JP7103213B2 - Image sensor for near-infrared absorbing composition, near-infrared absorbing film and solid-state image sensor - Google Patents

Description

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. The present invention relates to a near-infrared absorbing composition having excellent properties, a near-infrared absorbing film capable of reducing the film thickness, and an image sensor for a solid-state imaging device provided with the near-infrared absorbing film.

In recent years, CCDs and CMOS image sensors, which are solid-state image sensors for color images, have been used in video cameras, digital still cameras, mobile phones with camera functions, etc., and these solid-state image sensors have near-infrared wavelengths in their light-receiving parts. Since a silicon photodiode having sensitivity to light in the region is used, it is necessary to correct the visual sensitivity, and a near-infrared cut filter (hereinafter, also referred to as “IR cut filter”) is often used.

Such near-infrared cut filters are roughly divided into absorption type and reflection type, but since the reflection layer applied to the reflection type has the characteristic of being easily affected by the incident angle, the total absorption type is mainly used these days. It is being considered.

As one of the materials for forming such a near-infrared cut filter, a near-infrared absorbing composition using a copper compound is disclosed (see, for example, Patent Document 1).

The method disclosed in Patent Document 1 includes an infrared absorber formed of phenylphosphonic acid and copper ions, and is a value of the ratio of the number of moles of hydroxy groups of the constituent material to the number of moles of copper ions in each constituent material. It is an infrared absorbing composition that defines the above in a specific range, and it is said that the transmittance of light having a wavelength in a specific range in the visible light region can be increased and the cutoff wavelength on the infrared side can be shortened. ..

As for the spectral wavelength characteristics, the method disclosed in Patent Document 1 is insufficient to absorb about 1100 nm required for the IR cut filter only with the copper compound. In recent years, due to the problem of peak shift of the reflective layer, a shift to the full absorption type has been required, and even between 700 and 1100 nm, the absorption around 1100 nm is large, and the spectral characteristics that can assist around 700 nm are also required. There is.

In addition, in the method disclosed in Patent Document 1, phenylphosphonic acid is used to form a specific spectral waveform profile, but phenylphosphonic acid has a property of easily aggregating due to the strength of its interaction. It has, and it is necessary to add a large amount of phosphoric acid esters as a dispersant. Therefore, it is necessary to add a large amount of near-infrared absorbing material in order to exhibit sufficient absorption characteristics, and as a result, the film thickness of the near-infrared absorbing film formed becomes considerably thick, which is an obstacle to thinning. It has become.

Japanese Patent No. 6220107

The present invention has been made in view of the above problems and situations, and the problems to be solved are a near-infrared absorbing composition having excellent dispersion stability, visible light transmission and near-infrared light absorption. The present invention relates to a near-infrared absorbing film capable of reducing the film thickness and an image sensor for a solid-state imaging device provided with the near-infrared absorbing film.

As a result of investigating the cause of the above problem in order to solve the above problem, the present inventor has found that the near-infrared absorber contains at least one of the following component (A) and the following component (B). The molar standard content of copper ions is CC, the molar standard content of the compound having the structure represented by the following general formula (I) is _{C X} , and the compound having the structure represented by the following general formula (II). The molar content of the reactive hydroxy group is _CY and is contained in a compound having a structure represented by the following general formula (I) and a compound having a structure represented by the following general formula (II). When the total content is set to C _H specified by the following formula (1), the value of the ratio represented by C _H / C _C specified by the following formula (2) is in a specific range near infrared absorption. Depending on the composition, a near-infrared absorbing composition having excellent dispersion stability, visible light transmission and near-infrared light absorption, a near-infrared absorbing film capable of reducing the film thickness, and the near-infrared ray. We have found that an image sensor for a solid-state imaging device provided with an absorbent film can be realized, and have arrived at the present invention.

That is, the above problem according to the present invention is solved by the following means.

1. 1. A near-infrared absorbing composition containing a near-infrared absorber and a solvent.
The near-infrared absorber contains at least one of the following component (A) and the following component (B).
In a compound having a structure represented by the following general _formula (I), where the molar standard content of copper ions is CC , Z is represented by the following formulas (Z-1), (Z-2), and (Z-3). The molar standard content of the compound having the structure represented is C _X1 , C _X2 , and C _X3 , respectively, and the molar standard content of the compound having the structure represented by the following general formula (II) is _CY . , The total molar content of the reactive hydroxy groups contained in the compound having the structure represented by the following general formula (I) and the compound having the structure represented by the following general formula (II) is calculated by the following formula (1). A near-infrared absorbing composition characterized in that the conditions specified by the following formula (2) are satisfied when the _CH is specified in 1.

〔上記一般式（Ｉ）において、Ｒは炭素数が１～２０のアルキル基又は炭素数が６～２０のアリール基を表し、Ｒはさらに置換基を有してもよい。Ｚは、下記式（Ｚ－１）～（Ｚ－３）から選択される構造単位を表す。 Equation (1) _CH = C X1 ₊ C _X2 x 2 + C _X3 + _CY x 2
Equation (2) 1.720 ≤ C _H / C _C ≤ 2.070
Component (A) Component consisting of a compound having a structure represented by the following general formula (I), a compound having a structure represented by the following general formula (II), and copper ions (B) Component: The following general formula A component consisting of a compound having a structure represented by (I), a compound having a structure represented by the following general formula (II), and a copper complex obtained by reacting with a copper compound.

[In the above general formula (I), R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R may further have a substituent. Z represents a structural unit selected from the following formulas (Z-1) to (Z-3).

上記式（Ｚ－１）～（Ｚ－３）に記載の＊は結合部位を表し、上記一般式（Ｉ）におけるＯと結合する。

* Represented in the above formulas (Z-1) to (Z-3) represents a binding site and binds to O in the above general formula (I).

R ₂₁ to R ₂₄ represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.

However, the compound having the structure represented by the general formula (I) has at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the condition (ii) at the same time.

Condition (i): R ₂₁ to R ₂₄ are all hydrogen atoms.

Condition (ii): At least one of R ₂₁ to R ₂₄ is an alkyl group having 1 to 4 carbon atoms.

〔上記一般式（II）において、Ｒ^１は置換基を有してもよいフェニル基である。〕。 In the general formula (I), l represents the number of substructures satisfying the above condition (i), and is a number from 1 to 10. m represents the number of substructures satisfying the above condition (ii), and is a number from 1 to 10. ]

[In the above general formula (II), R ¹ is a phenyl group which may have a substituent. ].

2. The near-infrared absorbing composition according to item 1, further comprising a compound selected from the following phosphonic acid group.

Phosphonic acid group: 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.

3. 3. The near-infrared ray absorption according to item 1 or 2, wherein the compound having a structure represented by the general formula (I) is a compound having a structure represented by the following general formula (III). Sex composition.

〔上記一般式（III）において、Ｒ、Ｒ_２１～Ｒ_２４、ｌ及びｍは、前記一般式（Ｉ）におけるそれらと同義である。ｎは１又は２であり、ｎが２のとき、〔 〕内の構造は同一であっても異なっていてもよい。〕。

[In the general formula (III), R, R ₂₁ to R ₂₄ , l and m are synonymous with those in the general formula (I). n is 1 or 2, and when n is 2, the structures in [] may be the same or different. ].

4. Items 1 to 3 are characterized in that the compound having the structure represented by the general formula (I) contains a monoester and a diester, and the molar ratio of the monoester is in the range of 20 to 95%. The near-infrared absorbing composition according to any one of the above.

5. The first to fourth terms of the general formula (I) are characterized by having at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the following condition (iii) at the same time. The near-infrared absorbing composition according to any one of the above.

Condition (i): R ₂₁ to R ₂₄ are all hydrogen atoms.

Condition (iii): Any one of R ₂₁ to R ₂₄ is an alkyl group having 1 to 4 carbon atoms, and the remaining three are hydrogen atoms.

6. The near-infrared absorbing composition according to any one of items 1 to 5, wherein l and m in the general formula (I) are numbers in the range of 1 to 3, respectively. ..

7. The near-infrared absorbing composition according to any one of items 1 to 6, wherein the copper ion or the copper constituting the copper compound contains 100 mol% or less of acetic acid. ..

8. A near-infrared absorbing film according to any one of items 1 to 7, wherein the near-infrared absorbing composition is used.

9. The near-infrared absorbing film according to Item 8, which contains a matrix resin having a polysiloxane structure.

10. The near-infrared absorbing film according to Item 8, which contains a matrix resin having an epoxy group.

11. An image sensor for a solid-state image sensor, which comprises the near-infrared absorbing film according to any one of items 8 to 10.

By the above means of the present invention, a near-infrared absorbing composition having excellent dispersion stability, visible light transmittance and near-infrared light absorption, a near-infrared absorbing film capable of reducing the film thickness, and a near-infrared absorbing film. It is possible to provide an image sensor for a solid-state imaging device provided with the near-infrared external ray absorbing film.

Although the mechanism of expression and mechanism of action of the effects of the present invention have not been clarified, it is inferred as follows.

In the near-infrared absorbing composition of the present invention, the contained near-infrared absorber contains at least one of the component (A) and the component (B), and the molar standard content of copper ions is C. In the compound having a structure represented by the following general formula (I) as _C , the mole of the compound having a structure in which Z is represented by the following formulas (Z-1), (Z-2) and (Z-3). The standard content is C _X1 , C _X2 , and C _X3 , respectively, and the molar standard content of the compound having the structure represented by the following general formula (II) is _CY , and the standard content is represented by the following general formula (I). When the total molar content of the reactive hydroxy groups contained in the compound having the above-mentioned structure and the compound having the structure represented by the following general formula (II) is defined as _CH specified by the following formula (1), Due to the near _- infrared absorbing composition in which the ratio value represented by _CH / CC is in a specific range, the near-infrared absorbability is excellent in dispersion stability, visible light transmission and near-infrared light absorption. The composition can be obtained.

The technique composed of phenylphosphonic acid and copper can expand the near- infrared absorption region as compared with the conventional technique, but as described above, the phenylphosphonic acid compound itself has strong cohesiveness, so that it is dispersed. It was necessary to add a large amount of the agent, and there was a problem that the near-infrared absorbing film became thick.

In the present invention, by applying and using a phosphoric acid ester having a specific structure as a dispersant, excellent dispersion stability of an infrared absorber composed of phenylphosphonic acid having high cohesiveness and copper can be obtained. ..

As a result, it is possible to provide sufficient absorption in the near-infrared region while maintaining a high transmittance in the visible light region, and it is possible to prevent the near-infrared absorbing film from becoming thick.

Further, by substituting a part of the phenylphosphonic acid according to the present invention with an alkylphosphonic acid and using both of them in combination, the wavelength and the amount of absorption in the near infrared region can be adjusted.

Further, by setting the value of the ratio represented by _CH / CC in the range of 1.720 to _2.070 , infrared rays in the near infrared region can be efficiently cut, and visible light of 400 to 400 to CC . The transmittance of light in the wavelength range of 700 nm can be increased.

Schematic cross-sectional view showing an example of the configuration of a camera module including a solid-state image sensor provided with the near-infrared absorbing film of the present invention.

The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing a near-infrared absorber and a solvent, wherein the near-infrared absorber is one of the component (A) and the component (B). The molar standard content of copper ions containing at least one of the above components is defined as CC, and the molar standard content of a compound having a structure represented by the following general formula (I) is defined as _{C X.} The molar standard content of the compound having the structure represented by II) is defined as _CY , and the compound has the structure represented by the following general formula (I) and has the structure represented by the following general formula (II). When the total molar content of the reactive hydroxy groups contained in the compound is CH specified by the following formula (1), the condition specified by the following _formula (2) is satisfied. This feature is a technical feature common to the inventions according to the following embodiments.

In the near-infrared absorbing composition of the present invention, from the viewpoint that the desired effect of the present invention can be further exhibited, the combined use of an alkylphosphonic acid selected from the phosphonic acid group maintains the spectral transmission waveform. However, it is preferable in that the dispersion stability of phenylphosphonic acid can be further improved.

Further, the dispersion stability of the near-infrared absorbing composition is more excellent when the compound having the structure represented by the general formula (I) is a compound having the structure represented by the general formula (III). It is preferable in that excellent spectral wavelength characteristics in the near-infrared region can be obtained.

Further, the compound having the structure represented by the general formula (I) contains a monoester and a diester, and the molar ratio of the monoester is in the range of 20 to 95%, which is more excellent in near-infrared absorption. It is preferable in that the dispersion stability of the composition and excellent spectral wavelength characteristics in the near infrared region can be obtained.

Further, it is more excellent that the general formula (I) has at least one partial structure satisfying the above condition (i) and at least one partial structure satisfying the condition (iii) at the same time. It is preferable in that the dispersion stability of the above and excellent spectral wavelength characteristics in the near infrared region can be obtained.

Further, when l and m in the general formula (I) are numbers in the range of 1 to 3, respectively, the dispersion stability of the near-infrared absorbing composition and the excellent in the near-infrared region are excellent. It is preferable in that the spectral wavelength characteristics can be obtained.

Further, when acetic acid is contained in an amount of 100 mol% or less based on the copper content, more excellent dispersion stability of the near-infrared absorbing composition and excellent spectral wavelength characteristics in the near-infrared region can be obtained. It is preferable in that it can be performed.

The near-infrared absorbing film of the present invention is characterized by using the above-mentioned near-infrared absorbing composition of the present invention. Further, in the near-infrared absorbing film of the present invention, it is necessary to contain a matrix resin having a polysiloxane structure or a matrix resin having an epoxy group as a binder component to obtain a coating film having toughness and excellent transmission characteristics. It is preferable in that it can be obtained.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, "-" representing a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

<< Composition of near-infrared absorbing composition >>
The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing a near-infrared absorber and a solvent, and the near-infrared absorbing agent is one of the following components (A) and (B). In a compound having a structure represented by the following general _formula (I), which contains at least one of the above components and has a molar standard content of copper ions as CC , Z is represented by the following formulas (Z-1) and (Z). -2) The molar standard content of the compound having the structure represented by (Z-3) is C _X1 , C _X2 , and C _X3 , respectively, and the compound having the structure represented by the following general formula (II) The molar standard content is _CY , and the molar content of the reactive hydroxy group contained in the compound having the structure represented by the following general formula (I) and the compound having the structure represented by the following general formula (II). When the total amount is set to CH specified by the following formula (1), it is characterized by satisfying the condition specified by the following _formula (2).

Equation (1) _CH = C X1 ₊ C _X2 x 2 + C _X3 + _CY x 2
Equation (2) 1.720 ≤ C _H / C _C ≤ 2.070
Component (A) Component consisting of a compound having a structure represented by the following general formula (I), a compound having a structure represented by the following general formula (II), and copper ions (B) Component: The following general formula ( A component consisting of a compound having a structure represented by I), a compound having a structure represented by the following general formula (II), and a copper complex obtained by reacting with a copper compound.

Hereinafter, details of the constituent materials of the near-infrared absorbing composition of the present invention will be described.

[Near infrared absorber]
One of the features of the near-infrared absorber according to the present invention is that it contains at least one of the following component (A) and the following component (B).

Component (A) Component consisting of a compound having a structure represented by the following general formula (I), a compound having a structure represented by the following general formula (II), and copper ions (B) Component: The following general formula ( A component consisting of a compound having a structure represented by I), a compound having a structure represented by the following general formula (II), and a copper complex obtained by reacting with a copper compound.

(Mole ratio of copper ion and reactive hydroxy group _CH / _CC )
In the present invention, the molar standard content of copper ions is defined as CC, and in the compound having a structure represented by the following general _formula (I) , Z is represented by the following formulas (Z-1), (Z-2), (Z-2). The molar standard content of the compound having the structure represented by Z-3) is defined as C _X1 , C _X2 , and C _X3 , respectively, and the molar standard content of the compound having the structure represented by the following general formula (II) is defined as C X1, C X2, and C X3, respectively. The total molar content of the reactive hydroxy groups contained in the compound having a structure represented by the following general formula (I) and the compound having a structure represented by the following general formula (II) is defined as _CY . When the _CH specified by the following formula (1) is used, the condition specified by the following formula (2) is satisfied.

Equation (1) _CH = C X1 ₊ C _X2 x 2 + C _X3 + _CY x 2
Equation (2) 1.720 ≤ C _H / C _C ≤ 2.070
In the above formula (2), CC represents the molar standard content (number of moles) of copper ions or copper constituting the copper compound contained in the near _- infrared absorber. On the other hand, for CH, the molar standard content of the compound having the structure represented by the general _formula (I) is defined as C _X , and the molar standard content of the compound having the structure represented by the general formula (II) is defined as _CY . Then, it represents the total molar content of the reactive hydroxy groups contained in the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II). Further, when Z in the compound having the structure represented by the general formula (I) is the formula (Z-2) and when the compound has the structure represented by the general formula (II), each compound is used. The number of moles of the reactive hydroxy group is twice the number of moles of the reactive hydroxy group.

In the present invention, by setting the molar ratio _CH / CC of the copper ion and the reactive hydroxy group within the range specified by the _formula (2), the light transmittance in the wavelength range of 400 to 700 nm of visible light. In addition, there is no leakage of transmitted light near 1100 nm in the near-infrared region, the absorption performance is efficiently maintained, and the spectrum has some absorption characteristics even at 700 nm, which is the end of the long wavelength of visible light. Transmission characteristics can be realized.

Hereinafter, a compound having a structure represented by the general formula (I), a compound having a structure represented by the general formula (II), and a general formula (general formula), which are typical constituents of the near-infrared absorbing composition of the present invention. The compound having the structure represented by III), phosphonic acid, copper complex, solvent and the like will be described. However, the present invention is not limited to the configuration exemplified here.

[Compound having a structure represented by the general formula (I)]
First, a compound having a structure represented by the following general formula (I) according to the present invention will be described.

上記一般式（Ｉ）において、Ｒは炭素数が１～２０のアルキル基又は炭素数が６～２０のアリール基を表し、Ｒはさらに置換基を有してもよい。

In the above general formula (I), R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R may further have a substituent.

Z represents a structural unit selected from the following formulas (Z-1), (Z-2), and (Z-3).

上記式（Ｚ－１）～（Ｚ－３）に記載されている＊は結合部位を表し、上記一般式（Ｉ）におけるＯと結合する。

The * described in the above formulas (Z-1) to (Z-3) represents a binding site and binds to O in the above general formula (I).

In the structural unit selected from the above formulas (Z-1), (Z-2) and (Z-3), the formula (Z-) having one hydroxy group is preferable from the viewpoint of dispersibility of the copper complex. 1) or (Z-2).

In the above general formula (I), when Z is (Z-1), it is a diester, and when Z is (Z-2) or (Z-3), it is a monoester. From the viewpoint of dispersibility of the copper complex, the diester and the monoester are preferably a mixture, and the molar ratio of the monoester to the monoester is preferably in the range of 20 to 95%.

In the general formula (I), l represents the number of substructures satisfying the condition (i) described later, and is a number from 1 to 10. m represents the number of substructures satisfying the condition (ii) described later, and is a number from 1 to 10.

In the above general formula (I), the alkyl group having 1 to 20 carbon atoms represented by R may be linear or branched, and may be, for example, a methyl group, an ethyl group, an n-propyl group or isopropyl. Group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, 2-butyloctyl group, 2-hexyloctyl group, n-decyl group, 2-hexyldecyl group, Examples thereof include an n-dodecyl group and an n-stearyl group. Each alkyl group may further have a substituent. From the viewpoint of dispersibility and moisture resistance of the copper complex, an alkyl group having 6 to 16 carbon atoms is preferable.

Examples of the aryl group represented by R having 6 to 20 carbon atoms include a phenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthenyl group, a fluorenyl group and a phenanthryl group. , Indenyl group, pyrenyl group, biphenylyl group and the like, preferably a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenylyl group, a fluorenonyl group and the like. Each aryl group may further have a substituent.

Examples of the substituent that R may have include an alkyl group (for example, a methyl group, an ethyl group, a trifluoromethyl group, an isopropyl group, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), and a halogen atom. (For example, fluorine atom, etc.), cyano group, nitro group, dialkylamino group (for example, dimethylamino group, etc.), trialkylsilyl group (for example, trimethylsilyl group, etc.), triarylsilyl group (for example, triphenylsilyl group, etc.), etc. ), Triheteroarylsilyl group (eg, tripyridylsilyl group, etc.), benzyl group, aryl group (eg, phenyl group, etc.), heteroaryl group (eg, pyridyl group, carbazolyl group, etc.). Examples thereof include 9,9'-dimethylfluorene, carbazole, dibenzofuran and the like, but there is no particular limitation.

In the general formula (I), R ₂₁ to R ₂₄ represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. However, from the viewpoint of dispersibility of the copper complex, a methyl group is particularly preferable.

In the compound having a structure represented by the general formula (I) according to the present invention, at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the condition (ii) are molecular structures thereof. It is characterized by having at the same time inside.

Condition (i): R ₂₁ to R ₂₄ are all hydrogen atoms.

Condition (ii): At least one of R ₂₁ to R ₂₄ is an alkyl group having 1 to 4 carbon atoms.

In the partial structure satisfying the condition (ii), when at least one of R ₂₁ to R ₂₄ is an alkyl group having 1 to 4 carbon atoms and two are the alkyl groups, three are the alkyl groups and four. Includes structures in which all are the alkyl groups. From the viewpoint of dispersibility of the copper complex, it is preferable that only one of them is an alkyl group having 1 to 4 carbon atoms.

The partial structure satisfying the condition (i) is an ethylene oxide structure in which R ₂₁ to R ₂₄ are all hydrogen atoms, and has a high ability to form a complex with a metal, which contributes to enhancing dispersibility. On the other hand, the condition (ii) is an alkyl-substituted ethylene oxide structure, which has a large number of components and contributes to enhancing the dispersion stability when mixed with water due to the entropy effect.

In the general formula (I), l represents the number of substructures in which R ₂₁ to R ₂₄ defined in the above condition (i) are all hydrogen atoms, and the number is in the range of 1 to 10, preferably. It is in the range of 1 to 3. m represents the number of partial structures in which at least one of R ₂₁ to R ₂₄ defined in the above condition (ii) is an alkyl group having 1 to 4 carbon atoms, and the number is in the range of 1 to 10. , Preferably in the range of 1 to 3.

l and m represent the average number of moles added to the ethylene oxide structure and the alkyl-substituted ethylene oxide structure, respectively.

Further, the compound having the structure represented by the general formula (I) may have at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the condition (iii) at the same time. preferable.

Condition (i): R ₂₁ to R ₂₄ are all hydrogen atoms.

Condition (iii): Any one of R ₂₁ to R ₂₄ is an alkyl group having 1 to 4 carbon atoms, and the remaining three are hydrogen atoms.

For example, when the alkyl group represented by the condition (iii) is a methyl group, it is a compound having an ethylene oxide structure and a propylene oxide structure in the same structure.

In the present application, the "ethylene oxide structure" refers to a repeating unit structure of polyethylene oxide, that is, a structure in which ethylene oxide, which is a three-membered cyclic ether, is ring-opened. The "propylene oxide structure" refers to a repeating unit structure of polypropylene oxide, that is, a structure in which propylene oxide, which is a three-membered cyclic ether, is ring-opened.

Further, in the compound having the structure represented by the general formula (I), a phosphoric acid ester having the structure represented by the following general formula (II) is a more preferable embodiment.

In the general formula (III), R, R ₂₁ to R ₂₄ , l and m are synonymous with those in the general formula (I). n is 1 or 2, and when n is 2, the structures in [] may be the same or different.

Next, specific examples of the compound having the structure represented by the general formula (I) will be described.

First, an example of the structure of a typical exemplary compound will be described.

<Example compound 1>
Exemplified compound 1 is as shown in Table 1 below.
R: Methyl group,
Condition (i): R ₂₁ to R ₂₄ = H
Condition (ii): R ₂₁ = H, R ₂₂ = methyl group, R ₂₃ = methyl group, R ₂₄ = H
Z: Z-3
l: 1.0
m: 8.0
It has the structure of, for example, represented by the structure of the following exemplary compound (1-1).

上記例示化合物（１－１）においては、エチレンオキシド構造と、アルキル置換されたエチレンオキシド構造の順番は、適用する合成方法により、任意に変更が可能であり、下記例示化合物（１－２）も例示化合物１に包含される。

In the above-exemplified compound (1-1), the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure can be arbitrarily changed depending on the synthetic method to be applied, and the following exemplary compound (1-2) is also an exemplary compound. It is included in 1.

本発明においては、エチレンオキシド構造と、アルキル置換されたエチレンオキシド構造の順番は、特に限定されず、それぞれの構造がランダムに配列した化合物も本発明で規定する化合物に含まれる。

In the present invention, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure is not particularly limited, and compounds in which the respective structures are randomly arranged are also included in the compounds defined in the present invention.

<Example compound 2>
Exemplified compound 2 is as shown in Table 1 below.
R: Methyl group,
Condition (i): R ₂₁ to R ₂₄ = H
Condition (ii): R ₂₁ = H, R ₂₂ = H, R ₂₃ = methyl group, R ₂₄ = H
Z: Z-1, Z-2 l: 2.0
m: 3.0
It is represented by the structure of an exemplary compound (2-1) in which Z is Z-2 and an exemplary compound (2-2) in which Z is Z-1.

例示化合物２の場合は、モノエステル比率が５０％であり、上記例示化合物（２－１）と例示化合物（２－２）が、それぞれ同モル量ずつ含まれている。

In the case of the example compound 2, the monoester ratio is 50%, and the above-mentioned example compound (2-1) and the example compound (2-2) are each contained in the same molar amount.

Similar to the above-mentioned exemplified compound 1, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure in the exemplified compound 2 can be arbitrarily changed by the synthesis method, and the following exemplified compounds (2-3) and (2-4) can be arbitrarily changed. ) Is also included in Exemplified Compound 2.

本発明においては、エチレンオキシド構造と、アルキル置換されたエチレンオキシド構造の順番は、特に限定されず、それぞれの構造がランダムに配列した化合物も本発明で規定する化合物に含まれる。

In the present invention, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure is not particularly limited, and compounds in which the respective structures are randomly arranged are also included in the compounds defined in the present invention.

Next, specific examples of the compound having the structure represented by the general formula (I) are listed in Tables I to IV below, but the present invention is not limited to these exemplary compounds.

(Synthesis of Exemplified Compound)
Next, typical examples of the synthesis of the compound having the structure represented by the general formula (I) according to the present invention will be given, but the present invention is not limited to these synthesis methods.

<Synthesis of Exemplified Compound 49>
130 g (1.0 mol) of n-octanol was placed in an autoclave, potassium hydroxide was used as a catalyst, 116 g (2.0 mol) of propylene oxide was added under the conditions of a pressure of 147 kPa and a temperature of 130 ° C., and then 88 g of ethylene oxide was added. (2.0 mol) was added.

Next, after confirming that no n-octanol remained, the above additive was placed in a reactor, and 47 g (0.33 mol) of anhydrous phosphoric acid was reacted at 80 ° C. for 5 hours in a toluene solution, and then distilled. By washing with water and distilling off the solvent under reduced pressure, the following exemplary compound 49 (R = octyl group, condition (i): R ₂₁ = H, R ₂₂ = H, R ₂₃ = H, R ₂₄ = H) , Condition (ii): R ₂₁ = H, R ₂₂ = H, R ₂₃ = methyl group, R ₂₄ = H, l: 2.0, m: 2.0, Z: Phosphate monoester (Z-2) / Phosphate diester (Z-1)) was obtained.

〈例示化合物５６の合成〉
２－エチルヘキサノール１３０ｇ（１．０モル）をオートクレーブに入れ、水酸化カリウムを触媒とし、圧力１４７ｋＰａ、温度１３０℃の条件で、プロピレンオキシド１４５ｇ（２．５モル）を付加させた後、エチレンオキサイド１１０ｇ（２．５モル）を付加させた。

<Synthesis of Exemplified Compound 56>
130 g (1.0 mol) of 2-ethylhexanol was placed in an autoclave, potassium hydroxide was used as a catalyst, and 145 g (2.5 mol) of propylene oxide was added under the conditions of a pressure of 147 kPa and a temperature of 130 ° C., and then ethylene oxide. 110 g (2.5 mol) was added.

Next, after confirming that 2-ethylhexanol did not remain, the above-mentioned additive was taken in a reactor, and 47 g (0.33 mol) of anhydrous phosphoric acid was reacted with a toluene solution at 80 ° C. for 5 hours. By washing with distilled water and distilling off the solvent under reduced pressure, the following exemplary compound 56 (R = 2-ethylhexyl group, condition (i): R ₂₁ = H, R ₂₂ = H, R ₂₃ = H, R ₂₄ = H, condition (ii): R ₂₁ = H, R ₂₂ = H, R ₂₃ = methyl group, R ₂₄ = H, l: 2.5, m: 2.5, Z: phosphate monoester (Z) -2) / Phosphate diester (Z-1)) was obtained.

〈例示化合物５９の合成〉
２－エチルヘキサノール１３０ｇ（１．０モル）をオートクレーブに入れ、水酸化カリウムを触媒とし、圧力１４７ｋＰａ、温度１３０℃の条件で、プロピレンオキシド５８ｇ（１．０モル）を付加させた後、エチレンオキサイド１３２ｇ（３．０モル）を付加させた。

<Synthesis of Exemplified Compound 59>
130 g (1.0 mol) of 2-ethylhexanol was placed in an autoclave, potassium hydroxide was used as a catalyst, 58 g (1.0 mol) of propylene oxide was added under the conditions of a pressure of 147 kPa and a temperature of 130 ° C., and then ethylene oxide was added. 132 g (3.0 mol) was added.

Next, after confirming that 2-ethylhexanol did not remain, the above-mentioned additive was taken in a reactor, and 117 g (1.0 mol) of chlorosulfonic acid was added dropwise in a toluene solution over about 1 hour to react. Then, by washing with distilled water and distilling off the solvent under reduced pressure, the following exemplary compound 59 (R = 2-ethylhexyl group, condition (i): R ₂₁ = H, R ₂₂ = H, R ₂₃ = H, R ₂₄ = H, condition (ii): R ₂₁ = H, R ₂₂ = H, R ₂₃ = methyl group, R ₂₄ = H, l: 3.0, m: 1.0, Z: sulfonic acid (Z-3)) was obtained.

（銅成分）
本発明に係る近赤外線吸収剤においては、前述のとおり、前記一般式（Ｉ）で表される構造を有する化合物及前記一般式（II）で表される構造を有する化合物と、銅イオンからなる（Ａ）成分、又は前記一般式（Ｉ）で表される構造を有する化合物及び前記一般式（II）で表される構造を有する化合物と、銅化合物との反応により得られる銅錯体からなる（Ｂ）成分のうちの少なくともいずれかの成分を含有していることを特徴とする。

(Copper component)
As described above, the near-infrared absorber according to the present invention comprises a compound having a structure represented by the general formula (I), a compound having a structure represented by the general formula (II), and copper ions. It is composed of a component (A) or a compound having a structure represented by the general formula (I) and a copper complex obtained by reacting a compound having a structure represented by the general formula (II) with a copper compound ( B) It is characterized by containing at least one of the components.

As the copper salt in the copper complex obtained by the reaction with the copper ion in the component (A) or the copper compound as the component (B), a copper salt capable of supplying divalent copper ions is used. For example, anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous copper acetoacetate, anhydrous ethyl acetoacetate, anhydrous copper methacrylate, anhydrous copper pyrophosphate, anhydrous copper naphthenate, anhydrous copper citrate, etc. Copper salt of organic acid, hydrate or hydrate of copper salt of the organic acid; inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, basic copper carbonate, etc. Copper salt, hydrate or hydrate of the copper salt of the inorganic acid; copper hydroxide.

(Copper complex)
Regarding a method for synthesizing a copper complex obtained by reacting a compound having a structure represented by the general formula (I) or a compound having a structure represented by the general formula (II) and a copper compound according to the present invention, for example. , Patent No. 4422866 and Japanese Patent No. 5935322 can be applied.

The compound having the structure represented by the general formula (I) according to the present invention is bonded to a copper ion by a coordination bond and / or an ionic bond via a phosphoric acid group represented by Z or a sulfonic acid group. , This copper ion is dissolved or dispersed in a near-infrared light-absorbing film while being surrounded by a compound having a structure represented by the general formula (I), and is brought close by electron transition between d orbitals of the copper ion. Infrared light is selectively absorbed. When Z is a representative example of the phosphoric acid group, the content of phosphorus atoms in the near-infrared light-absorbing film is preferably 1.50 or less with respect to 1 mol of copper ions, and more preferably 0.3. When the content ratio of phosphorus atom to copper ion (hereinafter referred to as “P / Cu”) is 0.3 to 1.3 in terms of molar ratio, the moisture resistance of the near-infrared absorbing film and It was confirmed that it is very suitable from the viewpoint of the moisture resistance of the near-infrared absorbing film and the dispersibility of copper ions in the near-infrared light absorbing layer.

When the molar ratio of P / Cu is less than 0.3, the copper ions coordinate to the compound having the structure represented by the general formula (I) become excessive, and the copper ions become a near-infrared light absorbing film. It tends to be difficult to evenly disperse in it. On the other hand, when the molar ratio of P / Cu exceeds 1.3, devitrification tends to occur easily when the thickness of the near-infrared absorbing film is reduced to increase the copper ion content, resulting in high temperature. This tendency is particularly remarkable in a humid environment. Further, it is more preferable that P / Cu has a molar ratio of 0.8 to 1.3 mol. When this molar ratio is 0.8 or more, the dispersibility of copper ions in the resin can be reliably and sufficiently enhanced.

Further, when the content ratio of copper ions in the near-infrared absorbing film is less than the above lower limit value, sufficient near-infrared light absorption is obtained when the thickness of the near-infrared absorbing film is thinner than about 1 mm. Tends to be difficult. On the other hand, when the content ratio of copper ions exceeds the above upper limit value, it tends to be difficult to disperse the copper ions in the near-infrared light absorbing film.

(Compound having a structure represented by the general formula (II))
Next, a phenylphosphonic acid having a structure represented by the following general formula (II) according to the present invention will be described.

上記一般式（II）において、Ｒ^１は置換基を有してもよいフェニル基である。置換基としては、例えば、アルキル基（例えば、メチル基、エチル基、トリフルオロメチル基、イソプロピル基等）、アルコキシ基（例えば、メトキシ基、エトキシ基等）、ハロゲン原子（例えば、フッ素原子等）、シアノ基、ニトロ基、ジアルキルアミノ基（例えば、ジメチルアミノ基等）、トリアルキルシリル基（例えば、トリメチルシリル基等）、トリアリールシリル基（例えば、トリフェニルシリル基等）、トリヘテロアリールシリル基（例えば、トリピリジルシリル基等）、ベンジル基、ヘテロアリール基（例えば、ピリジル基、カルバゾリル基等）が挙げられ、縮合環としては、９，９′－ジメチルフルオレン、カルバゾール、ジベンゾフラン等が挙げられるが、特に制限はない。

In the above general formula (II), R ¹ is a phenyl group which may have a substituent. Examples of the substituent include an alkyl group (for example, a methyl group, an ethyl group, a trifluoromethyl group, an isopropyl group, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), a halogen atom (for example, a fluorine atom, etc.). , Cyano group, nitro group, dialkylamino group (eg, dimethylamino group, etc.), trialkylsilyl group (eg, trimethylsilyl group, etc.), triarylsilyl group (eg, triphenylsilyl group, etc.), triheteroarylsilyl group. (For example, tripyridylsilyl group etc.), benzyl group, heteroaryl group (for example, pyridyl group, carbazolyl group etc.) can be mentioned, and examples of the fused ring include 9,9'-dimethylfluorene, carbazole, dibenzofuran and the like. However, there are no particular restrictions.

Examples of the phenylphosphonic acid having the structure represented by the general formula (II) include phenylphosphonic acid, 4-methoxyphenylphosphonic acid, (4-aminophenyl) phosphonic acid, (4-bromophenyl) phosphonic acid, and 3-phosphono. Benzoic acid, 4-phosphonobenzoic acid, (4-hydroxyphenyl) phosphonic acid and the like can be mentioned.

<Copper phenylphosphonate complex>
Next, a copper phenylphosphonate complex suitable for the present invention will be described.

The copper phenylphosphonate complex has a structure represented by the following general formula (IV).

一般式（IV）において、置換基を有してもよいフェニル基である。

In the general formula (IV), it is a phenyl group which may have a substituent.

As the copper salt used for forming the phenylphosphonic acid copper complex having the structure represented by the general formula (IV), a copper salt capable of supplying divalent copper ions is used. For example, anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous copper acetoacetate, anhydrous ethyl acetoacetate, anhydrous copper methacrylate, anhydrous copper pyrophosphate, anhydrous copper naphthenate, anhydrous copper citrate, etc. Copper salt of organic acid, hydrate or hydrate of copper salt of the organic acid; inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, basic copper carbonate, etc. Copper salt, hydrate or hydrate of the copper salt of the inorganic acid; copper hydroxide.

In the present invention, the phosphonic acid constituting the copper phosphonate complex is preferably an alkylphosphonic acid, for example, an ethylphosphonic acid copper complex, a propylphosphonate copper complex, a butylphosphonate copper complex, and a pentylphosphonate copper complex. , Hexylphosphonic acid copper complex, octylphosphonic acid copper complex, 2-ethylhexylphosphonic acid copper complex, 2-chloroethylphosphonic acid copper complex, 3-bromopropylphosphonate copper complex, 3-methoxybutylphosphonate copper complex, 1, Examples thereof include 1-dimethylpropylphosphonate copper complex, 1,1-dimethylethylphosphonate copper complex, 1-methylpropylphosphonate copper complex and the like.

[Other constituent materials]
(Other phosphonic acid compounds)
In the near-infrared absorbing composition of the present invention, a compound selected from the phosphonic acid group shown below can be used in combination with phenylphosphonic acid having a structure represented by the general formula (II) according to the present invention.

The phosphonic acid group that can be used in combination includes ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, 2-ethylhexylphosphonic acid, 2-chloroethylphosphonic acid, and 3-bromopropyl. Examples thereof include phosphonic acid, 3-methoxybutylphosphonic acid, 1,1-dimethylpropylphosphonic acid, 1,1-dimethylethylphosphonic acid, and 1-methylpropylphosphonic acid.

In the near-infrared absorbing composition of the present invention, the amount of the phosphonic acid added to the phenylphosphonic acid having the structure represented by the general formula (II) according to the present invention is within a range that does not impair the effect of the phenylphosphonic acid. Although it can be applied in any ratio, it is generally less than 50%, preferably 30% or less, and more preferably 10% or less with respect to phenylphosphonic acid.

(Sulfonic acid compound)
In the near-infrared absorbing composition of the present invention, a sulfonic acid compound can also be used, and examples of the sulfonic acid compound include compounds described in JP-A-2015-430638.

(About acetic acid)
In the near-infrared absorbing composition of the present invention, 100 is compared with respect to copper ions constituting the component (A) contained in the near-infrared absorbing agent or copper constituting the copper compound in the copper complex constituting the component (B). It preferably contains less than a molar percent of acetic acid.

For example, acetic acid is generated when a copper complex compound is prepared using the general formula (I) and copper acetate. By setting the amount of acetic acid within the range specified above, durability (heat and humidity resistance) It is preferable in that a desired spectral spectrum can be obtained in the near-infrared region.

〔solvent〕
Next, a solvent applicable to the preparation of the near-infrared absorbing composition of the present invention will be described.

The solvent that can be used in the near-infrared absorbent composition of the present invention is not particularly limited, and examples thereof include hydrocarbon solvents, more preferably aliphatic hydrocarbon solvents and aromatic hydrocarbons. Hydrocarbon-based solvents and halogen-based solvents can be mentioned as preferable examples.

Examples of the aliphatic hydrocarbon solvent include acyclic aliphatic hydrocarbon solvents such as hexane and heptane, cyclic aliphatic hydrocarbon solvents such as cyclohexane, and alcohol solvents such as methanol, ethanol, n-propanol and ethylene glycol. Examples thereof include a solvent, a ketone solvent such as acetone and methyl ethyl ketone, and an ether solvent such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane and ethylene glycol monomethyl ether. Examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene, cyclohexylbenzene, isopropylbiphenyl and the like. Examples of the halogen-based solvent include methylene chloride, 1,1,2-trichloroethane, chloroform, etc.). In addition, anisole, 2-ethylhexane, sec-butyl ether, 2-pentanol, 2-methyltetrahydrofuran, 2-propylene glycol monomethyl ether, 2,3-dimethyl-1,4-dioxane, sec-butylbenzene, 2-methyl Cyclohexylbenzene and the like can be mentioned. Of these, toluene and tetrahydrofuran are preferable from the viewpoint of boiling point and solubility.

Further, the ratio of the solid content to the near-infrared absorbing composition is in the range of 5 to 30% by mass to obtain an appropriate concentration of solid matter (for example, copper complex particles), and particle aggregation during the storage period. It is preferable in that the property is suppressed and more excellent stability over time (dispersion stability of copper complex particles and near-infrared absorbing ability) can be obtained. It is more preferably in the range of 10 to 20% by mass.

(Near infrared absorption regulator)
In the near-infrared absorbing composition of the present invention, it is necessary to add at least one near-infrared absorbing adjusting agent having an absorption maximum wavelength in the wavelength range of 650 to 800 nm as an additive for adjusting the absorption waveform. Preferred from the point of view. As the near-infrared absorption adjusting agent applied to the present invention, it is preferable to apply a near-infrared absorbing dye having a maximum absorption wavelength in the wavelength range of 650 to 800 nm.

Examples of the near-infrared absorbing dye suitable for the present invention include cyanine dye, squarylium dye, croconium dye, azo dye, anthraquinone dye, naphthoquinone dye, phthalocyanine dye, naphthalocyanine dye, quaterylene dye, dithiol metal complex dye and the like. be able to. Among them, phthalocyanine pigments, naphthalocyanine pigments, and quaterylene pigments are particularly preferable because they sufficiently absorb near infrared rays, have high visible light transmittance, and have high heat resistance.

Specific examples of the phthalocyanine compound include, for example, JP-A-2000-26748, JP-A-2000-63691, JP-A-2001-106689, JP-A-2004-149752, JP-A-2004-18561. Examples of the compounds described in JP-A-2005-220060, JP-A-2007-169343, JP-A-2016-204536, JP-A-2016-218167, etc. are listed, and the methods described in these publications are followed. Can be synthesized.

Specific examples of the quaterylene dye include the compounds described in JP-A-2008-009206 and JP-A-2011-225608, which can be synthesized according to the methods described in these publications.

The near-infrared absorbing dye is also available as a commercial product, for example, FDR002, FDR003, FDR004, FDR005, FDN001 (above, manufactured by Yamada Chemical Industry Co., Ltd.), Exciton TX-EX720, Excolor TX-EX708K (above, Japan). (Catalyst), Lumogen IR765, Lumogen IR788 (above, BASF), ABS694, IRA735, IRA742, IRA751, IRA764, IRA788, IRA800 (above, Exciton), epolar5548, epolight5768 VIS680E, VIS695A, NIR700B, NIR735B, NIR757A, NIR762A, NIR775B, NIR778A, NIR783C, NIR783I, NIR790B, NIR795A Product names such as DLS775B, DLS780A, DLS780C, DLS782F (above, manufactured by Crystalin), B4360, B4361, D4773, D5013 (above, manufactured by Tokyo Chemical Industry Co., Ltd.) can be mentioned.

The amount of the near-infrared absorbing dye added is preferably in the range of 0.01 to 0.1% by mass with respect to 100% by mass of the near-infrared absorbing agent constituting the near-infrared absorbing composition.

When the amount of the near-infrared absorbing dye added is 0.01% by mass or more with respect to 100% by mass of the near-infrared absorbing agent, the near-infrared absorption can be sufficiently enhanced, and when it is 0.1% by mass or less. , The visible light transmittance of the obtained near-infrared absorbing composition is not impaired.

(UV absorber)
In the near-infrared absorbing composition of the present invention, it is preferable that the ultraviolet absorbing agent is further contained in addition to the near-infrared absorbing agent and the solvent from the viewpoint of spectral characteristics and light resistance.

The ultraviolet absorber is not particularly limited, and examples thereof include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylate ester-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a triazine-based ultraviolet absorber. Can be done.

Examples of the benzotriazole-based ultraviolet absorber include 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole and (2-2H-benzotriazole-2-yl). ) -6- (straight chain and side chain dodecyl) -4-methylphenol and the like can be mentioned. Benzotriazole-based UV absorbers can also be obtained as commercial products. For example, there are TINUVIN series such as TINUVIN109, TINUVIN171, TINUVIN234, TINUVIN326, TINUVIN327, TINUVIN328, and TINUVIN928, all of which are commercially available from BASF. It is a product.

Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2-hydroxy-4-methoxy-5-. Examples thereof include sulfobenzophenone and bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane).

Examples of the salicylic acid ester-based ultraviolet absorber include phenyl salicylate and p-tert-butyl salicylate.

Examples of the cyanoacrylate-based ultraviolet absorber include 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3- (3', 4'-methylenedioxyphenyl) -acrylate and the like. Can be mentioned.

Examples of the triazine-based ultraviolet absorber include 2- (2'-hydroxy-4'-hexyloxyphenyl) -4,6-diphenyltriazine. Examples of commercially available triazine-based ultraviolet absorbers include TINUVIN477 (manufactured by BASF).

The amount of the ultraviolet absorber added is preferably in the range of 0.1 to 5.0% by mass with respect to 100% by mass of the near-infrared absorber constituting the near-infrared absorbing composition.

If the amount of the ultraviolet absorber added is 0.1% by mass or more with respect to 100% by mass of the near-infrared absorber, the light resistance can be sufficiently enhanced, and if it is 5.0% by mass or less, the result is obtained. The visible light transmittance of the near-infrared absorbing composition is not impaired.

<< Near-infrared absorbing film and its application fields >>
One of the features of the present invention is the formation of a near-infrared absorbing film using the near-infrared absorbing composition of the present invention.

(Matrix resin)
In the near-infrared absorbing film of the present invention, a matrix resin is added to the near-infrared absorbing composition according to the present invention, and for example, fine particles of a copper complex and a copper phenylphosphonate complex are dispersed in the matrix resin. Is formed by. Further, as an additive for adjusting the absorption waveform, at least one of the near-infrared dyes having an absorption maximum wavelength in the wavelength range of 650 to 800 nm can be added.

A coating liquid for forming a near-infrared absorbing film having the above structure is applied onto a substrate by spin coating or a wet coating method using a dispenser to form a near-infrared absorbing film. Then, the coating film is subjected to a predetermined heat treatment to cure the coating film to form a near-infrared absorbing film.

The matrix resin (also referred to as a binder resin) used for forming the near-infrared absorbing film is a resin having light transmission to visible light and near infrared rays and capable of dispersing fine particles of the infrared absorbing composition. The copper phenylphosphonate complex is a substance with relatively low polarity and disperses well in hydrophobic materials. Therefore, as the matrix resin for forming the near-infrared absorbing film, a resin having an acrylic group, an epoxy group, or a phenyl group can be used. Further, the matrix resin having a polysiloxane structure is not easily thermally decomposed, has high light transmission to visible light and near infrared rays, and has high heat resistance, and is therefore advantageous as a material for an image sensor for a solid-state image sensor. Has characteristics. Therefore, it is also preferable to use a resin having a polysiloxane structure as the matrix resin for the near-infrared absorbing film. Specific examples of the resin having a polysiloxane structure that can be used as a matrix resin for a near-infrared absorbing film include KR-255, KR-300, KR-2621-1, KR-211, KR-511, and KR-216. KR-212 and KR-251 can be mentioned. All of these are silicone resins manufactured by Shin-Etsu Chemical Co., Ltd.

Examples of the silicone resin include SS-6203, SS-6309, VS-9301, and VS-9506, all of which are silicone resins manufactured by Sanyulek.

As the matrix resin used for forming the near-infrared absorbing film of the present invention, it is also a preferable embodiment to contain a matrix resin having an epoxy group from the viewpoint of low gas permeability.

In this case, the matrix resin having an epoxy group constituting the near-infrared absorbing film exhibits high moisture resistance, and therefore has suitable properties as a material for an image sensor for a solid-state image sensor.

Specific examples of resins having an epoxy group that can be used as a matrix resin for a near-infrared absorbing film include KJC-X5 (manufactured by Shin-Etsu Chemical Co., Ltd.), NLD-L-672 (manufactured by Sanyulek), and LE-1421 (manufactured by Sanyulek). (Manufactured by KISCO) and EpiFine series (manufactured by KISCO).

Further, as the matrix resin of the near-infrared absorbing film, it is also preferable to use the resin having both the polysiloxane and the epoxy group mentioned above.

In this case, the matrix resin having both the polysiloxane and the epoxy group exhibits high heat resistance and moisture resistance, and therefore has suitable properties as a material for an image sensor for a solid-state image sensor.

Specific examples of the resin having both a polysiloxane and an epoxy group that can be used as a matrix resin for a near-infrared absorbing film include the EpiFine series (manufactured by KISCO) and the ILLUMIKA series (manufactured by Kaneka Corporation).

The film thickness of the near-infrared absorbing film of the present invention is preferably in the range of 100 to 490 μm, and more preferably in the range of 150 to 300 μm.

(Other additives)
Other additives can be applied to the near-infrared absorbing film of the present invention as long as the objective effects of the present invention are not impaired. For example, a sensitizer, a cross-linking agent, a curing accelerator, a filler, and a thermosetting agent can be applied. Accelerators, thermal polymerization inhibitors, plasticizers, etc., as well as adhesion accelerators to the surface of the substrate and other auxiliaries (eg, conductive particles, fillers, defoaming agents, flame retardants, leveling agents, etc. Peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination.

By appropriately containing these components, properties such as stability and physical properties of the target near-infrared absorbing film can be adjusted.

These components are, for example, paragraph numbers 0183 to Japanese Patent Application Laid-Open No. 2012-003225, paragraph numbers 0101 to 0102 of Japanese Patent Application Laid-Open No. 2008-250074, paragraph numbers 0103 to 0104 of Japanese Patent Application Laid-Open No. 2008-250074, and Japanese Patent Application Laid-Open No. 2008-250074. The contents described in paragraph numbers 0107 to 0109 of the 2008-250074 can be referred to.

Since the near-infrared absorbing composition of the present invention can be a liquid wet coating liquid, for example, a near-infrared absorbing film, for example, near-infrared rays can be formed by a simple step of forming a film by spin coating. The cut filter can be easily manufactured.

<< Application to image sensors for solid-state image sensors >>
The near-infrared absorbing film of the present invention is, for example, a visual sensitivity correction member for CCD, CMOS or other light receiving elements, a photometric member, a heat ray absorbing member, a composite optical filter, a lens member (glasses, sunglasses, goggles). , Optical system, optical waveguide system), fiber member (optical fiber), noise cut member, display cover or display filter such as plasma display front plate, projector front plate, light source heat ray cut member, color tone correction member, illumination brightness adjustment member , Optical elements (optical amplification elements, wavelength conversion elements, etc.), Faraday elements, optical communication function devices such as isolators, optical fiber elements, and the like.

Applications of the near-infrared absorbing film having the near-infrared absorbing composition of the present invention are particularly for a near-infrared cut filter on the light receiving side of a solid-state image sensor substrate (for example, for a near-infrared cut filter for a wafer level lens) and a solid. It is characterized by being applied to an image sensor for a solid-state image sensor, such as for a near-infrared cut filter on the back surface side (the side opposite to the light receiving side) of the image sensor substrate.

By applying the near-infrared absorbing film of the present invention to an image sensor for a solid-state image sensor, it is possible to improve the line of visible part transmittance, near-infrared part absorption efficiency, heat and humidity, and the like.

Specifically, the near-infrared absorbing film (near-infrared cut filter) of the present invention is provided on an image sensor for a solid-state image sensor.

FIG. 1 is a schematic cross-sectional view showing the configuration of a camera module including a solid-state image sensor provided with an infrared cut filter which is a near-infrared absorbing film of the present invention.

The camera module 1 shown in FIG. 1 is connected to a circuit board 12 which is a mounting board via a solder ball 11 which is a connecting member.

Specifically, the camera module 1 is provided on the solid-state image sensor substrate 10 having the image sensor unit 13 on the first main surface of the silicone substrate and on the first main surface side (light receiving side) of the solid-state image sensor substrate 10. The flattening layer 8 provided, the near-infrared cut filter (near-infrared absorbing film) 9 provided on the flattening layer 8, and the glass substrate 3 (light transmissive) arranged above the near-infrared cut filter 9. A substrate), a lens holder 5 arranged above the glass substrate 3 and having an image pickup lens 4 in the internal space, a light-shielding and electromagnetic shield 6 arranged so as to surround the solid-state image sensor substrate 10 and the glass substrate 3. It is configured with. Each member is adhered by adhesives 2 and 7.

The present invention is a method for manufacturing a camera module having a solid-state image sensor substrate and an infrared cut filter arranged on the light-receiving side of the solid-state image sensor substrate. A near-infrared absorbing film can be formed by spin-coating the near-infrared absorbing composition.

Therefore, in the camera module 1, for example, a near-infrared absorbing film of the present invention is spin-coated on the flattening layer 8 to form a near-infrared absorbing film to form an infrared cut filter 9. ..

In the camera module 1, the incident light L from the outside passes through the image pickup lens 4, the glass substrate 3, the infrared cut filter 9, and the flattening layer 8 in that order, and then reaches the image pickup element portion of the solid-state image sensor substrate 10. It has become.

Further, the camera module 1 is connected to the circuit board 12 via a solder ball 11 (connecting material) on the second main surface side of the solid-state image sensor substrate 10.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. In the examples, the indication of "parts" or "%" is used, but unless otherwise specified, it indicates "parts by mass" or "% by mass". Unless otherwise specified, each operation was performed at room temperature (25 ° C.).

Example 1
<< Preparation of near-infrared absorbing composition >>
(Preparation of Near Infrared Absorbent Composition 1)
0.563 g (2.82 mmol) of copper (II) acetate monohydrate (manufactured by Kanto Chemical Co., Inc., hereinafter simply referred to as "copper acetate") and 30 g of tetrahydrofuran (THF) are mixed and stirred for 1 hour. A copper acetate solution was prepared.

Next, in the obtained copper acetate solution, as a phosphate ester compound having a structure represented by the general formula (I), 0.734 g (1.27 mmol, molar ratio of copper acetate) of Example Compound 100 was added to 1 mol of copper acetate. A solution containing 3 g of THF was added to 0.45 mol), and the mixture was stirred for 30 minutes to prepare solution A.

Next, 0.293 g (1.85 mmol, molar ratio of 0.66 per 1 mol of copper acetate) of phenylphosphonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), which is a compound having a structure represented by the general formula (II). 5 g of THF was added to the mole) and stirred for 30 minutes to prepare solution B.

Then, while stirring the solution A, the solution B was added to the solution A, and the mixture was stirred at room temperature for 1 minute. Next, 20 g of toluene was added to this solution, and the mixture was stirred at room temperature for 1 minute to prepare Solution C.

Put this solution C in a flask and heat it in an oil bath (manufactured by Tokyo Rika Kikai Co., Ltd., model: OSB-2100) at 120 ° C. with a rotary evaporator (manufactured by Tokyo Rika Kikai Co., Ltd., model: N-1000). , 30 minutes of desolvation treatment was performed.

Then, the amount of the solvent was adjusted so that the solid content concentration of the liquid C in the flask was 20% by mass, and this was used as the near-infrared absorbing composition 1.

In the near-infrared absorbing composition 1, in the exemplified compound 100 when the number of moles of copper is 1.00, the moles of the compounds having a structure in which Z is represented by the formulas (Z-1) and (Z-2). The contents are 0.225 and 0.225, respectively, and the molar content of phenylphosphonic acid, which is a compound represented by the general formula (II), is 0.66, which is represented by the general formula (I). The molar standard total content CH of the reactive hydroxy group contained in the exemplary compound 100, which is a compound having the above-mentioned structure, and phenylphosphonic acid, which is the compound having the structure represented by the general _formula (II), is 1 mol of copper. On the other hand, (exemplified compound 100 = 0.225 + 0.225 × 2 ) + (phenylphosphonic acid = 0.66 × 2) = 1.995 ( _CH / _CC ).

(Preparation of Near Infrared Absorbent Compositions 2-5)
In the preparation of the near _- infrared absorbing composition 1, the number of moles of Exemplified Compound 100 and phenylphosphonic acid with respect to 1 mol of copper was changed so as to have the molar content shown in Table V, and the value of _CH / CC was changed. The near-infrared absorbing compositions 2 to 5 were prepared in the same manner except that they were changed to 2.070, 1.830 , 1.855, and 1.720, respectively.

(Preparation of Near Infrared Absorbent Composition 6)
In the preparation of the near-infrared absorbing composition 1, instead of phenylphosphonic acid, the same mol (1.85 mmol, 0.66 mol with respect to 1 mol of copper acetate in molar ratio) was changed to 4-methoxyphenylphosphonic acid. The near-infrared absorbing composition 6 was prepared in the same manner except for the above.

(Preparation of Near Infrared Absorbent Compositions 7 to 12)
In the preparation of the near-infrared absorbing composition 1, the example compound 100 was changed to the same mol (1.27 mmol, 0.45 mol with respect to 1 mol of copper acetate in terms of molar ratio) of the example compounds 101 to 106. In the same manner, near infrared absorbing compositions 7 to 12 were prepared.

(Preparation of Near Infrared Absorbent Composition 13)
In the preparation of the near-infrared absorbing composition 2, the molar ratio of the example compound 100 added was changed to 0.29 mol with respect to 1 mol of copper acetate, and the total number of moles of phosphonic acid added was changed to 1 mol of copper acetate. On the other hand, the number of moles is 0.78 mol, and the number of moles of phenylphosphonic acid, which is a compound A having a structure represented by the general formula (II), is 0.70 mol with respect to 1 mol of copper, and the other phosphonic acid (compound B) is used. The near-infrared absorbing composition 13 was prepared in the same manner except that the number of moles per mole of copper hexylphosphonate was 0.08 mol (phenylphosphonic acid: hexylphosphonic acid = 9: 1 (molar ratio)). did.

(Preparation of Near Infrared Absorbent Compositions 14 and 15)
In the preparation of the near-infrared absorbing composition 13, the molar ratios of phenylphosphonic acid (Compound A) and hexylphosphonic acid (Compound B) were changed to 7: 3 and 5: 5, respectively, as the composition of the phosphonic acid. Near-infrared absorbing compositions 14 and 15 were prepared in the same manner except for the above.

(Preparation of Near Infrared Absorbent Composition 16)
In the preparation of the near-infrared absorbing composition 1, the molar ratio of the example compound 100 added was 0.45 mol with respect to 1 mol of copper acetate, and the total number of moles of phosphonic acid added was 0. The number of moles is 66 mol, and the number of moles of phenylphosphonic acid, which is a compound A having a structure represented by the general formula (II), is 0.59 mol with respect to 1 mol of copper, and hexylphosphonic acid, which is another phosphonic acid (compound B). The near-infrared absorbing composition 16 was prepared in the same manner except that the number of moles per 1 mole of copper was 0.07 mol (phenylphosphonic acid: hexylphosphonic acid = 9: 1 (molar ratio)).

(Preparation of Near Infrared Absorbent Composition 17)
In the preparation of the near-infrared absorbing composition 16, the same applies except that the molar ratio of phenylphosphonic acid (Compound A) to hexylphosphonic acid (Compound B) was changed to 7: 3 as the composition of the phosphonic acid. , A near-infrared absorbing composition 17 was prepared.

(Preparation of Near Infrared Absorbent Composition 18)
In the preparation of the near-infrared absorbing composition 3, the molar ratio of the example compound 100 added was 0.34 mol to 1 mol of copper acetate, and the total number of moles of phosphonic acid added was 0. The number of moles is 66 mol, and the number of moles of phenylphosphonic acid, which is a compound A having a structure represented by the general formula (II), is 0.59 mol with respect to 1 mol of copper, and hexylphosphonic acid, which is another phosphonic acid (compound B). The near-infrared absorbing composition 18 was prepared in the same manner except that the number of moles per 1 mole of copper was 0.07 mol (phenylphosphonic acid: hexylphosphonic acid = 9: 1 (molar ratio)).

(Preparation of Near Infrared Absorbent Compositions 19 and 20)
In the preparation of the near-infrared absorbing composition 16, the near-infrared absorbing compositions 19 and 20 were prepared in the same manner except that the hexylphosphonic acid was changed to the same molar amount of propylphosphonic acid and octylphosphonic acid, respectively.

(Preparation of Near Infrared Absorbent Composition 21: Comparative Example)
In the preparation of the near-infrared absorbing composition 1, the same procedure was used except that Prysurf A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkyl (C8) ether phosphate ester was used instead of the exemplary compound 100. The near-infrared absorbing composition 21 was prepared. The molar content of Plysurf A208F per 1 mol of copper is 0.89 mol.

(Preparation of Near Infrared Absorbent Composition 22: Comparative Example)
In the preparation of the near _- infrared absorbing composition 1, the number of moles of Exemplified Compound 100 per 1 mol of copper was 0.34 , the number of moles of phenylphosphonic acid per 1 mol of copper was 0.53 mol, and _CH / CC was set. The near-infrared absorbing composition 22 was prepared in the same manner except that it was changed to 1.570 .

(Preparation of Near Infrared Absorbent Composition 23: Comparative Example)
In the preparation of the near-infrared absorbing composition 13, the near-infrared absorbing composition 23 was prepared in the same manner except that phenylphosphonic acid was removed and hexylphosphonic acid was used alone.

Table V shows the configurations of the near-infrared absorbing compositions 1 to 23 prepared as described above. In addition, C _X refers to the molar standard content of the compound having a structure represented by the general formula (I), and is represented by C _X = C _X1 + C _X2 + C _{X 3} .

[Evaluation of spectral transmittance]
The prepared near-infrared absorbing compositions 1 to 23 were diluted with toluene so that the transmittance at the wavelength of 1100 nm was 5%, and sample A for evaluation was prepared.

Next, for each evaluation sample A, the spectral transmittance in the wavelength range of 300 to 1200 nm was measured using a spectrophotometer V-570 manufactured by JASCO Corporation as a measuring device. Next, the spectral transmittances at 500 nm, 600 nm, and 700 nm as the visible region were determined and evaluated according to the following criteria (Evaluation of transmittance 1: Evaluation of transmittance at 500 nm).
The transmittance of the near-infrared absorbing composition measured by the above method at 500 nm was ranked according to the following criteria, and the transmittance of 1 in the visible light region was evaluated.

⊚: Transmittance at 500 nm is 95% or more ◯: Transmittance at 500 nm is 90% or more and less than 95% Δ: Transmittance at 500 nm is 80% or more and less than 90% ×: 500 nm (Evaluation of transmittance 2: Evaluation of transmittance at 600 nm)
The transmittance of the near-infrared absorbing composition measured by the above method at 600 nm was ranked according to the following criteria, and the transmittance 2 in the visible light region was evaluated.

⊚: Transmittance at 600 nm is 90% or more ◯: Transmittance at 600 nm is 80% or more and less than 90% Δ: Transmittance at 600 nm is 60% or more and less than 80% ×: 600 nm (Evaluation of transmittance 3: Evaluation of transmittance at 700 nm)
The transmittance of the near-infrared absorbing composition measured by the above method at 700 nm was ranked according to the following criteria, and the transmittance 3 in the visible light region was evaluated.

⊚: Transmittance at 700 nm is less than 50% ◯: Transmittance at 700 nm is 50% or more and less than 60% ×: Transmittance at 700 nm is 60% or more [Evaluation of concentration characteristics]
For the evaluation samples A (transmittance of 1100 nm wavelength of 5%) of the near-infrared absorbing compositions 1 to 23 prepared above, the concentration of the near-infrared absorbing composition in each near-infrared absorbing composition was measured. Then, the concentration characteristics were evaluated according to the following criteria.

⊚: The concentration of the near-infrared absorbing composition of sample A is less than 2.0% by mass. ◯: The concentration of the near-infrared absorbing composition of sample A is 2.0% by mass or more and less than 5.0%. X: The concentration of the near-infrared absorbing composition of sample A is 5.0% by mass or more [evaluation of film thickness]
For the near-infrared absorbing compositions 1 to 23 prepared above, a matrix resin having a polysiloxane structure was used as a binder resin, and each coating for forming a near-infrared absorbing film was applied so that the solid content ratio of each was 1: 1. The liquid was prepared.

Next, each coating liquid for forming a near-infrared absorbing film was applied onto a glass substrate under a thickness condition such that the transmittance at a wavelength of 1100 nm was 5%, and cured. Then, it was dried on a hot plate by heating at 80 ° C. for 1 hour and at 150 ° C. for 2 hours to form each near-infrared absorbing film.

Next, the film thickness of each near-infrared absorbing film was measured using a film thickness meter with the following combination.

(Terminal, stand, reader)
Terminal: DIGIMICRO MH-15M (manufactured by NIKON)
Stand: DIGIMICRO STAND MS-5C (manufactured by NIKON)
Reader: DIGITAL READ OUT TC-101A (manufactured by NIKON)
The film thickness of each near-infrared absorbing film measured as described above was evaluated according to the following criteria.

⊚: The film thickness of the near-infrared absorbing film is less than 300 μm ◯: The film thickness of the near-infrared absorbing film is 300 μm or more and less than 500 μm ×: The film thickness of the near-infrared absorbing film is 500 μm or more The results obtained from the above are shown in Table VI.

表VI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、本発明に係る例示化合物を用いることにより、分光特性に優れており、可視部域（５００ｎｍ及び６００ｎｍ）での透過率が高く、近赤外領域（７００ｎｍ）の透過率が低い、優れた近赤外光のカット能力を有していることがわかる。加えて、本発明の近赤外線吸収性組成物は、１１００ｎｍ近傍での近赤外吸収性に優れ、かつ、近赤外線吸収性膜を形成した際に、薄膜化することができることが分かる。

As is clear from the results shown in Table VI, the near-infrared absorbing composition of the present invention has excellent spectral characteristics by using the exemplary compound according to the present invention with respect to the comparative example, and the visible region (visible region). It can be seen that it has a high transmittance at 500 nm and 600 nm) and a low transmittance in the near infrared region (700 nm), and has an excellent ability to cut near infrared light. In addition, it can be seen that the near-infrared absorbing composition of the present invention has excellent near-infrared absorbing property in the vicinity of 1100 nm and can be thinned when a near-infrared absorbing film is formed.

Further, in the evaluation of the film thickness, the same result could be obtained by using a matrix resin having an epoxy group instead of the matrix resin having a polysiloxane structure as the binder resin.

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 image sensor board 11 Solder ball 12 Circuit board 13 Image sensor

Claims (11)

A near-infrared absorbing composition containing a near-infrared absorber and a solvent.
The near-infrared absorber contains at least one of the following component (A) and the following component (B).
In a compound having a structure represented by the following general _formula (I), where the molar standard content of copper ions is CC , Z is represented by the following formulas (Z-1), (Z-2), and (Z-3). The molar standard content of the compound having the structure represented is C _X1 , C _X2 , and C _X3 , respectively, and the molar standard content of the compound having the structure represented by the following general formula (II) is _CY . The total molar content of the reactive hydroxy groups contained in the compound having the structure represented by the following general formula (I) and the compound having the structure represented by the following general formula (II) is calculated by the following formula (1). A near-infrared absorbing composition characterized in that the conditions specified by the following formula (2) are satisfied when the _CH is specified in 1.
Equation (1) _CH = C X1 ₊ C _X2 x 2 + C _X3 + _CY x 2
Equation (2) 1.720 ≤ C _H / C _C ≤ 2.070
Component (A) Component consisting of a compound having a structure represented by the following general formula (I), a compound having a structure represented by the following general formula (II), and copper ions (B) Component: The following general formula A component consisting of a compound having a structure represented by (I), a compound having a structure represented by the following general formula (II), and a metal complex obtained by reacting with a copper compound.

[In the above general formula (I), R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R may further have a substituent. Z represents a structural unit selected from the following formulas (Z-1) to (Z-3).

* Represented in the above formulas (Z-1) to (Z-3) represents a binding site and binds to O in the above general formula (I).
R ₂₁ to R ₂₄ represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.
However, the compound having the structure represented by the general formula (I) has at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the condition (ii) at the same time.
Condition (i): R ₂₁ to R ₂₄ are all hydrogen atoms.
Condition (ii): At least one of R ₂₁ to R ₂₄ is an alkyl group having 1 to 4 carbon atoms.
In the general formula (I), l represents the number of substructures satisfying the above condition (i), and is a number from 1 to 10. m represents the number of substructures satisfying the above condition (ii), and is a number from 1 to 10. ]

[In the above general formula (II), R ¹ is a phenyl group which may have a substituent. ] The near-infrared absorbing composition according to claim 1, further comprising a compound selected from the following phosphonic acid group.
Phosphonic acid group: 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. The near-infrared ray absorption according to claim 1 or 2, wherein the compound having a structure represented by the general formula (I) is a compound having a structure represented by the following general formula (III). Sex composition.

[In the general formula (III), R, R ₂₁ to R ₂₄ , l and m are synonymous with those in the general formula (I). n is 1 or 2, and when n is 2, the structures in [] may be the same or different. ] Claims 1 to 3 are characterized in that the compound having the structure represented by the general formula (I) contains a monoester and a diester, and the molar ratio of the monoester is in the range of 20 to 95%. The near-infrared absorbing composition according to any one of the above. Claims 1 to 4 are characterized in that the general formula (I) has at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the following condition (iii) at the same time. The near-infrared absorbing composition according to any one of the above.
Condition (i): R ₂₁ to R ₂₄ are all hydrogen atoms.
Condition (iii): Any one of R ₂₁ to R ₂₄ is an alkyl group having 1 to 4 carbon atoms, and the remaining three are hydrogen atoms. The near-infrared absorbing composition according to any one of claims 1 to 5, wherein l and m in the general formula (I) are numbers in the range of 1 to 3, respectively. .. The near-infrared absorbing composition according to any one of claims 1 to 6, wherein the copper ion or the copper constituting the copper compound contains 100 mol% or less of acetic acid. .. A near-infrared absorbing film according to any one of claims 1 to 7, wherein the near-infrared absorbing composition is used. The near-infrared absorbing film according to claim 8, which contains a matrix resin having a polysiloxane structure. The near-infrared absorbing film according to claim 8, which contains a matrix resin having an epoxy group. An image sensor for a solid-state image sensor, comprising the near-infrared absorbing film according to any one of claims 8 to 10.

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