JP6340078B2 - Near-infrared absorbing composition, near-infrared cut filter, method for producing near-infrared cut filter, solid-state imaging device, camera module - Google Patents

Description

  The present invention relates to a near-infrared absorbing composition, a near-infrared cut filter, a method for producing a near-infrared cut filter, a solid-state imaging device, and a camera module.

A CCD or CMOS image sensor, which is a solid-state imaging device, is used in a video camera, a digital still camera, a mobile phone with a camera function, and the like. Since the solid-state imaging device uses a silicon photodiode having sensitivity to near infrared rays in the light receiving portion thereof, it is necessary to perform visibility correction, and a near infrared cut filter is often used.
As a material for a near-infrared cut filter, Patent Document 1 discloses a metal compound as a copolymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof and a compound having an ethylenically unsaturated bond. An infrared shielding film containing an added infrared shielding resin is disclosed.
Patent Document 2 discloses a near-infrared absorbing composition using a copper sulfonate complex.
Patent Document 3 discloses an adhesive containing a polyester-based resin having a hydroxyl group and / or carboxyl group in the side chain and a reactive compound capable of reacting with the hydroxyl group and / or carboxyl group in the polyester-based resin. .

JP 2010-134457 A JP 2001-213918 A JP 2009-13200 A

However, since the infrared ray shielding resin disclosed in Patent Document 1 has an acid group containing phosphorus, it is considered that the heat resistance is insufficient.
Moreover, although the near-infrared absorptive composition disclosed by patent document 2 is making the monomer and the copper which have an ethylenically unsaturated bond react, the polymerization reaction of the monomer which has an ethylenically unsaturated bond is copper presence It is difficult to proceed below, and it tends to be difficult to polymerize. For this reason, it is thought that heat resistance may be insufficient.
Moreover, in the Example of patent document 3, although the trimethylol propane adduct body of toluene diisocyanate is used as a reactive compound, heat resistance was inadequate.
The present invention solves this problem, and maintains a high near-infrared shielding property while being capable of forming a cured film excellent in heat resistance, and a near-infrared cut filter using the same An object of the present invention is to provide a method for manufacturing a near-infrared cut filter, a solid-state imaging device, and a camera module.

式（Ａ１−１）中、Ｒ¹は水素原子または炭化水素基を表し、Ｌ¹は単結合または連結基を表し、Ｙ¹は、非共有電子対で配位する配位原子を１個以上有する基または非共有電子対で配位する配位原子を１個以上とアニオンで配位する配位部位を１個以上有する基を表す。
＜７＞ 重合体は、下記式（Ａ１−１−１）〜（Ａ１−１−４）から選ばれる少なくとも１種の構成単位を含む、＜１＞〜＜６＞のいずれかに記載の近赤外線吸収性組成物；

式（Ａ１−１−１）〜（Ａ１−１−４）中、Ｒ¹は水素原子または炭化水素基を表し、Ｌ²は単結合または連結基を表し、Ｙ¹は、非共有電子対で配位する配位原子を１個以上有する基または非共有電子対で配位する配位原子を１個以上とアニオンで配位する配位部位を１個以上有する基を表す。
＜８＞ ＜１＞〜＜７＞のいずれかに記載の近赤外線吸収性組成物を用いて得られた近赤外線カットフィルタ。
＜９＞ 固体撮像素子の受光側において、＜１＞〜＜７＞のいずれかに記載の近赤外線吸収性組成物を塗布する工程を含む、近赤外線カットフィルタの製造方法。
＜１０＞ ＜１＞〜＜７＞のいずれかに記載の近赤外線吸収性組成物を用いて得られた近赤外線カットフィルタを有する固体撮像素子。
＜１１＞ 固体撮像素子と、固体撮像素子の受光側に配置された近赤外線カットフィルタとを有し、近赤外線カットフィルタが＜８＞に記載の近赤外線カットフィルタである、カメラモジュール。As a result of intensive studies by the present inventors, a near-infrared absorptive composition containing a compound obtained by a reaction between a copper component and a polymer containing a coordinating atom that coordinates with the copper component by an unshared electron pair It was found that the product has good heat resistance and can form a film having high near-infrared shielding properties, and the present invention has been completed. The present invention provides the following.
<1> A near-infrared absorptive composition containing a compound obtained by a reaction between a copper component and a polymer containing a coordination atom that coordinates with the copper component by an unshared electron pair.
<2> The near-infrared absorbing composition according to <1>, wherein the coordination atom is one or more selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
<3> The near-infrared absorbing composition according to <1> or <2>, wherein the polymer further has a coordination site coordinated by an anion.
<4> The near-infrared absorbing composition according to <3>, wherein the anion is one or more selected from an oxygen anion, a nitrogen anion, and a sulfur anion.
<5> The near-infrared absorbing composition according to any one of <1> to <4>, wherein the polymer contains a group represented by the following formula (1) in a side chain;
* -L ¹ -Y ¹ (1)
In the general formula (1), L ¹ represents a single bond or a linking group, and Y ¹ is a group having one or more coordination atoms coordinated by an unshared electron pair or a coordination coordinated by an unshared electron pair. A group having at least one coordination site that coordinates with one or more atoms and an anion is represented, and * represents a bond with a polymer.
<6> The near-infrared absorbing composition according to any one of <1> to <5>, wherein the polymer includes a structural unit represented by the following formula (A1-1);

In formula (A1-1), R ¹ represents a hydrogen atom or a hydrocarbon group, L ¹ represents a single bond or a linking group, and Y ¹ represents one or more coordination atoms coordinated by a lone pair of electrons. Or a group having at least one coordination atom coordinated by an unshared electron pair and at least one coordination site coordinated by an anion.
<7> The polymer according to any one of <1> to <6>, comprising at least one structural unit selected from the following formulas (A1-1-1) to (A1-1-4): An infrared absorbing composition;

In formulas (A1-1-1) to (A1-1-4), R ¹ represents a hydrogen atom or a hydrocarbon group, L ² represents a single bond or a linking group, and Y ¹ represents an unshared electron pair. A group having one or more coordination atoms to be coordinated or a group having one or more coordination atoms coordinated by an lone pair and one or more coordination sites coordinated by an anion.
<8> A near-infrared cut filter obtained by using the near-infrared absorbing composition according to any one of <1> to <7>.
<9> A method for producing a near-infrared cut filter, comprising a step of applying the near-infrared absorbing composition according to any one of <1> to <7> on the light-receiving side of the solid-state imaging device.
<10> A solid-state imaging device having a near-infrared cut filter obtained using the near-infrared absorbing composition according to any one of <1> to <7>.
<11> A camera module that includes a solid-state imaging device and a near-infrared cut filter disposed on a light-receiving side of the solid-state imaging device, and the near-infrared cut filter is the near-infrared cut filter according to <8>.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the near-infrared absorptive composition which can form the cured film excellent in heat resistance, maintaining a high near-infrared shielding. Moreover, it has become possible to provide a near-infrared cut filter using such a near-infrared absorptive composition, a method for producing a near-infrared cut filter, a solid-state imaging device, and a camera module.

It is a schematic sectional drawing which shows the structure of the camera module which has a near-infrared cut off filter based on embodiment of this invention. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module.

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.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In this specification, a monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
In the present specification, the polymerizable compound refers to a compound having a polymerizable group. The polymerizable group refers to a group that participates in a polymerization reaction.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. is there.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, near-infrared light refers to light (electromagnetic wave) having a wavelength region of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
In this specification, solid content means solid content in 25 degreeC.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

<Near-infrared absorbing composition>
The near-infrared absorptive composition of the present invention comprises a compound (also referred to as a polymer copper compound) obtained by a reaction between a copper component and a polymer containing a coordination atom that coordinates with the copper component by an unshared electron pair. contains.
By using the near-infrared absorbing composition of the present invention, a cured film (near-infrared cut filter) having a high near-infrared shielding property can be obtained. In addition, the heat resistance of the cured film can be increased.
The reason why such an effect is obtained is not clear, but is estimated as follows.
A polymer containing a coordination atom that coordinates with a copper component by an unshared electron pair (hereinafter, also referred to as polymer (A)) acts as a ligand for the copper component. That is, the coordination atom (unshared electron pair) of the polymer (A) is coordinated with copper of the copper component, whereby the structure of the polymer copper compound is distorted, and high transparency in the visible light region is obtained. It is considered that the near-infrared light absorbing ability is improved and the color value is also improved. Moreover, it is thought that a crosslinked structure is formed between the side chains of a polymer (A) from a polymer copper compound, and a film | membrane excellent in heat resistance is obtained for a polymer copper compound. Moreover, it can be set as the polymer copper compound with a low water absorption rate and favorable moisture resistance.
The polymer copper compound is preferably a copper complex having the polymer (A) as a ligand.
The polymer copper compound preferably has a mass increase rate of 60% or less based on the condition before standing for 5 hours at 25 ° C. and a relative humidity of 95%. Hereinafter, a test that is allowed to stand at 25 ° C. and a relative humidity of 95% may be simply referred to as a water absorption test.
The polymer copper compound preferably has a mass increase rate of 60% or less, more preferably 25% or less, still more preferably 10% or less, and particularly preferably 3% or less. Moreover, the time of a water absorption rate test may be set long, 10 hours may be sufficient, and 20 hours may be sufficient. Even in this case, the mass increase rate of the compound preferably satisfies the above range. The near-infrared cut filter with higher moisture resistance can be obtained as the mass increase rate when the test time of the water absorption rate test is set to be long. The lower limit of the mass increase rate of the above compound is 0%, and it is preferable that the mass does not increase even after the water absorption test.

  In the near-infrared absorbing composition of the present invention, the content of the polymer copper compound is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70 to 100% by mass, and more preferably 80 to 100%. Mass% is particularly preferred. Near-infrared shielding can be improved by increasing the content of the polymer copper compound.

<< Polymer (A) >>
The polymer (A) is not particularly limited as long as it contains a coordinating atom coordinated by a lone pair with respect to the copper component.
In the polymer (A), the coordination atom coordinated by the lone pair is preferably one or more selected from an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom, and selected from an oxygen atom, a nitrogen atom and a sulfur atom. 1 or more types are more preferable, and a nitrogen atom is still more preferable. Moreover, the aspect in which the coordinating atom coordinated by a lone pair is a nitrogen atom, and the atom adjacent to this nitrogen atom is a carbon atom, and it is also preferable that this carbon atom has a substituent. By setting it as such a structure, since the structure of a copper complex becomes easier to distort, color value can be improved more. A substituent is synonymous with the substituent which the ring containing the coordinating | ligand atom coordinated by the unshared electron pair mentioned later may have, a C1-C10 alkyl group, a C6-C12 aryl. Group, a carboxyl group, a C1-C12 alkoxy group, a C2-C12 acyl group, a C1-C12 alkylthio group, and a halogen atom are preferable.
The coordinating atom coordinated by the lone pair may be contained in the ring, or may be contained in at least one partial structure selected from the following group (UE).

Group (UE)

In the group (UE), each R ¹ independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and each R ² independently represents a hydrogen atom, an alkyl group, or an alkenyl group. Represents a group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group or acyl group.

The alkyl group represented by R ¹ may be linear, branched or cyclic, but is preferably linear. 1-10 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, and 1-4 are more preferable. Examples of the alkyl group include a methyl group. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, a carboxyl group, and a heterocyclic group. The heterocyclic group as a substituent may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The number of heteroatoms constituting the heterocycle is preferably 1 to 3, and preferably 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom. When the alkyl group has a substituent, it may further have a substituent.
2-10 are preferable and, as for carbon number of the alkenyl group and alkynyl group which R < ¹ > represents, 2-6 are more preferable.
The aryl group represented by R ¹ may be monocyclic or polycyclic, but is preferably monocyclic. 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable.
The heteroaryl group represented by R ¹ may be monocyclic or polycyclic. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 6-18 are preferable and, as for carbon number of the ring of a heteroaryl group, 6-12 are more preferable.

The alkyl group represented by R ² has the same meaning as the alkyl group described for R ¹ , and the preferred range is also the same.
The number of carbon atoms of the alkenyl group represented by R ² is preferably 2 to 10, 2 to 6 is more preferred.
The number of carbon atoms of the alkynyl group represented by R ² is preferably 2 to 10, 2 to 6 is more preferred.
The aryl group represented by R ² has the same meaning as the aryl group described in the above group (UE), and the preferred range is also the same.
The heteroaryl group represented by R ² has the same meaning as the heteroaryl group described for R ¹ , and the preferred range is also the same.
Number of carbon atoms of the alkoxy group represented by R ^2, 1-12 is preferred.
The number of carbon atoms of the aryloxy group represented by R ^2, 6-18 is preferred.
The heteroaryloxy group represented by R ² may be monocyclic or polycyclic. Heteroaryl group constituting the heteroaryl group has the same meaning as the heteroaryl group described for R ^1, preferred ranges are also the same.
The number of carbon atoms of the alkylthio group represented by R ^2, 1-12 is preferred.
The number of carbon atoms of the arylthio group represented by R ^2, 6-18 is preferred.
The heteroarylthio group represented by R ² may be monocyclic or polycyclic. Heteroaryl group constituting the heteroarylthio group has the same meaning as the heteroaryl group described for R ^1, preferred ranges are also the same.
The number of carbon atoms of the acyl group represented by R ^2, 2-12 is preferred.

When a coordination atom coordinated by a lone pair is included in the ring, the ring containing the coordination atom may be monocyclic or polycyclic, and may be aromatic or non-aromatic. It may be a tribe. Preferably, it is a 5-12 membered ring, More preferably, it is a 5-7 membered ring, More preferably, it is a 5 membered ring or a 6 membered ring.
The ring containing a coordinating atom coordinated by a lone pair may have a substituent. Examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, a silicon atom, an alkoxy group having 1 to 12 carbon atoms, and 1 carbon atom. ˜12 acyl groups, C 1-12 alkylthio groups, carboxyl groups and the like.
The above substituent may further have a substituent. Examples of such a substituent include a group comprising a ring containing a coordinating atom coordinated by a lone pair, a group containing at least one partial structure selected from the group (UE) described above, and the number of carbon atoms. Examples thereof include an alkyl group having 1 to 12, an acyl group having 1 to 12 carbon atoms, and a hydroxy group.

The polymer (A) may further have a coordination site coordinated by an anion. Here, the coordination site | part coordinated with an anion contains the anion which can be coordinated to the copper atom in a copper component, for example, the thing containing an oxygen anion, a nitrogen anion, or a sulfur anion is mentioned.
The coordination site coordinated with an anion is preferably at least one selected from the following group (AN).
Group (AN)

In the above group (AN), X represents N or CR, and each R preferably independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
The alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group represented by R in the group (AN) are the same as the alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl represented by R ¹ in the above group (UE). It is synonymous and the preferable range is also the same.

It is preferable that a polymer (A) contains group represented by following formula (1) in a side chain.
* -L ¹ -Y ¹ (1)
In the general formula (1), L ¹ represents a single bond or a linking group, and Y ¹ is a group having one or more coordination atoms coordinated by an unshared electron pair or a coordination coordinated by an unshared electron pair. A group having at least one coordination site that coordinates with one or more atoms and an anion is represented, and * represents a bond with a polymer.
Y ¹ represents a group having two or more coordination atoms coordinated by an unshared electron pair, or 1 coordination site coordinated by one or more coordination atoms coordinated by an unshared electron pair and an anion. A group having at least one group is preferable, and a group having at least one coordination atom coordinated by an unshared electron pair and one or more coordination sites coordinated by an anion is more preferable.

In the general formula (1), when L ¹ represents a linking group, examples of the divalent linking group include an alkylene group, an arylene group, a heteroarylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group composed of a combination thereof, including an alkylene group, an arylene group, — A group consisting of CO—, —COO—, —NR ¹⁰ — and a combination thereof is preferable, and includes an alkylene group, an arylene group, —CO—, —COO—, —NR ¹⁰ —, a combination of an alkylene group and —COO—. A group consisting of a combination of —CO— and —NR ¹⁰ —, or a group consisting of a combination of an alkylene group, —CO— and —NR ¹⁰ —.
1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic.
6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, 6-10 are more preferable, and a phenylene group is especially preferable.
Although it does not specifically limit as a heteroarylene group, A 5-membered ring or a 6-membered ring is preferable. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 1 to 3. The heteroarylene group may be a single ring or a condensed ring, and is preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
In the case where L ¹ represents a trivalent or higher linking group, a group in which one or more hydrogen atoms have been removed from the above-described examples of the divalent linking group can be given.

式（１ａ１）および（１ａ２）において、ｐは、１以上の整数を表し、２以上が好ましい。上限は、例えば、５以下が好ましく、３以下がより好ましい。<<< Group having at least one coordination atom coordinated by an unshared electron pair >>>
In the above general formula (1), examples of the group represented by Y ¹ having one or more coordination atoms coordinated by a lone pair include groups represented by the following formula (1a1) or (1a2). Can be mentioned.
^{* -L 11 - (Y 11)} p ··· (1a1)
^{* -L 11 - (Y 11a -L} 12 -Y 11) p ··· (1a2)
“*” Represents a joint with L ^{1 in the} formula (1).
L ¹¹ represents a single bond or a (p + 1) -valent linking group. When L ¹¹ represents a divalent linking group, an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —CO—, —COO—, —OCO—, —SO ₂ —, —O—. , —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group composed of a combination thereof.
When L ¹¹ represents a trivalent or higher linking group, a group in which one or more hydrogen atoms have been removed among the groups listed as examples of the divalent linking group described above can be given.
L ¹² represents a single bond or a divalent linking group. Preferred examples of the divalent linking group include the divalent linking group described in L ¹¹ . L ¹² is more preferably a single bond, an alkylene group, or a group consisting of a combination of —NH— and —CO—.
Y ¹¹ represents a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by the group (UE) described above. When p represents an integer of 2 or more, the plurality of Y ¹¹ may be the same or different.
Y ^11a represents a ring containing a coordinating atom coordinated by an unshared electron pair, or at least one selected from the following group (UE-1). R ¹ in group (UE-1) has the same meaning as R ¹ group (UE). When p represents an integer of 2 or more, the plurality of Y ^11a may be the same or different.
Group (UE-1)

In formulas (1a1) and (1a2), p represents an integer of 1 or more, and preferably 2 or more. For example, the upper limit is preferably 5 or less, and more preferably 3 or less.

ｑは、１以上の整数を表し、１〜５が好ましく、１〜３が特に好ましい。
ｒは、１以上の整数を表し、１〜５が好ましく、１〜３が特に好ましい。
ｑ＋ｒは、２以上を表し、２〜５が好ましく、２〜３が特に好ましい。<<< Group having at least one coordination atom coordinated by an unshared electron pair and at least one coordination site coordinated by an anion >>>
In the general formula (1), the group represented by Y ¹ and having one or more coordination atoms coordinated by an unshared electron pair and one or more coordination sites coordinated by an anion is represented by the following formula, for example. And the group represented.
^{* -L 21 - (Y 21a -L} 23 -Y 22) q ··· (1b1)
^{* -L 21 - (Y 22a -L} 23 -Y 21) q ··· (1b2)
^{* -L 22 - (Y 21)} q (Y 22) r ··· (1b3)
^{* -L 22 - (Y 21a -L} 23 -Y 22) q (Y 21) r ··· (1b4)
^{* -L 22 - (Y 22a -L} 23 -Y 21) q (Y 21) r ··· (1b5)
^{* -L 22 - (Y 21a -L} 23 -Y 22) q (Y 22) r ··· (1b6)
^{* -L 22 - (Y 22a -L} 23 -Y 21) q (Y 22) r ··· (1b7)
“*” Represents a joint with L ^{1 in the} formula (1).
L ²¹ represents a single bond or a (q + 1) -valent linking group. L ²¹ has the same meaning as L ¹¹ in formula (1a), and the preferred range is also the same.
L ²² represents a single bond or a (q + r + 1) -valent linking group. L ²² has the same meaning as L ¹¹ in formula (1a), and the preferred range is also the same.
L ²³ represents a single bond or a divalent linking group. Preferred examples of the divalent linking group include the divalent linking group described for L ¹¹ in formula (1a). L ²³ is more preferably a single bond, an alkylene group, or a group consisting of a combination of —NH— and —CO—.
Y ²¹ represents a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by the group (UE) described above. When q and r represent an integer of 2 or more, the plurality of Y ²¹ may be the same or different.
Y ^21a represents a ring containing a coordination atom coordinated by an unshared electron pair or at least one selected from the group (UE-1) described above. When q and r represent an integer of 2 or more, the plurality of Y ^21a may be the same or different.
Y ²² represents a partial structure represented by the group (AN) described above. When q and r represent an integer of 2 or more, the plurality of Y ²² may be the same or different.
Y ^22a represents at least one selected from the following group (AN-1). X in group (AN-1) represents N or CR, and R has the same meaning as R described above for CR in group (AN). When q and r represent an integer of 2 or more, the plurality of Y ^22a may be the same or different.
Group (AN-1)

q represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 1 to 3.
r represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 1 to 3.
q + r represents 2 or more, preferably 2 to 5, and particularly preferably 2 to 3.

式（Ａ１−１）中、Ｒ¹は水素原子または炭化水素基を表し、Ｌ¹は単結合または連結基を表し、Ｙ¹は、非共有電子対で配位する配位原子を１個以上有する基または非共有電子対で配位する配位原子を１個以上とアニオンで配位する配位部位を１個以上有する基を表す。It is preferable that a polymer (A) contains the structural unit represented by a following formula (A1-1).

In formula (A1-1), R ¹ represents a hydrogen atom or a hydrocarbon group, L ¹ represents a single bond or a linking group, and Y ¹ represents one or more coordination atoms coordinated by a lone pair of electrons. Or a group having at least one coordination atom coordinated by an unshared electron pair and at least one coordination site coordinated by an anion.

In formula (A1-1), R ¹ represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include a linear, branched or cyclic aliphatic hydrocarbon group, and an aromatic hydrocarbon group. The hydrocarbon group may have a substituent, but is preferably unsubstituted. 1-10 are preferable, as for carbon number of a hydrocarbon group, 1-5 are more preferable, and 1-3 are more preferable. The hydrocarbon group is preferably a methyl group. R ¹ is preferably a hydrogen atom or a methyl group.
L ¹ and Y ¹ in formula (A1-1) has the same meaning as L ¹ and Y ¹ in formula (1) above, and preferred ranges are also the same.

Examples of the structural unit represented by the formula (A1-1) include structural units represented by the following (A1-1-1) to (A1-1-4). The following (A1-1-1) and (A1-1-2) are preferable.

In formulas (A1-1-1) to (A1-1-4), R ¹ represents a hydrogen atom or a hydrocarbon group, L ² represents a single bond or a linking group, and Y ¹ represents an unshared electron pair. A group having one or more coordination atoms to be coordinated or a group having one or more coordination atoms coordinated by an lone pair and one or more coordination sites coordinated by an anion.

R ¹ of formula (A1-1-1) ~ (A1-1-4) has the same meaning as R ¹ in formula (A1-1), and preferred ranges are also the same.
Y ¹ of the formula (A1-1-1) ~ (A1-1-4) has the same meaning as Y ¹ in the formula (A1-1), and preferred ranges are also the same.
L ^{2 in} formula (A1-1-2) represents a single bond or a linking group. Preferred examples of the linking group include the linking groups described for L ¹ in formula (A1-1), and an alkylene group or a group composed of a combination of an alkylene group and —COO— is more preferred.

The polymer (A) may contain other structural units in addition to the structural unit represented by the formula (A1-1).
As components constituting other structural units, those disclosed in paragraph Nos. 0068 to 0075 of JP-A 2010-106268 (corresponding to [0112] to [0118] of US Patent Application Publication No. 2011/0124824). The description of the copolymerization component can be taken into account, the contents of which are incorporated herein.
Preferable other structural units include structural units represented by the following formula (A2-1).

式（Ａ２−１）中、Ｒ⁵は水素原子または炭化水素基を表し、Ｌ⁴は単結合または連結基を表し、Ｒ¹⁰は、アルキル基またはアリール基を表す。
式（Ａ２−１）のＲ⁵は、式（Ａ１−１）のＲ¹と同義であり、好ましい範囲も同様である。
式（Ａ２−１）のＬ⁴は、単結合または連結基を表す。連結基としては、式（Ａ１−１）のＬ¹で説明した連結基が挙げられ、アルキレン基、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＮＲ¹⁰−（Ｒ¹⁰は水素原子あるいはアルキル基を表す。アルキル基の炭素数は１〜１０が好ましく、１〜５がより好ましい）、または、これらの組み合わせからなる基が好ましい。
式（Ａ２−１）のＲ¹⁰で表されるアルキル基は、直鎖状、分岐状または環状のいずれでもよい。アルキル基の炭素数は、１〜３０が好ましく、１〜２０がより好ましく、１〜１０がさらに好ましい。アルキル基は置換基を有していてもよく、置換基としては、上述したものが挙げられる。
式（Ａ２−１）のＲ¹⁰で表されるアリール基は、単環であっても多環であってもよいが単環が好ましい。アリール基の炭素数は６〜１８が好ましく、６〜１２がより好ましく、６がさらに好ましい。
重合体（Ａ）が、他の構成単位（好ましくは式（Ａ２−１）で表される構成単位）を含む場合、式（Ａ１−１）で表される構成単位と他の構成単位のモル比は、９５：５〜２０：８０であることが好ましく、９０：１０〜４０：６０であることがより好ましい。

In formula (A2-1), R ⁵ represents a hydrogen atom or a hydrocarbon group, L ⁴ represents a single bond or a linking group, and R ¹⁰ represents an alkyl group or an aryl group.
R ^{5 in} formula (A2-1) has the same meaning as R ^{1 in} formula (A1-1), and the preferred range is also the same.
L ^{4 in} formula (A2-1) represents a single bond or a linking group. Examples of the linking group include the linking groups described for L ¹ in formula (A1-1), an alkylene group, —O—, —CO—, —COO—, —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom or an alkyl group). 1 to 10 is preferable, and 1 to 5 is more preferable), or a group composed of a combination thereof is preferable.
The alkyl group represented by R ¹⁰ in formula (A2-1) may be linear, branched or cyclic. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may have a substituent, and examples of the substituent include those described above.
The aryl group represented by R ¹⁰ in formula (A2-1) may be monocyclic or polycyclic, but is preferably monocyclic. 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable.
When the polymer (A) contains another structural unit (preferably the structural unit represented by the formula (A2-1)), the mole of the structural unit represented by the formula (A1-1) and the other structural unit The ratio is preferably 95: 5 to 20:80, and more preferably 90:10 to 40:60.

2000 or more are preferable, as for the weight average molecular weight of a polymer (A), 2000-2 million are more preferable, and 6000-200,000 are more preferable. By making the weight average molecular weight of a polymer (A) into such a range, it exists in the tendency for the moisture resistance of the cured film obtained to improve more.
Specific examples of the polymer (A) include, but are not limited to, the following compounds and salts thereof. In addition, as an atom which comprises a salt, a metal atom is preferable and an alkali metal atom or an alkaline-earth metal atom is more preferable. Examples of the alkali metal atom include sodium and potassium. Examples of alkaline earth metal atoms include calcium and magnesium.

  A polymer (A) is obtained by carrying out the polymerization reaction of the monomer which comprises the structural unit mentioned above. The polymerization reaction can be carried out using a known polymerization initiator. As the polymerization initiator, an azo polymerization initiator can be used, and specific examples include a water-soluble azo polymerization initiator, an oil-soluble azo polymerization initiator, and a polymer polymerization initiator. Only one polymerization initiator may be used, or two or more polymerization initiators may be used in combination.

Examples of the monomer include those shown below.

  Examples of the water-soluble azo polymerization initiator include commercially available products VA-044, VA-046B, V-50, VA-057, VA-061, VA-067, VA-086, etc. Koyo Pure Chemical Industries, Ltd.) can be used. Examples of the oil-soluble azo polymerization initiator include commercially available products V-60, V-70, V-65, V-601, V-59, V-40, VF-096, VAm-110 and the like (trade names) : Wako Pure Chemical Industries, Ltd.) can be used. As the polymer polymerization initiator, for example, commercially available products such as VPS-1001 and VPE-0201 (trade names: all manufactured by Wako Pure Chemical Industries, Ltd.) can be used.

<< Copper component >>
As the copper component, copper or a compound containing copper can be used, and a compound containing divalent copper is preferable. By increasing the copper content, the near-infrared shielding properties are improved. Therefore, the total solid content of the near-infrared absorbing composition is preferably 10% or more on an element basis, and 20% or more. Is preferable, and 30% or more is more preferable. Although there is no upper limit in particular, 70% or less is preferable and 60% or less is more preferable. A copper component may use only 1 type and may use 2 or more types.
As the copper component, for example, copper oxide or copper salt can be used. Copper salts include, for example, copper carboxylate (eg, copper acetate, ethyl acetoacetate, copper formate, copper benzoate, copper stearate, copper naphthenate, copper citrate, copper 2-ethylhexanoate), copper sulfonate ( For example, copper methanesulfonate), copper phosphate, phosphate ester copper, phosphonate copper, phosphonate ester copper, phosphinate copper, amide copper, sulfonamide copper, imide copper, acylsulfonimide copper, bissulfonimide copper , Methide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper perchlorate, copper chloride, copper bromide, carboxylate copper, sulfonate copper, sulfonamide copper, imide Copper, acylsulfonimide copper, bissulfonimide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper chloride, copper sulfate are more preferable, carboxylic acid , Acyl sulfonimide copper, phenoxy copper, more preferably copper chloride, copper carboxylate, acyl sulfonimide copper is particularly preferred.

<Method for producing polymer copper compound>
The polymer copper compound can be produced by reacting the above-described polymer (A) with a copper component.
The amount of the copper component to be reacted with the polymer (A) is the total coordination part of the polymer (A) (the sum of the coordination atom coordinated by the lone pair and the coordination site coordinated by the anion). And the copper compound in a molar ratio, the total coordination part of the polymer (A): the copper compound is preferably 1: 0.05 to 2 mol, more preferably 1: 0.1 to 1.4 mol, 1: 0.2-1.0 mol is further more preferable. By setting it as such a range, it exists in the tendency for the cured film which has higher near-infrared shielding property to be obtained.
Moreover, the reaction conditions at the time of making a copper component and a polymer (A) react are 20-70 degreeC, for example, and it is preferable to set it as 0.5 hours or more.
Moreover, before making a copper component react with a polymer (A), it is a low molecular compound mentioned later, the compound which has a coordination site | part coordinated with an anion, and the coordination site | part coordinated with a lone pair You may make it react with 1 or more types chosen from the compound which has this. According to this aspect, the near infrared shielding property and heat resistance can be further improved. The low molecular compound is preferably a compound having a coordination site coordinated by an anion.
The amount of the low molecular compound to be reacted with the copper component is preferably such that the copper component and the low molecular compound are in a molar ratio of low molecular component: copper component = 1: 0.05-2, and 1: 0.2-1. 4 is more preferable.

  Although the near-infrared absorptive composition of this invention should just contain the compound (polymer copper compound) obtained by reaction with a copper component and a polymer (A), an unreacted copper component and a polymer (A ) And the like. Moreover, you may contain copper compounds other than the said copper component, a solvent, a sclerosing | hardenable compound, a binder polymer, surfactant, a polymerization initiator, and other components.

<< Other near-infrared absorbing compounds >>
The near-infrared absorbing composition of the present invention contains a near-infrared absorbing compound other than the above-described polymer copper compound (hereinafter also referred to as other near-infrared absorbing compound) for the purpose of further improving the near-infrared shielding property. May be.
The near-infrared absorbing compound used in the present invention is not particularly limited as long as it has a maximum absorption wavelength region in the range of 700 to 2500 nm, preferably 700 to 1000 nm (near infrared region).
The other near infrared absorbing compound is preferably a copper compound, and more preferably a copper complex.
When mix | blending another near-infrared absorptive compound, 10: 90-95: 5 are preferable, and ratios (mass ratio) of a polymer copper compound and another near-infrared absorptive compound are 20: 80-90: 10. More preferably, 20:80 to 80:20 is even more preferable.
Other near-infrared absorbing compounds include a copper compound obtained by a reaction between a low-molecular compound having a coordination site coordinated by an anion (for example, a molecular weight of 1000 or less) and a copper component, or coordination with an unshared electron pair. A copper compound obtained by a reaction between a low molecular compound having a coordination atom (for example, a molecular weight of 1000 or less) and a copper component can be used.

As the copper compound, for example, a copper complex represented by the following formula (B) can be used.
Cu (L) _n1・ (X) _n2 Formula (B)
In the above formula (B), L represents a ligand coordinated to copper, and X does not exist or is a halogen atom, H ₂ O, NO ₃ , ClO ₄ , SO ₄ , CN, SCN, or BF _4. , PF ₆ , BPh ₄ (Ph represents a phenyl group) or alcohol. n1 and n2 each independently represents an integer of 1 to 4.
The ligand L is a group having one or more selected from a coordination site coordinated with copper by an anion and a coordination atom coordinated with copper by a lone pair. The coordination site coordinated by an anion may be dissociated or non-dissociated. In the case of non-dissociation, X is not present.
The copper complex is a copper compound in which a ligand is coordinated to copper as a central metal, and copper is usually divalent copper. For example, it can be obtained by mixing and reacting a compound serving as a ligand or a salt thereof with a copper component.

Although it does not specifically limit as a compound used as a ligand or its salt, The compound represented with the following general formula (i) is preferable.
R ^100- (X ¹⁰⁰ ) _n3 (i)
(In the general formula (i), X ¹⁰⁰ represents a coordination site, n3 represents an integer of 1 to 6, R ¹⁰⁰ represents a single bond or n-valent group.)
In general formula (i), X ¹⁰⁰ is preferably at least one selected from a coordination site coordinated by an anion and a coordination atom coordinated by a lone pair, and a coordination coordinated by an anion It is more preferable to include one or more sites.

The said anion should just be coordinated to the copper atom in a copper component, and an oxygen anion, a nitrogen anion, or a sulfur anion is preferable.
The coordination site coordinated by an anion is preferably at least one selected from the above-described group (AN), for example.

  As an example of the coordination site coordinated by an anion, a monoanionic coordination site may also be mentioned. A monoanionic coordination site | part represents the site | part coordinated with a copper atom through the functional group which has one negative charge. For example, an acid group having an acid dissociation constant (pKa) of 12 or less can be mentioned. Specific examples include acid groups containing phosphorous atoms (phosphoric acid diester groups, phosphonic acid monoester groups, phosphinic acid groups, etc.), sulfo groups, carboxyl groups, imido acid groups, and the like. Preferably, a carboxyl group is more preferable.

The coordination atom coordinated by the lone pair preferably contains an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, more preferably contains an oxygen atom, a nitrogen atom or a sulfur atom, and contains a nitrogen atom. Is more preferable. Moreover, the aspect in which the coordinating atom coordinated by a lone pair is a nitrogen atom, and the atom adjacent to this nitrogen atom is a carbon atom, and it is also preferable that this carbon atom has a substituent. By setting it as such a structure, since the structure of a copper complex becomes easier to distort, color value can be improved more. A substituent is synonymous with the substituent which the ring containing the coordinating | ligand atom coordinated by the unshared electron pair mentioned later may have, a C1-C10 alkyl group, a C6-C12 aryl. Group, a carboxyl group, a C1-C12 alkoxy group, a C2-C12 acyl group, a C1-C12 alkylthio group, and a halogen atom are preferable.
The coordinating atom coordinated by the lone pair may be contained in the ring or in at least one partial structure selected from the group (UE) described above.

When a coordination atom coordinated by a lone pair is included in the ring, the ring containing the coordination atom may be monocyclic or polycyclic, and may be aromatic or non-aromatic. It may be a tribe. Preferably, it is a 5-12 membered ring, More preferably, it is a 5-7 membered ring, More preferably, it is a 5 membered ring or a 6 membered ring.
The ring containing a coordinating atom coordinated by a lone pair may have a substituent. Examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, a silicon atom, an alkoxy group having 1 to 12 carbon atoms, and 1 carbon atom. ˜12 acyl groups, C 1-12 alkylthio groups, carboxyl groups and the like.
The above substituent may further have a substituent. Examples of such a substituent include a group comprising a ring containing a coordinating atom coordinated by a lone pair, a group containing at least one partial structure selected from the group (UE) described above, and the number of carbon atoms. Examples thereof include an alkyl group having 1 to 12, an acyl group having 1 to 12 carbon atoms, and a hydroxy group.

In general formula (i), n3 represents an integer of 1 to 6, preferably 1 to 3, more preferably 2 or 3, and still more preferably 3.
In the general formula (i), R ¹⁰⁰ represents a single bond or n-valent group. As an n-valent group, an n-valent organic group or a combination of an n-valent organic group and —O—, —SO—, —SO ₂ —, —NR ^N1 —, —CO—, or —CS— The group consisting of Examples of the n-valent organic group include a hydrocarbon group, an oxyalkylene group, and a heterocyclic group. The n-valent group is a group containing at least one selected from the group (AN-1) described above, a ring containing a coordination atom coordinated by an unshared electron pair, or the group (UE- It may be a group containing at least one selected from 1).
The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group, a halogen atom (preferably a fluorine atom), a polymerizable group (for example, a vinyl group, a (meth) acryloyl group, an epoxy group, Oxetane group, etc.), sulfo group, carboxyl group, acid group containing phosphorus atom, carboxylic ester group (for example, —CO ₂ CH ₃ ), hydroxyl group, alkoxy group (for example, methoxy group), amino group, carbamoyl group, carbamoyl Examples thereof include an oxy group, a halogenated alkyl group (for example, a fluoroalkyl group and a chloroalkyl group), and a (meth) acryloyloxy group. When the hydrocarbon group has a substituent, the hydrocarbon group may further have a substituent, and examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.
When the hydrocarbon group is monovalent, an alkyl group, an alkenyl group or an aryl group is preferable, and an aryl group is more preferable. When the hydrocarbon group is divalent, an alkylene group, an arylene group, or an oxyalkylene group is preferable, and an arylene group is more preferable. When the hydrocarbon group is trivalent or higher, those corresponding to the monovalent hydrocarbon group or divalent hydrocarbon group are preferred.
The alkyl group and the alkylene group may be linear, branched or cyclic. 1-20 are preferable, as for carbon number of a linear alkyl group and an alkylene group, 1-12 are more preferable, and 1-8 are more preferable. 3-20 are preferable, as for carbon number of a branched alkyl group and an alkylene group, 3-12 are more preferable, and 3-8 are more preferable. The cyclic alkyl group and alkylene group may be monocyclic or polycyclic. 3-20 are preferable, as for carbon number of a cyclic | annular alkyl group and an alkylene group, 4-10 are more preferable, and 6-10 are more preferable.
2-10 are preferable, as for carbon number of an alkenyl group and alkenylene group, 2-8 are more preferable, and 2-4 are more preferable.
6-18 are preferable, as for carbon number of an aryl group and an arylene group, 6-14 are more preferable, and 6-10 are more preferable.
The heterocyclic group includes an alicyclic group having a hetero atom or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group is a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having 2 to 8 condensations, and more preferably a monocyclic ring or a condensed ring having 2 to 4 condensations. The heterocyclic group may have a substituent, and the substituent is synonymous with the substituent that the hydrocarbon group described above may have.
In —NR ^N1 —, R ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. The alkyl group in R ^N1 may be any of a chain, a branch, and a ring. 1-20 are preferable and, as for carbon number of a linear or branched alkyl group, 1-12 are more preferable. The cyclic alkyl group may be monocyclic or polycyclic. 3-20 are preferable and, as for carbon number of a cyclic | annular alkyl group, 4-14 are more preferable.
The number of carbon atoms of the aryl group in R ^N1 is 6 to 18 is preferable, 6 to 14 is more preferable. Specific examples include a phenyl group and a naphthyl group. The aralkyl group in R ^N1 is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an unsubstituted aralkyl group having 7 to 15 carbon atoms.

As a specific form of the compound to be a ligand, a compound having at least two coordination sites is preferable. Specifically, a compound containing at least one coordination site coordinated by an anion and at least one coordination atom coordinated by an unshared electron pair (hereinafter also referred to as compound (B1)), non-covalent A compound having two or more coordination atoms coordinated by an electron pair (hereinafter also referred to as compound (B2)), a compound containing two coordination sites coordinated by an anion (hereinafter also referred to as compound (B3)), etc. Is mentioned. These compounds can be used independently or in combination of two or more.
Moreover, the compound used as a ligand can also use the compound which has only one coordination site | part.

<< Compound (B1) >>
In the compound (B1), the total number of coordination atoms coordinated by an anion in one molecule and coordination atoms coordinated by a lone pair may be two or more, or three. There may be four.
As the compound (B1), for example, a compound represented by the following formula (i-1) is preferable.
^{X 11 -L 11 -Y 11 ··· (} i-1)
X ¹¹ represents a coordination site represented by the group (AN) described above.
Y ¹¹ represents a ring containing a coordination atom coordinated by the above-mentioned lone pair or a partial structure represented by a group (UE).
L ¹¹ represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —SO ₂ —, —O—, or a group consisting of a combination thereof.

As more detailed examples of the compound (B1), compounds represented by the following general formulas (i-2) to (i-9) are also exemplified.
^{X 12 -L 12 -Y 12 -L 13} -X 13 ··· (i-2)
^{Y 13 -L 14 -Y 14 -L 15} -X 14 ··· (i-3)
^{Y 15 -L 16 -X 15 -L 17} -X 16 ··· (i-4)
^{Y 16 -L 18 -X 17 -L 19} -Y 17 ··· (i-5)
^{X 18 -L 20 -Y 18 -L 21} -Y 19 -L 22 -X 19 ··· (i-6)
^{X 19 -L 23 -Y 20 -L 24} -Y 21 -L 25 -Y 22 ··· (i-7)
^{Y 23 -L 26 -X 20 -L 27} -X 21 -L 28 -Y 24 ··· (i-8)
^{Y 25 -L 29 -X 22 -L 30} -Y 26 -L 31 -Y 27 ··· (i-9)
In general formulas (i-2) to (i-9), X ^{12 to} X ¹⁴ , X ¹⁸ , and X ¹⁹ each independently represent a coordination site represented by the group (AN) described above. X ¹⁵ , X ¹⁷ , and X ^{20 to} X ²² each independently represent a coordination site represented by the group (AN-1) described above.
In general formulas (i-2) to (i-9), L ^{12 to} L ³¹ each independently represent a single bond or a divalent linking group. A bivalent coupling group is synonymous with the case where L < ¹ > in general formula (i-1) represents a bivalent coupling group.

式（ｉ−１０）中、Ｘ²は、アニオンで配位する配位部位を含む基を表す。Ｙ²は、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ａ¹およびＡ⁵は、それぞれ独立して炭素原子、窒素原子またはリン原子を表す。Ａ²〜Ａ⁴は、それぞれ独立して炭素原子、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ｒ¹は、置換基を表す。Ｒ^X2は、置換基を表す。ｎ２は０〜３の整数を表す。
式（ｉ−１０）中、Ｘ²は、上記アニオンで配位する配位部位を含む基のみからなっていてもよいし、上記アニオンで配位する配位部位を含む基が置換基を有していてもよい。アニオンで配位する配位部位を含む基が有していてもよい置換基は、ハロゲン原子、カルボキシル基、ヘテロ環基が挙げられる。置換基としてのヘテロ環基は、単環であっても多環であってもよく、また、芳香族であっても非芳香族であってもよい。ヘテロ環を構成するヘテロ原子の数は１〜３が好ましい。ヘテロ環を構成するヘテロ原子は、窒素原子が好ましい。
式（ｉ−１０）中、Ｙ²は、酸素原子、窒素原子または硫黄原子が好ましく、酸素原子または窒素原子がより好ましく、窒素原子がさらに好ましい。
式（ｉ−１０）中、Ａ¹およびＡ⁵は、炭素原子が好ましい。
式（ｉ−１０）中、Ａ²およびＡ³は、炭素原子を表すことが好ましい。Ａ⁴は、炭素原子または窒素原子を表すことが好ましい。
式（ｉ−１０）中、Ｒ¹は、上述した非共有電子対で配位する配位原子を含む環が有していてもよい置換基と同義である。
式（ｉ−１０）中、Ｒ^X2は、上述した非共有電子対で配位する配位原子を含む環が有していてもよい置換基と同義であり、好ましい範囲も同様である。
式（ｉ−１０）中、ｎ２は０〜３の整数を表し、０または１が好ましく、０がより好ましい。
式（ｉ−１０）で表される化合物は、Ｙ²を含むヘテロ環が、単環構造であってもよいし、多環構造であってもよい。Ｙ²を含むヘテロ環が単環構造である場合の具体例としては、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、トリアジン環、ピラン環等が挙げられる。Ｙ²を含むヘテロ環が多環構造である場合の具体例としては、キノリン環、イソキノリン環、キノキサリン環、アクリジン環等が挙げられる。As the compound (B1), a compound represented by the formula (i-10) or the formula (i-11) is preferable.

In formula (i-10), X ² represents a group containing a coordination site coordinated by an anion. Y ² represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ¹ and A ⁵ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ^{2 to} A ⁴ each independently represents a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. R ¹ represents a substituent. R ^X2 represents a substituent. n2 represents an integer of 0 to 3.
In formula (i-10), X ² may consist only of a group containing a coordination site coordinated with the anion, or the group containing a coordination site coordinated with the anion has a substituent. You may do it. Examples of the substituent that the group containing a coordination site coordinated by an anion may have include a halogen atom, a carboxyl group, and a heterocyclic group. The heterocyclic group as a substituent may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The number of heteroatoms constituting the heterocycle is preferably 1 to 3. The hetero atom constituting the hetero ring is preferably a nitrogen atom.
In formula (i-10), Y ² is preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom, and even more preferably a nitrogen atom.
In formula (i-10), A ¹ and A ⁵ are preferably carbon atoms.
In formula (i-10), A ² and A ³ preferably represent a carbon atom. A ⁴ preferably represents a carbon atom or a nitrogen atom.
In formula (i-10), R < ¹ > is synonymous with the substituent which the ring containing the coordinating | ligand atom coordinated by the lone pair mentioned above may have.
In formula (i-10), R ^X2 has the same meaning as the substituent that the ring containing the coordinating atom coordinated by the lone pair described above may have, and the preferred range is also the same.
In formula (i-10), n2 represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
In the compound represented by the formula (i-10), the heterocyclic ring containing Y ² may be a monocyclic structure or a polycyclic structure. Specific examples when the heterocycle containing Y ² has a monocyclic structure include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyran ring, and the like. Specific examples when the heterocycle containing Y ² has a polycyclic structure include a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring and the like.

In formula (i-11), X ³ represents a group containing a coordination site coordinated by the anion. Y ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ⁶ and A ⁹ each independently represents a carbon atom, a nitrogen atom or a phosphorus atom. A ⁷ and A ⁸ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. R ² represents a substituent. R ^X3 represents a substituent. n3 represents an integer of 0-2.
In formula (i-11), X ³ has the same meaning as X ² in formula (i-10), and the preferred range is also the same.
In formula (i-3), Y ³ is preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom.
In formula (i-11), A ⁶ is preferably a carbon atom or a nitrogen atom. A ⁹ is preferably a carbon atom.
In formula (i-11), A ⁷ is preferably a carbon atom. A ⁸ is preferably a carbon atom, a nitrogen atom or a sulfur atom.
In formula (i-11), R ² is preferably a hydrophobic substituent, more preferably a hydrocarbon group having 1 to 30 carbon atoms, an alkyl group having 3 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Is more preferable, and an alkyl group having 3 to 15 carbon atoms is particularly preferable.
In formula (i-11), R ^X3 has the same meaning as R ^X2 in formula (i-10), and the preferred range is also the same.
In formula (i-11), n3 is preferably 0 or 1, more preferably 0.
In the compound represented by the formula (i-11), the heterocyclic ring containing Y ³ may be a monocyclic structure or a polycyclic structure. Specific examples when the heterocycle containing Y ³ has a monocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, an isothiazole ring, and the like. Specific examples when the heterocycle containing Y ³ has a polycyclic structure include an indole ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring, and the like.
In particular, the compound represented by the formula (i-11) is a compound containing a pyrazole ring, and preferably has a secondary or tertiary alkyl group at the 5-position of the pyrazole ring. In this specification, when the compound represented by the formula (i-11) is a compound containing a pyrazole ring, the 5-position of the pyrazole ring means that Y ³ and A ⁶ in the above (i-3) are nitrogen. Represents an atom and the substitution position of R ² when A ^{7 to} A ⁹ represent a carbon atom. 3-15 are preferable and, as for carbon number of the secondary or tertiary alkyl group in 5-position of a pyrazole ring, 3-12 are more preferable.
The molecular weight of the compound (B1) is preferably 1000 or less, more preferably 750 or less, and even more preferably 600 or less. Moreover, 50 or more are preferable and, as for the molecular weight of a compound (B1), 80 or more are more preferable.

  Specific examples of the compound (B1) include the following compounds and salts thereof. Examples of the atoms constituting the salt include metal atoms and tetrabutylammonium. As the metal atom, an alkali metal atom or an alkaline earth metal atom is more preferable. Examples of the alkali metal atom include sodium and potassium. Examples of alkaline earth metal atoms include calcium and magnesium.

<< Compound (B2) >>
The compound (B2) only needs to have two or more coordination atoms coordinated by an unshared electron pair in one molecule, and may have three or more, or two to four. Preferably it is.
The compound (B2) is preferably, for example, a compound represented by the following general formula (ii-1).
Y ⁴⁰ -L ⁴⁰ -Y ⁴¹ (ii-1)
In the general formula (ii-1), Y ⁴⁰ and Y ⁴¹ each independently represent a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by the group (UE).
In General Formula (ii-1), L ⁴⁰ represents a single bond or a divalent linking group. When L ¹ represents a divalent linking group, a group consisting of an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —O—, —SO ₂ —, or a combination thereof. Are preferable, and an alkylene group having 1 to 3 carbon atoms, a phenylene group, or —SO ₂ — is preferable.

As a more detailed example of compound (B2), the compound represented by the following general formula (ii-2) or (ii-3) is also mentioned.
Y ⁴² -L ⁴¹ -Y ⁴³ -L ⁴² -Y ⁴⁴ (ii-2)
Y ⁴⁵ -L ⁴³ -Y ⁴⁶ -L ⁴⁴ -Y ⁴⁷ -L ⁴⁵ -Y ⁴⁸ (ii-3)
In the general formulas (ii-2) and (ii-3), Y ⁴² , Y ⁴⁴ , Y ⁴⁵ and Y ⁴⁸ are each independently a ring or group containing a coordination atom coordinated by a lone pair of electrons. The partial structure represented by (UE) is represented.
Y ⁴³ , Y ⁴⁶ , and Y ⁴⁷ are each independently a ring containing a coordinating atom coordinated by a lone pair or a partial structure represented by the group (UE-1) described above.
In the general formulas (ii-2) and (ii-3), L ^{41 to} L ⁴⁸ each independently represent a single bond or a divalent linking group. Divalent linking group has the same meaning as the L ⁴⁰ in the general formula (ii-1) represents a divalent linking group, and preferred ranges are also the same.
The molecular weight of the compound (B2) is preferably 1000 or less, more preferably 750 or less, and even more preferably 600 or less. Moreover, 50 or more are preferable and, as for the molecular weight of a compound (B2), 80 or more are more preferable.

Specific examples of the compound (B2) include the following.

<< Compound (B3) >>
The compound (B3) has two coordination sites coordinated by an anion. The coordination site | part coordinated with an anion is synonymous with the coordination site | part coordinated with the anion mentioned above.
As the compound (B3), a compound represented by the following general formula (iii-1) is preferable.
^{X 50 -L 50 -X 51 (iii} -1)
In the general formula (iii-1), X ⁵⁰ and X ⁵¹ each independently represent a coordination site coordinated with an anion, and are synonymous with the coordination site coordinated with an anion described above, and have a monoanionic configuration. A position site is preferred.
In general formula (iii-1), L ⁵⁰ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, a heterocyclic group, -O-, -S-, and -NR ^N1. A group consisting of —, —CO—, —CS—, —SO ₂ —, or a combination thereof is preferred. R ^N1 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
The compound (B3) preferably contains one or more selected from a sulfo group and a carboxyl group, and more preferably contains a sulfo group and a carboxyl group. By using a compound having at least one selected from a sulfo group and a carboxyl group, the color value can be further improved.
The molecular weight of the compound (B3) is preferably 1000 or less, more preferably 750 or less, and even more preferably 600 or less. Moreover, 50 or more are preferable and, as for the molecular weight of a compound (B3), 80 or more are more preferable.

Specific examples of the compound (B3) include the following compounds and salts thereof. As an atom which comprises a salt, it is synonymous with what was mentioned above, and its preferable range is also the same.

The near-infrared absorbing composition of the present invention includes pyrrolopyrrole compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxides as other near infrared absorbing compounds. It may further contain a physical compound, a squarylium compound, a quatarylene compound, a dithiol metal complex compound, a croconium compound, and the like.
The pyrrolopyrrole compound may be a pigment or a dye, but a pigment is preferred because it is easy to obtain a colored composition capable of forming a film having excellent heat resistance. Examples of the pyrrolopyrrole compound include pyrrolopyrrole compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614.
As the cyanine compound, the phthalocyanine compound, the iminium compound, the squarylium compound, and the croconium compound, the compounds described in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-1111750 may be used. Incorporated into. In addition, as for the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific” can be referred to, the contents of which are incorporated herein. It is. Moreover, the description of paragraphs 0013-0029 of Unexamined-Japanese-Patent No. 2013-195480 can be referred to for a phthalocyanine type compound, and this content is integrated in this specification.

<< Inorganic fine particles >>
The near-infrared absorbing composition of the present invention may contain inorganic fine particles. Only one type of inorganic fine particles may be used, or two or more types may be used.
The inorganic fine particles are particles that mainly play a role of shielding (absorbing) infrared rays. The inorganic fine particles are preferably metal oxide fine particles or metal fine particles from the viewpoint of better infrared shielding properties.
Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped). SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like.
Examples of the metal fine particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. In order to achieve both infrared shielding properties and photolithographic properties, it is desirable that the transmittance at the exposure wavelength (365-405 nm) is higher, and indium tin oxide (ITO) particles or antimony tin oxide (ATO) particles are preferable.
The shape of the inorganic fine particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.

As the inorganic fine particles, a tungsten oxide compound can be used. Specifically, a tungsten oxide compound represented by the following general formula (composition formula) (I) is more preferable.
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 represented by M, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al , Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, alkali metals are preferable, Rb or Cs is more preferable, and Cs is particularly preferable. . The metal of M may be one type or two or more types.
When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when 1.1 or less, the 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, etc., and Cs _0.33 WO ₃ Alternatively, Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.
The tungsten oxide compound is available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd., for example.

The average particle size of the inorganic fine particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average particle diameter of the inorganic fine particles is within such a range, 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 inorganic fine particles is usually 1 nm or more.
As for content of an inorganic fine particle, 0.01-30 mass% is preferable with respect to the total solid of a near-infrared absorptive composition. The lower limit is preferably 0.1% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less.

<< Solvent >>
The near infrared ray absorbing composition of the present invention may contain a solvent. The solvent is not particularly limited and may be appropriately selected depending on the purpose as long as each component can be uniformly dissolved or dispersed. For example, water or an organic solvent can be used.
Preferable examples of the organic solvent include alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used alone or in combination of two or more.
Specific examples of the alcohols, aromatic hydrocarbons and halogenated hydrocarbons include those described in paragraph 0136 of JP 2012-194534 A, the contents of which are incorporated herein.
Specific examples of esters, ketones and ethers include those described in paragraph 0497 of JP2012-208494A (corresponding to [0609] of the corresponding US Patent Application Publication No. 2012/0235099). Furthermore, acetic acid-n-amyl, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate and the like can be mentioned.
As the solvent, at least one selected from 1-methoxy-2-propanol, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, ethyl lactate and propylene glycol monomethyl ether Is preferably used.
The amount of the solvent is preferably such that the total solid content of the near-infrared absorbing composition of the present invention is 5 to 60% by mass. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 40% by mass or less.
Only one type of solvent may be used, or two or more types may be used, and in the case of two or more types, the total amount is preferably within the above range.

<< Curable compound >>
The near infrared ray absorbing composition of the present invention may contain a curable compound. The curable compound may be a compound having a polymerizable group (hereinafter sometimes referred to as “polymerizable compound”) or a non-polymerizable compound such as a binder. The curable compound may be in any chemical form such as a monomer, an oligomer, a prepolymer, or a polymer. Examples of the curable compound include paragraphs 0070 to 0191 in JP-A-2014-41318 (paragraphs 0071 to 0192 in pamphlet of international publication WO 2014/017669), paragraphs 0045 to 0216 in JP-A-2014-32380, and the like. Which is incorporated herein by reference.
As the curable compound, a polymerizable compound is preferable. As a polymeric compound, the compound containing polymeric groups, such as an ethylenically unsaturated bond and cyclic ether (epoxy, oxetane), is mentioned, for example. As the ethylenically unsaturated bond, a vinyl group, a styryl group, a (meth) acryloyl group, and an allyl group are preferable. The polymerizable compound may be a monofunctional compound having one polymerizable group or a polyfunctional compound having two or more polymerizable groups, but is preferably a polyfunctional compound. Heat resistance can be improved more because a near-infrared absorptive composition contains a polyfunctional compound.
Examples of the curable compound include monofunctional (meth) acrylates, polyfunctional (meth) acrylates (preferably 3 to 6 functional (meth) acrylates), polybasic acid-modified acrylic oligomers, epoxy resins, and polyfunctional epoxy resins. Etc.

<<< Compound containing an ethylenically unsaturated bond >>>
In the present invention, a compound containing an ethylenically unsaturated bond can be used as the curable compound. As examples of the compound containing an ethylenically unsaturated bond, the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, the contents of which are incorporated herein.
Examples of the compound containing an ethylenically unsaturated bond include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available product, KAYARAD D). -330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D- 310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and these No (meta) acrylic Yl group ethylene glycol, structures through a propylene glycol residue are preferable. These oligomer types can also be used.
Moreover, description of the polymeric compound of Paragraph 0034-0038 of Unexamined-Japanese-Patent No. 2013-253224 can be referred, This content is integrated in this specification.
Moreover, the polymerizable monomer etc. as described in Unexamined-Japanese-Patent No. 2012-208494 Paragraph 0477 ([0585] of corresponding US Patent application publication 2012/0235099) are mentioned, The content of these is integrated in this-application specification. It is.
Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.). Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferable. These oligomer types can also be used. For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

The compound containing an ethylenically unsaturated bond may have an acid group such as a carboxyl group, a sulfo group, or a phosphate group.
Examples of the compound containing an acid group and an ethylenically unsaturated bond include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. A compound in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group is preferred, and in this ester, the aliphatic polyhydroxy compound is preferably 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.
The acid value of the compound containing an acid group and an ethylenically unsaturated bond is preferably from 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

<<< Compound having epoxy group or oxetanyl group >>>
In the present invention, a compound having an epoxy group or an oxetanyl group can be used as the curable compound. Examples of the compound having an epoxy group or oxetanyl group include a polymer having an epoxy group in the side chain, and a monomer or oligomer having two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like can be mentioned. Moreover, a monofunctional or polyfunctional glycidyl ether compound is also mentioned, and a polyfunctional aliphatic glycidyl ether compound is preferable.
The weight average molecular weight is preferably 500 to 5000000, and more preferably 1000 to 500000.
As these compounds, commercially available products may be used, or those obtained by introducing an epoxy group into the side chain of the polymer may be used.

As a commercial item, description of Unexamined-Japanese-Patent No. 2012-155288 Paragraph 0191 etc. can be considered, and these content is integrated in this-application specification.
Moreover, polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation) can be mentioned. Although these are low chlorine products, they are not low chlorine products, and EX-212, EX-214, EX-216, EX-321, EX-850, etc. can be used as well.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries, Ltd.) ), Cyclo-P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (above, manufactured by Daicel Chemical Industries, Ltd.) and the like.
Furthermore, JER-157S65, JER-152, JER-154, JER-157S70 (above, Mitsubishi Chemical Corporation) etc. are mentioned as a commercial item of a phenol novolak type epoxy resin.
Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule include Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (and more Toagosei Co., Ltd.) can be used.
As the compound having an epoxy group, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but preferred are unsaturated compounds having an alicyclic epoxy group. As such a thing, description of Unexamined-Japanese-Patent No. 2009-265518 Paragraph 0045 etc. can be considered, and these content is integrated in this-application specification.
The compound containing an epoxy group or oxetanyl group may contain a polymer having an epoxy group or oxetanyl group as a repeating unit. Specific examples include polymers (copolymers) having the following repeating units.

<<< Other curable compounds >>>
As the curable compound, a polymerizable compound having a caprolactone-modified structure can be used.
As the polymerizable compound having a caprolactone-modified structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein.
Examples of the polymerizable compound having a caprolactone-modified structure include ethylene manufactured by Sartomer, such as DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd. SR-494, which is a tetrafunctional acrylate having four oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

As for content of a sclerosing | hardenable compound, 1-90 mass% is preferable with respect to the total solid of a near-infrared absorptive composition. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 75% by mass or less.
Moreover, when using the polymer containing the repeating unit which has a polymeric group as a sclerosing | hardenable compound, content of a sclerosing | hardenable compound has preferable 10-75 mass% with respect to the total solid of a near-infrared absorptive composition. . The lower limit is preferably 20% by mass or more. The upper limit is preferably 65% by mass or less, and more preferably 60% by mass or less.
Only one type of curable compound may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

<< Binder polymer >>
The near-infrared absorbing composition of the present invention can contain a binder polymer for the purpose of improving film properties. As the binder polymer, an alkali-soluble resin is preferably used. By containing an alkali-soluble resin, there is an effect in improving heat resistance and fine adjustment of coating properness. As the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof are as follows. It is incorporated herein.
As for content of a binder polymer, 1-80 mass% is preferable with respect to the total solid of a near-infrared absorptive composition. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 30% by mass or less.

<< Surfactant >>
The near infrared ray absorbing composition of the present invention may contain a surfactant. Only one type of surfactant may be used, or two or more types may be combined. As for content of surfactant, 0.0001-2 mass% is preferable with respect to the total solid of a near-infrared absorptive composition. The lower limit is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. The upper limit is preferably 1.0% by mass or less, and more preferably 0.1% by mass or less.
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. The near-infrared absorbing composition of the present invention preferably contains at least one of a fluorine-based surfactant and a silicone-based surfactant. According to this, the interfacial tension between the coated surface and the coating liquid is lowered, and the wettability to the coated surface is improved. For this reason, the liquid characteristic (especially fluidity | liquidity) of a near-infrared absorptive composition improves, and the uniformity of coating thickness and liquid-saving property improve more. As a result, even when a thin film of about several μm is formed with a small amount of liquid, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. When the fluorine content is within the above-described range, it is effective in terms of uniformity of coating film thickness and liquid-saving properties, and solubility in the near-infrared absorbing composition is also good.
Specific examples of the fluorosurfactant include the surfactants described in paragraphs 0060 to 0064 of JP 2014-41318 A (paragraphs 0060 to 0064 of the corresponding international publication WO 2014/17669 pamphlet) and the like. These contents are incorporated herein.

Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene Examples thereof include oxypropylene block copolymers, acetylene glycol surfactants, and acetylene polyoxyethylene oxide. These can be used alone or in combination of two or more.
Specific product names include Surfinol 61, 82, 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, 504, CT-111, CT- 121, CT-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF-37, DF-58, DF-75, DF-110D, DF-210, GA, OP- 340, PSA-204, PSA-216, PSA-336, SE, SE-F, TG, GA, Dinol 604 (Nippon Chemical Co., Ltd. and Air Products & Chemicals), Orphine A, B, AK-02, CT -151W, E1004, E1010, P, SPC, STG, Y, 32W, PD- 01, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, SK-14, AE-3 (all Nissin Chemical Co., Ltd.) acetylenol E00, E13T, E40, E60, E81, E100, E200 (all trade names, Kawaken Fine Chemical) (Manufactured by Co., Ltd.). Of these, Olfine E1010 is preferable.
In addition, specific examples of nonionic surfactants include nonionic surfactants described in paragraph 0553 of JP2012-208494A (corresponding to [0679] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.

Specific examples of the cationic surfactant include a cationic surfactant described in paragraph 0554 of JP2012-208494A (corresponding to [0680] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone surfactant include silicone surfactants described in paragraph 0556 of JP2012-208494A (corresponding to [0682] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference. In addition, “Toray Silicone SF8410”, “Same SF8427”, “Same SH8400”, “ST80PA”, “ST83PA”, “ST86PA” manufactured by Toray Dow Corning Co., Ltd., “TSF-400” manufactured by Momentive Performance Materials, Inc. “TSF-401”, “TSF-410”, “TSF-4446” “KP321”, “KP323”, “KP324”, “KP340”, etc. manufactured by Shin-Etsu Silicone Co., Ltd. are also exemplified.

<< Polymerization initiator >>
The near infrared ray absorbing composition of the present invention may contain a polymerization initiator. The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by light, heat, or both, but a photopolymerizable compound (photopolymerization initiator) is preferable. 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 polymerization initiator decomposed | disassembled at 150-250 degreeC is preferable.

As the polymerization initiator, a compound having an aromatic group is preferable. For example, acylphosphine compound, acetophenone compound, α-aminoketone compound, benzophenone compound, benzoin ether compound, ketal derivative compound, thioxanthone compound, oxime compound, hexaarylbiimidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazonium Examples thereof include onium salt compounds such as compounds, iodonium compounds, sulfonium compounds, azinium compounds, and metallocene compounds, organic boron salt compounds, disulfone compounds, and thiol compounds.
As for the polymerization initiator, the description in paragraphs 0217 to 0228 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein.

The polymerization initiator is preferably an oxime compound, an acetophenone compound or an acylphosphine compound.
Examples of commercially available oxime compounds include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 ( ADEKA), ADEKA ARKLES NCI-930 (ADEKA) and the like can be used.
As commercially available products of acetophenone compounds, IRGACURE-907, IRGACURE-369, IRGACURE-379 (trade names: all manufactured by BASF) and the like can be used.
As commercially available products of acylphosphine compounds, IRGACURE-819, DAROCUR-TPO (trade names: all manufactured by BASF) and the like can be used.
As for content of a polymerization initiator, 0.01-30 mass% is preferable with respect to the total solid of a near-infrared absorptive composition. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less.
Only one type of polymerization initiator may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

<< Other ingredients >>
Examples of other components that can be used in combination with the near-infrared absorbing composition of the present invention include a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, and a plasticizer. Furthermore, adhesion promoters to the substrate surface and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surfaces You may use together a tension adjuster, a chain transfer agent, etc.).
By appropriately containing these components, properties such as stability and film physical properties of the target near-infrared absorption filter can be adjusted.
These components are described, for example, in paragraph No. 0183 and later of JP2012-003225A (corresponding to [0237] and after of US Patent Application Publication No. 2013/0034812), JP2008-250074A, and the like. Descriptions of paragraph numbers 0101 to 0104, 0107 to 0109, and the like can be taken into consideration, and the contents thereof are incorporated in the present specification.

<Preparation and use of near-infrared absorbing composition>
Since the near-infrared absorbing composition of the present invention can be made into a liquid, for example, a near-infrared cut filter can be easily produced by applying the near-infrared absorbing composition of the present invention to a substrate and drying it. it can.
The viscosity of the near-infrared absorbing composition of the present invention is preferably 1 to 3000 mPa · s when a near-infrared cut filter is formed by coating. The lower limit is preferably 10 mPa · s or more, and more preferably 100 mPa · s or more. The upper limit is preferably 2000 mPa · s or less, and more preferably 1500 mPa · s or less.
Although the total solid content of the near-infrared absorptive composition of this invention is changed by the coating method, it is preferable that it is 1-50 mass%, for example. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less.

Although the use of the near-infrared absorptive composition of this invention is not specifically limited, It can use preferably for formation of a near-infrared cut filter etc. For example, it is preferable for a near-infrared cut filter (for example, for a near-infrared cut filter for a wafer level lens) on the light-receiving side of a solid-state image sensor, a near-infrared cut filter on the back side (the side opposite to the light-receiving side) of the solid-state image sensor, etc. Can be used. In particular, it can be preferably used as a near-infrared cut filter on the light receiving side of the solid-state imaging device.
Moreover, according to the near-infrared absorptive composition of this invention, the near-infrared cut filter which can implement | achieve high near-infrared shielding property is obtained, maintaining a high transmittance | permeability in visible region. Furthermore, the film thickness of the near-infrared cut filter can be reduced, which can contribute to a reduction in the height of the camera module.

<Near-infrared cut filter>
Next, the near infrared cut filter of the present invention will be described.
The near-infrared cut filter of the present invention is formed by curing the above-described near-infrared absorbing composition of the present invention.
The near-infrared cut filter of the present invention preferably has a light transmittance that satisfies at least one of the following conditions (1) to (9), and satisfies all the following conditions (1) to (8): It is more preferable that all the conditions (1) to (9) are satisfied.
(1) The light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(2) The light transmittance at a wavelength of 450 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(3) The light transmittance at a wavelength of 500 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(4) The light transmittance at a wavelength of 550 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(5) The light transmittance at a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(6) The light transmittance at a wavelength of 750 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(7) The light transmittance at a wavelength of 800 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(8) The light transmittance at a wavelength of 850 nm is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 5% or less.
(9) The light transmittance at a wavelength of 900 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

The near-infrared cut filter preferably has a light transmittance of 85% or more and more preferably 90% or more in the entire wavelength range of 400 to 550 nm. The higher the transmittance in the visible region, the better, and it is preferable that the transmittance is high at a wavelength of 400 to 550 nm. Further, the light transmittance at at least one point in the wavelength range of 700 to 800 nm is preferably 20% or less, and the light transmittance in the entire range of wavelength 700 to 800 nm is more preferably 20% or less. .
The film thickness of the near infrared cut filter can be appropriately selected according to the purpose. For example, 500 μm or less is preferable, 300 μm or less is more preferable, 250 μm or less is further preferable, and 200 μm or less is particularly preferable. The lower limit of the film thickness is, for example, preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.5 μm or more.
According to the near-infrared absorptive composition of this invention, since it has high near-infrared shielding, the film thickness of a near-infrared cut filter can be made thin.

In the near-infrared cut filter of the present invention, the change rate of the absorbance ratio obtained by the following formula is preferably 7% or less before and after being left for 1 hour at a high temperature and high humidity of 85 ° C./85% relative humidity. It is more preferably 4% or less, and further preferably 2% or less. If the change rate of the absorbance ratio is in the above range, the moisture resistance is excellent.
Rate of change in absorbance ratio (%) = | (absorbance ratio before test−absorbance ratio after test) / absorbance ratio before test | × 100 (%)
Here, the absorbance ratio is a value represented by the following formula.
Absorbance ratio = (maximum absorbance of near-infrared cut filter at wavelength 700-1400 nm / minimum absorbance of near-infrared cut filter at wavelength 400-700 nm)
In the near-infrared cut filter of the present invention, the change rate of absorbance at a wavelength of 400 nm and the change rate of absorbance at a wavelength of 800 nm before and after heating at 200 ° C. for 5 minutes are both preferably 7% or less, and 5% or less. It is particularly preferred. When the absorbance change rate is within the above range, the heat resistance is excellent.

  The near-infrared cut filter of the present invention has a function of absorbing / cutting near-infrared rays (a lens for a camera such as a digital camera, a mobile phone, or an in-vehicle camera, an optical lens such as an f-θ lens, a pickup lens) and a semiconductor light receiving device. Optical filters for elements, near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural coating agents for selective use of sunlight, recording media that use near-infrared absorbing heat, Used for electronic devices and photographic near infrared filters, protective glasses, sunglasses, heat ray blocking films, optical character reading and recording, confidential document copy prevention, electrophotographic photoreceptors, laser welding, and the like. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

<Method for manufacturing near-infrared cut filter>
The near-infrared cut filter of this invention can be manufactured through the process of forming a film | membrane by applying the near-infrared absorptive composition of this invention to a support body, and the process of drying a film | membrane. About a film thickness, laminated structure, etc., it can select suitably according to the objective. Further, a step of forming a pattern may be performed.
In the step of forming a film, for example, the near-infrared absorbing composition of the present invention is applied to a support using a dropping method (drop cast), a spin coater, a slit spin coater, a slit coater, screen printing, applicator application, etc. Can be implemented. In the case of the dropping method (drop casting), it is preferable to form a dropping region of the near-infrared absorbing composition having a photoresist as a partition on the support so that a uniform film can be obtained with a predetermined film thickness. A desired film thickness can be obtained by adjusting the dropping amount and solid content concentration of the near-infrared absorbing composition and the area of the dropping region. There is no restriction | limiting in particular as thickness of the film | membrane after drying, According to the objective, it can select suitably. For example, the thickness of the film is preferably 1 to 500 μm, more preferably 1 to 300 μm, and particularly preferably 1 to 200 μm. In the present invention, even when such a thin film is used, the near-infrared shielding property can be maintained.
The support may be a transparent substrate made of glass or the like. Moreover, a solid-state image sensor may be sufficient. Moreover, another board | substrate provided in the light-receiving side of the solid-state image sensor may be sufficient. Further, it may be a layer such as a flattening layer provided on the light receiving side of the solid-state imaging device.
In the step of drying the membrane, the drying conditions vary depending on each component, the type of solvent, the use ratio, and the like. For example, it is preferably 30 seconds to 15 minutes at a temperature of 60 to 150 ° C.
As a pattern forming step, for example, a step of applying the near infrared absorbing composition of the present invention on a support to form a film-like composition layer, a step of exposing the composition layer in a pattern, And a method including a step of forming a pattern by developing and removing an unexposed portion. As a pattern forming step, a pattern may be formed by a photolithography method, or a pattern may be formed by a dry etching method.
In the manufacturing method of the near-infrared cut filter, other steps may be included. There is no restriction | limiting in particular as another process, According to the objective, it can select suitably. For example, the surface treatment process of a base material, a pre-heating process (pre-baking process), a hardening process, a post-heating process (post-baking process), etc. are mentioned.

<< Pre-heating process / Post-heating process >>
The heating temperature in the preheating step and the postheating step is preferably 80 to 200 ° C. The upper limit is preferably 150 ° C. or lower. The lower limit is preferably 90 ° C. or higher.
The heating time in the preheating step and the postheating step is preferably 30 to 240 seconds. The upper limit is preferably 180 seconds or less. The lower limit is preferably 60 seconds or more.
<< Curing treatment process >>
The curing process is a process of curing the formed film as necessary, and the mechanical strength of the near-infrared cut filter is improved by performing this process.
There is no restriction | limiting in particular as a hardening process, According to the objective, it can select suitably. For example, a whole surface exposure process, a whole surface heat treatment, 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.
Examples of the exposure method include stepper exposure and exposure with a high-pressure mercury lamp.
The exposure amount is preferably 5 to 3000 mJ / cm ² . The upper limit is preferably 2000 mJ / cm ² or less, and more preferably 1000 mJ / cm ² or less. The lower limit is preferably 10 mJ / cm ² or more, and more preferably 50 mJ / cm ² or more.
Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed film. When the near-infrared absorbing composition contains a polymerizable compound, the entire surface exposure accelerates the curing of the polymerizable compound, the film is further cured, and the mechanical strength and durability are improved.
There is no restriction | limiting in particular as an apparatus which performs 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 given. By heating the entire surface, the film strength of the pattern is increased.
The heating temperature in the entire surface heating is preferably 120 to 250 ° C. The lower limit is preferably 160 ° C. or higher. The upper limit is preferably 220 ° C. or higher. When the heating temperature is in the above range, a film having excellent strength is easily obtained.
The heating time in the entire surface heating is preferably 3 to 180 minutes. The lower limit is preferably 5 minutes or more. The upper limit is preferably 120 minutes or less.
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.

<Camera module and camera module manufacturing method>
The camera module of the present invention includes a solid-state image sensor and a near-infrared cut filter arranged on the light receiving side of the solid-state image sensor.
Moreover, the manufacturing method of the camera module of this invention has the process of apply | coating the near-infrared absorptive composition of this invention mentioned above in the light-receiving side of a solid-state image sensor.

FIG. 1 is a schematic cross-sectional view showing the configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention.
The camera module 10 is disposed, for example, above the solid-state image sensor 11, the flattening layer 12 provided on the main surface side (light-receiving side) of the solid-state image sensor, the near-infrared cut filter 13, and the near-infrared cut filter. A lens holder 15 having an imaging lens 14 in the internal space.
In the camera module 10, incident light hν from the outside passes through the imaging lens 14, the near-infrared cut filter 13, and the planarizing layer 12 in order, and then reaches the imaging device portion of the solid-state imaging device 11.
The solid-state imaging device 11 has, for example, a photodiode, an interlayer insulating film (not shown), a base layer (not shown), a color filter 17 and an overcoat (not shown) on the main surface of a silicon substrate 16 as a base. The microlens 18 is provided in this order. The color filter 17 (red color filter, green color filter, blue color filter) and the microlens 18 are respectively disposed so as to correspond to the solid-state imaging device 11.
Further, instead of providing the near-infrared cut filter 13 on the surface of the flattening layer 12, the surface of the microlens 18, between the base layer and the color filter 17, or between the color filter 17 and the overcoat, The form in which the infrared cut filter 13 is provided may be sufficient. For example, the near-infrared cut filter 13 may be provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens. If it is provided at this position, the process of forming the near infrared cut filter can be simplified, and unnecessary near infrared rays to the microlens can be sufficiently cut, so that the near infrared shielding property can be further improved.
The near-infrared cut filter of the present invention can be subjected to a solder reflow process. By manufacturing the camera module through the solder reflow process, it is possible to automatically mount electronic component mounting boards, etc. that need to be soldered, making the productivity significantly higher than when not using the solder reflow process. Can be improved. Furthermore, since it can be performed automatically, the cost can be reduced. When used in the solder reflow process, the near-infrared cut filter is exposed to a temperature of about 250 to 270 ° C. Therefore, the near-infrared cut filter is also referred to as heat resistance that can withstand the solder reflow process (hereinafter also referred to as “solder reflow resistance”). ).
In this specification, “having solder reflow resistance” means that the characteristics as a near-infrared cut filter are maintained before and after heating at 200 ° C. for 10 minutes. More preferably, the characteristics are maintained before and after heating at 230 ° C. for 10 minutes. More preferably, the characteristics are maintained before and after heating at 250 ° C. for 3 minutes. When it does not have solder reflow resistance, the near-infrared shielding property of the near-infrared cut filter may be deteriorated or the function as a film may be insufficient when held under the above conditions.
The present invention also relates to a method for manufacturing a camera module, including a reflow process. The near-infrared cut filter of the present invention maintains the near-infrared shielding property even if there is a reflow process, and thus does not impair the characteristics of a small, lightweight and high-performance camera module.

2 to 4 are schematic cross-sectional views showing an example of the vicinity of the near-infrared cut filter in the camera module.
As shown in FIG. 2, the camera module includes a solid-state imaging device 11, a planarization layer 12, an ultraviolet / infrared light reflection film 19, a transparent base material 20, and a near infrared absorption layer (near infrared cut filter) 21. And an antireflection layer 22 in this order.
The ultraviolet / infrared light reflection film 19 has an effect of imparting or enhancing the function of a near-infrared cut filter. For example, paragraphs 0033 to 0039 of Japanese Patent Application Laid-Open No. 2013-68688 can be referred to. Incorporated in the description.
The transparent substrate 20 transmits light having a wavelength in the visible region. For example, paragraphs 0026 to 0032 of JP2013-68688A can be referred to, and the contents thereof are incorporated in the present specification.
The near-infrared absorbing layer 21 can be formed by applying the above-described near-infrared absorbing composition of the present invention.
The antireflection layer 22 has a function of improving the transmittance by preventing reflection of light incident on the near-infrared cut filter and efficiently using incident light. For example, JP 2013-68688 A Paragraph 0040, which is incorporated herein by reference.

As shown in FIG. 3, the camera module includes a solid-state imaging device 11, a near infrared absorption layer (near infrared cut filter) 21, an antireflection layer 22, a planarization layer 12, an antireflection layer 22, and a transparent substrate. The material 20 and the ultraviolet / infrared light reflection film 19 may be provided in this order.
As shown in FIG. 4, the camera module includes a solid-state imaging device 11, a near infrared absorption layer (near infrared cut filter) 21, an ultraviolet / infrared light reflection film 19, a planarization layer 12, and an antireflection layer 22. And you may have the transparent base material 20 and the reflection preventing layer 22 in this order.

  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.

<Synthesis Example 1> (Synthesis of Polymers (P-1) to (P-10))
1-Methoxy-2-propanol (21 g) was placed in a three-necked flask and heated to 85 ° C. in a nitrogen atmosphere.
Next, 4-vinylpyridine (11.21 g), benzyl methacrylate (18.79 g), and V-601 (an azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd., 1.06 g) were substituted with 1-methoxy- A solution dissolved in 2-propanol (49 g) was added dropwise over 2 hours.
After completion of dropping, the mixture was stirred for 4 hours to complete the reaction, thereby obtaining a polymer (P-1). The weight average molecular weight of the polymer (P-1) was 20,000.
The polymers (P-2) to (P-10) were also obtained in the same manner as the polymer (P-1). The weight average molecular weights of the polymers (P-2) to (P-9) were 20,000. Moreover, the weight average molecular weight of the polymer (P-10) was 30,000.

<Near-infrared absorbing composition>
Example 1
In an eggplant flask, 2,6-pyridinedicarboxylic acid (17.82 g) and methanol (50 g) were added and dissolved at room temperature. A solution in which copper acetate (19.37 g) was dissolved in methanol (50 g) and water (20 g) was added, and the mixture was stirred at room temperature for 30 minutes to confirm the formation of a precipitate. The polymer copper compound was obtained by adding the 1-methoxy-2-propanol solution (100g, 30 mass%) of a polymer (P-1) there, and stirring it at room temperature for 1 hour, and a near-infrared absorptive composition was obtained. Prepared. The solid content concentration (polymer copper compound content) was 21% by mass.
In addition, the molar ratio of all coordination parts (coordination atoms coordinated by unshared electron pairs and coordination sites coordinated by anions) of the polymer (P-1) and copper is Coordination part: Copper = 1: 1.

(Examples 2 to 6)
In Example 1, a polymer copper compound was obtained according to Example 1 except that the polymers (P-2) to (P-6) were used instead of the polymer (P-1). An infrared absorbing composition was prepared. The solid content concentration (content of polymer copper compound) of each near-infrared absorbing composition was 21% by mass.
In Examples 2 to 5, the molar ratio of all coordination parts of the polymer (the total of coordination atoms coordinated by unshared electron pairs and coordination sites coordinated by anions) and copper The total coordination part: copper = 1: 1. In Example 6, the molar ratio of the total coordination part of the polymer (the total of coordination atoms coordinated by an unshared electron pair and coordination sites coordinated by anions) and copper is as follows: Total coordination part: copper = 2: 1. Moreover, the quantity of methanol was adjusted so that solid content concentration might be 21 mass%.
(Example 7)
In Example 6, except that itaconic acid was used instead of 2,6-pyridinedicarboxylic acid, a polymer copper compound was obtained in the same manner as in Example 6 to prepare a near-infrared absorbing composition. The solid content concentration (polymer copper compound content) of the near-infrared absorbing composition was 21% by mass. In Example 7, the molar ratio of all coordination parts of the polymer (the total of coordination atoms coordinated by unshared electron pairs and coordination sites coordinated by anions) and copper is Position: Copper = 2: 1. Moreover, the quantity of methanol was adjusted so that solid content concentration might be 21 mass%.
(Example 8)
In Example 6, except that 2,6-pyridinedicarboxylic acid was not used and copper 2-ethylhexanoate was used instead of copper acetate, a polymer copper compound was obtained, and a near infrared ray was obtained. An absorbent composition was prepared. The solid content concentration (polymer copper compound content) of the near-infrared absorbing composition was 21% by mass. In Example 8, the molar ratio of all coordination parts of the polymer (the total of coordination atoms coordinated by unshared electron pairs and coordination sites coordinated by anions) and copper is Position: Copper = 2: 1. Moreover, the quantity of methanol was adjusted so that solid content concentration might be 21 mass%.
Example 9
In Example 6, except that 2,6-pyridinedicarboxylic acid was not used and copper methanesulfonate was used instead of copper acetate, a polymer copper compound was obtained, and near-infrared absorptivity was obtained. A composition was prepared. The solid content concentration (polymer copper compound content) of the near-infrared absorbing composition was 21% by mass. In Example 9, the molar ratio of the total coordination part of the polymer (the total of the coordination atoms coordinated by the lone pair and the coordination site coordinated by the anion) and copper is Position: Copper = 2: 1. Moreover, the quantity of methanol was adjusted so that solid content concentration might be 21 mass%.
(Example 10)
In Example 1, a polymer copper compound was obtained according to Example 1 except that the polymer (P-7) was used instead of the polymer (P-1), and the near-infrared absorbing composition was obtained. Prepared. The solid content concentration (polymer copper compound content) of the near-infrared absorbing composition was 21% by mass. In Example 10, the molar ratio of the total coordination part of the polymer (the total of the coordination atom coordinated by the lone pair and the coordination site coordinated by the anion) and copper is Position: Copper = 2: 1. Moreover, the quantity of methanol was adjusted so that solid content concentration might be 21 mass%.
(Example 11)
In Example 1, (not using 2,6-pyridinedicarboxylic acid, using polymer (P-8) instead of polymer (P-1), using copper methanesulfonate instead of copper acetate Except for the above, a polymer copper compound was obtained and a near-infrared absorbing composition was prepared in the same manner as in Example 1. The solid content concentration (polymer copper compound content) of the near-infrared absorbing composition was 21% by mass. In Example 11, the molar ratio of the total coordination part of the polymer (the total of coordination atoms coordinated by unshared electron pairs and coordination sites coordinated by anions) and copper The total coordination part: copper = 1: 1, and the amount of methanol was adjusted so that the solid content concentration was 21% by mass.
(Example 12)
In Example 1, except that 2,6-pyridinedicarboxylic acid is not used and the polymer (P-9) is used instead of the polymer (P-1), the polymer copper compound is similar to Example 1. And a near infrared ray absorbing composition was prepared. The solid content concentration (polymer copper compound content) of the near-infrared absorbing composition was 21% by mass. In Example 12, the molar ratio of the total coordination part of the polymer (the total of coordination atoms coordinated by lone pairs and coordination sites coordinated by anions) and copper is Position: Copper = 2: 1. Moreover, the quantity of methanol was adjusted so that solid content concentration might be 21 mass%.
(Example 13)
In Example 1, do not use 2,6-pyridinedicarboxylic acid, use polymer (P-10) instead of polymer (P-1), use copper methanesulfonate instead of copper acetate Except for the above, a polymer copper compound was obtained in the same manner as in Example 1 to prepare a near-infrared absorbing composition. The solid content concentration (polymer copper compound content) of the near-infrared absorbing composition was 21% by mass. In Example 13, the molar ratio of the total coordination part of the polymer (the sum of the coordination atoms coordinated by the lone pair and the coordination site coordinated by the anion) and copper is the total coordination. Position: Copper = 1: 1. Moreover, the quantity of methanol was adjusted so that solid content concentration might be 21 mass%.

(Comparative Example 1)
A near-infrared absorbing composition was prepared according to Example 1 of JP2010-134457A.

<< Creation of near infrared cut filter >>
A near-infrared cut filter was produced using each near-infrared absorbing composition.
A photoresist was applied on a glass substrate and patterned by lithography to form a partition wall of the photoresist to form a dripping region of the near infrared absorbing composition. 3 ml of each near-infrared absorbing composition was dropped on the dropping region on the glass substrate and dried by standing at room temperature for 24 hours. When the film thickness of the coating film after drying was evaluated, the film thickness was 200 μm.

<< Near-infrared shielding evaluation >>
The transmittance at a wavelength of 800 nm in the near-infrared cut filter obtained as described above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Near-infrared shielding was evaluated according to the following criteria. The results are shown in the table below.
A: Transmittance at 800 nm ≦ 5%
B: 5% <800 nm transmittance ≦ 7%
C: 7% <800 nm transmittance ≦ 10%
D: 10% <800 nm transmittance

<< Heat resistance evaluation >>
The near-infrared cut filter obtained as described above was left at 200 ° C. for 5 minutes. Before and after the heat resistance test, the absorbance at 800 nm of the near-infrared cut filter was measured, and ((absorbance before the test−absorbance after the test) / absorbance before the test) × 100 (%) The change rate of the absorbance at 800 nm was calculated. The absorbance at 400 nm was also measured, and the change rate of the absorbance at 400 nm represented by ((absorbance after test−absorbance before test) / absorbance before test) × 100 (%) was determined. The heat resistance at each wavelength was evaluated according to the following criteria. A spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation) was used for the measurement of absorbance.
A: Change rate of absorbance ≦ 3%
B: 3% <change rate of absorbance ≦ 6%
C: 6% <change rate of absorbance ≦ 10%
D: 10% <change rate of absorbance

<< Moisture resistance evaluation >>
The near-infrared cut filter obtained as described above was allowed to stand for 1 hour at a high temperature and high humidity of 85 ° C./85% relative humidity. Before and after the moisture resistance test, the maximum absorbance (Absλmax) at a wavelength of 700 to 1400 nm and the minimum absorbance (Absλmin) at a wavelength of 400 to 700 nm of the near-infrared cut filter are measured with a spectrophotometer U-4100. (Abstract of Hitachi High-Technologies) was used to determine the absorbance ratio represented by “Absλmax / Absλmin”. | (Absorbance ratio before the test−absorbance ratio after the test) / absorbance ratio before the test × 100 | (%) was evaluated based on the following criteria.
A: Absorbance ratio change rate ≦ 2%
B: 2% <absorbance ratio change rate ≦ 4%
C: 4% <absorbance ratio change rate ≦ 7%
D: 7% <Change rate of absorbance ratio << Evaluation of water absorption >>
The sufficiently dried copper complex (polymer copper complex) powder was allowed to stand for 5 hours at 25 ° C. and a relative humidity of 95% (water absorption test). Based on the mass before the water absorption test, the mass increase rate of the copper complex powder after the water absorption test was calculated and evaluated according to the following criteria.
A1: 0 ≦ mass increase rate ≦ 3%
A2: 3% <mass increase rate ≦ 10%
B: 10% <mass increase rate ≦ 25%
C: 25% <mass increase rate ≦ 60%
D: 60% <mass increase rate

As is apparent from Table 1 above, the near-infrared absorbing composition of the present invention was able to form a cured film excellent in heat resistance while maintaining high near-infrared shielding properties. Moreover, the cured film excellent also in moisture resistance was able to be formed. Further, the light transmittance in the wavelength range of 450 to 550 nm can be 85% or more, and the light transmittance in the wavelength range of 800 to 900 nm can be 20% or less.
On the other hand, Comparative Example 1 was inferior in heat resistance.
In the near-infrared absorptive compositions of Examples 1 to 13, even when the content of the polymer copper compound with respect to the total solid content of the composition was 15% by mass, 20% by mass, 30% by mass or 40% by mass, Similarly, excellent near-infrared shielding properties can be obtained.

(Example 20)
In the near-infrared absorbing composition of Example 1, the low molecular copper complex A shown below was further added so that the ratio of the polymer copper compound to the low molecular copper complex A was 7: 3 on the basis of the solid content. A near-infrared absorbing composition of Example 20 was obtained in the same manner as Example 1 except that.
(Examples 21 to 24)
In the near-infrared absorbing composition of Example 20, Examples 21 to 24 were carried out in the same manner as Example 20 except that the low molecular copper complex A was changed to low molecular copper complexes B, C, D, or E, respectively. A near infrared ray absorbing composition was obtained.
(Examples 25 to 28)
In the near-infrared absorptive composition of Example 20, except that the ratio of the polymer copper compound and the low-molecular copper complex A was changed to 5: 5, 6: 4, and 8: 2 on the basis of solid content, respectively. In the same manner as in Example 20, the near-infrared absorbing compositions of Examples 25 to 28 were obtained.
It was confirmed that even a mixed type of the polymer copper compound and the low-molecular copper complex can achieve higher near-infrared shielding properties.
(Low molecular copper complex)
Low molecular copper complex A: a copper complex having the following (M-1) as a ligand. The synthesis method will be described later.
Low molecular copper complex B: a copper complex having the following compound (B1-21) as a ligand. The synthesis method will be described later.
Low molecular copper complex C: Monobutyl copper phthalate, Tokyo Chemical Industry Co., Ltd. Low molecular copper complex D: Copper complex having the following compound (B2-1) as a ligand. The synthesis method will be described later.
Low molecular copper complex E: a copper complex having the following compound (B3-18) as a ligand. The synthesis method will be described later.

<Synthesis of low molecular copper complex A>
Under a nitrogen atmosphere, 4.0 g of ethyl pyrazole-3-carboxylate, 11.16 g of cesium carbonate, 5.17 g of 3-bromopentane, and 60 mL of 2,6-dimethyl-4-heptanone were added to a three-necked flask at 150 ° C. Heated for hours. After cooling to room temperature, insolubles are removed by filtration, and the filtrate is concentrated to purify the crude product by silica gel column chromatography (solvent: hexane / ethyl acetate) to give 1- (3-pentyl). 3.3 g of ethyl pyrazole-3-carboxylate was obtained.
To the flask, 0.87 g of the above product and 6 mL of ethanol were added, and 0.1 g of water and 0.46 g of tert-butoxypotassium were added while stirring at room temperature, followed by stirring at 70 ° C. for 30 minutes. After cooling to room temperature, a solution prepared by dissolving 0.52 g of copper sulfate in 5 mL of water was added, and the mixture was stirred at room temperature for 1 hour. The precipitated solid was separated by filtration and dried under reduced pressure to obtain 0.7 g of low-molecular copper complex A.
<Synthesis of Copper Complex B>
Compound B1-21 (886 mg, 9.84 mmol) was dissolved in 20 ml of methanol. After the temperature of this solution was raised to 50 ° C., a methanol solution (160 ml) of copper hydroxide (449 mg, 4.60 mmol) was added dropwise and reacted at 50 ° C. for 2 hours. After completion of the reaction, the low-molecular copper complex B (1.00 g) was obtained by distilling off the water and the solvent generated in the evaporator.
<Synthesis of Copper Complex D>
Compound B2-1 (0.2 g, 1.1 mmol) was dissolved in 5 ml of ethanol. After heating this solution to 70 degreeC, the ethanol solution (5 ml) of copper acetate (0.2g, 1.1mmol) was dripped, and it was made to react at 70 degreeC for 2 hours. After completion of the reaction, the low-molecular copper complex D (0.6 g) was obtained by distilling off the water and the solvent generated in the evaporator.
<Synthesis of copper complex E>
Compound B3-18 (sulfophthalic acid) 53.1 mass% aqueous solution (13.49 g, 29.1 mmol) was dissolved in 50 mL of methanol, and this solution was heated to 50 ° C., and then copper hydroxide (2.84 g, 29.29). 1 mmol) was added and reacted at 50 ° C. for 2 hours. After completion of the reaction, a low molecular copper complex E (8.57 g) was obtained by distilling off the solvent and generated water with an evaporator.

DESCRIPTION OF SYMBOLS 10 Camera module, 11 Solid-state image sensor, 12 Flattening layer, 13 Near-infrared cut filter, 14 Imaging lens, 15 Lens holder, 16 Silicon substrate, 17 Color filter, 18 Micro lens, 19 Ultraviolet / infrared light reflection film, 20 Transparent substrate, 21 Near infrared absorbing layer, 22 Antireflection layer

Claims (10)

Carboxylic acid copper, sulfonic acid copper, phosphoric acid copper, phosphoric acid ester copper, phosphonic acid copper, phosphonic acid ester copper, phosphinic acid copper, amide copper, sulfonamide copper, imide copper, acylsulfonimide copper, bissulfonimide copper, At least one copper component selected from methide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper perchlorate, copper chloride and copper bromide, and a formula (A1-1- 1) to a polymer copper compound which is a compound obtained by reacting a polymer containing at least one of the structural units represented by (A1-1-4);
Solvent,
A near-infrared absorbing composition containing
The content of the polymer copper compound is 30% by mass or more of the total solid content of the near-infrared absorbing composition,
The content of the solvent is an amount such that the total solid content of the near-infrared absorbing composition is 5 to 60% by mass.
Near-infrared absorbing composition.

(In the formulas (A1-1-1) to (A1-1-4), R ¹ Represents a hydrogen atom or a hydrocarbon group, and L ² Represents a single bond or a linking group,
Y ¹ Is a group having one or more coordinating atoms coordinated by a lone pair with respect to a copper component, or a coordinating atom coordinated by a lone pair with respect to a copper component and an anion with respect to the copper component And a group having at least one coordination site coordinated with each other;
However, Y ¹ Includes a ring having a coordination atom coordinated by a lone pair to a copper component, and the coordination atom contained in the ring is a nitrogen atom. ) The polymer is represented by the structural unit represented by the formula (A1-1-2), the structural unit represented by the formula (A1-1-3), and the formula (A1-1-4). The near-infrared absorptive composition of Claim 1 containing at least 1 of a structural unit. The near-infrared absorptive composition of Claim 1 or 2 in which the said polymer further contains the structural unit represented by a formula (A2-1).

(In formula (A2-1), R ^Five Represents a hydrogen atom or a hydrocarbon group, and L ^Four Represents a single bond or a linking group, R ^Ten Represents an alkyl group or an aryl group. ) The polymer has a molar ratio of the structural unit represented by the formulas (A1-1-1) to (A1-1-4) to the structural unit represented by the formula (A2-1) of 95: 5. The near-infrared absorptive composition of Claim 3 which is -20: 80. The near-infrared absorptive composition of any one of Claims 1-4 whose said copper component is at least 1 sort (s) chosen from carboxylate copper and sulfonate copper. The near-infrared absorptive composition of any one of Claims 1-5 whose said anion is 1 or more types chosen from an oxygen anion, a nitrogen anion, and a sulfur anion. The near-infrared cut off filter obtained using the near-infrared absorptive composition of any one of Claims 1-6 . The manufacturing method of the near-infrared cut filter including the process of apply | coating the near-infrared absorptive composition of any one of Claims 1-6 in the light-receiving side of a solid-state image sensor. The solid-state image sensor which has a near-infrared cut off filter obtained using the near-infrared absorptive composition of any one of Claims 1-6 . The camera module which has a solid-state image sensor and the near-infrared cut filter arrange | positioned at the light-receiving side of the said solid-state image sensor, and the said near-infrared cut filter is the near-infrared cut filter of Claim 7 .

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