン酸銅の微粒子が分散している状態とすることによって形成されている。また、吸収波形調整用の添加剤として、６５０～８００ｎｍの波長域に吸収極大波長を有する近赤外色素を少なくとも１種、添加することができる。近赤外色素としては、例えば、シアニン色素、スクアリリウム色素、クロコニウム色素、フロシアニン色素、ナフタロシアニン色素等を挙げることができる。 In the near-infrared absorbing film of the present invention, a matrix resin is added to the near-infrared absorbing composition containing two or more dispersants of the present invention and a copper phosphonate complex, and fine particles of copper phosphonate are dispersed in the matrix resin. It is formed by putting it in the state of doing. In addition, as an additive for adjusting the absorption waveform, at least one near-infrared dye having an absorption maximum wavelength in a wavelength range of 650 to 800 nm can be added. Examples of near infrared dyes include cyanine dyes, squarylium dyes, croconium dyes, phlocyanine dyes, naphthalocyanine dyes and the like.
　上記構成よりなる近赤外線吸収性膜形成用塗布液をスピンコーティング又はディスペンサーによる塗布方法で基板上に塗布して、近赤外線吸収性膜を形成する。その後、この塗膜に対して所定の加熱処理を行って塗膜を硬化させて、近赤外線吸収性膜を形成する。 The coating solution for forming a near infrared ray absorbing film having the above configuration is applied onto a substrate by a spin coating method or a coating method using a dispenser to form a near infrared ray absorbing film. Thereafter, the coating film is subjected to a predetermined heat treatment to cure the coating film, thereby forming a near infrared absorbing film.
　近赤外線吸収性膜の形成に用いるマトリクス樹脂は、可視光線及び近赤外線に対し光透明性を有し、かつ、ホスホン酸銅錯体微粒子の分散が可能な樹脂である。ホスホン酸銅錯体は、比較的極性が低い物質であり、疎水性材料に良好に分散する。このため、近赤外線吸収性膜形成用のマトリクス樹脂としては、アクリル基、エポキシ基、又はフェニル基を有する樹脂を用いることができる。その中でも、特に、近赤外線吸収性膜のマトリクス樹脂としては、フェニル基を有する樹脂を用いることが好ましい。この場合、近赤外線吸収性膜のマトリクス樹脂は高い耐熱性を発揮する。また、ポリシロキサンシリコーン樹脂は、熱分解しにくく、可視光線及び近赤外線に対して高い光透過性を有し、耐熱性も高いので、固体撮像素子用イメージセンサー用の材料として好適な特性を有する。このため、近赤外線吸収性膜のマトリクス樹脂として、ポリシロキサンを用いることも好ましい。近赤外線吸収性膜のマトリクス樹脂として使用可能なポリシロキサンの具体例としては、ＫＲ－２５５、ＫＲ－３００、ＫＲ－２６２１－１、ＫＲ－２１１、ＫＲ－３１１、ＫＲ－２１６、ＫＲ－２１２、及びＫＲ－２５１を挙げることができる。これらはいずれも信越化学工業社製のシリコーン樹脂である。 The matrix resin used to form the near-infrared absorbing film is a resin having light transparency to visible light and near-infrared light and capable of dispersing fine particles of copper phosphonate complex. Copper phosphonate complexes are relatively less polar substances and disperse well in hydrophobic materials. For this reason, as a matrix resin for near-infrared absorptive film formation, resin which has an acryl group, an epoxy group, or a phenyl group can be used. Among them, it is particularly preferable to use a resin having a phenyl group as a matrix resin of the near infrared ray absorbing film. In this case, the matrix resin of the near infrared absorptive film exhibits high heat resistance. In addition, polysiloxane silicone resin is difficult to be decomposed by heat, has high light transmittance to visible light and near infrared light, and has high heat resistance, and thus has a characteristic suitable as a material for an image sensor for a solid-state imaging device. . For this reason, it is also preferable to use polysiloxane as a matrix resin of a near-infrared absorptive film. Specific examples of the polysiloxane that can be used as a matrix resin of a near infrared absorbing film include KR-255, KR-300, KR-2621-1, KR-211, KR-311, KR-216, KR-212, And KR-251. All of these are silicone resins manufactured by Shin-Etsu Chemical Co., Ltd.
　また、シリコーン樹脂としては、例えば、ＳＳ－６２０３、ＳＳ－６３０９、ＶＳ－９３０１、ＶＳ－９５０６を挙げることができ、これらはいずれもサンユレック社製のシリコーン樹脂である。 Further, as the silicone resin, for example, SS-6203, SS-6309, VS-9301, and VS-9506 can be mentioned, and all of them are silicone resins manufactured by San Yuleck.
　本発明の近赤外線吸収性膜の形成に用いるマトリクス樹脂としては、低ガス透過性の観点から、エポキシ基を有するマトリックス樹脂を含有することが好ましい態様である。 As a matrix resin used for formation of the near-infrared absorptive film of this invention, it is a preferable aspect to contain the matrix resin which has an epoxy group from a low gas permeability viewpoint.
　この場合、近赤外線吸収性膜を構成するエポキシ基を有するマトリクス樹脂は、高い耐湿性を発揮するため、固体撮像素子用イメージセンサー用の材料として好適な特性を有する。 In this case, the matrix resin having an epoxy group constituting the near-infrared absorptive film exhibits high moisture resistance, and thus has a characteristic suitable as a material for an image sensor for a solid-state imaging device.
　近赤外線吸収性膜のマトリクス樹脂として使用可能なエポキシ基を有する樹脂の具体例としては、ＫＪＣ－Ｘ５（信越化学工業社製）、ＮＬＤ－Ｌ－６７２（サンユレック社製）、ＬＥ－１４２１（サンユレック社製）、ＥｐｉＦｉｎｅシリーズ（ＫＩＳＣＯ社製）を挙げることができる。 Specific examples of the resin having an epoxy group that can be used as a matrix resin of a near infrared absorbing film include KJC-X5 (manufactured by Shin-Etsu Chemical Co., Ltd.), NLD-L-672 (manufactured by San Yurec Co., Ltd.), LE-1421 (San Yulek) Company) and EpiFine series (made by KISCO company) can be mentioned.
　また、近赤外線吸収性膜のマトリクス樹脂として、上記に挙げたポリシロキサンとエポキシ基の両方を有する樹脂を用いることも好ましい。 Moreover, it is also preferable to use resin which has both the polysiloxane mentioned above and an epoxy group as matrix resin of a near-infrared absorptive film.
　この場合、これらのポリシロキサンとエポキシ基の両方を有するマトリクス樹脂は、高い耐熱性、耐湿性を発揮するため、固体撮像素子用イメージセンサー用の材料として好適な特性を有する。 In this case, a matrix resin having both of these polysiloxanes and an epoxy group exhibits high heat resistance and moisture resistance, and thus has properties suitable as a material for an image sensor for a solid-state imaging device.
　近赤外線吸収性膜のマトリクス樹脂として使用可能なポリシロキサンとエポキシ基の両方を有する樹脂の具体例としては、ＥｐｉＦｉｎｅシリーズ（ＫＩＳＣＯ社製）、ＩＬＬＵＭＩＫＡシリーズ（カネカ社製）を挙げることができる。 Specific examples of the resin having both polysiloxane and epoxy group that can be used as a matrix resin of a near infrared absorbing film include EpiFine series (manufactured by KISCO) and ILLUMIKA series (manufactured by Kaneka).
　（その他の添加剤）
　本発明の近赤外線吸収性膜には、本発明の目的効果を損なわない範囲で、従来公知の各種添加剤を適用することができ、例えば、増感剤、架橋剤、硬化促進剤、フィラー、熱硬化促進剤、熱重合禁止剤、可塑剤などが挙げられ、更に基材表面への密着促進剤及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、香料、表面張力調整剤、連鎖移動剤など）を併用してもよい。 (Other additives)
Various additives known in the prior art can be applied to the near-infrared absorptive film of the present invention as long as the object effects of the present invention are not impaired. For example, sensitizers, crosslinking agents, curing accelerators, fillers, Thermal curing accelerators, thermal polymerization inhibitors, plasticizers, etc., and adhesion promoters to the substrate surface and other auxiliary agents (eg, conductive particles, fillers, antifoaming agents, flame retardants, leveling) Agents, peeling accelerators, antioxidants, perfumes, surface tension regulators, chain transfer agents, etc.) may be used in combination.
　これらの成分を適宜含有させることにより、目的とする近赤外線吸収フィルターの安定性、膜物性などの性質を調整することができる。 By appropriately containing these components, it is possible to adjust properties such as stability and film physical properties of the targeted near-infrared absorption filter.
　これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号（０１８３）～（０２６０）、特開２００８－２５００７４号公報の段落番号（０１０１）～（０１０２）、特開２００８－２５００７４号公報の段落番号（０１０３）～（０１０４）、特開２００８－２５００７４号公報の段落番号（０１０７）～（０１０９）等の記載を参酌できる。 As these components, for example, paragraph numbers (0183) to (0260) of JP 2012-003225 A, paragraph numbers (0101) to (0102) of JP 2008-250074 A, and JP 2008-250074 A. The description of Paragraph Nos. (0103) to (0104) in Paragraph No. and Paragraph Nos. (0107) to (0109) in JP-A 2008-250074 can be referred to.
　本発明の近赤外線吸収性組成物は、液状とすることができるため、例えば、スピンコーティングすることにより膜を形成するという簡単な工程によって、近赤外線吸収性膜、例えば、近赤外線カットフィルターを容易に製造できる。 The near-infrared absorbing composition of the present invention can be in the form of a liquid, so it is easy to form a near-infrared-absorbing film, for example, a near-infrared cut filter, by a simple process of forming a film by spin coating, for example. Can be manufactured.
　《固体撮像素子用イメージセンサーへの適用》
　本発明の近赤外線吸収性膜は、例えば、ＣＣＤ用、ＣＭＯＳ用、又は他の受光素子用の視感度補正部材、測光用部材、熱線吸収用部材、複合光学フィルター、レンズ部材（例えば、眼鏡、サングラス、ゴーグル、光学系、光導波系等）、ファイバ部材（例えば、光ファイバ等）、ノイズカット用部材、プラズマディスプレイ前面板等のディスプレイカバー又はディスプレイフィルター、プロジェクタ前面板、光源熱線カット部材、色調補正部材、照明輝度調節部材、光学素子（例えば、光増幅素子、波長変換素子等）、ファラデー素子、アイソレータ等の光通信機能デバイス、光ディスク用素子等を構成するものとして好適である。 << Application to image sensor for solid-state imaging device >>
The near-infrared absorptive film of the present invention is, for example, a visibility correction member for CCD, CMOS, or other light receiving element, a member for photometry, a member for heat ray absorption, a composite optical filter, a lens member (for example, glasses, Sunglasses, goggles, optical systems, optical waveguide systems, etc., fiber members (eg, optical fibers), noise cutting members, display covers or display filters such as plasma display front plates, projector front plates, light source heat ray cutting members, color tone The correction member, the illumination luminance adjustment member, the optical element (for example, a light amplification element, a wavelength conversion element, etc.), a Faraday element, an optical communication function device such as an isolator, an optical disc element, etc. are suitable.
　本発明の近赤外線吸収性組成物の用途は、特に、固体撮像素子基板の受光側に配置する近赤外線カットフィルター用（例えば、ウエハーレベルレンズに対する近赤外線カットフィルター用等）、固体撮像素子基板の裏面側（受光側とは反対側）における近赤外線カットフィルター用などとして、固体撮像素子用イメージセンサーに適用することが特徴である。 The application of the near-infrared absorbing composition of the present invention is particularly for a near-infrared cut filter disposed on the light receiving side of a solid-state imaging element substrate (for example, for a near-infrared cut filter for wafer level lens) The present invention is characterized in that it is applied to an image sensor for a solid-state imaging device as a near infrared cut filter or the like on the back surface side (the opposite side to the light receiving side).
　詳しくは、本発明の近赤外線吸収性膜（近赤外線カットフィルター）は、固体撮像素子用イメージセンサー上に配置する。 In detail, the near-infrared absorptive film (near-infrared cut filter) of this invention is arrange | positioned on the image sensor for solid-state image sensors.
　図１は、本発明の近赤外線吸収性膜である赤外線カットフィルターを具備した固体撮像素子を備えたカメラモジュールの構成を示す概略断面図である。なお、図１の説明において、構成要素の末尾に括弧内で記載した数字は、各図における符号を表す。 FIG. 1 is a schematic cross-sectional view showing a configuration of a camera module provided with a solid-state imaging device provided with an infrared cut filter that is a near infrared absorptive film of the present invention. In addition, in description of FIG. 1, the number described in the parenthesis at the end of a component represents the code | symbol in each figure.
　図１に示すカメラモジュール（１）は、実装基板である回路基板（１２）に接続部材であるハンダボール（６０）を介して接続されている。 The camera module (1) shown in FIG. 1 is connected to a circuit board (12) which is a mounting board via a solder ball (60) which is a connecting member.
　詳細には、カメラモジュール（１）は、シリコーン基板の第１の主面に撮像素子部を備えた固体撮像素子基板（１０）と、固体撮像素子基板（１０）の第１の主面側（受光側）に設けられた平坦化層（８）と、平坦化層（８）の上に設けられた近赤外線カットフィルター（９、近赤外線吸収性膜）と、近赤外線カットフィルター（９）の上方に配置されるガラス基板（３、光透過性基板）と、ガラス基板（３）の上方に配置され内部空間に撮像レンズ（４）を有するレンズホルダー（５）と、固体撮像素子基板（１０）及びガラス基板（３）の周囲を囲うように配置された遮光兼電磁シールド（６）と、を備えて構成されている。各部材は、接着剤（２、７）により接着されている。 In detail, the camera module (1) comprises a solid-state imaging device substrate (10) including an imaging device portion on a first main surface of a silicone substrate, and a first major surface side of the solid-state imaging device substrate (10) And a near infrared cut filter (9, a near infrared absorptive film) provided on the flattening layer (8), and a near infrared cut filter (9). A glass substrate (3; light transmitting substrate) disposed above, a lens holder (5) disposed above the glass substrate (3) and having an imaging lens (4) in an internal space; And a light shielding and electromagnetic shield (6) disposed to surround the glass substrate (3). Each member is bonded by an adhesive (2, 7).
　本発明は、固体撮像素子基板と、上記固体撮像素子基板の受光側に配置された赤外線カットフィルターとを有するカメラモジュールの製造方法であって、固体撮像素子基板の受光側において、上記本発明の赤外線吸収性液状組成物をスピンコーティングすることにより、近赤外線吸収性膜を形成することができる。 The present invention is a method of manufacturing a camera module having a solid-state imaging device substrate and an infrared cut filter disposed on the light-receiving side of the solid-state imaging device substrate, wherein the light-receiving side of the solid-state imaging device substrate A near infrared absorptive film can be formed by spin coating an infrared absorptive liquid composition.
　よって、カメラモジュール（１）においては、例えば、平坦化層（８）の上に、本発明の近赤外線吸収性組成物をスピンコーティングすることにより近赤外線吸収性膜を形成して、近赤外線カットフィルター（９）を形成する。 Therefore, in the camera module (1), for example, a near infrared absorptive film is formed by spin coating the near infrared absorptive composition of the present invention on the planarizing layer (8) to cut the near infrared radiation. Form a filter (9).
　カメラモジュール（１）では、外部からの入射光（Ｌ）が、撮像レンズ（４）、ガラス基板（３）、近赤外線カットフィルター（９）、平坦化層（８）を順次透過した後、固体撮像素子基板（１０）の撮像素子部に到達するようになっている。 In the camera module (1), the incident light (L) from the outside passes through the imaging lens (4), the glass substrate (3), the near infrared cut filter (9), and the flattening layer (8) sequentially, and then solid It reaches the imaging element portion of the imaging element substrate (10).
　また、カメラモジュール（１）は、固体撮像素子基板（１０）の第２の主面側で、ハンダボール（１１、接続材料）を介して回路基板（１２）に接続されている。 The camera module (1) is connected to the circuit board (12) via the solder balls (11, connection material) on the second principal surface side of the solid-state imaging element substrate (10).
　以下、実施例により本発明を具体的に説明するが、本発明はこれにより限定されるものではない。なお、実施例において「部」又は「％」の表示を用いるが、特に断りがない限り「質量部」又は「質量％」を表す。また、特記しない限り、各操作は、室温（２５℃）で行った。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, it represents "mass part" or "mass%." Also, unless otherwise stated, each operation was performed at room temperature (25 ° C.).
　実施例１
　《近赤外線吸収性組成物の調製》
　（近赤外線吸収性組成物１の調製）
　近赤外線吸収性組成物１を下記の方法に従って調製した。 Example 1
<< Preparation of Near-Infrared Absorbent Composition >>
(Preparation of Near-Infrared Absorbent Composition 1)
A near infrared absorbing composition 1 was prepared according to the following method.
　酢酸銅を１．８ｇ、溶媒としてのテトラヒドロフラン（略称：ＴＨＦ）を６０ｇ、分散剤Ａとしてプロピレングリコールモノメチルエーテルアセテート（略称：ＰＧＭＥＡ、以下、「分散剤Ａ１」と称す。）を１２ｇのそれぞれを混合し、超音波照射機を用いて溶解し、遠心分離による濾過操作を行って、不溶解である酢酸銅を除去して、分散剤Ａ１（ＰＧＭＥＡ）を含む酢酸銅溶液を調製した。 1.8 g of copper acetate, 60 g of tetrahydrofuran (abbreviation: THF) as a solvent, and 12 g of propylene glycol monomethyl ether acetate (abbreviation: PGMEA, hereinafter referred to as “dispersion agent A1”) as dispersant A are mixed respectively. Then, the solution was dissolved using an ultrasonic irradiator, and a filtration operation by centrifugation was performed to remove undissolved copper acetate to prepare a copper acetate solution containing dispersant A1 (PGMEA).
　次いで、上記調製した酢酸銅溶液の６０ｇに対して、分散剤Ｂとして、官能基としてカルボキシ基を有するポリカルボン酸型高分子分散剤（花王社製、製品名：ホモゲノールＬ１８、以下、「分散剤Ｂ１」と称す。）を１．０ｇ加えて撹拌し、Ａ液を得た。一方、アルキルホスホン酸としてプロピルホスホン酸の０．６３ｇにＴＨＦ６．０ｇを加えて撹拌し、Ｂ液を調製した。 Next, a polycarboxylic acid type polymer dispersant having a carboxy group as a functional group as a dispersant B (60 wt% of the copper acetate solution prepared above (Product name: Homogen L 18 by Kao Corporation, hereinafter, “Dispersant”) A) A was obtained by adding 1.0 g of the compound B1) and stirring. On the other hand, 6.0 g of THF was added to 0.63 g of propyl phosphonic acid as the alkyl phosphonic acid and stirred to prepare a solution B.
　次に、Ａ液を撹拌しながらＢ液を添加し、室温で１６時間撹拌した。次いで、８５℃の環境下で３時間かけて溶媒であるＴＨＦを揮発させた。このようにして、プロピルホスホン酸銅微粒子と、分散剤Ａ及び分散剤Ｂを含む近赤外線吸収性組成物１の５．４ｇを調製した。最後に、プロピルホスホン酸銅微粒子以外の非固形成分の添加量を適宜調整し、最終的な固形分比率が２０質量％となるようにして、近赤外線吸収性組成物１を調製した。 Next, solution B was added while stirring solution A, and the solution was stirred at room temperature for 16 hours. Next, the solvent THF was volatilized over 3 hours under an environment of 85 ° C. Thus, 5.4 g of a near infrared absorbing composition 1 containing copper propylphosphonate fine particles, Dispersant A and Dispersant B was prepared. Finally, the addition amount of non-solid components other than copper propylphosphonate fine particles was appropriately adjusted so that the final solid content ratio was 20% by mass, to prepare a near-infrared absorptive composition 1.
　（近赤外線吸収性組成物２の調製）
　上記近赤外線吸収性組成物１の調製において、分散剤Ｂである分散剤Ｂ１（ポリカルボン酸型高分子分散剤）に代えて、第２の分散剤として下記分散剤Ｃ１を用いた以外は同様にして、近赤外線吸収性組成物２を調製した。 (Preparation of Near-Infrared Absorbent Composition 2)
In the preparation of the above-mentioned near-infrared absorptive composition 1, it is replaced with the dispersing agent B1 (polycarboxylic acid type polymer dispersing agent) which is the dispersing agent B, and the following dispersing agent C1 is used as a 2nd dispersing agent similarly Then, a near infrared absorbing composition 2 was prepared.
　分散剤Ｃ１：リン酸エーテル系分散剤、プライサーフＡ２０８Ｆ（第一工業製薬社製、ポリオキシエチレンアルキル（Ｃ８）エーテルリン酸エステル、一般式（１）で表される構造を有する化合物）
　（近赤外線吸収性組成物３の調製）
　上記近赤外線吸収性組成物１の調製において、アルキルホスホン酸として、プロピルホスホン酸に代えて、オクチルホスホン酸を用いた以外は同様にして、近赤外線吸収性組成物３を調製した。 Dispersant C1: Phosphate ether dispersant, Plysurf A 208 F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkyl (C8) ether phosphate, compound having a structure represented by the general formula (1))
(Preparation of Near Infrared Absorbent Composition 3)
A near infrared absorbing composition 3 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that octylphosphonic acid was used as the alkylphosphonic acid in place of propylphosphonic acid.
　（近赤外線吸収性組成物４の調製）
　上記近赤外線吸収性組成物１の調製において、アルキルホスホン酸として、プロピルホスホン酸に代えて、ヘキシルホスホン酸を用いた以外は同様にして、近赤外線吸収性組成物４を調製した。 (Preparation of Near-Infrared Absorbent Composition 4)
A near infrared absorptive composition 4 was prepared in the same manner as in the preparation of the near infrared absorptive composition 1 except that hexylphosphonic acid was used as the alkylphosphonic acid in place of propylphosphonic acid.
　（近赤外線吸収性組成物５の調製）
　上記近赤外線吸収性組成物１の調製において、アルキルホスホン酸として、プロピルホスホン酸に代えて、エチルホスホン酸を用いた以外は同様にして、近赤外線吸収性組成物５を調製した。 (Preparation of Near-Infrared Absorbent Composition 5)
A near infrared absorbing composition 5 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that ethylphosphonic acid was used as the alkylphosphonic acid in place of propylphosphonic acid.
　（近赤外線吸収性組成物６の調製）
　上記近赤外線吸収性組成物１の調製において、分散剤Ｂである分散剤Ｂ１（ポリカルボン酸型高分子分散剤）を除いた以外は同様にして、比較例の近赤外線吸収性組成物６を調製した。 (Preparation of Near-Infrared Absorbent Composition 6)
In the preparation of the above-mentioned near-infrared ray absorbing composition 1, a near-infrared ray absorbing composition 6 of the comparative example is similarly prepared except that the dispersant B1 (polycarboxylic acid type polymer dispersant) which is the dispersant B is removed. Prepared.
　（近赤外線吸収性組成物７の調製）
　上記近赤外線吸収性組成物１の調製において、分散剤Ａである分散剤Ａ１（ＰＧＭＥＡ）に代えて、同量のトルエン（分子量：９２）を用いた以外は同様にして、比較例の近赤外線吸収性組成物７を調製した。 (Preparation of Near-Infrared Absorbent Composition 7)
The near infrared rays of the comparative example are prepared similarly except that the same amount of toluene (molecular weight: 92) is used instead of the dispersant A1 (PGMEA) which is the dispersant A in the preparation of the near infrared radiation absorbing composition 1 described above. Absorbent composition 7 was prepared.
　（近赤外線吸収性組成物８の調製）
　上記近赤外線吸収性組成物１の調製において、プロピルホスホン酸銅微粒子以外の非固形成分の添加量を適宜調整し、最終的な固形分比率が３５質量％となるように変更した以外は同様にして、近赤外線吸収性組成物８を調製した。 (Preparation of Near Infrared Absorbent Composition 8)
The same procedure as in the preparation of the near infrared absorbing composition 1 was repeated except that the addition amount of non-solid components other than copper propylphosphonate fine particles was appropriately adjusted and the final solid content ratio was changed to 35% by mass. Thus, a near infrared absorbing composition 8 was prepared.
　（近赤外線吸収性組成物９の調製）
　上記近赤外線吸収性組成物１の調製において、プロピルホスホン酸銅微粒子以外の非固形成分の添加量を適宜調整し、最終的な固形分比率が５質量％となるように変更した以外は同様にして、近赤外線吸収性組成物９を調製した。 (Preparation of Near-Infrared Absorbent Composition 9)
The same procedure as in the preparation of the near-infrared absorptive composition 1 was repeated except that the addition amount of non-solid components other than copper propylphosphonate fine particles was appropriately adjusted and the final solid content ratio was changed to 5% by mass. Thus, a near infrared absorbing composition 9 was prepared.
　（近赤外線吸収性組成物１０の調製）
　上記近赤外線吸収性組成物１の調製において、プロピルホスホン酸銅錯体調製時の酢酸銅と、プロピルホスホン酸の添加量を、銅に対するリンのモル比が２．０となるように適宜変更した以外は同様にして、近赤外線吸収性組成物１０を調製した。 (Preparation of Near-Infrared Absorbent Composition 10)
In the preparation of the above-mentioned near-infrared ray absorbing composition 1, except that the addition amount of copper acetate and propylphosphonic acid at the time of preparation of the propylphosphonic acid copper complex was appropriately changed so that the molar ratio of phosphorus to copper would be 2.0. Similarly prepared near infrared absorbing composition 10.
　（近赤外線吸収性組成物１１の調製）
　上記近赤外線吸収性組成物１の調製において、分散剤Ａである分散剤Ａ１（ＰＧＭＥＡ）に代えて、下記分散剤Ａ２を用いた以外は同様にして、近赤外線吸収性組成物１１を調製した。 (Preparation of Near Infrared Absorbent Composition 11)
A near infrared absorbing composition 11 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the following dispersing agent A2 was used instead of the dispersing agent A (PGMEA) as the dispersing agent A. .
　分散剤Ａ２：プロピレングリコールモノエチルエーテルアセテート（分子量：１４６）
　（近赤外線吸収性組成物１２の調製）
　上記近赤外線吸収性組成物１の調製において、分散剤Ａである分散剤Ａ１（ＰＧＭＥＡ）に代えて、下記分散剤Ａ３を用いた以外は同様にして、近赤外線吸収性組成物１２を調製した。 Dispersant A2: Propylene glycol monoethyl ether acetate (molecular weight: 146)
(Preparation of Near-Infrared Absorbent Composition 12)
A near infrared absorptive composition 12 was prepared in the same manner except that the following dispersant A3 was used instead of the dispersant A1 (PGMEA) which is the dispersant A in the preparation of the near infrared absorptive composition 1 described above. .
　分散剤Ａ３： プロピレングリコールモノブチルエーテルアセテート（分子量：１７４）
　（近赤外線吸収性組成物１３の調製）
　上記近赤外線吸収性組成物１の調製において、分散剤Ｂとして、分散剤Ｂ１（ポリカルボン酸型高分子分散剤）に代えて、下記分散剤Ｂ２を用いた以外は同様にして、近赤外線吸収性組成物１３を調製した。 Dispersant A3: Propylene glycol monobutyl ether acetate (molecular weight: 174)
(Preparation of Near Infrared Absorbent Composition 13)
In the preparation of the above-mentioned near-infrared ray absorbing composition 1, near-infrared ray absorption is carried out in the same manner, except that the following dispersant B2 is used in place of the dispersant B1 (polycarboxylic acid type polymer dispersant) as the dispersant B. Sex composition 13 was prepared.
　分散剤Ｂ２：ネオハイテノールＬ－３０（第一工業製薬社製、ポリオキシエチレンスルホコハク酸、官能基：スルホン基）
　（近赤外線吸収性組成物１４の調製）
　上記近赤外線吸収性組成物１の調製において、分散剤Ｂとして、分散剤Ｂ１（ポリカルボン酸型高分子分散剤）に代えて、下記分散剤Ｂ３を用いた以外は同様にして、近赤外線吸収性組成物１４を調製した。 Dispersant B2: Neohytenol L-30 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene sulfosuccinic acid, functional group: sulfone group)
(Preparation of Near-Infrared Absorbent Composition 14)
In the preparation of the above-mentioned near-infrared ray absorbing composition 1, near-infrared ray absorption is carried out in the same manner, except that the following dispersant B3 is used in place of the dispersant B1 (polycarboxylic acid type polymer dispersant) as the dispersant B. Sex composition 14 was prepared.
　分散剤Ｂ３：カチオーゲンＴＭＬ（第一工業製薬社製、ラウリルトリメチルアンモニウムクロザイド、官能基：アミノ基）
　（近赤外線吸収性組成物１５の調製）
　２－エチルヘキシル－２－エチルヘキシルホスホネートの１０．０ｇをトルエンの１５ｇに溶解させた溶液に、酢酸銅一水和物の３．２９ｇを加え、この溶液を加熱還流しながら酢酸を溜去して、２－エチルヘキシル－２－エチルヘキシルホスホネートの銅錯体（表Ｉには、*１と表示）が固形分比で４０質量％である近赤外線吸収性組成物１５を調製した。 Dispersant B3: Cathogen TML (Daiichi Kogyo Seiyaku Co., Ltd., lauryltrimethylammonium clothide, functional group: amino group)
(Preparation of Near Infrared Absorbent Composition 15)
3.29 g of copper acetate monohydrate was added to a solution of 10.0 g of 2-ethylhexyl-2-ethylhexyl phosphonate in 15 g of toluene, and acetic acid was distilled off while the solution was heated to reflux. A near infrared absorptive composition 15 was prepared in which the copper complex of 2-ethylhexyl-2-ethylhexyl phosphonate (represented as * 1 in Table I) is 40% by mass in terms of solid content ratio.
　（近赤外線吸収性組成物１６の調製）
　上記近赤外線吸収性組成物１の調製において、分散剤Ａである分散剤Ａ１（ＰＧＭＥＡ）に代えて、下記分散剤Ａ４を用いた以外は同様にして、近赤外線吸収性組成物１６を調製した。 (Preparation of Near Infrared Absorbent Composition 16)
A near infrared absorbing composition 16 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1 except that the following dispersing agent A4 was used in place of the dispersing agent A (PGMEA) as the dispersing agent A. .
　分散剤Ａ４：１，３－ブチレングリコールジメタクリレート（分子量：２２６）
　（近赤外線吸収性組成物１７の調製）
　上記近赤外線吸収性組成物１の調製において、プロピルホスホン酸の０．６３ｇを、フェニルホスホン酸の０．８７ｇに変更した以外は同様にして、近赤外線吸収性組成物１７を調製した。 Dispersant A4: 1,3-butylene glycol dimethacrylate (molecular weight: 226)
(Preparation of Near Infrared Absorbent Composition 17)
A near infrared absorbing composition 17 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that 0.63 g of propylphosphonic acid was changed to 0.87 g of phenylphosphonic acid.
　（近赤外線吸収性組成物１８の調製）
　上記近赤外線吸収性組成物２の調製において、プロピルホスホン酸の０．６３ｇを、フェニルホスホン酸の０．８７ｇに変更した以外は同様にして、近赤外線吸収性組成物１８を調製した。 (Preparation of Near Infrared Absorbent Composition 18)
A near infrared absorbing composition 18 was prepared in the same manner as in the preparation of the near infrared absorbing composition 2 except that 0.63 g of propylphosphonic acid was changed to 0.87 g of phenylphosphonic acid.
　上記作製した近赤外線吸収性組成物１～１８の基本構成を表Ｉに示す。 Table 1 shows the basic composition of the above-prepared near infrared ray absorbing compositions 1 to 18.
　なお、表Ｉに略称で記載した各添加剤の詳細は、以下のとおりである。 In addition, the detail of each additive described in Table I by abbreviation is as follows.
　〈ホスホン酸銅塩〉
　＊１：２－エチルヘキシル－２－エチルヘキシルホスホネートの銅錯体
　〈分散剤Ａ〉
　分散剤Ａ１:プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ、分子量：１３２）
　分散剤Ａ２：プロピレングリコールモノエチルエーテルアセテート（分子量：１４６）
　分散剤Ａ３：プロピレングリコールモノブチルエーテルアセテート（分子量：１７４）
　分散剤Ａ４：１，３－ブチレングリコールジメタクリレート（分子量：２２６）
　〈分散剤Ｂ〉
　分散剤Ｂ１：ホモゲノールＬ１８（花王社製、ポリカルボン酸型高分子界面活性剤）
　分散剤Ｂ２：ネオハイテノールＬ－３０（第一工業製薬社製、ポリオキシエチレンスルホコハク酸、官能基：スルホン基）
　分散剤Ｂ３：カチオーゲンＴＭＬ（第一工業製薬社製、ラウリルトリメチルアンモニウムクロザイド、官能基：アミノ基）
　〈分散剤Ｃ：その他の分散剤〉
　分散剤Ｃ１：プライサーフＡ２０８Ｆ（第一工業製薬社製、ポリオキシエチレンアルキル（Ｃ８）エーテルリン酸エステル）
　《近赤外線吸収性組成物の評価》
　上記調製した各近赤外線吸収性組成物について、下記の方法に従って、粒径安定性及び可視光透過率安定性の評価を行った。 <Phosphonic acid phosphonate>
* 1: 2-Ethylhexyl 2-ethylhexyl phosphonate copper complex <Dispersant A>
Dispersant A1: Propylene glycol monomethyl ether acetate (PGMEA, molecular weight: 132)
Dispersant A2: Propylene glycol monoethyl ether acetate (molecular weight: 146)
Dispersant A3: Propylene glycol monobutyl ether acetate (molecular weight: 174)
Dispersant A4: 1,3-butylene glycol dimethacrylate (molecular weight: 226)
Dispersant B
Dispersant B1: Homogenol L18 (manufactured by Kao Corporation, polycarboxylic acid type polymer surfactant)
Dispersant B2: Neohytenol L-30 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene sulfosuccinic acid, functional group: sulfone group)
Dispersant B3: Cathogen TML (Daiichi Kogyo Seiyaku Co., Ltd., lauryltrimethylammonium clothide, functional group: amino group)
Dispersant C: Other Dispersants
Dispersant C1: Plysurf A 208 F (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkyl (C8) ether phosphate ester)
<< Evaluation of near infrared absorbing composition >>
The particle size stability and the visible light transmittance stability of each of the prepared near infrared absorptive compositions were evaluated according to the following method.
　〔粒径安定性の評価〕
　（調製直後の平均粒径の測定）
　近赤外線吸収性組成物について、粒子であるアルキルホスホン酸銅錯体の粒子濃度が１．０質量％となるように、近赤外線吸収性組成物の溶媒成分で希釈したサンプル１を調製した。 [Evaluation of particle size stability]
(Measurement of average particle size immediately after preparation)
Sample 1 was prepared by diluting the solvent component of the near infrared absorptive composition such that the particle concentration of the alkylphosphonic acid copper complex which is the particle was 1.0% by mass for the near infrared absorptive composition.
　次いで、サンプル１の平均粒径を、測定装置として大塚電子株式会社製のＥＬＳＺ－１０００を用い、動的光散乱法により測定した。 Subsequently, the average particle diameter of the sample 1 was measured by a dynamic light scattering method using ELSZ-1000 manufactured by Otsuka Electronics Co., Ltd. as a measurement device.
　上記方法で測定した調製直後の平均粒径を、下記の基準に従ってランク付けを行った。 The average particle diameter immediately after preparation measured by the above method was ranked according to the following criteria.
　◎：平均粒径が、１０～３００ｎｍの範囲内である
　○：平均粒径が、３０１～５００ｎｍの範囲内である
　△：平均粒径が、５０１～７００ｎｍの範囲内である
　×：平均粒径が、７０１ｎｍ以上である
　（保存後の平均粒径の測定）
　近赤外線吸収性組成物の原液をガラス容器に収納し、容器内を窒素ガスで充填した状態で密閉し、このガラス容器を５℃で３日間暗所保存した後、上記と同様の方法で、粒子であるアルキルホスホン酸銅錯体の粒子濃度が１．０質量％となるように、近赤外線吸収性組成物の溶媒成分で希釈した保存処理後のサンプル２を調製した。 ◎: Average particle size is in the range of 10 to 300 nm ○: Average particle size is in the range of 301 to 500 nm Δ: Average particle size is in the range of 501 to 700 nm ×: Average particle size Is at least 701 nm (measurement of average particle size after storage)
A stock solution of a near infrared absorbing composition is housed in a glass container, the container is sealed in a state of being filled with nitrogen gas, and this glass container is stored in the dark at 5 ° C. for 3 days. Sample 2 after storage processing was prepared by diluting with the solvent component of the near-infrared absorptive composition such that the particle concentration of the alkylphosphonic acid copper complex which is the particles was 1.0% by mass.
　次いで、サンプル２について、上記と同様の方法で平均粒径を測定し、同様のランク付けを行った。 Subsequently, the average particle diameter was measured by the method similar to the above about sample 2, and the same ranking was performed.
　〔可視光透過率安定性の評価〕
　（調製直後の可視光透過率の測定）
　近赤外線吸収性組成物について、粒子であるアルキルホスホン酸銅錯体の粒子濃度が１．０質量％となるように、近赤外線吸収性組成物の溶媒成分で希釈したサンプル１を調製した。 [Evaluation of visible light transmittance stability]
(Measurement of visible light transmittance immediately after preparation)
Sample 1 was prepared by diluting the solvent component of the near infrared absorptive composition such that the particle concentration of the alkylphosphonic acid copper complex which is the particle was 1.0% by mass for the near infrared absorptive composition.
　次いで、サンプル１を、測定装置として日本分光社製の分光光度計Ｖ－５７０を用い、３８０～１２００ｎｍの波長域における分光透過率を測定した。次いで、７５０～１１００ｎｍの波長域における平均分光透過率を１．０％としたときの、可視光領域（４００～７５０ｎｍ）における最大透過率Ｔｍａｘ１を測定した。 Next, the spectral transmittance of the sample 1 in the wavelength range of 380 to 1200 nm was measured using a spectrophotometer V-570 manufactured by JASCO Corporation as a measurement apparatus. Next, when the average spectral transmittance in a wavelength range of 750 to 1100 nm was 1.0%, the maximum transmittance T max1 in a visible light region (400 to 750 nm) was measured.
　次いで、上記方法で測定した調製直後の近赤外線吸収性組成物の可視光領域での最大透過率Ｔｍａｘ１を、下記の基準に従ってランク付けを行った。 Next, the maximum transmittance T max1 in the visible light region of the near-infrared absorbing composition immediately after preparation measured by the above method was ranked according to the following criteria.
　◎：最大透過率Ｔｍａｘ１が、９５％以上である
　○：最大透過率Ｔｍａｘ１が、９３％以上、９５％未満である
　△：最大透過率Ｔｍａｘ１が、９０％以上、９３％未満である
　×：最大透過率Ｔｍａｘ１が、９０％未満である
　（保存後の可視光透過率の測定）
　近赤外線吸収性組成物の原液を、ガラス容器に収納し、容器内を窒素ガスで充填した状態で密閉し、このガラス容器を、５℃で３日間暗所保存した後、上記と同様の方法で、粒子であるアルキルホスホン酸銅錯体の粒子濃度が１．０質量％となるように、近赤外線吸収性組成物の溶媒成分で希釈した保存処理後のサンプル２を調製した。 A: Maximum transmittance T max1 is 95% or more B: Maximum transmittance T max1 is 93% or more and less than 95% C : Maximum transmittance T max1 is 90% or more and less than 93% X: Maximum transmittance T max1 is less than 90% (measurement of visible light transmittance after storage)
A stock solution of a near infrared absorbing composition is housed in a glass container, the container is sealed in a state filled with nitrogen gas, and the glass container is stored in the dark at 5 ° C. for 3 days, and then the same method as described above Then, a sample 2 after storage treatment was prepared which was diluted with the solvent component of the near infrared ray absorbing composition so that the particle concentration of the alkylphosphonic acid copper complex which is the particle was 1.0% by mass.
　次いで、サンプル２について、上記と同様の方法で３８０～１２００ｎｍの波長域における分光透過率を測定し、７５０～１１００ｎｍの波長域における平均分光透過率を１．０％としたときの、保存後の可視光領域（４００～７５０ｎｍ）における最大透過率Ｔｍａｘ２を測定した。 Next, the spectral transmittance of the sample 2 in the wavelength range of 380 to 1200 nm is measured by the same method as above, and the average spectral transmittance in the wavelength range of 750 to 1100 nm is 1.0% after storage. The maximum transmittance T max2 in the visible light region (400 to 750 nm) was measured.
　次いで、上記測定した調製直後のサンプル１の最大透過率Ｔｍａｘ１に対する、保存後のサンプル２の最大透過率Ｔｍａｘ２の可視光透過率の低下幅ΔＴ（Ｔｍａｘ１－Ｔｍａｘ２）を求め、下記の基準に従って、保存後の可視光透過率のランク付けを行った。 Next, the decrease width ΔT (T max1 -T max2 ) of the visible light transmittance of the maximum transmittance T max2 of the sample 2 after storage with respect to the maximum transmittance T max1 of the sample 1 immediately after the preparation measured above is determined. According to the criteria, the visible light transmittance after storage was ranked.
　◎：可視光透過率の低下幅ΔＴが、１．０％未満である
　○：可視光透過率の低下幅ΔＴが、１．０％以上、３．０％未満である
　△：可視光透過率の低下幅ΔＴが、３．０％以上、５．０％未満である
　×：可視光透過率の低下幅ΔＴが、５．０％未満である
　以上により得られた結果を、表Ｉに示す。 :: The reduction width ΔT of visible light transmittance is less than 1.0% ○: The reduction width ΔT of visible light transmittance is 1.0% or more and less than 3.0% Δ: visible light transmittance The reduction width ΔT of is 3.0% or more and less than 5.0%. ×: The reduction width ΔT of the visible light transmittance is less than 5.0%. The results obtained according to the above are shown in Table I. .
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表Ｉに記載の結果より明らかなように、本発明の近赤外線吸収性組成物は、比較例に対し、調製直後のアルキルホスホン酸銅錯体粒子の平均粒子が小さく、かつ、保存されたのちの平均粒径の劣化率が低く、保存安定性に優れていることが分かる。更に、本発明の近赤外線吸収性組成物は、比較例に対し、近赤外領域の透過率に対する可視光領域における透過率が高く、可視光の透過率への影響が少なく、優れた近赤外光のカット能を有していることが分かる。更に、保存処理を行っても、その特性は変化しないことが分かる。 As apparent from the results described in Table I, the near-infrared absorbing composition of the present invention is smaller than the comparative example in average particles of alkylphosphonic acid copper complex particles immediately after preparation and after being stored. It can be seen that the deterioration rate of the average particle size is low and the storage stability is excellent. Furthermore, the near-infrared absorbing composition of the present invention is superior to the comparative example in the transmittance in the visible light region with respect to the transmittance in the near-infrared region, and the effect on the visible light transmittance is small. It can be seen that it has the ability to cut ambient light. Furthermore, it can be seen that the characteristics do not change even if storage processing is performed.
　実施例２
　《近赤外線吸収性膜の作製》
　実施例１で調製した各近赤外線吸収性組成物に、ポリシロキサンシリコーン樹脂（ＫＲ－２５５、信越化学工業社製）を加えて撹拌して、近赤外線吸収性膜形成用の塗布液を調製した。調製した塗布液をスピンコーティング法により基板上に塗布して近赤外線吸収性膜を形成した。 Example 2
<< Preparation of near-infrared absorbing film >>
A polysiloxane silicone resin (KR-255, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to each of the near infrared absorbing compositions prepared in Example 1 and stirred to prepare a coating solution for forming a near infrared absorbing film. . The prepared coating solution was applied onto a substrate by spin coating to form a near infrared absorptive film.
　次いで、形成した近赤外線吸収性膜に対し、所定の加熱処理を行って塗膜を硬化させ、固体撮像素子用イメージセンサーに適用可能な近赤外線カットフィルターを作製した。 Subsequently, predetermined heat processing were performed with respect to the formed near-infrared absorptive film, the coating film was hardened, and the near-infrared cut off filter applicable to the image sensor for solid-state image sensors was produced.
　次いで、実施例１に記載の方法と同様にして保存処理後の各近赤外線吸収性組成物を用いて、同様にして、近赤外線カットフィルターを作製した。 Subsequently, a near-infrared cut filter was produced in the same manner using each near-infrared absorptive composition after storage treatment in the same manner as in the method described in Example 1.
　上記作製した各近赤外線カットフィルターについて、実施例１に記載の方法と同様にして、可視光透過率安定性の評価した結果、フィルム系でも同様の効果が得られることを確認した。 About each produced said near-infrared cut off filter, it carried out similarly to the method as described in Example 1, and as a result of evaluating visible light transmittance stability, it confirmed that the same effect was acquired also with a film type | system | group.
　実施例３
　《近赤外線吸収性膜の作製》
　実施例１で調製した各近赤外線吸収性組成物に、エポキシ基を有する樹脂（ＫＪＣ－Ｘ５、信越化学工業社製）を加えて撹拌して、近赤外線吸収性膜形成用の塗布液を調製した。調製した塗布液をスピンコーティング法により基板上に塗布して近赤外線吸収性膜を形成した。 Example 3
<< Preparation of near-infrared absorbing film >>
A resin (KJC-X5, manufactured by Shin-Etsu Chemical Co., Ltd.) having an epoxy group is added to each of the near infrared absorbing compositions prepared in Example 1 and stirred to prepare a coating solution for forming a near infrared absorbing film. did. The prepared coating solution was applied onto a substrate by spin coating to form a near infrared absorptive film.
　次いで、形成した近赤外線吸収性膜に対し、所定の加熱処理を行って塗膜を硬化させ、固体撮像素子用イメージセンサーに適用可能な近赤外線カットフィルターを作製した。 Subsequently, predetermined heat processing were performed with respect to the formed near-infrared absorptive film, the coating film was hardened, and the near-infrared cut off filter applicable to the image sensor for solid-state image sensors was produced.
　次いで、実施例１に記載の方法と同様にして保存処理後の各近赤外線吸収性組成物を用いて、同様にして、近赤外線カットフィルターを作製した。 Subsequently, a near-infrared cut filter was produced in the same manner using each near-infrared absorptive composition after storage treatment in the same manner as in the method described in Example 1.
　上記作製した各近赤外線カットフィルターについて、実施例１に記載の方法と同様にして、可視光透過率安定性の評価した結果、フィルム系でも同様の効果が得られることを確認した。 About each produced said near-infrared cut off filter, it carried out similarly to the method as described in Example 1, and as a result of evaluating visible light transmittance stability, it confirmed that the same effect was acquired also with a film type | system | group.
　本発明の近赤外線吸収性組成物は、長期間にわたる保存における、構成材料の分散安定性及び近赤外線カット安定性に優れ、近赤外線吸収性組成物により作製された近赤外線吸収性膜は、ビデオカメラ、デジタルスチルカメラ、カメラ機能付き携帯電話などに適用される固体撮像素子用イメージセンサー等に好適に利用できる。 The near-infrared absorptive composition of the present invention is excellent in the dispersion stability and near-infrared cut stability of constituent materials in storage over a long period of time, and the near-infrared absorptive film produced by the near-infrared absorptive composition is a video The present invention can be suitably used as an image sensor for a solid-state imaging device applied to a camera, a digital still camera, a mobile phone with a camera function, and the like.
　１　カメラモジュール
　２、７　接着剤
　３　ガラス基板
　４　撮像レンズ
　５　レンズホルダー
　６　遮光兼電磁シールド
　８　平坦化層
　９　近赤外線吸収性膜（近赤外線カットフィルター）
　１０　固体撮像素子基板
　１１　ハンダボール
　１２　回路基板 Reference Signs List 1 camera module 2 7 adhesive 3 glass substrate 4 imaging lens 5 lens holder 6 light shielding and electromagnetic shield 8 flattening layer 9 near infrared absorbing film (near infrared cut filter)
10 solid-state imaging device substrate 11 solder ball 12 circuit substrate

Claims (11)

  1. 　ホスホン酸銅錯体と、２種以上の分散剤を含有する近赤外線吸収性組成物であって、当該分散剤の少なくとも１種が、下記一般式（１）で表される構造を有し、かつ分子量が１９０以下の分散剤Ａであることを特徴とする近赤外線吸収性組成物。
    Figure JPOXMLDOC01-appb-C000001
     〔式中、Ｒ１は水素原子又は１～４価の有機基を表す。Ｒ２は炭素数２～４のアルキレン基を表す。Ｒ３は、水素原子、アルキル基又はアシル基を表す。ａは０～１０の整数である。ｂは１～４の整数である。〕     It is a near-infrared absorptive composition containing a phosphonic acid copper complex and 2 or more types of dispersing agents, wherein at least one of the dispersing agents has a structure represented by the following general formula (1), and A near-infrared absorptive composition characterized by being a dispersant A having a molecular weight of 190 or less.
    Figure JPOXMLDOC01-appb-C000001
     [Wherein, R 1 represents a hydrogen atom or a monovalent to tetravalent organic group. R 2 represents an alkylene group having 2 to 4 carbon atoms. R 3 represents a hydrogen atom, an alkyl group or an acyl group. a is an integer of 0 to 10. b is an integer of 1 to 4; ]
  2. 　前記２種以上の分散剤のうちの少なくとも１種が、下記官能基群から選ばれる少なくとも一つの官能基を有する分散剤Ｂであることを特徴とする請求項１に記載の近赤外線吸収性組成物。
    　官能基群：ヒドロキシ基、チオール基、カルボニル基、カルボキシ基、スルホン酸基、シアノ基、アミノ基、及びピリジル基。     The near-infrared absorptive composition according to claim 1, wherein at least one of the two or more dispersants is a dispersant B having at least one functional group selected from the following functional group group: object.
    Functional groups: hydroxy group, thiol group, carbonyl group, carboxy group, sulfonic acid group, cyano group, amino group, and pyridyl group.
  3. 　前記２種以上の分散剤のうち、前記分散剤Ａを除く分散剤が、前記一般式（１）で表される構造を有していない分散剤であることを特徴とする請求項１又は請求項２に記載の近赤外線吸収性組成物。 Among the two or more dispersants, the dispersant excluding the dispersant A is a dispersant which does not have a structure represented by the general formula (1). The near-infrared absorptive composition of claim 2.
  4. 　前記ホスホン酸銅錯体を構成するホスホン酸が、下記ホスホン酸群Ａから選ばれる少なくとも１種のホスホン酸であることを特徴とする請求項１から請求項３までのいずれか一項に記載の近赤外線吸収性組成物。
    　ホスホン酸群Ａ：エチルホスホン酸、プロピルホスホン酸、ブチルホスホン酸、ペンチルホスホン酸、ヘキシルホスホン酸、オクチルホスホン酸、２－エチルヘキシルホスホン酸、２－クロロエチルホスホン酸、３－ブロモプロピルホスホン酸、３－メトキシブチルホスホン酸、１，１－ジメチルプロピルホスホン酸、１，１－ジメチルエチルホスホン酸、１－メチルプロピルホスホン酸。     The phosphonic acid which comprises the said phosphonic acid copper complex is at least 1 sort (s) of phosphonic acid chosen from the following phosphonic acid group A, The near any one of Claim 1 to 3 characterized by the above-mentioned Infrared absorbing composition.
    Phosphonic acid group A: Ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, 2-ethylhexylphosphonic acid, 2-chloroethylphosphonic acid, 3-bromopropylphosphonic acid, 3 Methoxybutylphosphonic acid, 1,1-dimethylpropylphosphonic acid, 1,1-dimethylethylphosphonic acid, 1-methylpropylphosphonic acid.
  5. 　前記ホスホン酸銅錯体を構成するホスホン酸が、下記ホスホン酸群Ｂから選ばれる少なくとも１種のホスホン酸であることを特徴とする請求項１から請求項３までのいずれか一項に記載の近赤外線吸収性組成物。
    　ホスホン酸群Ｂ：フェニルホスホン酸、４－メトキシフェニルホスホン酸、（４－アミノフェニル）ホスホン酸、（４－ブロモフェニル）ホスホン酸、３－ホスホノ安息香酸、４－ホスホノ安息香酸、及び（４－ヒドロキシフェニル）ホスホン酸。     The phosphonic acid which comprises the said phosphonic acid copper complex is at least 1 sort (s) of phosphonic acid chosen from the following phosphonic acid group B, The near any one of Claim 1 to 3 characterized by the above-mentioned Infrared absorbing composition.
    Phosphonic acid group B: phenylphosphonic acid, 4-methoxyphenylphosphonic acid, (4-aminophenyl) phosphonic acid, (4-bromophenyl) phosphonic acid, 3-phosphonobenzoic acid, 4-phosphonobenzoic acid, and (4- Hydroxyphenyl) phosphonic acid.
  6. 　近赤外線吸収性組成物全質量に対する固形分の比率が、１０～３４質量％の範囲内であることを特徴とする請求項１から請求項５までのいずれか一項に記載の近赤外線吸収性組成物。 The ratio of the solid content to the total weight of the near infrared absorbing composition is in the range of 10 to 34% by mass, the near infrared absorbing composition according to any one of claims 1 to 5 Composition.
  7. 　前記ホスホン酸銅錯体を構成するリンの銅に対するモル比（リン／銅）の値が、１．５以下であることを特徴とする請求項１から請求項６までのいずれか一項に記載の近赤外線吸収性組成物。 The value of the molar ratio (phosphorus / copper) with respect to copper of the phosphorus which comprises the said phosphonic acid copper complex is 1.5 or less, The said Claim 1 to 6 characterized by the above-mentioned Near infrared absorbing composition.
  8. 　少なくとも請求項１から請求項７までのいずれか一項に記載の近赤外線吸収性組成物を用いたことを特徴とする近赤外線吸収性膜。 A near-infrared-absorbing film characterized by using the near-infrared-absorbing composition according to any one of claims 1 to 7.
  9. 　ポリシロキサンを有するマトリックス樹脂を含有することを特徴とする請求項８に記載の近赤外線吸収性膜。 The near-infrared absorptive film according to claim 8, comprising a matrix resin having a polysiloxane.
  10. 　エポキシ基を有するマトリックス樹脂を含有することを特徴とする請求項８に記載の近赤外線吸収性膜。 The near-infrared absorptive film according to claim 8, comprising a matrix resin having an epoxy group.
  11. 　請求項８から請求項１０までのいずれか一項に記載の近赤外線吸収性膜を具備していることを特徴とする固体撮像素子用イメージセンサー。 An image sensor for a solid-state imaging device, comprising the near-infrared absorptive film according to any one of claims 8 to 10.
PCT/JP2018/033735 2017-09-14 2018-09-12 Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging device WO2019054394A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019542077A JP7103362B2 (en) 2017-09-14 2018-09-12 Method for Producing Near Infrared Absorbent Composition and Near Infrared Absorbent Film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017176412 2017-09-14
JP2017-176412 2017-09-14

Publications (1)

Publication Number Publication Date
WO2019054394A1 true WO2019054394A1 (en) 2019-03-21

Family

ID=65723355

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/033735 WO2019054394A1 (en) 2017-09-14 2018-09-12 Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging device

Country Status (2)

Country Link
JP (1) JP7103362B2 (en)
WO (1) WO2019054394A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020195701A1 (en) * 2019-03-26 2020-10-01

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009242650A (en) * 2008-03-31 2009-10-22 Kureha Corp Copper salt composition, resin composition using the same, infrared-absorbing film and optical member
JP2012185385A (en) * 2011-03-07 2012-09-27 Kureha Corp Manufacturing method of near-infrared ray absorbent fluid dispersion
WO2016068037A1 (en) * 2014-10-28 2016-05-06 富士フイルム株式会社 Near-infrared absorbing composition, near-infrared blocking filter, solid-state imaging element and camera module
JP2016124903A (en) * 2014-12-26 2016-07-11 株式会社クレハ Production method of fine particle dispersion of near-infrared absorber, fine particle dispersion of near-infrared absorber, and application thereof
WO2017006571A1 (en) * 2015-07-09 2017-01-12 日本板硝子株式会社 Infrared cutoff filter, imaging device, and method for manufacturing infrared cutoff filter
WO2017056803A1 (en) * 2015-09-28 2017-04-06 富士フイルム株式会社 Near-infrared cutoff filter, method for manufacturing near-infrared cutoff filter, and solid image-pickup element

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009242650A (en) * 2008-03-31 2009-10-22 Kureha Corp Copper salt composition, resin composition using the same, infrared-absorbing film and optical member
JP2012185385A (en) * 2011-03-07 2012-09-27 Kureha Corp Manufacturing method of near-infrared ray absorbent fluid dispersion
WO2016068037A1 (en) * 2014-10-28 2016-05-06 富士フイルム株式会社 Near-infrared absorbing composition, near-infrared blocking filter, solid-state imaging element and camera module
JP2016124903A (en) * 2014-12-26 2016-07-11 株式会社クレハ Production method of fine particle dispersion of near-infrared absorber, fine particle dispersion of near-infrared absorber, and application thereof
WO2017006571A1 (en) * 2015-07-09 2017-01-12 日本板硝子株式会社 Infrared cutoff filter, imaging device, and method for manufacturing infrared cutoff filter
WO2017056803A1 (en) * 2015-09-28 2017-04-06 富士フイルム株式会社 Near-infrared cutoff filter, method for manufacturing near-infrared cutoff filter, and solid image-pickup element

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020195701A1 (en) * 2019-03-26 2020-10-01
WO2020195701A1 (en) * 2019-03-26 2020-10-01 コニカミノルタ株式会社 Near-infrared-absorbing composition, near-infrared-absorbing film, and image sensor for solid-state imaging element
CN113614195A (en) * 2019-03-26 2021-11-05 柯尼卡美能达株式会社 Near-infrared-absorbing composition, near-infrared-absorbing film, and image sensor for solid-state imaging element
CN113614195B (en) * 2019-03-26 2023-10-20 柯尼卡美能达株式会社 Near infrared ray absorbing composition, near infrared ray absorbing film, and image sensor for solid-state imaging element
JP7452530B2 (en) 2019-03-26 2024-03-19 コニカミノルタ株式会社 Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging devices

Also Published As

Publication number Publication date
JP7103362B2 (en) 2022-07-20
JPWO2019054394A1 (en) 2020-10-29

Similar Documents

Publication Publication Date Title
CN105308124B (en) Curable adhensive compositions, cured film, near infrared ray cut-off filter, camera module and these manufacturing method
JP2024020208A (en) Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging element
WO2019054394A1 (en) Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging device
JP7099251B2 (en) Image sensor for near-infrared absorbing composition, near-infrared absorbing film and solid-state image sensor
JP7103213B2 (en) Image sensor for near-infrared absorbing composition, near-infrared absorbing film and solid-state image sensor
JP7156366B2 (en) Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging device
KR102532381B1 (en) Near-infrared absorbing composition, near-infrared absorbing film and image sensor for solid-state imaging device
JP7452530B2 (en) Near-infrared absorbing composition, near-infrared absorbing film, and image sensor for solid-state imaging devices
JP6237986B2 (en) High refractive index film forming composition for solid-state imaging device
WO2023032722A1 (en) Method for manufacturing lens module and thermosetting adhesive
JP7552193B2 (en) Near-infrared absorbing composition, near-infrared absorbing film, near-infrared cut filter, image sensor for solid-state imaging device, and camera module
TW202346373A (en) Near-infrared absorbing composition, near-infrared absorbing cured film and optical member wherein the near-infrared absorbing composition includes a dispersion medium containing a solvent whose polar item of the Hansen solubility parameter is in the range of 3 to 6, and whose hydrogen bonding item is in the range of 3 to 6
CN108026402A (en) The manufacture method of pigment dispersion, the manufacture method of solidification compound, the manufacture method of cured film, possess cured film solid-state imager manufacture method, possess cured film colour filter manufacture method and possess cured film image display device manufacture method
JP2010018700A (en) Optical element and process for manufacturing electronic equipment
JP2015017194A (en) High refractive index film forming composition for solid-state imaging element containing alkoxysilane
JP2009265232A (en) Optical element, and method of manufacturing electronic equipment using the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18855633

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019542077

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18855633

Country of ref document: EP

Kind code of ref document: A1