JP2019168611A - Optical filter - Google Patents

Abstract

To provide an optical filter composition that has a wide half-width in an absorption region and a high transmittance in the visible light region when used in an optical filter.SOLUTION: The optical filter composition contains a cyanine compound (A) represented by the general formula (1) in the figure, and a binder resin (B). (In the formula, A and A' represent specific substituents; Q represents a linking group comprising a C1-9 methine chain that may include a ring structure; Anrepresents a q-valent anion; q represents 1 or 2; and p represents a coefficient to keep the electric charge neutral.)SELECTED DRAWING: Figure 1

Description

  The present invention relates to an optical filter composition containing a cyanine compound and a binder resin, and an optical filter obtained using the optical filter composition.

  The sensitivity of a solid-state imaging device (CCD, CMOS, etc.) used for a digital still camera, a video camera, a mobile phone camera, etc. extends from the ultraviolet region to the infrared region of the light wavelength. On the other hand, human visibility is only in the visible region of the wavelength of light. Therefore, by providing an infrared cut filter between the imaging lens and the solid-state imaging device, the sensitivity of the solid-state imaging device is corrected so as to approach human visibility. (For example, see Patent Documents 1 to 4).

JP 2004-354735 A JP 2011-118255 A JP 2012-008532 A JP, 2006-090781, A

  Accordingly, an object of the present invention is to provide a composition for an optical filter having a wide half width of an absorption region and a high transmittance in the visible light region when used in an optical filter.

  As a result of intensive studies, the present inventor has found that when a composition for an optical filter containing a cyanine compound having a specific structure and a binder resin is used for an optical filter, the half-value width is wide and transmission in the visible light region is achieved. The inventors have found that the ratio is high and can absorb infrared rays efficiently, and have reached the present invention.

  The present invention provides a composition for optical filters containing a cyanine compound (A) represented by the following general formula (1) and a binder resin (B).

（式中、Ａは下記の群Ｉの（ａ）〜（ｍ）から選ばれる基を表し、Ａ’は下記の群ＩＩの（ａ’）〜（ｍ’）から選ばれる基を表し、
Ｑは炭素原子数１〜９のメチン鎖で構成され、鎖中に環構造を含んでいる場合もある連結基を表し、該メチン鎖中の水素原子は水酸基、ハロゲン原子、シアノ基、−ＮＲＲ’、アリール基、アリールアルキル基又はアルキル基で置換されている場合もあり、該−ＮＲＲ’、アリール基、アリールアルキル基及びアルキル基中のメチレン基は更に水酸基、ハロゲン原子、シアノ基又は−ＮＲＲ’で置換されている場合もあり、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で中断されている場合もあり、
Ｒ及びＲ’は、アリール基、アリールアルキル基又はアルキル基を表し、
Ａｎ^−ｑはｑ価のアニオンを表し、ｑは１又は２を表し、ｐは電荷を中性に保つ係数を表す。）

(In the formula, A represents a group selected from (a) to (m) of the following group I, A ′ represents a group selected from (a ′) to (m ′) of the following group II,
Q is composed of a methine chain having 1 to 9 carbon atoms and represents a linking group that may contain a ring structure in the chain. The hydrogen atom in the methine chain is a hydroxyl group, a halogen atom, a cyano group, -NRR. ', An aryl group, an arylalkyl group or an alkyl group may be substituted. The —NRR ′, the aryl group, the arylalkyl group and the methylene group in the alkyl group are further a hydroxyl group, a halogen atom, a cyano group or —NRR. May be substituted with —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, —CONH—, —NHCO—, —N═. It may be interrupted by CH- or -CH = CH-
R and R ′ represent an aryl group, an arylalkyl group or an alkyl group,
An, ^-q represents the q-valent anion, q is 1 or 2, p represents a coefficient to maintain neutral electric charge. )

（式中、環Ｃ及び環Ｃ’は、ベンゼン環、ナフタレン環、フェナントレン環又はピリジン環を表し、
Ｒ¹及びＲ¹’は、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、−ＮＲＲ’、アミド基、フェロセニル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数１〜８のアルキル基を表し、
該炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基及び炭素原子数１〜８のアルキル基は、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、−ＮＲＲ’、アミド基又はフェロセニル基で置換されている場合もあり、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で中断されている場合もあり、
Ｒ²〜Ｒ⁹及びＲ²’〜Ｒ⁹’は、Ｒ¹及びＲ¹’と同様の基又は水素原子を表し、
Ｘ及びＸ’は、酸素原子、硫黄原子、セレン原子、−ＣＲ⁵¹Ｒ⁵²−、炭素原子数３〜６のシクロアルカン−１，１−ジイル基、−ＮＨ−又は−ＮＹ²−を表し、
Ｒ⁵¹及びＲ⁵²は、Ｒ¹及びＲ¹’と同様の基又は水素原子を表し、
Ｙ、Ｙ’及びＹ²は、水素原子、又は水酸基、ハロゲン原子、シアノ基、カルボキシル基、−ＮＲＲ’、アミド基、フェロセニル基、−ＳＯ³Ｈ若しくはニトロ基で置換されている場合もある炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基若しくは炭素原子数７〜３０のアリールアルキル基を表し、
該Ｙ、Ｙ’及びＹ²中のアルキル基、アリール基及びアリールアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ²−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で中断されている場合もあり、
ｒ及びｒ’は、０又は（ａ）〜（ｅ）、（ｇ）〜（ｊ）、（ｌ）、（ｍ）、（ａ’）〜（ｅ’）、（ｇ’）〜（ｊ’）、（ｌ’）及び（ｍ’）において置換可能な数を表す。）

(Wherein, ring C and ring C ′ represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,
R ¹ and R ¹ ′ are a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, a carboxyl group, —NRR ′, an amide group, a ferrocenyl group, an aryl group having 6 to 30 carbon atoms, and the number of carbon atoms. Represents a 7-30 arylalkyl group or a C1-C8 alkyl group,
The aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms and the alkyl group having 1 to 8 carbon atoms are a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, carboxyl Group, —NRR ′, amide group or ferrocenyl group, and may be substituted with —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, — May be interrupted by CONH-, -NHCO-, -N = CH- or -CH = CH-,
R ^{2 to} R ⁹ and R ² ′ to R ⁹ ′ represent the same group or hydrogen atom as R ¹ and R ¹ ′,
X and X ′ represent an oxygen atom, a sulfur atom, a selenium atom, —CR ⁵¹ R ⁵² —, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, —NH— or —NY ² —;
R ⁵¹ and R ⁵² represent the same group or hydrogen atom as R ¹ and R ¹ ′,
Y, Y ′, and Y ² are each a hydrogen atom, or a carbon atom that may be substituted with a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, —NRR ′, an amide group, a ferrocenyl group, —SO ³ H, or a nitro group. Represents an alkyl group having 1 to 20 atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms;
The alkyl group, the aryl group and the methylene group in the arylalkyl group in Y, Y ′ and Y ² are —O—, —S—, —CO—, —COO—, —OCO—, —SO ² —, May be interrupted by —NH—, —CONH—, —NHCO—, —N═CH— or —CH═CH—,
r and r ′ are 0 or (a) to (e), (g) to (j), (l), (m), (a ′) to (e ′), (g ′) to (j ′) ), (L ′) and (m ′) represent the number that can be substituted. )

  Moreover, this invention provides the optical filter which used the said composition for optical filters for at least one part.

  Moreover, this invention provides the camera module which comprises the said optical filter.

  The optical filter of the present invention is excellent in that the half width of the absorption region is wide and the transmittance in the visible light region is high. Moreover, the optical filter obtained from the composition for optical filters of the present invention is suitable for a solid-state imaging device and a camera module.

It is sectional drawing which shows one form of a structure of the camera module of this invention.

  Hereinafter, the composition for optical filters of this invention is demonstrated based on preferable embodiment.

  The composition for optical filters of the present invention contains a cyanine compound (A) represented by the general formula (1) and a binder resin (B).

Examples of the halogen atom represented by R ⁵¹ and R ⁵² in R ^{1 to} R ⁹ and R ¹ ′ to R ⁹ ′ and X and X ′ in the general formula (1) include fluorine, chlorine, bromine and iodine. And
Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2, 3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl 2,5-di-tert-butylphenyl, 2,6-di-tert-butyl Ruphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1 , 1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like,
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl and ferrocenylpropyl. ,
Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, 2- Examples include hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl and tert-octyl.
The aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms and the alkyl group having 1 to 8 carbon atoms are a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, carboxyl There group, an amino group, may have been substituted with an amide group or a ferrocenyl group, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH It may be interrupted by-, -NHCO-, -N = CH- or -CH = CH-, and the number and position of these substitutions and interruptions are arbitrary.
For example, examples of the group in which the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, and nonafluorobutyl.
Examples of the group in which the alkyl group having 1 to 8 carbon atoms is interrupted by -O- include methyloxy, ethyloxy, iso-propyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, heptyloxy , Alkoxy groups such as octyloxy and 2-ethylhexyloxy, 2-methoxyethyl, 2- (2-methoxy) ethoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl and 3-methoxybutyl An alkoxyalkyl group, etc.
Examples of the group in which the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom and interrupted by -O- include, for example, chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, difluoromethyloxy , Trifluoromethyloxy, and nonafluorobutyloxy.

  In the general formula (1), the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X and X ′ includes cyclopropane-1,1-diyl, cyclobutane-1,1- Examples include diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl and cyclohexane-1,1-diyl.

In the general formula (1), a halogen atom represented by Y, Y ′ and Y ² , an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms and an aryl having 7 to 30 carbon atoms Examples of the alkyl group include the groups exemplified in the description of R ^{1 and the} like, and hydrogen atoms in these substituents are a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an amino group, an amide group, a ferrocenyl group,- Any number of SO ₃ H or nitro groups may be substituted.
In addition, the alkyl group, the aryl group and the methylene group in the arylalkyl group in Y, Y ′, and Y ² are —O—, —S—, —CO—, —COO—, —OCO—, —SO. _2- , -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH- may be interrupted. For example, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1- Methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, iso-nonyl, decyl, dodecyl, tridecyl, tetradecyl Alkyl groups such as pentadecyl, hexadecyl, heptadecyl, octadecyl; phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propi Phenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert- Aryl groups such as butylphenyl and cyclohexylphenyl; arylalkyl groups such as benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, and cinnamyl are interrupted by ether bonds, thioether bonds, etc. Such as 2-methoxye 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-phenoxyethyl, 3-phenoxypropyl, 2-methylthioethyl, 2-phenylthio And ethyl.

As the linking group which is composed of a methine chain having 1 to 9 carbon atoms and represented by Q in the general formula (1) and may contain a ring structure in the chain, the following (Q-1) to ( The group represented by any one of Q-11) is preferable because of easy production. The number of carbon atoms in the methine chain having 1 to 9 carbon atoms does not include the carbon atom of the group that replaces the hydrogen atom of the methine chain. For example, when Z ′ or R ^{14 to} R ¹⁹ in the linking groups (Q-1) to (Q-11) includes a carbon atom, the carbon atom is not included. Moreover, carbon atoms other than the methine chain in the ring structure in (Q-4) to (Q-9) are not included.

（式中、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹及びＺ’は、各々独立に、水素原子、水酸基、ハロゲン原子、シアノ基、−ＮＲＲ’、アリール基、アリールアルキル基又はアルキル基を表し、該−ＮＲＲ’、アリール基、アリールアルキル基及びアルキル基は、水酸基、ハロゲン原子、シアノ基又は−ＮＲＲ’で置換されている場合もあり、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で中断されている場合もある、
Ｒ及びＲ’は、アリール基、アリールアルキル基又はアルキル基を表す。）

Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z ′ are each independently a hydrogen atom, hydroxyl group, halogen atom, cyano group, —NRR ′, aryl group, arylalkyl Represents a group or an alkyl group, and the —NRR ′, aryl group, arylalkyl group and alkyl group may be substituted with a hydroxyl group, a halogen atom, a cyano group or —NRR ′, and —O—, —S— , —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, —CONH—, —NHCO—, —N═CH— or —CH═CH— may be interrupted,
R and R ′ represent an aryl group, an arylalkyl group or an alkyl group. )

Examples of the halogen atom, aryl group, arylalkyl or alkyl group represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z ′ include those exemplified in the description of R ^{1 and the} like. As the aryl group, arylalkyl group or alkyl group represented by R and R ′, those exemplified in the description of R ^{1 and the} like can be mentioned.

Examples of the q-valent anion represented by pAn ^-q in the general formula (1) include methanesulfonate ion, dodecylsulfonate ion, butanesulfonate ion, fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate. Ions, trinitrobenzene sulfonate ions, camphor sulfonate ions, nonafluorobutane sulfonate ions, hexadecafluorooctane sulfonate ions, benzene sulfonate ions, toluene sulfonate ions, trifluoromethane sulfonate ions, naphthalene sulfonate ions, diphenylamine -4-sulfonic acid ion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid ion, 2-amino-5-nitrobenzenesulfonic acid ion, JP-A-10-235999, JP-A-10-33795 No. 1, JP-A No. 11-102808, JP-A No. 2000-108510, JP-A No. 2000-168223, JP-A No. 2001-209969, JP-A No. 2001-322354, and JP-A No. 2006-248180. Sulfonate ions described in JP-A-2006-297907, JP-A-8-253705, JP-T-2004-503379, JP-A-2005-336150, and International Publication No. 2006/28006. Organic sulfonate ion; borate ion such as tetraarylborate ion and tetrakis (pentafluorophenyl) borate ion; methanecarboxylate ion, ethanecarboxylate ion, propanecarboxylate ion, butanecarboxylate ion, octanecarboxylate ion, trifluoro Methanesulfonic acid ion, benzene carboxylic acid ion and p- toluenesulfonic acid ion such as a carboxylic acid ion; trifluoromethyl sulfite ion (CF ₃ SO ₃₎ ^-, methyl sulfate ion _(CH 3 _OSO 3) ^-, bis (trifluoromethanesulfonyl (Sulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion, (CF ₃ CF ₂ ) ₃ PF ³⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , (( CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , chloride ion, bromide ion, iodide ion, fluoride ion, chlorate ion, thiocyanate ion, perchlorate ion, hexafluorophosphate ion, hexafluoroantimony Acid ion, tetrafluoroborate ion, octyl phosphate ion, dode Silphosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphonate ion, tetrakis (pentafluorophenyl) borate Quencher anions that have the function of de-exciting (quenching) active molecules that are in an ion or excited state, and ferrocenes that have an anionic group such as a carboxyl group, phosphonic acid group, or sulfonic acid group on the cyclopentadienyl ring In addition to metallocene compound anions such as luteocene, those selected from the following group can be mentioned.

  Specific examples of the cyanine compound used in the present invention include the following compound Nos. 1-185 is mentioned. In the following examples, cyanine cations without anions are shown.

  The production method of the cyanine compound represented by the general formula (1) is not particularly limited, and can be obtained by a method using a known general reaction. For example, the route described in JP2010-209191A As described above, there is a method of synthesizing by reacting a compound having a corresponding structure with an imine derivative.

  The cyanine compound represented by the general formula (1) preferably has a maximum absorption wavelength (λmax) of 650 to 1200 nm, and more preferably 650 to 900 nm. When the maximum absorption wavelength (λmax) exceeds 1200 nm, the effect of the present invention is not exhibited, and when it is less than 650 nm, visible light is absorbed, which is not preferable. A cyanine compound can be used individually or in combination of multiple types.

  Examples of the binder resin (B) include natural polymer materials such as gelatin, casein, starch, cellulose derivatives, and alginic acid, or polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, and styrene-butadiene. Synthetic polymer materials such as copolymers, polystyrene, polycarbonate and polyamide are used.

  In the optical filter composition of the present invention, the content of the cyanine compound represented by the general formula (1) is single or a total of a plurality of types, and preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the binder resin. 0.0 part by mass. When the content of the cyanine compound is less than 0.001 part by mass, an optical filter having sufficient characteristics may not be obtained. When the content of the cyanine compound is greater than 10.0 parts by mass, precipitation of the cyanine compound occurs when forming the optical filter. May happen.

  You may mix | blend another component with the composition for optical filters of this invention as needed. Other ingredients to be blended include UV absorbers such as benzotriazole, triazine and benzoate; antioxidants such as phenol, phosphorus and sulfur; cationic surfactants, anionic surfactants, Antistatic agent comprising nonionic surfactant, amphoteric surfactant, etc .; halogen compound, phosphate ester compound, phosphate amide compound, melamine compound, fluororesin or metal oxide, (poly) melamine phosphate And flame retardants such as (poly) phosphate piperazine; lubricants such as hydrocarbons, fatty acids, aliphatic alcohols, aliphatic esters, aliphatic amides and metal soaps; fumed silica, fine particle silica, silica , Diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder Silica-based inorganic additives such as meteorite, attapulgite, talc, mica, minesotite, pyrophyllite and silica; fillers such as glass fiber and calcium carbonate; crystallization agents such as nucleating agents and crystal accelerators, silane coupling Examples thereof include rubber elasticity imparting agents such as agents and flexible polymers. The amount of these other components used is 50% by mass or less in total in the components excluding the solvent in the optical filter composition of the present invention.

The optical filter of the present invention is prepared by dissolving or dispersing the optical filter composition in an appropriate solvent to prepare a coating solution, and applying the obtained coating solution on a support substrate to remove the solvent. can get.
Application methods include spin coating, dip coating, spray coating, bead coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, die coating and hopper. Examples include the extrusion coating method.
Examples of the support substrate include soda glass, quartz glass, a semiconductor substrate, metal, paper, and plastic. In addition, once an optical filter is formed on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and the application method is not limited.

  The solvent is not particularly limited and various known solvents can be used as appropriate. Examples thereof include alcohols such as isopropanol; ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and butyl diglycol; acetone, Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol; esters such as ethyl acetate, butyl acetate and methoxyethyl acetate; acrylic acid esters such as ethyl acrylate and butyl acrylate; Fluorinated alcohols such as 3-tetrafluoropropanol; hydrocarbons such as hexane, benzene, toluene and xylene; chlorinated hydrocarbons such as methylene dichloride, dichloroethane and chloroform; dimethylformamide And amides such as dimethylacetamide and the like. These organic solvents can be used alone or in combination.

  The thickness of the optical filter is preferably 1 to 200 μm because a uniform film can be obtained and it is advantageous for thinning. If it is less than 1 μm, the function cannot be sufficiently expressed, and if it exceeds 200 μm, the solvent may remain.

  Specific applications of the optical filter of the present invention include a heat ray cut filter mounted on a window glass of an automobile or a building; a digital still camera, a digital video camera, a surveillance camera, an in-vehicle camera, a web camera, and a mobile phone camera And the like. For a solid-state imaging device such as a CCD or CMOS in a solid-state imaging device such as: Visibility correction for solid-state imaging devices; Automatic exposure meter; Display device such as a plasma display.

Next, the camera module of the present invention will be described.
The camera module of the present invention can be manufactured by providing the optical filter of the present invention on the front surface of the image sensor. As shown in FIG. 1, the optical filter 1 of the present invention may be fixed to a portion other than the solid-state image sensor on the light incident side of the solid-state image sensor 2, or directly fixed to the front surface of the solid-state image sensor. .

  In the camera module of the present invention, an optical low-pass filter, an antireflection filter, a color filter, and the like can be arranged as necessary, and the order of stacking these is not particularly limited.

Hereinafter, the case where the optical filter 1 of the present invention is fixed to a portion other than the solid-state image sensor on the light incident side of the solid-state image sensor 2 will be specifically described with respect to the camera module of the present invention.
FIG. 1 is a cross-sectional view showing one embodiment of the configuration of the camera module of the present invention. The camera module includes a solid-state image sensor 2 formed in a rectangular shape in plan view on a semiconductor substrate, and an optical filter 1 on the opposite side of the light-receiving unit 3 of the solid-state image sensor 2. The solid-state image sensor 2 and the optical filter 1 are joined by an adhesive 4 formed in a region excluding the light receiving portion 3 on one surface of the solid-state image sensor 2. The camera module takes in light from the outside through the optical filter 1 and receives the light by a light receiving element disposed in the light receiving unit 3 of the solid-state imaging element 2.

  As the adhesive 4, a UV curable adhesive such as an acrylic resin and an epoxy resin, or a thermosetting resin can be used. After the adhesive 4 is uniformly applied, a known photolithography may be used as necessary. The adhesive 4 is patterned using a technique and bonded by thermosetting. When joining, vacuum pressurization may be performed after bonding in a vacuum environment.

The mounting substrate 8 is a rigid substrate using a glass epoxy substrate, a ceramic substrate, or the like, and is provided with a control circuit for controlling the solid-state imaging device 2.
The solid-state imaging device 2 is disposed on the mounting substrate 8, and then an adhesive is applied in advance to a position where the base portion 7 a of the lens holder of the mounting substrate 8 is fixed.
The lens cap 6 protects the lens 5. The lens barrel portion 7 b of the lens holder holds the lens 5.

  Subsequently, the lens holder 7 is disposed on the mounting substrate 8 so that the lower end surface of the base portion 7a of the lens holder is in contact with the applied adhesive, and the light receiving portion 3 of the solid-state imaging device 2 and the lens barrel portion of the lens holder. The position of the lens holder 7 is adjusted so that the distance from the lens 5 held by the lens 7b matches the focal length of the lens 5.

After adjusting the position of the lens holder 7, the adhesive 4 can be irradiated with ultraviolet rays to cure the adhesive 4, and a camera module can be manufactured.
The entire mounting substrate 8 to which the lens holder 7 is fixed may be heated at about 85 ° C., and the adhesive 4 may be sufficiently cured by thermal curing.

  Since the camera module manufacturing method includes a step of heating the entire mounting substrate 8 after the step of irradiating ultraviolet rays, the lens holder 7, the lens 5 and the optical filter 1 are all made of a material having high heat resistance. It is necessary to use. Specifically, in addition to heating for thermosetting the adhesive 4 as described above, a plurality of solders disposed on the lower surface of the mounting substrate 8 are heated and melted at about 260 ° C. to be soldered to other substrates. For this reason, it is desirable that the material is made of a material having reflow resistance.

  Hereinafter, although an example etc. are given and the present invention is explained still in detail, the present invention is not limited to these examples.

  Examples 1 to 16 show preparation examples of the optical filter composition of the present invention. Comparative Examples 1-6 show the preparation examples of the composition for comparative optical filters. In Evaluation Examples 1 to 16, the compositions for optical filters obtained in Examples 1 to 16 were evaluated. In Comparative Evaluation Examples 1 to 6, the compositions for comparative optical filters manufactured in Comparative Examples 1 to 6 were evaluated. .

[Examples 1 to 16 and Comparative Examples 1 to 6] Composition Nos. 1-No. 16 and comparative optical filter composition No. 1-No. Preparation of No. 6 After mixing the binder resin (B) in toluene with the formulation shown in Tables 1 to 3, the cyanine dye (A) and the solvent were added, and the components were mixed. 1-No. 16 and comparative optical filter composition No. 1-No. 6 was obtained. In addition, the number in a table | surface represents a mass part.

Comparative optical filter composition No. 1-No. Comparative compound No. 4 used for the adjustment of No. 4 1-No. 4 is the following compound.

[Evaluation Examples 1 to 16 and Comparative Evaluation Examples 1 to 6]
Optical filter composition No. 1-No. 16 and comparative optical filter composition No. 1-No. 6 was applied to a PET film (Toyobo A4300, 100 μm thickness) so that the film thickness after drying was 8 to 10 μm, and dried in an oven at 100 ° C. for 15 minutes to prepare an evaluation test piece.
About the obtained evaluation test piece, a transmission spectrum is measured using the visible ultraviolet absorptiometer V-670 made from JASCO, and the maximum absorption wavelength (λmax) which is a wavelength at which the transmittance is minimum in the range of 380 nm to 1500 nm is obtained. It was. Moreover, the half value ((100% −transmittance (%) at the maximum absorption wavelength) / 2) at the maximum absorption wavelength was calculated.
From the obtained transmission spectrum and the half-value calculation result, obtain the wavelength at which the transmittance is half-valued on the long wavelength side and the short wavelength side from the maximum absorption wavelength, respectively, and the absolute value of the difference between the two as the half-value width The transmittance was calculated as the half width of transmittance.
Furthermore, the average value of the transmittance | permeability of 380-620 nm was computed as a transmittance | permeability average value from the transmission spectrum obtained with the maximum absorption wavelength of hardened | cured material.
The results are shown in Tables 1 to 3.

  From the above results, the optical filter composition of the present invention containing the cyanine compound (A) represented by the general formula (1) and the binder resin (B) has a wide half-value width of the absorption region and a visible light region. The transmittance at is high. Therefore, the optical filter which can absorb infrared rays efficiently and is obtained from the composition for optical filters of the present invention is useful for a solid-state imaging device and a camera module.

1. 1. Optical filter 2. Solid-state imaging device Light receiving unit 4. 4. Adhesive Lens 6. Lens cap 7. Lens holder 7a. Base part 7b. Lens barrel 8. Mounting board

Claims (4)

The composition for optical filters containing the cyanine compound (A) represented by following General formula (1), and binder resin (B).

(In the formula, A represents a group selected from (a) to (m) of the following group I, A ′ represents a group selected from (a ′) to (m ′) of the following group II,
Q is composed of a methine chain having 1 to 9 carbon atoms and represents a linking group that may contain a ring structure in the chain. The hydrogen atom in the methine chain is a hydroxyl group, a halogen atom, a cyano group, -NRR. ', An aryl group, an arylalkyl group or an alkyl group may be substituted. The —NRR ′, the aryl group, the arylalkyl group and the methylene group in the alkyl group are further a hydroxyl group, a halogen atom, a cyano group or —NRR. May be substituted with —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, —CONH—, —NHCO—, —N═. It may be interrupted by CH- or -CH = CH-
R and R ′ represent an aryl group, an arylalkyl group or an alkyl group,
An, ^-q represents the q-valent anion, q is 1 or 2, p represents a coefficient to maintain neutral electric charge. )

(Wherein, ring C and ring C ′ represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,
R ¹ and R ¹ ′ are a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, a carboxyl group, —NRR ′, an amide group, a ferrocenyl group, an aryl group having 6 to 30 carbon atoms, and the number of carbon atoms. Represents a 7-30 arylalkyl group or a C1-C8 alkyl group,
The aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms and the alkyl group having 1 to 8 carbon atoms are a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, carboxyl Group, —NRR ′, amide group or ferrocenyl group, and may be substituted with —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, — May be interrupted by CONH-, -NHCO-, -N = CH- or -CH = CH-,
R ^{2 to} R ⁹ and R ² ′ to R ⁹ ′ represent the same group or hydrogen atom as R ¹ and R ¹ ′,
X and X ′ represent an oxygen atom, a sulfur atom, a selenium atom, —CR ⁵¹ R ⁵² —, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, —NH— or —NY ² —;
R ⁵¹ and R ⁵² represent the same group or hydrogen atom as R ¹ and R ¹ ′,
Y, Y ′, and Y ² are each a hydrogen atom, or a carbon atom that may be substituted with a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, —NRR ′, an amide group, a ferrocenyl group, —SO ³ H, or a nitro group. Represents an alkyl group having 1 to 20 atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms;
The alkyl group, the aryl group and the methylene group in the arylalkyl group in Y, Y ′ and Y ² are —O—, —S—, —CO—, —COO—, —OCO—, —SO ² —, May be interrupted by —NH—, —CONH—, —NHCO—, —N═CH— or —CH═CH—,
r and r ′ are 0 or (a) to (e), (g) to (j), (l), (m), (a ′) to (e ′), (g ′) to (j ′) ), (L ′) and (m ′) represent the number that can be substituted. )   The optical filter which used the composition for optical filters of Claim 1 for at least one part.   The optical filter according to claim 2, which is for a solid-state imaging device. A camera module comprising the optical filter according to claim 2.

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