JP2013195480A - Infrared absorbing composition and infrared cut filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an infrared absorbing composition excellent in visible ray transmission performance and infrared ray shielding performance.SOLUTION: An infrared absorbing composition contains a phthalocyanine compound (A) whose maximum absorption wavelength is 650 nm or more and less than 750 nm, a phthalocyanine compound (B) whose maximum absorption wavelength is 750 nm or more and 900 nm or less, a metal oxide (C), and a polymerizable compound (D). The phthalocyanine compound (A) contains at least one of an alkoxy group, an aryloxy group, and an amino group.

Description

  The present invention relates to an infrared absorbing composition and an infrared cut filter using the same. Furthermore, the present invention relates to a camera module having such an infrared cut filter.

  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., but these solid-state image sensors are sensitive to near infrared rays in their light receiving parts. Therefore, it is necessary to perform visibility correction, and an infrared cut filter is often used.

  Patent Document 1 describes that a phthalocyanine compound is used for a near-infrared absorbing member. In Cited Document 1, a phthalocyanine compound is kneaded into a pellet such as PET and molded into a film.

JP-A-9-279125

  The subject of this invention is providing the infrared cut filter which can shield infrared rays more effectively, improving the transmittance | permeability of visible light. More specifically, an object of the present invention is to provide an infrared absorbing composition that can achieve such an object. It is another object of the present invention to provide an infrared absorbing composition having excellent heat resistance and light resistance.

（一般式（Ｉ）中、Ｒα¹〜Ｒα⁸は、それぞれ、水素原子、アルコキシ基、アリールオキシ基、またはアミノ基であり、Ｒβ¹〜Ｒβ⁸は、それぞれ、水素原子またはアミノ基であり、Ｍは金属原子である。但し、Ｒα¹とＲα²の一方、Ｒα³とＲα⁴の一方、Ｒα⁵とＲα⁶の一方、およびＲα⁷とＲα⁸の一方は、それぞれ、アルコキシ基、アリールオキシ基、またはアミノ基であるか、Ｒβ¹とＲβ²の一方、Ｒβ³とＲβ⁴の一方、Ｒβ⁵とＲβ⁶の一方、およびＲβ⁷とＲβ⁸の一方は、それぞれ、アミノ基である。）
＜３＞前記フタロシアニン化合物（Ａ）の極大吸収波長と前記フタロシアニン化合物（Ｂ）の極大吸収波長の差が１０〜１２０ｎｍである、＜１＞または＜２＞に記載の赤外線吸収性組成物。
＜４＞前記一般式（Ｉ）におけるＲα¹〜Ｒα⁸および／またＲβ¹〜Ｒβ⁸が下記から選択される、＜２＞または＜３＞に記載の赤外線吸収性組成物。
Ｒα¹〜Ｒα⁸

Ｒβ¹〜Ｒβ⁸

＜５＞前記金属酸化物（Ｃ）の極大吸収波長が８００〜２０００ｎｍである、＜１＞〜＜４＞のいずれかに記載の赤外線吸収性組成物。
＜６＞＜１＞〜＜５＞のいずれかに記載の赤外線吸収性組成物を用いて得られる赤外線カットフィルタ。
＜７＞固体撮像素子基板の受光側において、＜１＞〜＜５＞のいずれかに記載の赤外線吸収性組成物を塗布することにより膜を形成することを含む、赤外線カットフィルタの製造方法。
＜８＞固体撮像素子基板と、前記固体撮像素子基板の受光側に配置された赤外線カットフィルタとを有するカメラモジュールであって、前記赤外線カットフィルタが＜６＞に記載の赤外線カットフィルタである、カメラモジュール。
＜９＞固体撮像素子基板と、前記固体撮像素子基板の受光側に配置された赤外線カットフィルタとを有するカメラモジュールの製造方法であって、固体撮像素子基板の受光側において、＜１＞〜＜５＞のいずれかに記載の赤外線吸収性組成物を塗布することにより膜を形成することを含む、カメラモジュールの製造方法。 Under such circumstances, as a result of intensive studies by the inventor of the present application, it is possible to use a phthalocyanine compound having a maximum absorption wavelength of 650 nm or more and less than 750 nm and a phthalocyanine compound having a maximum absorption wavelength of 750 nm or more and 900 nm or less in combination. The inventors have found that it is possible to suppress the transmittance in the infrared region while maintaining the above, and have completed the present invention.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <10>.
<1> a phthalocyanine compound (A) having a maximum absorption wavelength of 650 nm or more and less than 750 nm, a phthalocyanine compound (B) having a maximum absorption wavelength of 750 nm or more and 900 nm or less, a metal oxide (C), and a polymerizable compound (D), An infrared absorbing composition, wherein the phthalocyanine compound (A) contains at least one of an alkoxy group, an aryloxy group, and an amino group.
<2> The infrared absorbing composition according to <1>, wherein the phthalocyanine compound (A) is represented by the following general formula (I).
Formula (I)

(In General Formula (I), Rα ^{1 to} Rα ⁸ are each a hydrogen atom, an alkoxy group, an aryloxy group, or an amino group, and Rβ ^{1 to} Rβ ⁸ are each a hydrogen atom or an amino group, M is a metal atom, provided that ^one of Rα ¹ and Rα ² , one of Rα ³ and Rα ⁴ , one of Rα ⁵ and Rα ⁶ , and one of Rα ⁷ and Rα ⁸ are each an alkoxy group, aryloxy Or one of Rβ ¹ and Rβ ² , one of Rβ ³ and Rβ ⁴ , one of Rβ ⁵ and Rβ ⁶ , and one of Rβ ⁷ and Rβ ⁸ are each an amino group. )
<3> The infrared absorbing composition according to <1> or <2>, wherein the difference between the maximum absorption wavelength of the phthalocyanine compound (A) and the maximum absorption wavelength of the phthalocyanine compound (B) is 10 to 120 nm.
<4> the formula Rα in (I) ¹ ~Rα ⁸ and / or Rβ ¹ ~Rβ ⁸ is selected from the following, <2> or infrared absorbing composition according to <3>.
Rα ^{1 to} Rα ⁸

Rβ ^{1 to} Rβ ⁸

<5> The infrared absorbing composition according to any one of <1> to <4>, wherein a maximum absorption wavelength of the metal oxide (C) is 800 to 2000 nm.
<6> An infrared cut filter obtained using the infrared absorbing composition according to any one of <1> to <5>.
<7> A method for producing an infrared cut filter, comprising forming a film by applying the infrared absorbing composition according to any one of <1> to <5> on the light receiving side of the solid-state imaging device substrate.
<8> A camera module having a solid-state image sensor substrate and an infrared cut filter arranged on a light receiving side of the solid-state image sensor substrate, wherein the infrared cut filter is the infrared cut filter according to <6>. The camera module.
<9> A method for manufacturing a camera module having a solid-state image sensor substrate and an infrared cut filter disposed on a light-receiving side of the solid-state image sensor substrate, wherein <1> to <5> The manufacturing method of a camera module including forming a film | membrane by apply | coating the infrared rays absorptive composition in any one of.

  According to the present invention, it is possible to suppress the transmittance in the infrared region while maintaining a high visible region transmittance.

It is a schematic sectional drawing which shows the structure of the camera module provided with the solid-state image sensor which concerns on embodiment of this invention. It is a schematic sectional drawing of the solid-state image sensor board | substrate which concerns on embodiment of this invention.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Moreover, in this specification, a viscosity value points out the value in 25 degreeC.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous.The monomer in the present invention is distinguished from oligomer and polymer, and refers to a compound having a mass average molecular weight of 2,000 or less. In the specification, a polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer, and a polymerizable group is a group involved in a polymerization reaction. say.
Infrared rays in the present invention refers to those having a wavelength region of 700 to 1000 nm.

  In principle, phthalocyanine compounds synthesized from monosubstituted phthalonitriles have four types of positional isomers. R in the following formula I-IV represents a substituent. In the present application, type I having the highest production ratio from the viewpoint of steric hindrance is described as a representative example for the sake of convenience, but it is not denied that the mixture is an arbitrary ratio of I to IV. In the present invention, a compound having a smaller number of isomers is preferred, and most preferred is a substantially single isomer (the same applies to phthalocyanine compounds unless otherwise specified). The same applies to phthalocyanine compounds synthesized from phthalonitrile having two or more substitutions.

The infrared absorbing composition of the present invention includes a phthalocyanine compound (A) having a maximum absorption wavelength of 650 nm to less than 750 nm, a phthalocyanine compound (B) having a maximum absorption wavelength of 750 nm to 900 nm, a metal oxide (C), and a polymerizable compound. (D), and the phthalocyanine compound (A) contains at least one of an alkoxy group, an aryloxy group, and an amino group. By adopting such a composition, it is possible to provide an infrared-absorbing composition that is excellent in visible light permeability and excellent in infrared shielding properties. Furthermore, the infrared ray absorbing composition of the present invention is excellent in heat resistance and light resistance.
Hereinafter, the present invention will be described in detail, but it goes without saying that the present invention is not limited thereto.

<Phthalocyanine compound (A) having a maximum absorption wavelength of 650 nm or more and less than 750 nm>
In the present invention, a phthalocyanine compound (A) having a maximum absorption wavelength of 650 nm or more and less than 750 nm is used. The maximum absorption wavelength of the phthalocyanine compound (A) is preferably 650 to 750 nm, and more preferably 690 to 720 nm.
The phthalocyanine compound (A) is preferably represented by the following general formula (I).

（一般式（Ｉ）中、Ｒα¹〜Ｒα⁸は、それぞれ、水素原子、基アルコキシ基、アリールオキシ基、またはアミノ基であり、Ｒβ¹〜Ｒβ⁸は、それぞれ、水素原子またはアミノ基であり、Ｍは金属原子である。但し、Ｒα¹とＲα²の一方、Ｒα³とＲα⁴の一方、Ｒα⁵とＲα⁶の一方、およびＲα⁷とＲα⁸の一方が、それぞれ、アルコキシ基、アリールオキシ基、またはアミノ基であるか、Ｒβ¹とＲβ²の一方、Ｒβ³とＲβ⁴の一方、Ｒβ⁵とＲβ⁶の一方、およびＲβ⁷とＲβ⁸の一方が、それぞれ、アミノ基である。）
Ｒα¹〜Ｒα⁸は、それぞれ、水素原子、アルコキシ基、アリールオキシ基、またはアミノ基であり、置換基を有していてもよい。
アルコキシ基としては、炭素数３〜１０の分岐のアルキル鎖−Ｏ−であることが好ましい。アリールオキシ基としては、フェノキシ基が好ましい。フェノキシ基は置換基を有していることが好ましく、炭素数３〜１０の分岐アルキル基を置換基として有していることが好ましい。アミノ基は、アルキルアミノ基が好ましく、ジアルキルアミノ基がより好ましい。この場合のアルキル基は、炭素数１〜５の直鎖または分岐のアルキル基が好ましい。
Ｒα¹とＲα²の一方、Ｒα³とＲα⁴の一方、Ｒα⁵とＲα⁶の一方、およびＲα⁷とＲα⁸の一方が、それぞれ、アルコキシ基、アリールオキシ基、またはアミノ基である場合、他方は、それぞれ、水素原子、アルコキシ基、アリールオキシ基、またはアミノ基であり、水素原子であることが好ましい。さらに、極大吸収波長が、６５０ｎｍ以上７５０ｎｍ未満である限り、Ｒβ¹とＲβ²の一方、Ｒβ³とＲβ⁴の一方、Ｒβ⁵とＲβ⁶の一方、およびＲβ⁷とＲβ⁸の一方が、それぞれ、水素原子であってもアミノ基であってもよい。
本発明では、Ｒα¹とＲα²の一方、Ｒα³とＲα⁴の一方、Ｒα⁵とＲα⁶の一方、およびＲα⁷とＲα⁸の一方が、同じ基であり、Ｒα¹とＲα²の他方、Ｒα³とＲα⁴の他方、Ｒα⁵とＲα⁶の他方、およびＲα⁷とＲα⁸の他方も同じ基であることが好ましい。
以下にＲα¹〜Ｒα⁸の好ましい例を挙げるが本発明はこれらに限定されるものではないことは言うまでもない。

Formula (I)

(In General Formula (I), Rα ^{1 to} Rα ⁸ are each a hydrogen atom, a group alkoxy group, an aryloxy group, or an amino group, and Rβ ^{1 to} Rβ ⁸ are each a hydrogen atom or an amino group. , M is a metal atom, provided that ^one of Rα ¹ and Rα ² , one of Rα ³ and Rα ⁴ , one of Rα ⁵ and Rα ⁶ , and one of Rα ⁷ and Rα ⁸ are each an alkoxy group, aryl An oxy group or an amino group, or one of Rβ ¹ and Rβ ² , one of Rβ ³ and Rβ ⁴ , one of Rβ ⁵ and Rβ ⁶ , and one of Rβ ⁷ and Rβ ⁸ are each an amino group .)
Rα ^{1 to} Rα ⁸ are each a hydrogen atom, an alkoxy group, an aryloxy group, or an amino group, and may have a substituent.
As an alkoxy group, it is preferable that it is a C3-C10 branched alkyl chain -O-. As the aryloxy group, a phenoxy group is preferable. The phenoxy group preferably has a substituent, and preferably has a branched alkyl group having 3 to 10 carbon atoms as a substituent. The amino group is preferably an alkylamino group, more preferably a dialkylamino group. In this case, the alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms.
When ^one of Rα ¹ and Rα ² , one of Rα ³ and Rα ⁴ , one of Rα ⁵ and Rα ⁶ , and one of Rα ⁷ and Rα ⁸ are each an alkoxy group, an aryloxy group, or an amino group, The other is a hydrogen atom, an alkoxy group, an aryloxy group, or an amino group, and preferably a hydrogen atom. Further, as long as the maximum absorption wavelength is 650 nm or more and less than 750 nm, one of Rβ ¹ and Rβ ² , one of Rβ ³ and Rβ ⁴ , one of Rβ ⁵ and Rβ ⁶ , and one of Rβ ⁷ and Rβ ⁸ are each , May be a hydrogen atom or an amino group.
In the present invention, ^one of Rα ¹ and Rα ² , one of Rα ³ and Rα ⁴ , one of Rα ⁵ and Rα ⁶ , and one of Rα ⁷ and Rα ⁸ are the same group, and the other of Rα ¹ and Rα ² The other of Rα ³ and Rα ^4, the other of Rα ⁵ and Rα ⁶ , and the other of Rα ⁷ and Rα ⁸ are preferably the same group.
Although the preferable example of R (alpha) ^1- R (alpha) ⁸ is given to the following, it cannot be overemphasized that this invention is not limited to these.

  By placing such a bulky substituent at the α-position of the phthalocyanine skeleton, the slope of the boundary between the visible region and the near-infrared region can be made steep, and the visible light and infrared light are more distinct. Spectroscopic can be achieved. The bulky substituent is preferably a group that becomes negative according to Hammett's rule, and is preferably a group that becomes negative according to Hammett's rule containing at least one sp2 or sp3 carbon or sp2 or sp3 nitrogen. .

When ^one of Rβ ¹ and Rβ ² , one of Rβ ³ and Rβ ⁴ , one of Rβ ⁵ and Rβ ⁶ , and one of Rβ ⁷ and Rβ ⁸ are each an amino group, the other is a hydrogen atom Although an amino group may be sufficient, an amino group is preferable.
In the present invention, ^one of Rβ ¹ and Rβ ² , one of Rβ ³ and Rβ ⁴ , one of Rβ ⁵ and Rβ ⁶ and one of Rβ ⁷ and Rβ ⁸ are the same group, and the other of Rβ ¹ and Rβ ² The other of Rβ ³ and Rβ ^4, the other of Rβ ⁵ and Rβ ⁶ , and the other of Rβ ⁷ and Rβ ⁸ are preferably the same group.
The amino group in Rβ ^{1 to} Rβ ⁸ is more preferably —NHX (X is a substituent). Here, X is not particularly defined, and is a divalent group consisting of one or a combination of two or more of —C (═O) —, —CH ₂ —, —O—, an unsubstituted phenylene group. A group having a hydrogen atom bonded to the terminal is preferred.

Although the preferable example of R (beta) ^1- R (beta) ⁸ is given to the following, it cannot be overemphasized that this invention is not limited to these.
The part of the American mark is the part that binds to the phthalocyanine ring.

  By introducing an electron donating group as described above at the β-position of the phthalocyanine skeleton, a large association peak can be developed in cooperation with the phthalocyanine compound (B), and the visible light and infrared light are more distinct. Spectroscopic can be achieved.

The metal atom represented by M, preferably, Cu, Zn, Pb, Fe , Ni, Co, AlCl, AlI, InCl, InI, GaCl, GaI, TiCl 2, Ti = O, VCl 2, V = O, SnCl 2 or a GeCl _2, and more preferably Cu, V = O, Mg, Zn, Ti = O.

Examples of the phthalocyanine compound (A) preferably used in the present invention are shown below, but it goes without saying that the present invention is not limited thereto. The metal atom represented by M is Cu, but Zn, Pb, Fe, Ni, Co, AlCl, AlI, InCl, InI, GaCl, GaI, TiCl ₂ , Ti═O, VCl ₂ , V═O. , SnCl ₂ or GeCl ₂ is also preferably used in the present invention.

The infrared absorbing composition of the present invention may contain only one type of phthalocyanine compound (A), or may contain two or more types.
The blending amount of the phthalocyanine compound (A) in the infrared absorbing composition of the present invention is preferably 1 to 40% by mass of the components excluding the solvent. When two or more types are included, the total amount is within the above range.

<Phthalocyanine compound (B) having a maximum absorption wavelength of 750 nm to 900 nm>
In the present invention, in addition to the phthalocyanine compound (A), the phthalocyanine compound (B) having a maximum absorption wavelength of 750 nm to 900 nm is included. The phthalocyanine compound (B) preferably has a maximum absorption wavelength of 750 to 800 nm, and more preferably 750 to 780 nm. Further, the difference between the maximum absorption wavelength of the phthalocyanine compound (A) and the maximum absorption wavelength of the phthalocyanine compound (B) is preferably 10 to 120 nm, and more preferably 20 to 100 nm. By setting it as such a structure, it exists in the tendency for the effect of this invention to be exhibited more effectively.

（一般式（ＩＩ）中、Ｒ¹〜Ｒ⁸は、それぞれ、水素原子、アルコキシ基、アリールオキシ基、またはアミノ基であり、Ｍは金属原子である。）
一般式（ＩＩ）中、Ｒ¹〜Ｒ⁸は、それぞれ、アルコキシ基またはアミノ基が好ましい。アルコキシ基としては、−Ｏ−炭素数２〜１０の直鎖のアルキル鎖であることが好ましい。アミノ基としては、−ＮＨＸ（Ｘは置換基）が好ましい。ここで、Ｘは、特に定めるものではなく、−Ｃ（＝Ｏ）−、−ＣＨ₂−、−Ｏ−、フェニレン基の１つまたは２つ以上の組み合わせからなる２価の基の末端に水素原子が結合した基が好ましい。
Ｒ¹〜Ｒ⁸は、−Ｏ−直鎖のアルキル基、−ＮＨ−直鎖のアルキル基、−Ｏ−フェニル基、−ＮＨ−フェニル基がより好ましい。
Ｒ¹とＲ²の一方、Ｒ³とＲ⁴の一方、Ｒ⁵とＲ⁶の一方、およびＲ⁷とＲ⁸の一方は、それぞれ、アルコキシ基、アリールオキシ基、またはアミノ基であることが好ましい。
Ｒ¹とＲ²の一方、Ｒ³とＲ⁴の一方、Ｒ⁵とＲ⁶の一方、およびＲ⁷とＲ⁸の一方は、同じ基であり、Ｒ¹とＲ²の他方、Ｒ³とＲ⁴の他方、Ｒ⁵とＲ⁶の他方、およびＲ⁷とＲ⁸の他方も同じ基であることが好ましい。 As the phthalocyanine compound (B), a compound represented by the following general formula (II) is preferable.
Formula (II)

(In general formula (II), R ^{1 to} R ⁸ are each a hydrogen atom, an alkoxy group, an aryloxy group, or an amino group, and M is a metal atom.)
In general formula (II), R ^{1 to} R ⁸ are each preferably an alkoxy group or an amino group. The alkoxy group is preferably a -O-C2-C10 straight alkyl chain. As the amino group, —NHX (X is a substituent) is preferable. Here, X is not particularly defined, and —C (═O) —, —CH ₂ —, —O—, a hydrogen atom at the end of a divalent group consisting of one or a combination of two or more phenylene groups. Groups in which atoms are bonded are preferred.
R ^{1 to} R ⁸ are more preferably an —O—linear alkyl group, an —NH—linear alkyl group, an —O-phenyl group, and an —NH-phenyl group.
One of R ¹ and R ² , one of R ³ and R ⁴ , one of R ⁵ and R ⁶ , and one of R ⁷ and R ⁸ may be an alkoxy group, an aryloxy group, or an amino group, respectively. preferable.
One of R ¹ and R ² , one of R ³ and R ⁴ , one of R ⁵ and R ⁶ , and one of R ⁷ and R ⁸ are the same group, and the other of R ¹ and R ² , R ³ and The other of R ^4, the other of R ⁵ and R ⁶ , and the other of R ⁷ and R ⁸ are preferably the same group.

The metal atom represented by M, preferably, Cu, Zn, Pb, Fe , Ni, Co, AlCl, AlI, InCl, InI, GaCl, GaI, TiCl 2, Ti = O, VCl 2, V = O, SnCl 2 or a GeCl _2, and more preferably Cu, V = O, Mg, Zn, Ti = O.

Examples of the phthalocyanine compound (B) preferably used in the present invention are shown below, but it goes without saying that the present invention is not limited thereto. The metal atom represented by M is Zn, but in addition, Cu, Pb, Fe, Ni, Co, AlCl, AlI, InCl, InI, GaCl, GaI, TiCl ₂ , Ti═O, VCl ₂ , V═O , SnCl ₂ or GeCl ₂ is also preferably used in the present invention.

The infrared absorbing composition of the present invention may contain only one type of phthalocyanine compound (B), or may contain two or more types.
It is preferable that the compounding quantity of the phthalocyanine compound (B) in the infrared absorptive composition of this invention is 1-40 mass% of the components except a solvent. When two or more types are included, the total amount is within the above range.

  In this invention, it is preferable that the compounding ratio (mass ratio) of a phthalocyanine compound (A) and a phthalocyanine compound (B) is 90: 10-10: 90, and it is more preferable that it is 80: 20-20: 80.

<Metal oxide>
The infrared ray absorbing composition of the present invention contains a metal oxide. As the metal oxide, a metal oxide having a maximum absorption wavelength within a wavelength range of 800 nm to 2000 nm is preferable.
The metal oxide used in the infrared absorbing composition of the present invention is not particularly limited as long as it has a maximum absorption wavelength (λ _max ) in a wavelength range of 800 nm to 2000 nm. For example, cesium tungsten oxide (CsWO _x ) And metal oxides such as quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), spinel (MgAl ₂ O ₄ ). Cesium tungsten oxide is preferred.
Tungsten oxide compounds have high absorption for infrared rays (especially light having a wavelength of about 800 to 1200 nm) (that is, high light shielding properties (shielding properties) for infrared rays) and low absorption for visible light. It is a shielding material. Therefore, when the composition of the present invention contains a tungsten compound, an infrared cut filter having a high light-shielding property (infrared shielding property) in the infrared region and a high light-transmitting property (visible light transmittance) in the visible region. Can be manufactured.
According to the infrared absorbing composition of the present invention, the metal oxide having the maximum absorption wavelength in the wavelength range of 800 nm to 2000 nm and the phthalocyanine compound having the maximum absorption wavelength in the wavelength range of 650 to 900 nm are contained. Thus, it is considered that an infrared cut filter having a high shielding property against infrared rays including near infrared rays having a wavelength of around 700 nm can be formed. Moreover, since the metal oxide is used as the compound having the maximum absorption wavelength in the wavelength range of 800 nm to 2000 nm, the detailed reason is unknown, but the transparency to visible light is good and the light resistance and It is considered that an infrared cut filter having excellent weather resistance such as moisture resistance can be formed.

The tungsten oxide compound is more preferably a tungsten oxide compound represented by the following general formula (composition formula) (I).
M _x W _y O _z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0

  As the metal of M, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Examples include Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, and Bi, and an alkali metal is preferable. The metal of M may be one type or two or more types.

M is preferably an alkali metal, preferably Rb or Cs, and more preferably Cs.
That is, the metal oxide is more preferably cesium tungsten oxide.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when 1.1 or less, generation of an impurity phase in the tungsten oxide compound is more reliably avoided. Can do.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like, and Cs _0.33 WO ₃ Alternatively, Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

  The metal oxide is preferably fine particles. The average particle diameter of the metal oxide is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average particle diameter is in such a range, it becomes difficult for the metal oxide to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible, but for reasons such as ease of handling during production, the average particle size of the metal oxide is usually 1 nm or more.

The content of the metal oxide is preferably 20 to 85% by mass, more preferably 30 to 80% by mass, and 40 to 75% by mass with respect to the total solid mass of the composition of the present invention. More preferably.
Two or more tungsten compounds can be used.

A metal oxide is available as a commercial product. When the metal oxide is, for example, a tungsten oxide compound, the tungsten oxide compound is a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. (See Japanese Patent No. 4,096,205).
The tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

<Polymerizable compound>
The infrared ray absorbing composition of the present invention can be suitably constituted by containing at least one polymerizable compound.

  Specifically, the polymerizable compound is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as annulate, glycerin and trimethylolethane; Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
As other preferable polymerizable compounds, compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and cardo resins. Can also be used.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an -OC (= O) C (CH 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used as a polymerizable compound.

  Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid value of the entire polyfunctional monomer should be adjusted so that it falls within the above range. Is essential.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

Such polyfunctional monomers having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (the above formula (
In 1) to (3), m = 1, the number of groups represented by formula (2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, formula (2) ), The number of groups represented by formula (2) = 6, and R ¹ is RCA = 3, a compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, formula (2)) A compound in which all are hydrogen atoms), DPCA-120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and R ¹ is all hydrogen atoms), and the like.
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  In addition, the polymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) yCH} 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents, Each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (i), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side ends Is preferred in which X is bonded to X.

  The compounds represented by the general formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable and 50 mass% or more is more preferable.

  The compound represented by the general formula (i) or (ii) is a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (i) or (ii), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available polymerizable compounds represented by the general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  A polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule is also suitable as the polymerizable compound. Particularly preferred are those represented by the following general formula (I).

(In the formula, R ¹ is an alkyl group, R ² is an n-valent aliphatic group that may contain atoms other than carbon, R ⁰ is an alkyl group that is not H, and n represents 2 to 4).

  If the polyfunctional thiol compound represented by the general formula (I) is specifically exemplified, 1,4-bis (3-mercaptobutyryloxy) butane [formula (II)] having the following structural formula: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H5H) -trione [formula (III)] and pentaerythritol tetrakis (3 -Mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols can be used alone or in combination.

  About the compounding quantity of the polyfunctional thiol in an infrared rays absorptive composition, it is 0.3-8.9 weight% with respect to the total solid except a solvent, More preferably, it is the range of 0.8-6.4 weight%. It is desirable to add in. By adding a polyfunctional thiol, the stability, odor, sensitivity, adhesion, etc. of the infrared absorbing composition can be improved.

  About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of an infrared absorptive composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In addition, from the viewpoint of increasing the strength of the infrared cut filter, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic esters, methacrylic esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. Also, selection and use of polymerizable compounds for compatibility and dispersibility with other components (for example, metal oxides, dyes, polymerization initiators, binders, etc.) contained in the infrared absorbing composition. Is an important factor. For example, compatibility may be improved by the use of a low-purity compound or a combination of two or more. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  The content of the polymerizable compound in the infrared absorbing composition of the present invention is preferably 0.1% by mass to 90% by mass, and 1.0% by mass to 80% by mass with respect to the solid content in the infrared absorbing composition. % By mass is more preferable, and 2.0% by mass to 70% by mass is particularly preferable.

<Polymerization initiator>
The infrared absorbing composition of the present invention may contain a polymerization initiator, and as the polymerization initiator, as long as it has the ability to initiate polymerization of a polymerizable compound by either light or heat, or both, There is no limitation, and it can be appropriately selected according to the purpose, but is preferably a photopolymerizable compound. When polymerization is initiated by light, those having photosensitivity to visible light from the ultraviolet region are preferred.
Moreover, when starting superposition | polymerization with a heat | fever, the initiator decomposed | disassembled at 150 to 250 degreeC is preferable.

The polymerization initiator that can be used in the present invention is preferably a compound having at least an aromatic group, such as an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, and a ketal derivative. Compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, metallocene compounds, etc. Onium salt compounds, organoboron salt compounds, disulfone compounds, and the like.
From the viewpoint of sensitivity, an oxime compound, an acetophenone compound, an α-aminoketone compound, a trihalomethyl compound, a hexaarylbiimidazole compound, and a thiol compound are preferable.
Examples of the polymerization initiator suitable for the present invention will be given below, but the present invention is not limited thereto.

  Specific examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and p-dimethylaminoacetophenone. 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-methyl -1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Examples include -1-butanone and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

  As the trihalomethyl compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris (Monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compound, IRGACURE OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), IRGACURE OXE 02 (ethanone, 1- [9-ethyl) manufactured by BASF Japan -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)), 2- (acetyloxyiminomethyl) thioxanthen-9-one and the like.
Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A.
Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime compound is preferably a compound represented by the following formula (1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group. Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among them, the structure shown below is particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (2).

(In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improved absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the group shown below, * represents the bonding position between Y and the adjacent carbon atom in the formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (3).

  R, X, A, Ar, and n in Formula (3) have the same meanings as R, X, A, Ar, and n in Formula (2), respectively, and preferred examples are also the same.

  Specific examples (C-4) to (C-13) of oxime compounds that are suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and has a high absorbance at 365 nm and 455 nm. Particularly preferred.

From the viewpoint of sensitivity, the oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm of 3,000 to 300,000, more preferably 5,000 to 300,000, and 10,000 to 200. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

The photopolymerization initiator is more preferably a compound selected from the group consisting of oxime compounds, acetophenone compounds, and acylphosphine compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969, an acylphosphine oxide initiator described in Japanese Patent No. 4225898, and the oxime initiator described above, As the oxime initiator, compounds described in JP-A No. 2001-233842 can also be used.
As the acetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.

A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
The content of the polymerization initiator relative to the total solid mass of the polymerizable composition of the present invention is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, and 0.1% by mass. % To 15% by mass is particularly preferable.

<Binder>
The infrared absorbing composition of the present invention preferably contains a binder.
The binder is not particularly limited, but the binder is preferably an alkali-soluble resin.

The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, and (meth) acrylic acid is particularly preferable. It is done. These acid groups may be used alone or in combination of two or more.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when an acid group is introduced using a monomer that can impart an acid group after polymerization as a monomer component, a treatment for imparting the acid group after polymerization is required.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as monomers and polymethylmethacrylate macromonomers include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  As the alkali-soluble resin, a polymer (a) obtained by polymerizing a monomer component having a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”) as an essential component is used. It is also preferable to contain as a polymer component (A) which is. Thereby, the infrared-absorbing composition of this invention can form the cured coating film which was extremely excellent also in heat resistance and transparency.

(In formula (ED), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

In the general formula (ED), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, linear or branched alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butyl An alicyclic group such as cyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; an alkyl group substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  As a specific example of the ether dimer, for example, the one described in paragraph No. 0171 of JP2012-032754A is preferable. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde. The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

  Moreover, in order to improve the crosslinking efficiency of the infrared cut filter obtained from the infrared absorbing composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-described polymer containing a polymerizable group include: NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Viscoat R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series such as cyclomer P ACA230AA, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), etc. Is mentioned. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, JP 2002-229207 A And a resin obtained by subjecting a resin having a side chain with an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer. As a commercial item, acrylic base FF-187, FF-426 (made by Fujikura Kasei Co., Ltd.) etc. are mentioned, for example.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Moreover, as a weight average molecular weight (Mw) of alkali-soluble resin, 2,000-50,000 are preferable, 5,000-40,000 are more preferable, 7,000-35,000 are the most preferable.

  As content in the infrared rays absorptive composition of a binder, 1-20 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-15 mass%, Most preferably, it is 3 ˜12% by mass.

<Dispersant>
The infrared absorbing composition of the present invention may be used by dispersing with a known dispersant for the purpose of improving the dispersibility and dispersion stability of the metal oxide and the dye.

Examples of the dispersant that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (Meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], and surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and alkanol amine.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  Examples of the terminal-modified polymer having an anchor site to the surface include a polymer having a phosphate group at its terminal described in JP-A-3-112992, JP-T2003-533455, and the like. A polymer having a sulfonic acid group at its terminal described in JP-A-273191, a polymer having a partial skeleton or a heterocyclic ring of an organic dye described in JP-A-9-77994, or the like in JP-A-2008-29901 Examples thereof include a polymer produced by modifying an oligomer or polymer having a hydroxyl group or an amino group at one end and an acid anhydride. In addition, a high molecular weight terminal in which two or more anchor portions (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) to the surface of the infrared shielding material are introduced at the polymer ends described in JP-A-2007-277514. Molecules are also preferred because of their excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the surface include poly (lower alkyleneimine) described in JP-A No. 54-37082, JP-A No. 8-507960, JP-A No. 2009-258668, and the like. Reaction product of polyester and polyester, reaction product of polyallylamine and polyester described in JP-A-9-169821 and the like, amphoteric dispersion resin having basic group and acidic group described in JP-A-2009-203462, Copolymers of macromonomer and nitrogen atom monomer described in Kaihei 10-339949, JP-A-2004-37986, etc., JP-A-2003-238837, JP-A-2008-9426, JP-A-2008- JP-A-201032, a graft polymer having a partial skeleton of an organic dye or a heterocyclic ring, They include copolymers of macromonomer and acid group-containing monomers described in 6268 JP like.

  As a macromonomer used when producing a graft polymer having an anchor site on the surface by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal group) manufactured by Toa Gosei Co., Ltd. Is a methacryloyl group polymethyl methacrylate), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (terminal Polybutyl acrylate whose group is a methacryloyl group), Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd. (2-hydroxyethyl methacrylate, ε-caprolactone 5 molar equivalent addition product), FA10L (ε of 2-hydroxyethyl acrylate) -Caprolactone 10 molar equivalent addition product), and JP-A-2-272009 Polyester macromonomer described in the publication No. and the like. Among these, a polyester-based macromonomer that is particularly flexible and excellent in solvent-solubility is particularly preferable from the viewpoints of dispersibility and dispersion stability of the infrared shielding material in the composition, and further described in JP-A-2-272009. Most preferred is a polyester macromonomer represented by the following polyester macromonomer.

  As the block polymer having an anchor site to the surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

As the dispersant, for example, a known dispersant or surfactant can be appropriately selected and used.
Specific examples include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, and 163, manufactured by BYK Chemie. 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050-4010-4165 (polyurethane system), EFKA4330, manufactured by EFKA. -4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) ", Ajinomoto Fan Techno "Ajispa" “PB821, PB822, PB880, PB881”, “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon” manufactured by Enomoto Kasei Co., Ltd. KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725, “Demol RN, N” manufactured by Kao Corporation (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), “homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935” , 985 (polyoxyethylene nonylphenyl ether), “acetamine 86 (stearyl amine) N-acetate ”, manufactured by Nippon Lubrizol Co., Ltd.“ Solsperse 5000 (phthalocyanine derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (Graft type polymer) ", Nikko Chemical's" Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd. “W001: Cationic Surfactant”, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as “W004, W005, W017” Agents, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450” manufactured by Morishita Sangyo Co., Ltd., “Disperse Aid 6, Disp. Polymer dispersants such as Perth Aid 8, Disperse Aid 15, Disperse Aid 9100, “Adeka Pluronic L31, F38, L42, L44, L61, L64, F manufactured by ADEKA Corporation 8, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ", and Sanyo Kasei Co., Ltd." Ionet (trade name) S-20 ", and the like.

These dispersants may be used alone or in combination of two or more. In addition, the dispersant of the present invention may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the surface of the infrared shielding material. . Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.
From the viewpoints of dispersibility and sedimentation, the following resins described in JP 2010-106268 A are preferable, and in particular, from the viewpoint of dispersibility, a polymer dispersant having a polyester chain in the side chain is preferable. Also preferred are resins having acid groups and polyester chains. As a preferable acid group in the dispersant, an acid group having a pKa of 6 or less is preferable from the viewpoint of adsorptivity, and carboxylic acid, sulfonic acid, and phosphoric acid are particularly preferable.

The dispersion resin described in JP 2010-106268 A, which is preferably used in the present invention, will be described below.
A preferred dispersant is a graft copolymer having a graft chain selected from a polyester structure, a polyether structure, and a polyacrylate structure, in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000 in the molecule. It is preferable that at least a structural unit represented by any one of the following formulas (1) to (4) is included, and at least the following formula (1A), the following formula (2A), the following formula (3A), the following formula ( 3B) and a structural unit represented by any one of the following formulas (4) are more preferable.

In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthesis restrictions, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
In the formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, and an oxygen atom is particularly preferable.
In the formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently a divalent linking group and are not particularly limited in structure. Specific examples include the following (Y-1) to (Y-21) linking groups. In the following structures, A and B each represent a bond with the left terminal group and the right terminal group in formulas (1) to (4). Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In Formula (1) to Formula (4), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly limited, Specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Among these, from the viewpoint of improving dispersibility, it is preferable to have a steric repulsion effect, and the monovalent substituents represented by Z ^{1 to} Z ³ are each independently an alkyl group having 5 to 24 carbon atoms or carbon. An alkoxy group having 5 to 24 carbon atoms is preferable, and among them, an alkoxy group having a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms is particularly preferable. The monovalent substituent represented by Z ⁴ is preferably an alkyl group having 5 to 24 carbon atoms, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms or a cyclic group having 5 to 24 carbon atoms. Alkyl groups are preferred.
In Formula (1)-Formula (4), n, m, p, and q are integers of 1 to 500, respectively.
In Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoint of dispersion stability.

In the formula (3), R ′ represents a branched or straight chain alkylene group. R ′ in formula (3) is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
Further, as R ′ in the formula (3), two or more types of R ′ having different structures may be mixed and used in the dispersion resin.
In formula (4), R represents a hydrogen atom or a monovalent organic group and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom. An atom or an alkyl group. When R is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
Moreover, as R in Formula (4), two or more types of R having different structures may be mixed and used in the specific resin.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability.

Wherein (1A), X ^1, Y ^1, Z ¹ and n are as defined X ^1, Y ^1, Z ¹ and n in Formula (1), and preferred ranges are also the same.
Wherein (2A), X ^2, Y ^2, Z ² and m are as defined X ^2, Y ^2, Z ² and m in the formula (2), and preferred ranges are also the same.
The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or the following formula (3B) from the viewpoint of dispersion stability.

Wherein (3A) or ^{(3B), X 3, Y} 3, Z 3 and p, the formula ^{(3) X 3, Y 3} , have the same meaning as Z ³ and p in, preferred ranges are also the same.

  Specific examples include the compounds described in paragraph numbers 0241 to 0257 of JP2012-032556A.

When the infrared absorbing composition of the present invention contains a polymerizable compound and a dispersant, first, the dispersion composition of the metal oxide, the dye and the dispersant is prepared with an appropriate solvent, and then the polymerizable composition. From the viewpoint of improving dispersibility, it is preferable to blend the product.
The infrared absorbing composition may or may not contain a dispersant, but when it is contained, the content of the dispersant in the composition is the mass of the metal oxide in the composition and the amount of the dye. 1 mass%-90 mass% is preferable with respect to the sum with mass, and 3 mass%-70 mass% is more preferable.

<Sensitizer>
The infrared absorbing composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable. Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.

Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg, Thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthrone) Laquinone), squalium (for example, squalium), acridine orange, coumarins (for example, 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, Distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone , Aromatic ketone compounds such as Michler's ketone, and heterocyclic compounds such as N-aryloxazolidinones.
Further, in European Patent No. 568,993, US Pat. No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11-271969, etc. And the like.
The infrared absorbing composition may or may not contain a sensitizer, but when it is included, the content of the sensitizer is 0. 0 relative to the total solid mass of the infrared absorbing composition of the present invention. The content is preferably from 01% by mass to 10% by mass, and more preferably from 0.1% by mass to 2% by mass.

<Crosslinking agent>
The infrared absorbing composition of the present invention may further contain a crosslinking agent for the purpose of improving the strength of the infrared cut filter.
The crosslinking agent is preferably a compound having a crosslinkable group, and more preferably a compound having two or more crosslinkable groups. As specific examples of the crosslinkable group, oxetane group, cyanate group, and the same groups as those mentioned for the crosslinkable group which the alkali-soluble binder may have can be suitably exemplified. , An oxetane group or a cyanate group. That is, the crosslinking agent is particularly preferably an epoxy compound, an oxetane compound or a cyanate compound.
Examples of the epoxy compound that can be suitably used as a crosslinking agent in the present invention include an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound having at least two epoxy groups having an alkyl group at the β-position in one molecule. Compound etc. are mentioned.

  Examples of the epoxy compound having at least two oxirane groups in one molecule include the compounds described in paragraph numbers 0263 to 0264 of JP2012-032556A. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position in one molecule can be used, and the β-position is an alkyl group. A compound containing a substituted epoxy group (more specifically, a β-alkyl-substituted glycidyl group or the like) is particularly preferable.
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

Examples of the oxetane compound include oxetane resins having at least two oxetanyl groups in one molecule.
Specifically, for example, the compounds described in paragraph No. 0266 of JP2012-032556A can be mentioned. Examples of the bismaleimide compound include 4,4′-diphenylmethane bismaleimide, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 2,2′-bis- [4- (4-maleimide). Phenoxy) phenyl] propane, and the like.

  Examples of the cyanate compound include a bis A type cyanate compound, a bis F type cyanate compound, a cresol novolac type cyanate compound, and a phenol novolac type cyanate compound.

Moreover, a melamine or a melamine derivative can be used as the crosslinking agent.
Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like).
A crosslinking agent may be used individually by 1 type, and may use 2 or more types together. The crosslinking agent has good storage stability and is effective in improving the surface hardness of the cured film (the film after the crosslinking reaction by the crosslinking agent is performed by energy such as light or heat) or the film strength itself. Melamine or alkylated methylol melamine is preferred, and hexamethylated methylol melamine is particularly preferred.

  The infrared absorbing composition may or may not contain a crosslinking agent, but when it is included, the content of the crosslinking agent is 1% by mass or more based on the total solid content of the infrared absorbing composition of the present invention. It is preferably 40% by mass or less, and more preferably 3% by mass or more and 20% by mass or less.

<Curing accelerator>
The infrared absorbing composition of the present invention may further contain a curing accelerator for the purpose of accelerating the thermal curing of the crosslinking agent such as the epoxy compound or the oxetane compound.
As a hardening accelerator, the compound of the paragraph number 0269 of Unexamined-Japanese-Patent No. 2012-032556 is mentioned, for example. A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
The infrared absorbing composition may or may not contain a curing accelerator, but when it is contained, the content of the curing accelerator with respect to the total solid content of the composition is usually 0.01 to 15% by mass. is there.

<Filler>
The infrared absorbing composition of the present invention may further contain a filler. Examples of the filler that can be used in the present invention include spherical silica surface-treated with a silane coupling agent.
When the polymerizable composition of the present invention contains a filler, it is preferable in that a highly durable infrared cut filter is obtained.

The “spherical” in the spherical filler is not necessarily a needle shape, a columnar shape, or an indeterminate shape, but may be rounded and does not necessarily need to be “true spherical”. "Spherical" is mentioned as a mobile phone.
It can be confirmed that the filler is spherical by observing with a scanning electron microscope (SEM).

There is no restriction | limiting in particular in the volume average particle diameter of the primary particle of the said filler, Although it can select suitably according to the objective, 0.05 micrometer-3 micrometers are preferable, and 0.1 micrometer-1 micrometer are more preferable. When the volume average particle size of the primary particles of the filler is in the above range, the reduction in workability due to the development of thixotropic properties is suppressed, and the maximum particle size is not increased, so that the foreign matter in the obtained infrared cut filter This is advantageous because the occurrence of defects due to adhesion and non-uniform coating is suppressed.
The volume average particle size of the primary particles of the filler can be measured by a dynamic light scattering particle size distribution measuring device.
The filler can be dispersed by using the aforementioned dispersant and binder. As described above, an alkali-soluble binder polymer having a crosslinkable group in the side chain is particularly preferable from the viewpoint of curability.

-Surface treatment-
Next, the surface treatment of the filler will be described. There is no restriction | limiting in particular as surface treatment of a filler, Although it can select suitably according to the objective, The process which coat | covers a silica with a silane coupling agent is preferable.

-Silane coupling agent-
There is no restriction | limiting in particular as a silane coupling agent used for the surface treatment of a filler, Although it can select suitably according to the objective, At least 1 sort (s) selected from an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group A functional group (hereinafter also referred to as “first functional group”) and at least one functional group selected from a (meth) acryloyl group, an amino group and an epoxy group (hereinafter also referred to as “second functional group”). The second functional group is more preferably a (meth) acryloyl group or an amino group, the second functional group is more preferably a (meth) acryloyl group, and the second functional group is a (meth) acryloyl group. This is advantageous in terms of storage stability.

  Further, as described in JP-B-7-68256, the first functional group is at least one selected from an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group, and the second functional group is an imidazole group or an alkyl group. Those having at least one selected from an imidazole group and a vinylimidazole group can also be preferably used.

  The silane coupling agent is not particularly limited. For example, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)- γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, JP 7- [Alpha]-[[3- (trimethoxysilyl) propoxy] methyl] -imidazole-1-ethanol, 2-ethyl-4-methyl- [alpha]-[[3- (trimethoxysilyl) propoxy] described in Japanese Patent No. 68256 Methyl] -imidazole-1-ethanol, 4-vinyl-α-[[3 (Trimethoxysilyl) propoxy] methyl] - imidazole-1-ethanol, 2-ethyl-4-methyl-imidazo-trimethoxysilane, and their salts, intramolecular condensates, intermolecular condensates, and the like preferably. These may be used individually by 1 type and may be used in combination of 2 or more types.

The surface treatment of the spherical silica with the silane coupling agent may be performed only on the spherical silica in advance (this case is also referred to as “pretreatment” hereinafter), and is included in the infrared absorbing composition. You may carry out together with a part or all of other fillers.
The method for performing the pretreatment is not particularly limited, and examples thereof include a dry method, an aqueous solution method, an organic solvent method, and a spray method. The temperature for performing the pretreatment is not particularly limited, but is preferably from room temperature to 200 ° C.
It is also preferable to add a catalyst during the pretreatment. There is no restriction | limiting in particular as this catalyst, For example, an acid, a base, a metal compound, an organometallic compound etc. are mentioned.

  The amount of the silane coupling agent added in the pretreatment is not particularly limited, but is preferably in the range of 0.01 to 50 parts by mass with respect to 100 parts by mass of spherical silica, and 0.05 to The range of 50 parts by mass is more preferable. When the addition amount is in the above range, a surface treatment sufficient to exhibit the effect is performed, and a decrease in handleability due to aggregation of spherical silica after the treatment is suppressed.

  In the silane coupling agent, the first functional group reacts with the substrate surface, the spherical silica surface, and the active group of the binder, and the second functional group further includes a carboxyl group and an ethylenically unsaturated group of the binder. In order to react with, it has the effect | action which improves the adhesiveness of a base material and an infrared cut filter. On the other hand, since the silane coupling agent is highly reactive, when it is added to the polymerizable composition, the second functional group mainly reacts or deactivates during storage due to the diffusion action, Shelf life and pot life may be shortened.

However, as described above, if the spherical silica pretreated with a silane coupling agent is used, the diffusion effect is suppressed, so that the shelf life and pot life problems are greatly improved. It is also possible to do. Furthermore, when pre-treating spherical silica, conditions such as stirring conditions, temperature conditions, and use of a catalyst can be freely selected, so that the silane coupling agent is compared with the case of adding without pre-treatment. The reaction rate between the first functional group and the active group in the spherical silica can be remarkably increased. Therefore, very good results can be obtained particularly in severe required characteristics such as electroless gold plating, electroless solder plating, and moisture resistance load test. Moreover, the amount of the silane coupling agent used can be reduced by performing the pretreatment, and the shelf life and pot life can be further improved.
Examples of the spherical silica surface-treated with a silane coupling agent that can be used in the present invention include, for example, Electrochemical Industry: FB, SFP series, Tatsumori: 1-FX, Toa Gosei: HSP series, Fuso Chemical Industries: SP series etc. are mentioned.

  The infrared-absorbing composition may or may not contain a filler, but when it is contained, the filler content relative to the total solid content mass of the infrared-absorbing composition is not particularly limited and is appropriately determined depending on the purpose. Although it can select, 1 mass%-60 mass% are preferable. When the addition amount is in the above range, a sufficient reduction in the coefficient of linear expansion is achieved, the embrittlement of the formed infrared cut filter is suppressed, and the function as an infrared cut filter is fully expressed.

<Elastomer>
The infrared absorbing composition of the present invention may further contain an elastomer.
By containing an elastomer, the adhesiveness between the substrate and the infrared cut filter can be further improved, and the heat resistance, thermal shock resistance, flexibility and toughness of the infrared cut filter can be further improved.

There is no restriction | limiting in particular as an elastomer which can be used for this invention, According to the objective, it can select suitably, For example, a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer And silicone elastomers. These elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. Among these, polyester elastomers are advantageous in terms of compatibility with other materials.
Examples of the elastomer include compounds described in paragraph numbers 0284 to 0292 of JP2012-032556A.

  Among elastomers, from the viewpoints of shear adhesion and thermal shock resistance, both terminal carboxyl group-modified butadiene-acrylonitrile copolymers, espels having hydroxyl groups which are polyester elastomers (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.), epoxy Polybutadiene is preferred.

  The infrared absorbing composition of the present invention may or may not contain an elastomer, but when it is contained, the content of the elastomer with respect to the total solid mass of the infrared absorbing composition is not particularly limited. Although it can select suitably according to it, 0.5 mass%-30 mass% in solid content are preferable, 1 mass%-10 mass% are more preferable, 3 mass%-8 mass% are especially preferable. When the content is within a preferable range, it is advantageous in that the shear adhesiveness and the thermal shock resistance can be further improved.

<Surfactant>
Various surfactants may be added to the infrared absorbing composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, since the infrared absorbing composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, in the case of forming a film using a coating liquid to which an infrared absorbing composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in an infrared-absorbing composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored photosensitive composition. More preferably, it is 0.01 to 0.1% by mass or less.

<Other ingredients>
In the infrared absorbing composition of the present invention, in addition to the essential components and the preferred additives, other components may be appropriately selected according to the purpose as long as the effects of the present invention are not impaired.
Examples of other components that can be used in combination include a thermosetting accelerator, a thermal polymerization inhibitor, and a plasticizer. Further, adhesion promoters to the substrate surface and other auxiliary agents (for example, conductive particles, Fillers, antifoaming agents, flame retardants, leveling agents, 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 film physical properties of the target infrared absorption filter can be adjusted.
The thermal polymerization inhibitor is described in detail, for example, in paragraphs [0101] to [0102] of JP-A-2008-250074.
The plasticizer is described in detail, for example, in paragraphs [0103] to [0104] of JP-A-2008-250074.
The adhesion promoter is described in detail, for example, in paragraphs [0107] to [0109] of JP-A-2008-250074.
Any of the additives described in these publications can be used in the infrared absorbing composition of the present invention.

<Solvent>
The infrared absorbing composition of the present invention preferably contains a solvent.
The solvent is not particularly limited, and can be appropriately selected depending on the purpose as long as it can uniformly dissolve or disperse each component of the infrared absorbing composition of the present invention. For example, methanol, ethanol, Alcohols such as normal-propanol, isopropanol, normal-butanol, secondary-butanol, normal-hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, cyclohexanone, cyclopentanone; ethyl acetate, butyl acetate, Esters such as acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate and methoxypropyl acetate; toluene, xyle Aromatic hydrocarbons such as benzene, ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether And ethers such as ethylene glycol monoethyl ether, 1-methoxy-2-propanol and propylene glycol monomethyl ether; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  The infrared absorbing composition of the present invention thus obtained preferably has a solid content concentration of 5 to 90% by mass, more preferably 7 to 80% by mass, and most preferably 10 to 60% by mass. is there.

  The infrared absorbing composition of the present invention is preferably liquid. If a solvent is contained in the composition to form a liquid composition, an infrared cut filter can be easily produced by a simple process of forming a film by, for example, applying (preferably spin coating) the liquid composition. Therefore, inadequate manufacturing aptitude in the above-described conventional infrared cut filter can be improved.

The use of the infrared absorbing composition of the present invention is not particularly limited, but for infrared cut filters on the light receiving side of the solid-state image sensor substrate (for example, for infrared cut filters for wafer level lenses), the back side of the solid-state image sensor substrate An infrared cut filter for the light receiving side (opposite to the light receiving side) can be used, and it is preferably for the light shielding film on the light receiving side of the solid-state imaging device substrate.
The viscosity of the infrared absorbing composition of the present invention is preferably in the range of 1 mPa · s to 3000 mPa · s, more preferably in the range of 10 mPa · s to 2000 mPa · s, most preferably , 100 mPa · s or more and 1500 mPa · s or less.
When the infrared-absorbing composition of the present invention is for an infrared cut filter on the light-receiving side of a solid-state imaging device substrate, it is in the range of 10 mPa · s or more and 3000 mPa · s or less from the viewpoint of thick film formation and uniform coating properties. It is preferably in the range of 500 mPa · s to 1500 mPa · s, and most preferably in the range of 700 mPa · s to 1400 mPa · s.

The present invention also relates to an infrared cut filter obtained using the above-described infrared absorbing composition of the present invention. Since such an infrared cut filter is formed from the infrared absorbing composition of the present invention, it has a high light shielding property (infrared shielding property) in the infrared region (including the near infrared region near the wavelength of 700 nm) and is visible. It is an infrared cut filter having high translucency (visible light transmissivity) in the light region and excellent weather resistance such as light resistance and moisture resistance.
Furthermore, the present invention also relates to a method for manufacturing an infrared cut filter, which includes a step of forming a film by applying (preferably spin coating) the infrared absorbing composition of the present invention on the light receiving side of a solid-state imaging device substrate. Related.

  In order to form an infrared cut filter, first, a film is formed from the infrared absorbing composition of the present invention. The film is not particularly limited as long as it is a film formed by including the infrared absorbing composition, and the film thickness, the laminated structure, and the like can be appropriately selected according to the purpose.

  As the method for forming the film, the infrared absorbing composition of the present invention (a coating solution in which the solid content in the composition is dissolved, emulsified or dispersed) is directly applied (preferably coated) on the support. And forming by drying.

The support is provided on the light receiving side of the solid-state imaging device substrate, whether it is a solid-state imaging device substrate or another substrate (for example, a glass substrate 30 described later) provided on the light-receiving side of the solid-state imaging device substrate. A layer such as a flattening layer may also be used.
The method of applying (preferably spin coating) the infrared absorbing composition (coating liquid) on the support can be carried out by using, for example, a spin coater, a slit spin coater or the like.
Moreover, as drying conditions of a coating film, although it changes also with each component, the kind of solvent, a usage rate, etc., it is about 30 seconds-15 minutes normally at the temperature of 60 to 150 degreeC.

  There is no restriction | limiting in particular as thickness of the said film | membrane, Although it can select suitably according to the objective, For example, 1 micrometer-100 micrometers are preferable, 1 micrometer-50 micrometers are more preferable, 1.0 micrometer-4.0 micrometers are especially preferable.

  The method of forming an infrared cut filter using the infrared absorbing composition of the present invention may include other steps.

  There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a preheating process (prebaking process), a hardening process process, a post-heating process (post-baking) Process).

<Pre-heating process / Post-heating process>
The heating temperature in the preheating step and the postheating step is usually 80 ° C to 200 ° C, and preferably 90 ° C to 150 ° C.
The heating time in the preheating step and the postheating step is usually 30 seconds to 240 seconds, and preferably 60 seconds to 180 seconds.

<Curing process>
The curing process is a process of curing the formed film as necessary, and the mechanical strength of the infrared cut filter is improved by performing this process.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably. Here, in the present invention, “exposure” is used to include not only light of various wavelengths but also irradiation of radiation such as electron beams and X-rays.
The exposure is preferably performed by irradiation of radiation, and as the radiation that can be used for the exposure, ultraviolet rays such as electron beams, KrF, ArF, g rays, h rays, i rays and visible light are particularly preferably used. Preferably, KrF, g line, h line, and i line are preferable.
As an exposure method. Examples include stepper exposure and exposure with a high-pressure mercury lamp.
Exposure is more preferably 5mJ / cm ² ~3000mJ / cm ² is preferably ^{10mJ / cm 2 ~2000mJ / cm 2} , 50mJ / cm 2 ~1000mJ / cm 2 being most preferred.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed film. When the infrared absorbing composition contains a polymerizable compound, the entire surface exposure promotes curing of the polymerization component in the film formed from the composition, and the film is further cured, resulting in mechanical strength and durability. Improved.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Moreover, as a method of the whole surface heat treatment, a method of heating the entire surface of the formed film can be mentioned. By heating the entire surface, the film strength of the pattern is increased.
120 to 250 degreeC is preferable and the heating temperature in a whole surface heating has more preferable 120 to 250 degreeC. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the components in the film are decomposed and the film quality is prevented from becoming weak and brittle.
The heating time in the entire surface heating is preferably 3 minutes to 180 minutes, and more preferably 5 minutes to 120 minutes.
There is no restriction | limiting in particular as an apparatus which performs whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

  Further, the present invention is a camera module having a solid-state image sensor substrate and an infrared cut filter disposed on a light receiving side of the solid-state image sensor substrate, wherein the infrared cut filter is the infrared cut filter of the present invention. Also related to camera modules.

Hereinafter, although the camera module which concerns on embodiment of this invention is demonstrated, referring FIG.1 and FIG.2, this invention is not limited by the following specific examples.
Throughout FIGS. 1 and 2, common portions are denoted by common reference numerals.
In the description, “upper”, “upper”, and “upper” refer to the side far from the silicon substrate 10, and “lower”, “lower”, and “lower” are the sides closer to the silicon substrate 10. Point to.

FIG. 1 is a schematic cross-sectional view illustrating a configuration of a camera module including a solid-state imaging device.
A camera module 200 shown in FIG. 1 is connected to a circuit board 70 that is a mounting board via solder balls 60 that are connection members.
Specifically, the camera module 200 is provided on the first main surface side (light receiving side) of the solid-state image sensor substrate 100 and the solid-state image sensor substrate 100 provided with an image sensor section on the first main surface of the silicon substrate. The flattening layer 46 (not shown in FIG. 1), the infrared cut filter 42 provided on the flattening layer 46, and the glass substrate 30 (light transmissive substrate) disposed above the infrared cut filter 42 A lens holder 50 having an imaging lens 40 disposed in an internal space above the glass substrate 30, and a light shielding / electromagnetic shield 44 disposed to surround the solid-state imaging device substrate 100 and the glass substrate 30. Configured. Each member is bonded by an adhesive 20 (not shown in FIG. 1) and 45.
The present invention is a method of manufacturing a camera module having a solid-state image pickup device substrate and an infrared cut filter disposed on the light-receiving side of the solid-state image pickup device substrate. The present invention also relates to a step of forming a film by applying an infrared absorbing composition (preferably spin coating).
Therefore, in the camera module according to this embodiment, for example, a film is formed on the planarizing layer 46 by applying (preferably spin-coating) the infrared absorbing composition of the present invention to form an infrared cut filter. 42 is formed. The method for producing an infrared cut filter by forming a film by coating (preferably spin coating) is as described above.
In the camera module 200, incident light hν from the outside passes through the imaging lens 40, the glass substrate 30, the infrared cut filter 42, and the flattening layer 46 in order, and then reaches the imaging device portion of the solid-state imaging device substrate 100. It has become.
The camera module 200 is connected to the circuit board 70 via a solder ball 60 (connection material) on the second main surface side of the solid-state imaging device substrate 100.

FIG. 2 is an enlarged cross-sectional view of the solid-state imaging device substrate 100 in FIG.
The solid-state image sensor substrate 100 includes a silicon substrate 10 as a base, an image sensor 12, an interlayer insulating film 13, a base layer 14, a red color filter 15R, a green color filter 15G, a blue color filter 15B, an overcoat 16, a micro The lens 17, the light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27 are configured.
However, the solder resist layer 24 may be omitted.

First, the configuration on the first main surface side of the solid-state imaging device substrate 100 will be mainly described.
As shown in FIG. 2, an imaging element unit in which a plurality of imaging elements 12 such as CCDs and CMOSs are two-dimensionally arranged is provided on the first main surface side of the silicon substrate 10 that is a base of the solid-state imaging element substrate 100. ing.
An interlayer insulating film 13 is formed on the image sensor 12 in the image sensor section, and a base layer 14 is formed on the interlayer insulating film 13. Furthermore, on the base layer 14, a red color filter 15 R, a green color filter 15 G, and a blue color filter 15 B (hereinafter collectively referred to as “color filter 15”) corresponding to the image sensor 12. ) Are arranged.
A light shielding film (not shown) may be provided around the boundary between the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and the periphery of the imaging element unit. This light shielding film can be produced using, for example, a known black color resist.
An overcoat 16 is formed on the color filter 15, and a microlens 17 is formed on the overcoat 16 so as to correspond to the imaging element 12 (color filter 15).
The planarizing layer 46 is provided on the microlens 17.

In addition, a peripheral circuit (not shown) and an internal electrode 26 are provided in the periphery of the image sensor section on the first main surface side, and the internal electrode 26 is electrically connected to the image sensor 12 via the peripheral circuit. Has been.
Furthermore, an element surface electrode 27 is formed on the internal electrode 26 with the interlayer insulating film 13 interposed therebetween. In the interlayer insulating film 13 between the internal electrode 26 and the element surface electrode 27, a contact plug (not shown) for electrically connecting these electrodes is formed. The element surface electrode 27 is used for applying a voltage and reading a signal through the contact plug and the internal electrode 26.
A base layer 14 is formed on the element surface electrode 27. An overcoat 16 is formed on the base layer 14. The base layer 14 and the overcoat 16 formed on the element surface electrode 27 are opened to form a pad opening, and a part of the element surface electrode 27 is exposed.

The above is the configuration of the first main surface side of the solid-state imaging device substrate 100, but instead of providing the infrared cut filter 42 on the planarization layer 46, between the base layer 14 and the color filter 15, or An infrared cut filter may be provided between the color filter 15 and the overcoat 16.
On the first main surface side of the solid-state image sensor substrate 100, an adhesive 20 is provided around the image sensor section, and the solid-state image sensor substrate 100 and the glass substrate 30 are bonded via the adhesive 20.

  The silicon substrate 10 has a through hole that penetrates the silicon substrate 10, and a through electrode that is a part of the metal electrode 23 is provided in the through hole. The imaging element portion and the circuit board 70 are electrically connected by the through electrode.

Next, the configuration on the second main surface side of the solid-state imaging device substrate 100 will be mainly described.
On the second main surface side, an insulating film 22 is formed from the second main surface to the inner wall of the through hole.
On the insulating film 22, a metal electrode 23 patterned so as to extend from a region on the second main surface of the silicon substrate 10 to the inside of the through hole is provided. The metal electrode 23 is an electrode for connecting the image pickup element portion in the solid-state image pickup element substrate 100 and the circuit board 70.
The through electrode is a portion of the metal electrode 23 formed inside the through hole. The through electrode penetrates part of the silicon substrate 10 and the interlayer insulating film, reaches the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.

Further, a solder resist layer 24 (protective layer) is provided on the second main surface side, which covers the second main surface on which the metal electrode 23 is formed and has an opening that exposes a portion on the metal electrode 23. Insulating film).
Further, on the second main surface side, there is provided a light shielding film 18 that covers the second main surface on which the solder resist layer 24 is formed and has an opening through which a part of the metal electrode 23 is exposed. It has been.
In FIG. 2, the light shielding film 18 is patterned so as to cover a part of the metal electrode 23 and expose the remaining part, but may be patterned so as to expose the entire metal electrode 23. (The same applies to the patterning of the solder resist layer 24).
The solder resist layer 24 may be omitted, and the light shielding film 18 may be directly formed on the second main surface on which the metal electrode 23 is formed.

  A solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state imaging device substrate 100 and a connection electrode (not shown) of the circuit board 70 are connected via the solder ball 60. , Are electrically connected.

As mentioned above, although the structure of the solid-state image sensor substrate 100 was demonstrated, the method as described in Paragraph 0033-0068 of Unexamined-Japanese-Patent No. 2009-158863, the method as described in Paragraph 0036-0065 of Unexamined-Japanese-Patent No. 2009-99951, etc. It can be formed by a known method.
The interlayer insulating film 13 is formed as a SiO ₂ film or a SiN film, for example, by sputtering, CVD (Chemical Vapor Deposition), or the like.
The color filter 15 is formed by photolithography using a known color resist, for example.
The overcoat 16 and the base layer 14 are formed, for example, by photolithography using a known organic interlayer film forming resist.
The microlens 17 is formed by using styrene resin or the like, for example, by photolithography.
The solder resist layer 24 is preferably formed by photolithography using a known solder resist including, for example, a phenol resin, a polyimide resin, or an amine resin.
The solder ball 60 is formed using, for example, Sn—Ag, Sn—Cu, Sn—Ag—Cu as Sn—Pb (eutectic), 95Pb—Sn (high lead high melting point solder), and Pb free solder. . The solder ball 60 is formed in a spherical shape having a diameter of 100 μm to 1000 μm (preferably a diameter of 150 μm to 700 μm), for example.
The internal electrode 26 and the element surface electrode 27 are formed as a metal electrode such as Cu by CMP (Chemical Mechanical Polishing) or photolithography and etching, for example.
The metal electrode 23 is formed as a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, and Mo compound by sputtering, photolithography, etching, and electrolytic plating, for example. The metal electrode 23 may have a single layer configuration or a stacked configuration including two or more layers. The film thickness of the metal electrode 23 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm). The silicon substrate 10 is not particularly limited, but a silicon substrate that is thinned by scraping the back surface of the substrate can be used. Although the thickness of the substrate is not limited, for example, a silicon wafer having a thickness of 20 μm to 200 μm (preferably 30 to 150 μm) is used.
The through hole of the silicon substrate 10 is formed by, for example, photolithography and RIE (Reactive Ion Etching).

  As mentioned above, although one Embodiment of the camera module was described with reference to FIG.1 and FIG.2, the said one embodiment is not restricted to the form of FIG.1 and FIG.2.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis Example-Synthesis of Exemplified Compound 1>
(1) (hereinafter referred to as “Exemplary Compound 1”, which is the same as Exemplified Compound 2) among the exemplary compounds described above was synthesized.
8.7 g (manufactured by Wako Pure Chemical Industries, Ltd.) of sodium hydride (oil-based 60%) was added to 300 mL of dimethylacetamide in 25.2 g of 2,4-dimethylpentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at room temperature for 30 minutes. Thereafter, the mixture was cooled to 0 ° C., 25 g of 3-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 5 hours. The disappearance of 3-nitrophthalonitrile was confirmed by TLC. After cooling to 0 ° C., 1N hydrochloric acid was added, followed by addition of ethyl acetate and water, and the organic matter was extracted into the ethyl acetate layer. After the solvent was distilled off, the organic substance was purified by column chromatography (developing solvent hexane / ethyl acetate = 2/1). Thereafter, the solvent was distilled off to obtain 23.4 g (yield: 67%) of a pale yellow solid of the precursor of Example Compound 1 (3- (2,4-dimethylpentoxy) phthalonitrile). 10 g of 1-pentanol was added to 3 g of the precursor of Example Compound 1 and 0.31 g of copper (I) chloride (manufactured by Wako Pure Chemical Industries, Ltd.), stirred at 150 ° C. overnight, cooled to room temperature, and then methanol was added to the reaction solution. The solid obtained was filtered and air-dried (40 ° C., overnight) to obtain 1.61 g (yield 50%) of a blue-green solid of Exemplary Compound 1. Identification was performed by MALDI-MASS.
Other phthalocyanine compounds were synthesized in the same manner as in the above synthesis examples.

<Preparation of infrared absorbing composition>
Example 1
The following composition components were mixed with a stirrer to prepare an infrared absorbing composition of Example 1.
· YMF-02 (Sumitomo Metal Mining Co., Ltd. Cesium tungsten oxide (Cs _0.33 WO ₃ (average dispersed particle diameter 800nm or less; the maximum absorption wavelength (lambda _max) = 18.5% by weight of 1550～1650Nm (film)) dispersion Liquid) 108.3 parts by mass-Phthalocyanine compound (Exemplary Compound 1 described above) 1.0 part by mass-KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (polymerizable compound) 5.8 parts by mass-Acrybase FF-187 ( Copolymer of benzyl methacrylate and methacrylic acid manufactured by Fujikura Kasei Co., Ltd. (molar ratio of repeating units = 70: 30; acid value = 110 mg KOH / g) (binder) 5.8 parts by mass / propylene glycol monomethyl ether acetate (PGMEA ) 48.3 parts by mass-Megafac F-781 (manufactured by DIC Corporation) (surfactant) 0.3 parts by mass

(Other Examples and Comparative Examples)
In Example 1, the phthalocyanine compound or cesium tungsten oxide was changed as shown in the following table, and the others were performed in the same manner.

<Phthalocyanine compound (A)>
Exemplary Compound 2
Exemplary Compound 3
Exemplary Compound 4
Exemplary Compound 5
Exemplary Compound 6
Exemplary Compound 7

<Phthalocyanine compound (B)>
Exemplary Compound 11
Exemplary Compound 12
Exemplary Compound 13
Exemplary Compound 14

比較化合物２ 比較化合物３ 比較化合物４ 比較化合物５

比較化合物６ 比較化合物７

<Comparison phthalocyanine compound>
Comparative compound 1

Comparative compound 2 Comparative compound 3 Comparative compound 4 Comparative compound 5

Comparative Compound 6 Comparative Compound 7

<Evaluation of infrared absorbing liquid>
(Create infrared cut filter)
A coating film is formed from each of the obtained infrared absorbing compositions of Examples and Comparative Examples by using a spin coating method (using MIKASA SPINCOATER 1H-D7 manufactured by MIKASA Co., LTD; 340 rpm) at 100 ° C. , 120 seconds of pre-heating (pre-baking), and then exposure was performed at 2000 mJ / cm ² using an i-line stepper. Subsequently, post heating (post-baking) was performed at 200 ° C. for 5 minutes to obtain an infrared cut filter having a film thickness of about 2 μm.
I can say that.

(Visible light transmittance and infrared shielding evaluation)
The transmittance at a wavelength of 1200 nm in the infrared cut filter obtained as described above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The lower the numerical value, the better the infrared shielding property. It can be said that the transmittance is 5% or less and a practically good infrared shielding property is exhibited.
Further, the transmittance at a wavelength of 550 nm and the transmittance at a wavelength of 700 nm of the infrared cut filter were measured using an ultraviolet-visible near-infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation). The higher the numerical value, the higher the visible light transmittance. With respect to the transmittance at a wavelength of 550 nm, it can be said that the visible light transmittance is 70% or more, and practically good visible light transmittance is exhibited. With respect to the transmittance at a wavelength of 700 nm, it can be said that the visible light transmittance is 30% or less and a practically good near-infrared shielding property is exhibited.

(Light resistance evaluation)
Using a Super Xenon Fade Meter SX75 manufactured by Suga Test Instruments Co., Ltd., a light resistance test was performed by irradiating the infrared cut filters of Examples and Comparative Examples with a xenon lamp light source for 20 hours.

The visible light transmittance (wavelength 550 nm) of the infrared cut filter after the light resistance test was measured according to the above method, and | (visible light transmittance (%) before test-visible light transmittance (%) after test) / Visible light transmittance before test × 100 | (%) Visible light transmittance change rate is classified as follows and shown in the table below.
A: Absorbance ratio change rate ≦ 4%
B: 4% <absorbance ratio change rate ≦ 7%
C: 7% <absorbance ratio change rate

(Heat resistance evaluation)
The heat resistance test which heated the infrared cut filter of an Example and a comparative example using a DIGITAL HOT PLATE NINOD ND-2 for 5 minutes at 260 degreeC was done. The visible light transmittance (wavelength 550 nm) of the infrared cut filter after the heat resistance test was measured according to the above method, and | (visible light transmittance (%) before test-visible light transmittance (%) after test) / Visible light transmittance before test × 100 | (%) Visible light transmittance change rate is classified as follows and shown in the table below.
A: Absorbance ratio change rate ≦ 20%
B: 20% <absorbance ratio change rate ≦ 30%
C: 30% <absorbance ratio change rate

(Solubility evaluation)
The solubility test of the exemplified compound was conducted. 40 g of PGMEA was stirred for 30 minutes with respect to 120 mg of phthalocyanine.
After 5 minutes, turbidity was measured with an integrating sphere turbidimeter manufactured by Mitsubishi Chemical Corporation.
A: Absorbance ratio change rate ≦ 20 ppm
B: 50 ppm <absorbance ratio change rate ≦ 80%
C: 80% <absorbance ratio change rate

As is apparent from the above table, when the infrared absorbers of the phthalocyanine compound (A) and the phthalocyanine compound (B) were used in combination, they were excellent in all of visible light transmittance, infrared shielding properties, heat resistance, light resistance and solubility. It was a thing.
On the other hand, even if it was a phthalocyanine compound, when phthalocyanine compounds other than a phthalocyanine compound (A) were used (comparative example 1), it turned out that visible-light transmittance and infrared shielding property are remarkably inferior.

From the above, it was found that the infrared-absorbing composition of the present invention can produce an infrared cut filter that is excellent in all of infrared shielding properties, light resistance and heat resistance.
In addition, since the infrared absorbing composition of the present invention is liquid, an infrared cut filter can be easily manufactured by a simple process of forming a film by, for example, coating (preferably spin coating). Insufficient manufacturing suitability in the infrared cut filter can be improved.
Thus, the infrared absorbing composition of the present invention has an infrared absorbing property suitable for producing a camera module having a solid-state imaging device substrate and an infrared cut filter disposed on the light-receiving side of the solid-state imaging device substrate. It is a composition.

DESCRIPTION OF SYMBOLS 10 Silicon substrate 12 Image pick-up element 13 Interlayer insulating film 14 Base layer 15 Color filter 16 Overcoat 17 Micro lens 18 Light shielding film 20 Adhesive 22 Insulating film 23 Metal electrode 24 Solder resist layer 26 Internal electrode 27 Element surface electrode 30 Glass substrate 40 Imaging Lens 42 Infrared cut filter 44 Light shielding / electromagnetic shield 45 Adhesive 46 Flattening layer 50 Lens holder 60 Solder ball 70 Circuit board 100 Solid-state imaging device substrate

Claims (9)

A phthalocyanine compound (A) having a maximum absorption wavelength of 650 nm to less than 750 nm; a phthalocyanine compound (B) having a maximum absorption wavelength of 750 nm to 900 nm; a metal oxide (C); and a polymerizable compound (D), wherein the phthalocyanine compound (A) The infrared rays absorptive composition in which at least 1 of an alkoxy group, an aryloxy group, and an amino group contains. The infrared absorbing composition according to claim 1, wherein the phthalocyanine compound (A) is represented by the following general formula (I).
Formula (I)

(In General Formula (I), Rα ^{1 to} Rα ⁸ are each a hydrogen atom, an alkoxy group, an aryloxy group, or an amino group, and Rβ ^{1 to} Rβ ⁸ are each a hydrogen atom or an amino group, M is a metal atom, provided that ^one of Rα ¹ and Rα ² , one of Rα ³ and Rα ⁴ , one of Rα ⁵ and Rα ⁶ , and one of Rα ⁷ and Rα ⁸ are each an alkoxy group, aryloxy Or one of Rβ ¹ and Rβ ² , one of Rβ ³ and Rβ ⁴ , one of Rβ ⁵ and Rβ ⁶ , and one of Rβ ⁷ and Rβ ⁸ are each an amino group. ) The infrared ray absorbing composition according to claim 1 or 2, wherein a difference between a maximum absorption wavelength of the phthalocyanine compound (A) and a maximum absorption wavelength of the phthalocyanine compound (B) is 10 to 120 nm. Formula (I) Rα ¹ ~Rα ⁸ and / or Rβ ¹ ~Rβ ⁸ in is selected from the following, the infrared absorbing composition according to claim 2 or 3.
Rα ^{1 to} Rα ⁸

Rβ ^{1 to} Rβ ⁸

The infrared absorbing composition according to any one of claims 1 to 4, wherein the maximum absorption wavelength of the metal oxide (C) is 800 to 2000 nm. The infrared cut filter obtained using the infrared absorptive composition of any one of Claims 1-5. The manufacturing method of the infrared cut filter including forming a film | membrane by apply | coating the infrared absorptive composition of any one of Claims 1-5 in the light-receiving side of a solid-state image sensor board | substrate. A camera module having a solid-state image sensor substrate and an infrared cut filter arranged on a light receiving side of the solid-state image sensor substrate, wherein the infrared cut filter is the infrared cut filter according to claim 6. It is a manufacturing method of the camera module which has a solid-state image sensor board | substrate and the infrared cut filter arrange | positioned at the light-receiving side of the said solid-state image sensor board | substrate, Comprising: In the light-receiving side of a solid-state image sensor board | substrate, A method for producing a camera module, comprising forming a film by applying the infrared absorbing composition according to item 1.

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