JP5909936B2 - Optical filter, solid-state imaging device, camera module - Google Patents

Description

  The present invention relates to an optical filter, a solid-state imaging device, and a camera module. More specifically, an optical filter, a solid-state imaging device, and a solvent-soluble dye compound capable of playing an important role in a color separation filter used in a display element such as a liquid crystal television or an imaging tube, a color copying machine, and the like It relates to a camera module.

  Conventionally, a phthalocyanine compound having a substituent at the β-position is known as a dye compound used for filters (Patent Document 1).

JP-A-1-233401

  However, the compound described in Patent Document 1 has poor solubility in the solvent and the binder resin due to the association of the compound itself. Moreover, when a color separation filter is produced using the compound, practical filter characteristics (transmittance characteristics) are not sufficient, and the obtained filter is restricted when used.

  An object of the present invention is to provide a filter having excellent transmittance characteristics, comprising a compound having excellent solubility in a solvent and a binder resin, improving the drawbacks of conventional filters and filter dye compounds. There is to do.

  As a result of intensive studies to achieve the above object, the present inventors have found that the dye compound represented by the following formula (1) is excellent in solubility in a solvent and a binder resin, and by using such a compound, transmission is possible. The inventors have found that an optical filter having excellent rate characteristics can be obtained, and have completed the present invention.

  [1] An optical filter comprising a resin substrate containing a dye compound having a structure derived from a compound represented by the following formula (1).

（式（１）中、Ｘ^2-は２価の陰イオンであり、Ｒ_x1、Ｒ_y1、Ｒ_x2およびＲ_y2は炭素原子であり、ｎは１〜３の整数であり、ｍは１〜３の整数であり、複数あるＲ₁およびＲ₂はそれぞれ独立して
水素原子、
ハロゲン原子、
水酸基、
シアノ基、
ニトロ基、
炭素数１〜９の炭化水素基を有しても良いアミノ基、もしくはカルボニル基、
炭素数１〜９の炭化水素基を有しても良い、炭素数１〜９のアルキル基、アルケニル基、アルキニル基、もしくはアルコキシル基、
炭素数１〜９の炭化水素基を有しても良い、炭素数３〜１４の芳香族炭化水素基、もしくは芳香族複素環基、または、
Ｒ₁およびＲ₂が結合し、Ｒ₂−Ｒ_y1＝Ｒ_x1−Ｒ₁が、下記式（２）〜（４）から選ばれる少なくとも１種の基、もしくはＲ₂−Ｒ_y2−Ｒ_x2−Ｒ₁が、下記式（５）〜（７）から選ばれる少なくとも１種の基である。）

(In the formula (1), X ²⁻ is a divalent anion, R _x1 , R _y1 , R _x2 and R _y2 are carbon atoms, n is an integer of 1 to 3, and m is 1 to Each of R ₁ and R ₂ independently represents a hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
Nitro group,
An amino group which may have a hydrocarbon group having 1 to 9 carbon atoms, or a carbonyl group,
An alkyl group having 1 to 9 carbon atoms, an alkenyl group, an alkynyl group, or an alkoxyl group, which may have a hydrocarbon group having 1 to 9 carbon atoms,
An aromatic hydrocarbon group having 3 to 14 carbon atoms or an aromatic heterocyclic group, which may have a hydrocarbon group having 1 to 9 carbon atoms, or
R ₁ and R ₂ are bonded, and R ₂ -R _y1 = R _x1 -R ₁ is at least one group selected from the following formulas (2) to (4), or R ₂ -R _y2 -R _x2- R ₁ is at least one group selected from the following formulas (5) to (7). )

（式（２）〜（７）中、Ｒ_x1、Ｒ_y1、Ｒ_x2およびＲ_y2は炭素原子であり、複数あるＲ₁およびＲ₂はそれぞれ独立してＣＲ（但し、Ｒは水素原子または炭素数１〜９の炭化水素基である。）または窒素原子であり、複数あるＲ₃およびＲ₄はそれぞれ独立して
水素原子、
ハロゲン原子、
水酸基、
シアノ基、
ニトロ基、
炭素数１〜９の炭化水素基を有しても良いアミノ基、もしくはカルボニル基、
炭素数１〜９の炭化水素基を有しても良い、炭素数１〜９のアルキル基、アルケニル基、アルキニル基、もしくはアルコキシル基、または
炭素数１〜９の炭化水素基を有しても良い、炭素数３〜１４の芳香族炭化水素基、もしくは芳香族複素環基である。）

(In the formulas (2) to (7), R _x1 , R _y1 , R _x2 and R _y2 are carbon atoms, and a plurality of R ₁ and R ₂ are each independently CR (where R is a hydrogen atom or carbon Or a nitrogen atom, and a plurality of R ₃ and R ₄ are each independently a hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
Nitro group,
An amino group which may have a hydrocarbon group having 1 to 9 carbon atoms, or a carbonyl group,
It may have a C1-C9 hydrocarbon group, may have a C1-C9 alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, or a C1-C9 hydrocarbon group A good aromatic hydrocarbon group having 3 to 14 carbon atoms or an aromatic heterocyclic group. )

  [2] The optical filter according to [1], wherein the optical filter is for a solid-state imaging device.

  [3] A solid-state imaging device comprising the optical filter according to any one of [1] to [2].

  [4] A camera module comprising the optical filter according to any one of [1] to [2].

  ADVANTAGE OF THE INVENTION According to this invention, the filter excellent in the transmittance | permeability characteristic formed by containing the compound excellent in the solubility to a solvent and binder resin can be provided.

FIG. 1A is a schematic cross-sectional view showing an example of a conventional camera module. FIG. 1B is a schematic cross-sectional view showing an example of a camera module when the optical filter 6 ′ obtained by the present invention is used. FIG. 2 is a schematic diagram showing a method for measuring the transmittance when measured from the vertical direction of the optical filter. FIG. 3 is a schematic diagram illustrating a method for measuring the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter.

  Hereinafter, the present invention will be specifically described.

  The optical filter according to the present invention has a resin substrate containing a dye compound having a structure derived from a compound represented by the following formula (1).

<Dye compound>
The dye compound has a structure derived from a compound represented by the following formula (1).
The dye compound is excellent in solubility in a solvent and a binder resin. For this reason, by using this compound, an optical filter having excellent transmittance characteristics can be obtained, and an optical filter which is not restricted when used can be obtained.
The dye compound is a solvent-soluble compound that can play an important role in a color separation filter used in a display element such as a liquid crystal television, an image pickup tube, a color copier, or the like.

（式（１）中、Ｘ^2-は２価の陰イオンであり、Ｒ_x1、Ｒ_y1、Ｒ_x2およびＲ_y2は炭素原子であり、ｎは１〜３の整数であり、ｍは１〜３の整数であり、複数あるＲ₁およびＲ₂はそれぞれ独立して
水素原子、
ハロゲン原子、
水酸基、
シアノ基、
ニトロ基、
炭素数１〜９の炭化水素基を有しても良いアミノ基、もしくはカルボニル基、
炭素数１〜９の炭化水素基を有しても良い、炭素数１〜９のアルキル基、アルケニル基、アルキニル基、もしくはアルコキシル基、
炭素数１〜９の炭化水素基を有しても良い、炭素数３〜１４の芳香族炭化水素基、もしくは芳香族複素環基、または、
Ｒ₁およびＲ₂が結合し、Ｒ₂−Ｒ_y1＝Ｒ_x1−Ｒ₁が、下記式（２）〜（４）から選ばれる少なくとも１種の基、もしくはＲ₂−Ｒ_y2−Ｒ_x2−Ｒ₁が、下記式（５）〜（７）から選ばれる少なくとも１種の基である。）

(In the formula (1), X ²⁻ is a divalent anion, R _x1 , R _y1 , R _x2 and R _y2 are carbon atoms, n is an integer of 1 to 3, and m is 1 to Each of R ₁ and R ₂ independently represents a hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
Nitro group,
An amino group which may have a hydrocarbon group having 1 to 9 carbon atoms, or a carbonyl group,
An alkyl group having 1 to 9 carbon atoms, an alkenyl group, an alkynyl group, or an alkoxyl group, which may have a hydrocarbon group having 1 to 9 carbon atoms,
An aromatic hydrocarbon group having 3 to 14 carbon atoms or an aromatic heterocyclic group, which may have a hydrocarbon group having 1 to 9 carbon atoms, or
R ₁ and R ₂ are bonded, and R ₂ -R _y1 = R _x1 -R ₁ is at least one group selected from the following formulas (2) to (4), or R ₂ -R _y2 -R _x2- R ₁ is at least one group selected from the following formulas (5) to (7). )

（式（２）〜（７）中、Ｒ_x1、Ｒ_y1、Ｒ_x2およびＲ_y2は炭素原子であり、複数あるＲ₁およびＲ₂はそれぞれ独立してＣＲ（但し、Ｒは水素原子または炭素数１〜９の炭化水素基である。）または窒素原子であり、複数あるＲ₃およびＲ₄はそれぞれ独立して
水素原子、
ハロゲン原子、
水酸基、
シアノ基、
ニトロ基、
炭素数１〜９の炭化水素基を有しても良いアミノ基、もしくはカルボニル基、
炭素数１〜９の炭化水素基を有しても良い、炭素数１〜９のアルキル基、アルケニル基、アルキニル基、もしくはアルコキシル基、または
炭素数１〜９の炭化水素基を有しても良い、炭素数３〜１４の芳香族炭化水素基、もしくは芳香族複素環基である。）

(In the formulas (2) to (7), R _x1 , R _y1 , R _x2 and R _y2 are carbon atoms, and a plurality of R ₁ and R ₂ are each independently CR (where R is a hydrogen atom or carbon Or a nitrogen atom, and a plurality of R ₃ and R ₄ are each independently a hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
Nitro group,
An amino group which may have a hydrocarbon group having 1 to 9 carbon atoms, or a carbonyl group,
It may have a C1-C9 hydrocarbon group, may have a C1-C9 alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, or a C1-C9 hydrocarbon group A good aromatic hydrocarbon group having 3 to 14 carbon atoms or an aromatic heterocyclic group. )

In R _{1 to} R ₄ , the amino group which may have a hydrocarbon group having 1 to 9 carbon atoms (hereinafter also simply referred to as “substituent”) is specifically an ethylamino group or a dimethylamino group. , Methylethylamino group, dibutylamino group and the like.

  Specific examples of the carbonyl group which may have a substituent include a carboxyl group, a methylcarbonyl group, an ethylcarbonyl group, an isopropylcarbonyl group, a t-butylcarbonyl group, and a cyclohexylcarbonyl group.

  Specific examples of the alkyl group having 1 to 9 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Hexyl group, cyclohexyl group, octyl group and the like.

  Specific examples of the alkenyl group that may have a substituent include a vinyl group, a propenyl group, a butenyl group, a 2-methyl-1-propenyl group, a hexenyl group, and an octenyl group.

  Specific examples of the alkynyl group which may have a substituent include ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group, octynyl group and the like.

  Specific examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a hexyloxy group, An octyloxy group etc. are mentioned.

  Specific examples of the aromatic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent include a phenyl group, an α-naphthyl group, a β-naphthyl group, an anthracenyl group, a phenanthryl group, an acenaphthyl group, and a phenalenyl group. In addition to a tetrahydronaphthyl group, an indanyl group, a biphenylyl group, etc., those aromatic hydrocarbon groups having an aryl group, an alkyl group or the like as a substituent may be mentioned.

  Specific examples of the aromatic heterocyclic group which may have a substituent include a pyridyl group, a thienyl group, an oxazole group, a thiazole group, an oxadiazole group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, and a pyrazyl group. In addition to a group, a pyrimidyl group, a pyrazoyl group, an imidazolyl group, and the like, those having an aryl group, an alkyl group, or the like as a substituent on these aromatic heterocyclic groups may be mentioned.

X is not particularly limited, but specifically, inorganic ions such as nitrate ion, nitrite ion, sulfate ion, sulfite ion, halogen ion, phosphate ion; alkyl nitrate ion, aryl nitrate ion, perfluoroalkyl nitrate ion And organic ions such as alkyl sulfate ions, aryl sulfate ions, perfluoroalkyl sulfate ions, alkyl phosphate ions, aryl phosphate ions, and perfluoroalkyl phosphate ions.
From the viewpoint of enhancing the solubility of the dye compound in a transparent resin or solvent, it is preferable to use an alkyl phosphate ion or an aryl phosphate ion.

  Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (A) and (B).

  Furthermore, examples of the compound represented by the formula (1) include compounds in which eight monomers represented by the following formulas (D), (E), and (F) each have a cyclic structure.

  The pigment compound is preferably contained in an amount of 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the resin used for the resin substrate.

  Since the dye compound has a wavelength selectivity of absorption at 500 to 700 nm, a band pass filter (for correcting the visibility of a video camera or the like), a laser cut filter (laser cut of 630 nm, 680 nm, etc.), an agricultural plant growth control Filter (for controlling plant growth by cutting light of 600 to 700 nm) and the like.

<Resin substrate>
The resin substrate is not particularly limited as long as it contains the dye compound, but a substrate comprising a dye compound and a resin (binder resin) is preferable.

  Examples of the resin include cyclic olefin resins, aromatic polyether resins, polyarylate resins (PAR), polysulfone resins (PSF), polyethersulfone resins (PES), polyparaphenylene resins (PPP), and polyarylenes. Mention ether phosphine oxide resin (PEPO), polyimide resin (PPI), polyamideimide resin (PAI), (modified) acrylic resin, polycarbonate resin (PC), polyethylene naphthalate (PEN) and organic-inorganic nanohybrid materials Can do.

{Cyclic olefin resin}
The cyclic olefin-based resin is obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ). Resins are preferred.

（式（Ｘ₀）中、Ｒ^x1〜Ｒ^x4は、それぞれ独立に下記（ｉ'）〜（ｖｉｉｉ'）より選ばれる原子または基を表し、ｋ^x、ｍ^xおよびｐ^xは、それぞれ独立に、０または正の整数を表す。）
（ｉ'）水素原子
（ｉｉ'）ハロゲン原子
（ｉｉｉ'）トリアルキルシリル基
（ｉｖ'）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１〜３０の炭化水素基
（ｖ'）置換または非置換の炭素数１〜３０の炭化水素基
（ｖｉ'）極性基（但し（ｉｖ'）を除く）
（ｖｉｉ'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成されたアルキリデン基を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表す
（ｖｉｉｉ'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表すか、Ｒ^x2とＲ^x3とが、相互に結合して形成された単環の炭化水素環または複素環を表し、該結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表す

(In the formula (X ₀ ), R ^{x1 to} R ^x4 each independently represents an atom or group selected from the following (i ′) to (viii ′), and k ^x , ^mx and p ^x are each independently Represents 0 or a positive integer.)
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom -30 hydrocarbon group (v ') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi') polar group (excluding (iv '))
(Vii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent an alkylidene group formed by bonding to each other, and R ^{x1 to} R ^x4 not participating in the bond are each independently the above (i ′ (Vi ') represents a monocyclic or polycyclic hydrocarbon ring formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other, or R ^{x1 to} R ^x4 representing a heterocyclic ring and not involved in the bond each independently represent an atom or group selected from the above (i ′) to (vi ′), or R ^x2 and R ^x3 are mutually R ^{x1 to} R ^x4 each representing a monocyclic hydrocarbon ring or heterocyclic ring formed by bonding are independently selected from the atoms or groups selected from the above (i ′) to (vi ′). Express

（式（Ｙ₀）中、Ｒ^y1およびＲ^y2は、それぞれ独立に前記（ｉ'）〜（ｖｉ'）より選ばれる原子または基を表すか、下記（ｉｘ'）を表し、Ｋ^yおよびＰ^yは、それぞれ独立に、０または正の整数を表す。）
（ｉｘ'）Ｒ^y1とＲ^y2とが、相互に結合して形成された単環または多環の脂環式炭化水素、芳香族炭化水素または複素環を表す

(In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i ′) to (vi ′) or the following (ix ′), and K ^y and P each ^y independently represents 0 or a positive integer.)
(Ix ′) R ^y1 and R ^y2 each represent a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding to each other

{Aromatic polyether resin}
The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

（式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、ａ〜ｄは、それぞれ独立に０〜４の整数を示す。）

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

（式（２）中、Ｒ¹〜Ｒ⁴およびａ〜ｄは、それぞれ独立に前記式（１）中のＲ¹〜Ｒ⁴およびａ〜ｄと同義であり、Ｙは単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、Ｒ⁷およびＲ⁸は、それぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｇおよびｈは、それぞれ独立に０〜４の整数を示し、ｍは０または１を示す。但し、ｍが０の時、Ｒ⁷はシアノ基ではない。）

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

  The aromatic polyether-based resin may further include at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). preferable.

（式（３）中、Ｒ⁵およびＲ⁶は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、Ｚは、単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｅおよびｆは、それぞれ独立に０〜４の整数を示し、ｎは０または１を示す。）

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

（式（４）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈは、それぞれ独立に前記式（２）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆは、それぞれ独立に前記式（３）中のＲ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆと同義である。）

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)

[Polyimide resin]
Furthermore, as resin which can be used for this invention, a polyimide resin can be mentioned.
The polyimide resin is not particularly limited as long as it is a polymer containing an imide bond in a repeating unit. For example, the polyimide resin can be synthesized by a method described in JP-A-2008-163107.

  The resin is preferably a transparent resin, and examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic olefin-based resins include Arton manufactured by JSR Corporation, ZEONOR manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available polyethersulfone resins include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polycarbonate resin include Teijin Limited Pure Ace. Examples of commercially available organic-inorganic nanohybrid materials include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

[Other ingredients]
In the range not impairing the effects of the present invention, additives such as antioxidants, ultraviolet absorbers, dyes and pigments that absorb near infrared rays, and metal complex compounds may be added to the resin substrate. it can. Moreover, when manufacturing a resin-made board | substrate by the solution casting method mentioned later, manufacture of a resin-made board | substrate can be made easy by adding a leveling agent and an antifoamer. These other components may be used alone or in combination of two or more.

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

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

  These additives may be mixed with a resin or the like when producing a resin substrate, or may be added when producing a resin. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the resin. Part.

<Manufacturing method of resin substrate>
The resin substrate can be formed by, for example, melt molding or cast molding, and if necessary, is manufactured by a method of coating a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding. be able to.

(A) Melt molding The resin substrate is a method of melt molding a pellet obtained by melt-kneading the resin and a pigment compound; a method of melt molding a resin composition containing the resin and the pigment compound A pellet compound obtained by removing the solvent from the resin composition containing the dye compound, the resin, and the solvent can be produced by a method such as melt molding. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

(B) Cast molding The resin substrate is formed by casting a resin composition containing a dye compound, the resin and a solvent on an appropriate base material to remove the solvent; an anti-reflection agent and a hard coating agent. And / or casting a resin composition containing a coating agent such as an antistatic agent, a dye compound and the resin on an appropriate substrate; an antireflection agent, a hard coat agent and / or an antistatic agent, etc. It can also be produced by casting a curable composition containing the coating agent, the dye compound, and the resin on a suitable substrate, and curing and drying.

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

The resin substrate can be obtained by peeling from the base material, and unless the effect of the present invention is impaired, the laminate of the base material and the coating film is made from the resin without peeling from the base material. It may be a substrate.
Further, by coating the resin composition on an optical component such as a glass plate, quartz or transparent plastic and drying the solvent, or coating and curing and drying the curable composition, the optical component It is also possible to directly form a resin substrate thereon.

  The amount of residual solvent in the resin substrate obtained by the above method should be as small as possible, and is usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. When the amount of residual solvent is in the above range, a resin substrate can be obtained in which the deformation and characteristics are hardly changed and a desired function can be easily exhibited.

  Furthermore, an organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Examples include amides such as methylpyrrolidone. These solvents may be used alone or in combination of two or more.

<Optical filter>
The optical filter of the present invention has the resin substrate.
For this reason, the optical filter of this invention is excellent in the transmittance | permeability characteristic, and is not subject to restrictions when using it. In addition, since the dye compound contained in the resin substrate has a wavelength selectivity of absorption at 500 to 700 nm, the optical filter of the present invention includes a band-pass filter (for correcting visibility of a video camera or the like), a laser cut filter (630 nm). , Laser cut of 680 nm, etc.), a plant growth control filter for agriculture (control of plant growth by cutting light of 600 to 700 nm) and the like.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the optical filter.

<Camera module>
The camera module of the present invention includes the optical filter.
Here, the case where the optical filter obtained by this invention is used for a camera module is demonstrated concretely.

FIG. 1 is a schematic sectional view of the camera module.
FIG. 1 (a) is a schematic cross-sectional view of the structure of a conventional camera module, and FIG. 1 (b) shows a camera module that can be obtained when the optical filter 6 ′ obtained in the present invention is used. It is the cross-sectional schematic showing one of the structures.

  In FIG. 1 (b), the optical filter 6 ′ obtained by the present invention is used in the upper part of the lens 5. However, the optical filter 6 ′ obtained by the present invention is the same as the lens 5 as shown in FIG. 1 (a). It can also be used between the sensors 7.

  In the conventional camera module, light has to be incident substantially perpendicular to the optical filter 6. Therefore, the filter 6 has to be disposed between the lens 5 and the sensor 7.

  Here, since the sensor 7 has high sensitivity and there is a possibility that the sensor 7 may not operate correctly just by touching dust or dust of about 5 μm, the filter 6 used on the upper part of the sensor 7 is one that does not generate dust or dust. There was a need to include no foreign matter. In addition, due to the characteristics of the sensor 7, it is necessary to provide a predetermined distance between the filter 6 and the sensor 7, which is one factor that hinders the reduction in the height of the camera module.

  On the other hand, in the optical filter 6 ′ obtained by the present invention, there is no significant difference between the transmission wavelengths of light incident from the vertical direction of the filter 6 ′ and light incident from 30 ° with respect to the vertical direction of the filter 6 ′. For this reason (the incident angle dependency of the absorption (transmission) wavelength is small), the filter 6 ′ does not have to be disposed between the lens 5 and the sensor 7 and can be disposed on the upper portion of the lens.

  For this reason, when the optical filter 6 ′ obtained in the present invention is used in a camera module, the camera module is easy to handle, and it is necessary to provide a predetermined interval between the filter 6 ′ and the sensor 7. Therefore, it is possible to reduce the height of the camera module.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example.

  A method for measuring each physical property value and a method for evaluating the physical property will be described below.

(1) Dye solubility The solubility was evaluated by visually observing the prepared film. O represents a transparent film, and x represents a film in which crystals are clearly present on the surface.

(2) Wavelength selectivity The spectral transmittance was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation, and the wavelength selectivity of dye absorption was determined as follows.
(A) Average transmittance at 400 nm ± 20 nm (%)
(B) Average transmittance at 600 nm ± 20 nm (%)
It represents having wavelength selectivity when the difference between (A) and (B) is 40% or more.

[Example 1]
By adding 100 parts by weight of cyclic olefin resin “Arton G” manufactured by JSR Corporation, 0.04 part by weight of the compound (A) represented by the following formula, and methylene chloride to the container, the resin concentration is 20% by weight. Solution was obtained.
Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain an optical filter having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. The dye solubility and spectral transmittance of this optical filter were evaluated. The results are shown in Table 1.

  The optical filter of the present invention is a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, an automobile camera, a TV, a car navigation system, a personal digital assistant, a personal computer, a video game, a medical device, a USB memory, a mobile phone. It can be suitably used for game machines, fingerprint authentication systems, digital music players, toy robots, toys and the like.

  Furthermore, it can be suitably used as a heat ray cut filter or the like attached to glass or the like of automobiles and buildings.

1: camera module 2: lens barrel 3: flexible substrate 4: hollow package 5: lens 6: optical filter 6 ': optical filter 7 obtained by the present invention: CCD or CMOS image sensor 8: optical filter 9: spectrophotometer

Claims (6)

An optical filter comprising a resin substrate containing a dye compound represented by the following formula (1).

(In formula (1), X ²⁻ is nitrate ion, nitrite ion, sulfate ion, sulfite ion, halogen ion, phosphate ion, alkyl nitrate ion, aryl nitrate ion, perfluoroalkyl nitrate ion, alkyl sulfate ion, aryl sulfate ion. A divalent anion selected from an ion, a perfluoroalkyl sulfate ion, an alkyl phosphate ion, an aryl phosphate ion and a perfluoroalkyl phosphate ion, wherein R _x1 , R _y1 , R _x2 and R _y2 are carbon atoms, n Is an integer of 1 to 3, m is an integer of 1 to 3, and a plurality of R ₁ and R ₂ are each independently a hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
Nitro group,
An amino group which may have a hydrocarbon group having 1 to 9 carbon atoms, or a carbonyl group,
May have a hydrocarbon group having 1 to 9 carbon atoms, A alkenyl group, an alkynyl group or an alkoxyl group,
An aromatic hydrocarbon group having 3 to 14 carbon atoms or an aromatic heterocyclic group, which may have a hydrocarbon group having 1 to 9 carbon atoms, or
R ₁ and R ₂ are bonded, and R ₂ -R _y1 = R _x1 -R ₁ is at least one group selected from the following formulas (2) to (4), or R ₂ -R _y2 -R _x2- R ₁ is at least one group selected from the following formulas (5) to (7). )

(In the formulas (2) to (7), R _x1 , R _y1 , R _x2 and R _y2 are carbon atoms, and a plurality of R ₁ and R ₂ are each independently CR (where R is a hydrogen atom or carbon Or a nitrogen atom, and a plurality of R ₃ and R ₄ are each independently a hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
Nitro group,
An amino group which may have a hydrocarbon group having 1 to 9 carbon atoms, or a carbonyl group,
It may have a C1-C9 hydrocarbon group, may have a C1-C9 alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, or a C1-C9 hydrocarbon group A good aromatic hydrocarbon group having 3 to 14 carbon atoms or an aromatic heterocyclic group. ) An optical filter comprising a resin substrate containing a dye compound represented by the following formula (1).

(In formula (1), X ^2- Is nitrate ion, nitrite ion, sulfate ion, sulfite ion, halogen ion, phosphate ion, alkyl nitrate ion, aryl nitrate ion, perfluoroalkyl nitrate ion, alkyl sulfate ion, aryl sulfate ion, perfluoroalkyl sulfate ion, alkyl phosphate A divalent anion selected from an ion, an aryl phosphate ion and a perfluoroalkyl phosphate ion; _x1 , R _y1 , R _x2 And R _y2 Is a carbon atom, n is an integer of 1 to 3, m is an integer of 1 to 3, and a plurality of R ₁ And R ₂ Each independently
  An aromatic hydrocarbon group having 3 to 14 carbon atoms or an aromatic heterocyclic group, which may have a hydrocarbon group having 1 to 9 carbon atoms, or
  R ₁ And R ₂ And R ₂ -R _y1 = R _x1 -R ₁ Is at least one group selected from the following formulas (2) to (4), or R ₂ -R _y2 -R _x2 -R ₁ Is at least one group selected from the following formulas (5) to (7). )

(In the formulas (2) to (7), R _x1 , R _y1 , R _x2 And R _y2 Is a carbon atom and a plurality of R ₁ And R ₂ Are each independently CR (wherein R is a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms) or a nitrogen atom, and a plurality of R _Three And R _Four Each independently
  Hydrogen atom,
  Halogen atoms,
  Hydroxyl group,
  A cyano group,
  Nitro group,
  An amino group which may have a hydrocarbon group having 1 to 9 carbon atoms, or a carbonyl group,
  An alkyl group having 1 to 9 carbon atoms, an alkenyl group, an alkynyl group, or an alkoxyl group, which may have a hydrocarbon group having 1 to 9 carbon atoms, or
  It is a C3-C14 aromatic hydrocarbon group or aromatic heterocyclic group which may have a C1-C9 hydrocarbon group. ) The optical filter according to claim 1, wherein the dye compound has a wavelength selectivity of absorption at 500 to 700 nm. The optical filter according to any one of claims 1 to 3, wherein the optical filter is for a solid-state imaging device. A solid-state imaging apparatus characterized by comprising an optical filter according to any one of claims 1-4. Camera module characterized by comprising the optical filter according to any one of claims 1-4.

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