KR20170007365A - Near-infrared-absorbent composition, near-infrared cut filter, method for manufacturing near-infrared cut filter, solid-state imaging element, and camera module - Google Patents

Abstract

A near infrared ray absorbing composition capable of forming a cured film excellent in heat resistance while maintaining a high near infrared ray shielding property, a near infrared ray shielding filter using the same, a method of manufacturing a near infrared ray shielding filter, a solid state image sensor and a camera module. The near infrared ray absorbent composition includes a compound obtained by a reaction of a copper component and a polymer containing coordination atoms coordinated to a copper component with a non-covalent electron pair. The coordinating atom is preferably at least one selected from oxygen atom, nitrogen atom, sulfur atom and phosphorus atom. A near infrared ray blocking filter and a camera module are manufactured using this near infrared absorbing composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a near-infrared absorbing composition, a near-infrared ray blocking filter, a manufacturing method of a near-infrared ray blocking filter, a solid-state image pickup device, and a camera module (NEAR-INFRARED- ABSORBENT COMPOSITION, NEAR-INFRARED CUT FILTER, METHOD FOR MANUFACTURING NEAR- INFRARED CUT FILTER, SOLID- STATE IMAGING ELEMENT, AND CAMERA MODULE}

The present invention relates to a near-infrared light absorbing composition, a near-infrared ray blocking filter, a manufacturing method of a near-infrared ray blocking filter, a solid-state image sensor, and a camera module.

CCD or CMOS image sensor, which is a solid-state image sensor, is used for a video camera, a digital still camera, and a mobile phone having a camera function. Since the solid-state image pickup device uses a silicon photodiode having sensitivity to the near-infrared rays in the light-receiving portion, it is necessary to correct the visual sensitivity (luminosity), and a near-infrared ray cut filter is often used.

As a material of the near infrared ray blocking filter, Patent Document 1 discloses an infrared blocking resin comprising a metal compound added to a copolymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof and a compound having an ethylenically unsaturated bond Discloses an infrared shielding film comprising

Patent Document 2 discloses a near infrared absorbing composition using a copper sulfonate complex.

Patent Document 3 discloses an adhesive comprising a polyester resin having a hydroxyl group and / or a carboxyl group in a side chain and a reactive compound capable of reacting with a hydroxyl group and / or a carboxyl group in the polyester resin.

Patent Document 1: JP-A-2010-134457 Patent Document 2: JP-A-2001-213918 Patent Document 3: JP-A-2009-13200

However, the infrared shielding resin disclosed in Patent Document 1 is considered to have insufficient heat resistance because it has an acid group containing phosphorus.

The near infrared absorptive composition disclosed in Patent Document 2 reacts with a monomer having an ethylenically unsaturated bond, but the polymerization reaction of the monomer having an ethylenically unsaturated bond is difficult to proceed in the presence of copper, . Therefore, it is considered that the heat resistance is insufficient.

In the example of Patent Document 3, a trimethylolpropane duct body of toluene diisocyanate was used as the reactive compound, but the heat resistance was insufficient.

The present invention solves the above-mentioned problems and provides a near infrared absorbing composition capable of forming a cured film having excellent heat resistance while maintaining a high near infrared ray shielding property, a near infrared ray shielding filter using the same, a method of manufacturing near infrared ray shielding filter, a solid state image sensor and a camera module .

As a result of intensive studies by the present inventors, it has been found that the near infrared absorptive composition comprising a compound obtained by the reaction of a copper component and a polymer containing a coordinating atom coordinated to a copper component with a non-covalent electron pair has good heat resistance and high near infrared ray shielding property And thus the present invention has been accomplished. The present invention provides the following.

<1> A near infrared ray absorbing composition comprising a compound obtained by a reaction of a copper component and a polymer containing coordination atoms coordinated to a copper component with a non-covalent electron pair.

<2> The near infrared absorbing composition according to <1>, wherein the near infrared absorbing composition is at least one selected from coordination atoms, oxygen atoms, nitrogen atoms, sulfur atoms and phosphorus atoms.

&Lt; 3 > The near infrared absorptive composition according to < 1 > or < 2 >, further comprising a coordination site coordinated with an anion.

<4> The near infrared ray absorbing composition according to <3>, wherein the anion is at least one 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 comprises a group represented by the following formula (1) in the side chain:

-L ¹ -Y ¹ ... (One)

In the general formula (1), L ¹ represents a single bond or a linking group, Y ¹ represents a group having one or more coordination atoms coordinated with a non-covalent electron pair or a coordination atom coordinating to a pair of non- Represents a group having at least one coordination site to be coordinated, and * denotes a link to a polymer.

<6> The near infrared absorbing composition according to any one of <1> to <5>, wherein the polymer comprises a constitutional unit represented by the following formula (A1-1)

[Chemical Formula 1]

In the formula (A1-1), R ¹ represents a hydrogen atom or a hydrocarbon group, L ¹ represents a single bond or a linking group, Y ¹ represents a group having one or more coordination atoms coordinated with a pair of non- A group having one or more coordination atoms coordinating to one or more coordination atoms and anions coordinated to anions.

<7> The polymer according to any one of <1> to <6>, which contains at least one kind of structural unit selected from the following formulas (A1-1-1) to Composition;

(2)

In the 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, Y ¹ represents a coordination atom coordinated with a non- Or a group having one or more coordination sites for coordinating one or more coordinating atoms coordinated with a pair of non-covalent electrons and anions.

<8> A near infrared ray blocking filter obtained by using the near infrared absorbing composition according to any one of <1> to <7>.

<9> A method of manufacturing a near-infrared light blocking filter, comprising the step of applying a near-infrared absorbing composition according to any one of <1> to <7> on the light receiving side of a solid-state imaging element.

&Lt; 10 > A solid-state image pickup element having a near-infrared ray blocking filter obtained using the near infrared absorbing composition according to any one of < 1 >

<11> A camera module having a solid-state imaging device and a near-infrared ray blocking filter disposed on the light-receiving side of the solid-state imaging device, wherein the near-infrared ray blocking filter is a near-infrared ray blocking filter described in <8>.

According to the present invention, it becomes possible to provide a near infrared ray absorbing composition capable of forming a cured film excellent in heat resistance while maintaining a high near infrared ray shielding property. In addition, it has become possible to provide a near-infrared ray blocking filter, a method of manufacturing a near-infrared ray blocking filter, a solid-state image sensor and a camera module using such a near infrared ray absorbing composition.

1 is a schematic cross-sectional view showing a configuration of a camera module having a near-IR cut filter according to an embodiment of the present invention.
2 is a schematic cross-sectional view showing an example of a peripheral portion of the near-infrared cut filter in the camera module.
3 is a schematic cross-sectional view showing an example of a peripheral portion of the near-infrared cut filter in the camera module.
4 is a schematic cross-sectional view showing an example of a peripheral portion of the near-infrared cut filter in the camera module.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "~" is used to mean that the numerical values described before and after the numerical value are included as the lower limit value and the upper limit value.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acrylic and methacrylic, "(meth) acryloyl" And methacryloyl.

In the present 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 means a compound having a polymerizable group. The polymerizable group means a group involved in the polymerization reaction.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent.

In the present specification, Me in the formula represents a methyl group, Et represents an ethyl group, Pr indicates a propyl group, Bu indicates a butyl group, and Ph indicates a phenyl group.

In the present specification, the near-infrared ray means light (electromagnetic wave) having a wavelength range of 700 to 2500 nm.

In the present specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the composition.

In this specification, the solid content refers to the solid content at 25 占 폚.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values 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 , 6.0 mm ID x 15 cm) can be obtained by using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

&Lt; Near-infrared absorbing composition >

The near infrared absorbing composition of the present invention contains a compound (also referred to as a polymeric copper compound) obtained by a reaction between a copper component and a polymer containing a coordinating atom coordinated to a copper component with a non-covalent electron pair.

By using the near infrared absorbing composition of the present invention, a cured film (near infrared ray shielding filter) having high near infrared ray 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 presumed as follows.

A polymer containing coordination atoms coordinated with a pair of non-covalent electrons with respect to the copper component (hereinafter also referred to as polymer (A)) acts as a ligand to the copper component. That is, the coordination atom (unshared electron pair) of the polymer (A) coordinates with copper of the copper component, thereby deforming the structure of the polymer copper compound to obtain high transmittance in the visible light region and improve the absorptivity of near- It is considered that the color value is also improved. The polymer copper compound is considered to have a crosslinked structure between the side chains of the polymer (A) starting from copper, and a film excellent in heat resistance can be obtained. Further, a polymer copper compound having a low water absorption (water absorption) and a good moisture resistance can be obtained.

The polymeric copper compound is preferably a copper complex having the polymer (A) as a ligand.

It is preferable that the polymeric copper compound has a mass increase rate of 60% or less based on a condition before being allowed to stand at 25 DEG C and a relative humidity of 95% for 5 hours. Hereinafter, the test in which the sample is allowed to stand at 25 캜 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, more preferably 10% or less, and particularly preferably 3% or less. The time of the absorption rate test may be set long, or may be 10 hours or 20 hours. Also in this case, it is preferable that the mass increase rate of the compound satisfies the above range. As the mass increase rate when the test time of the water absorption test is set to a long time, the closer to the infrared ray shielding filter is, the higher the moisture resistance is. The lower limit of the mass increase rate of the compound is 0%, and it is preferable that the mass does not increase even after the water absorption test.

The content of the polymeric copper compound in the near infrared absorbing composition of the present invention is preferably 30 mass% or more, more preferably 50 mass% or more, further preferably 70 to 100 mass%, and most preferably 80 to 100 mass% % By mass is particularly preferable. By increasing the content of the polymer copper compound, the near infrared ray shielding property can be improved.

&Lt; Polymer (A) &gt;

The polymer (A) is not particularly limited as long as it contains coordination atoms coordinated with a pair of non-covalent electrons to the copper component.

In the polymer (A), coordination atoms coordinated with a pair of non-covalent electrons are preferably at least one selected from oxygen atom, nitrogen atom, sulfur atom and phosphorus atom, and at least one selected from oxygen atom, nitrogen atom and sulfur atom Or more, and more preferably a nitrogen atom. It is also preferable that the coordination atom coordinated with the unshared electron pair is a nitrogen atom and the atom adjacent to the nitrogen atom is a carbon atom, and such a carbon atom preferably has a substituent. With this structure, the structure of the copper complex is more easily deformed, so that the color value can be further improved. The substituent is the same as the substituent which the ring containing the coordinating atom coordinated by a non-covalent electron pair described below may have and includes an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a carboxyl group, an alkoxy group having 1 to 12 carbon atoms, An acyl group having 2 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, and a halogen atom are preferable.

The coordinating atoms coordinated with a non-covalent electron pair may be included in the ring or may be contained in at least one partial structure selected from the following group (UE).

The UE (UE)

(3)

In the groups (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, an alkenyl group, An aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, an amino group or an acyl group.

The alkyl group represented by R ¹ may be linear, branched or cyclic, but is preferably straight-chain. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. 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 from 1 to 3, and is preferably 1 or 2. The hetero atom constituting the heterocycle is preferably a nitrogen atom. When the alkyl group has a substituent, it may further have a substituent.

The carbon number of the alkenyl group and the alkynyl group represented by R ¹ is preferably from 2 to 10, more preferably from 2 to 6.

The aryl group represented by R ¹ may be monocyclic or polycyclic, but monocyclic is preferred. The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and more preferably 6 carbon atoms.

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 from 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. The carbon number of the ring of the heteroaryl group is preferably from 6 to 18, more preferably from 6 to 12.

The alkyl group represented by R ² is synonymous with the alkyl group described for R ¹ , and the preferable range is also the same.

The carbon number of the alkenyl group represented by R ² is preferably from 2 to 10, more preferably from 2 to 6.

The carbon number of the alkane group represented by R ² is preferably from 2 to 10, more preferably from 2 to 6.

The aryl group represented by R ² is in agreement with the aryl group described in the above-mentioned group (UE), and the preferable range is also the same.

The heteroaryl group represented by R ² is synonymous with the heteroaryl group described for R ¹ , and the preferred range is also the same.

The carbon number of the alkoxy group represented by R ² is preferably from 1 to 12.

The carbon number of the aryloxy group represented by R ² is preferably 6 to 18.

The heteroaryloxy group represented by R ² may be monocyclic or polycyclic. The heteroaryl group constituting the heteroaryloxy group is in agreement with the heteroaryl group described for R ¹ , and the preferable range is also the same.

The alkyl thio group represented by R ² preferably has 1 to 12 carbon atoms.

The carbon number of the arylthio group represented by R ² is preferably 6 to 18.

The heteroarylthio group represented by R ² may be monocyclic or polycyclic. The heteroaryl group constituting the heteroarylthio is in agreement with the heteroaryl group described for R ¹ , and the preferable range is also the same.

The carbon number of the acyl group represented by R ² is preferably from 2 to 12.

When the coordinating atoms coordinated with the unshared electron pair are included in the ring, the ring containing the coordinating atom may be monocyclic or polycyclic, and may be aromatic or non-aromatic. Is preferably a 5- to 12-membered ring, more preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring.

A ring containing a coordinating atom coordinated with a non-covalent electron pair may have a substituent. Examples of the substituent include a linear, branched or cyclic alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms, a halogen atom, a silicon atom, an alkoxy group of 1 to 12 carbon atoms, an acyl group of 1 to 12 carbon atoms, An alkylthio group having 1 to 12 carbon atoms, and a carboxyl group.

The substituent may further have a substituent. Examples of such a substituent include a group comprising a ring containing a coordinating atom coordinated with a non-covalent electron pair, a group containing at least one partial structure selected from the above-mentioned group (UE), an alkyl group having 1 to 12 carbon atoms, An acyl group having 1 to 12 carbon atoms, and a hydroxyl group.

The polymer (A) may further have a coordination site coordinated with an anion. Here, the coordination moiety coordinated with the anion includes an anion capable of coordinating to the copper atom in the copper component, and includes, for example, an oxygen anion, a nitrogen anion or a sulfur anion.

The coordination moiety coordinated with the anion is preferably at least one selected from the following group (AN).

County (AN)

[Chemical Formula 4]

In the above group (AN), it is preferable that X represents N or CR and each R 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) may be any of alkyl group, alkenyl group, alkynyl group, aryl group and alkynyl group represented by R ¹ in the above- It is synonymous with heteroaryl and the preferred range is the same.

The polymer (A) preferably contains a group represented by the following formula (1) in the side chain.

-L ¹ -Y ¹ ... (One)

In the general formula (1), L ¹ represents a single bond or a linking group, Y ¹ represents a group having one or more coordination atoms coordinated with a non-covalent electron pair or a coordination atom coordinating to a pair of non- Represents a group having at least one coordination site to be coordinated, and * denotes a link to a polymer.

Y ¹ is preferably a group having two or more coordination atoms coordinated with a non-covalent electron pair, or a group having at least one coordination site coordinating one or more coordination atoms coordinated with a non-covalent electron pair with an anion, And a group having at least one coordination site for coordinating at least one coordinating atom with 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-, , -SO ₂ -, -NR ¹⁰ - (R ¹⁰ represents a hydrogen atom or an alkyl group and preferably a hydrogen atom), or a combination thereof, and examples thereof include an alkylene group, an arylene group, -CO-, -COO -, -NR ¹⁰ -, and a combination thereof, and is preferably a group consisting of a combination of an alkylene group, an arylene group, -CO-, -COO-, -NR ¹⁰ -, an alkylene group and -COO-, And -NR ¹⁰ -, or a group formed by a combination of an alkylene group and -CO- and -NR ¹⁰ - is more preferable.

The number of carbon atoms in the alkylene group is preferably from 1 to 30, more preferably from 1 to 15, and even more preferably from 1 to 10. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. The cyclic alkylene group may be either monocyclic or polycyclic.

The carbon number of the arylene group is preferably from 6 to 18, more preferably from 6 to 14, still more preferably from 6 to 10, and particularly preferably a phenylene group.

The heteroarylene group is not particularly limited, but 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 either a monocyclic or condensed ring, preferably a monocyclic or condensed ring having 2 to 8 condensed rings, and more preferably a monocyclic or condensed ring having 2 to 4 condensed rings.

When L ¹ represents a linking group having three or more valences, examples of the above-mentioned divalent linking group include groups in which one or more hydrogen atoms have been removed.

<<< Group having one or more coordination atoms coordinated by unpaired electron pair >>>

Examples of the group represented by Y ¹ in the above general formula (1) and having at least one coordination atom coordinated with a non-covalent electron pair include groups represented by the following formulas (1a 1) and (1a 2).

* -L¹¹- (Y¹¹)_p ... (1a1)

* -L¹¹- (Y^11a-L¹²-Y¹¹)_p ... (1a2)

"*" Indicates the connection with L ¹ in Eq. (1).

L ¹¹ represents a single bond or a linking group of (p + 1). When L ¹¹ represents a divalent connecting 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 - (wherein R ¹⁰ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a combination thereof.

When L ¹¹ represents a linking group having three or more atoms, examples of the above-mentioned divalent linking groups include groups in which one or more hydrogen atoms have been removed.

L ¹² represents a single bond or a divalent linking group. As the divalent linking group, the divalent linking group described in L ¹¹ is preferable. L ¹² is more preferably a group consisting of a single bond, an alkylene group, or a combination of -NH- and -CO-.

Y ¹¹ represents a partial structure represented by a ring containing a coordinating atom coordinated with a non-covalent electron pair, or the above-mentioned group (UE). When p represents an integer of 2 or more, a plurality of Y ^{11 s} may be the same or different.

Y ^11a represents a ring containing coordination atoms coordinated to a non-covalent electron pair, or at least one selected from the following group (UE-1). R ¹ in the group UE-1 agrees with R ¹ of the group UE. When p represents an integer of 2 or more, a plurality of Y ^11a may be the same or different.

The group UE-

[Chemical Formula 5]

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

<<< Group having one or more coordination atoms coordinated with non-covalent electron pairs and coordination sites coordinating with anions >>>

In the above general formula (1), the group represented by Y ¹ having one or more coordination sites coordinating one or more coordination atoms coordinated with a non-covalent electron pair and anions includes, for example, a group represented by the following formula .

-L ²¹ - (Y ^21a -L ²³ -Y ²² ) _q ... (1b1)

* -L²¹- (Y^22a-L²³-Y²¹)_q ... (1b2)

* -L²²- (Y²¹)_q(Y²²)_r ... (1b3)

* -L²²- (Y^21a-L²³-Y²²)_q(Y²¹)_r ... (1b4)

* -L²²- (Y^22a-L²³-Y²¹)_q(Y²¹)_r ... (1b5)

* -L²²- (Y^21a-L²³-Y²²)_q(Y²²)_r ... (1b6)

* -L²²- (Y^22a-L²³-Y²¹)_q(Y²²)_r ... (1b7)

"*" Indicates the connection with L ¹ in Eq. (1).

L ²¹ represents a single bond or a linking group of (q + 1). L ²¹ agrees with L ^{11 in} formula (1a), and the preferred range is also the same.

L ²² represents a single bond or a linking group of (q + r + 1). L ²² is synonymous with L ^{11 in} formula (1a), and the preferred range is also the same.

L ²³ represents a single bond or a divalent linking group. As the divalent linking group, the divalent linking group described in L ¹¹ in the formula (1a) is preferably exemplified. L ²³ is more preferably a single bond, an alkylene group, or a combination of -NH- and -CO-.

Y ²¹ represents a ring including a coordinating atom coordinated to a non-covalent electron pair, or a partial structure represented by the above-mentioned group (UE). When q and r represent an integer of 2 or more, a plurality of Y ^{21 s} may be the same or different.

Y ^21a represents a ring containing a coordinating atom coordinated to a non-covalent electron pair, or at least one selected from the group (UE-1) described above. q and r represent integers of 2 or more, a plurality of Y ^21a may be the same or different.

Y ²² represents a partial structure represented by the aforementioned group (AN). When q and r represent integers of 2 or more, a plurality of Y ²² may be the same or different.

Y ^22a represents at least one kind selected from the following group (AN-1). X in the group (AN-1) represents N or CR, and R is synonymous with R described in CR in the aforementioned group (AN). When q and r represent integers of 2 or more, a plurality of Y ^22a may be the same or different.

Group (AN-1)

[Chemical Formula 6]

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.

The polymer (A) preferably contains a constitutional unit represented by the following formula (A1-1).

(7)

In the formula (A1-1), R ¹ represents a hydrogen atom or a hydrocarbon group, L ¹ represents a single bond or a linking group, Y ¹ represents a group having one or more coordination atoms coordinated with a pair of non- A group having one or more coordination atoms coordinating to one or more coordination atoms and anions coordinated to anions.

In the formula (A1-1), R ¹ represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include linear, branched or cyclic aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The hydrocarbon group may have a substituent, but is preferably unsubstituted. The number of carbon atoms in the hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3. 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 the formula (A1-1) are, and L ¹ and Y ¹ and consent of the equation (1), are also the same preferable range.

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.

[Chemical Formula 8]

In the 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, Y ¹ represents a coordination atom coordinated with a non- Or a group having one or more coordination sites for coordinating one or more coordinating atoms coordinated with a pair of non-covalent electrons and anions.

Equation (A1-1-1) ~ R ¹ of (A1-1-4) is a, and R ¹ and consent of the formula (A1-1), it is also the same preferable range.

Y ¹ of formula (A1-1-1) ~ (A1-1-4) is a Y ¹ and consent of the formula (A1-1), it is also the same preferable range.

L ² in the formula (A1-1-2) represents a single bond or a linking group. As the linking group, a linking group described in L ¹ of the formula (A1-1) is preferable, and a group formed by a combination of an alkylene group or an alkylene group and -COO- is more preferable.

The polymer (A) may contain other constituent units in addition to the constituent units represented by the formula (A1-1).

Examples of the components constituting the other constituent units are described in detail in JP-A-2010-106268, paragraphs 0068 to 0075 (corresponding to [0112] to [0118] of U.S. Patent Application Publication No. 2011/0124824) , The contents of which are incorporated herein by reference.

As a preferable other structural unit, a structural unit represented by the following formula (A2-1) may be mentioned.

[Chemical Formula 9]

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 the formula (A2-1) agrees with R ^{1 in the} formula (A1-1), and the preferable range is also the same.

L ⁴ in the formula (A2-1) represents a single bond or a linking group. Examples of the linking group include linking groups described in L ¹ of formula (A1-1), and examples thereof include an alkylene group, -O-, -CO-, -COO-, -NR ¹⁰ - (R ¹⁰ represents a hydrogen atom or an alkyl group). The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5), or a combination thereof.

The alkyl group represented by R ¹⁰ in the formula (A2-1) may be any of linear, branched and cyclic. The number of carbon atoms of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. 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 monocyclic is preferred. The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and more preferably 6 carbon atoms.

When the polymer (A) contains another constituent unit (preferably a constituent unit represented by the formula (A2-1)), the molar ratio of the constituent unit represented by the formula (A1-1) to the other constituent unit is preferably 95: To 20:80, and more preferably 90:10 to 40:60.

The weight average molecular weight of the polymer (A) is preferably 2000 or more, more preferably 2,000 to 2,000, and still more preferably 6,000 to 200,000. When the weight average molecular weight of the polymer (A) is set in this range, the moisture resistance of the resulting cured film tends to be further improved.

Specific examples of the polymer (A) include the following compounds and salts thereof, but are not limited thereto. The atom constituting the salt is preferably a metal atom, more preferably an alkali metal atom or an alkaline earth metal atom. Examples of the alkali metal atom include sodium, potassium and the like. Examples of the alkaline earth metal atom include calcium, magnesium and the like.

[Chemical formula 10]

(11)

[Chemical Formula 12]

The polymer (A) is obtained by subjecting a monomer constituting the above-mentioned constituent unit to polymerization reaction. The polymerization reaction can be carried out by using a known polymerization initiator. As the polymerization initiator, an azo polymerization initiator can be used. Specific examples thereof include a water-soluble azo polymerization initiator, an oil-soluble azo polymerization initiator, and a polymeric polymerization initiator. The polymerization initiator may be used alone or in combination of two or more.

Examples of the monomer include those shown below.

[Chemical Formula 13]

[Chemical Formula 14]

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

<< Copper Ingredients >>

The copper component may be a compound containing copper or copper, and is preferably a compound containing divalent copper. It is preferable that copper is contained in an amount of 10% or more, preferably 20% or more, more preferably 30% or more in terms of the total solid content of the near infrared absorptive composition in view of improving near infrared ray shielding property by increasing the content of copper desirable. The upper limit is not particularly limited, but is preferably 70% or less, more preferably 60% or less. The copper component may be used alone, or two or more copper components may be used.

As the copper component, for example, copper oxide or copper salt can be used. Examples of the copper salt include copper carboxylate (for example, copper acetate, ethylacetoacetic acid, copper formate, copper benzoate, copper stearate, copper naphthenate, copper citrate and copper 2-ethylhexanoate) (For example, copper methanesulfonate), copper phosphate, phosphoric acid ester copper, copper phosphonate, phosphonate ester copper, copper phosphinate, amide copper, sulfonamide copper, imide copper, acylsulfonimide copper, bis Copper sulfide, copper sulfate, copper sulfide, copper sulfide, copper sulfide, copper sulfide, copper sulfide, copper sulfide, copper sulfide, copper sulfide, Copper, imide copper, acyl sulfone imide copper, bissulfone imide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper chloride, And more preferable are copper carboxylate, acylsulfonimide copper, phenoxy copper and copper chloride, and particularly preferable are copper carboxylate and acylsulfonimide copper.

&Lt; Process for producing polymer copper compound >

The polymeric copper compound can be produced by reacting the above-mentioned polymer (A) with a copper component.

The amount of the copper component to be reacted with the polymer (A) is such that the total coordination portion of the polymer (A) (the coordination atom coordinated with the unshared electron pair and the coordination site coordinated with the anion) Preferably 1: 0.1 to 1.4 moles, more preferably 1: 0.2 to 1.0 moles of the total coordination portion: copper compound = 1: 0.05 to 2 moles. By setting this range, a cured film having a higher near infrared ray shielding property tends to be obtained.

The reaction conditions at the time of reacting the copper component with the polymer (A) are preferably set at 20 to 70 캜 for 0.5 hour or more, for example.

The copper component is reacted with at least one member selected from a compound having a coordination site coordinated with an anion and a compound having a coordination site coordinated with a non-covalent electron pair, which is a low molecular compound, which will be described later, before being reacted with the polymer (A) . According to this embodiment, near infrared ray shielding property and heat resistance can be further improved. The low-molecular compound is preferably a compound having a coordination site coordinated with an anion.

The amount of the low molecular compound to be reacted with the copper component is preferably 1: 0.05 to 2, more preferably 1: 0.2 to 1.4 in terms of the molar ratio of the low molecular weight component and the low molecular weight component.

The near infrared absorbing composition of the present invention may contain a compound (polymer copper compound) obtained by the reaction of the copper component and the polymer (A), but may contain the unreacted copper component or the polymer (A). In addition, copper compounds other than the copper component, a solvent, a curing compound, a binder polymer, a surfactant, a polymerization initiator, and other components may be contained.

<< Other Near Infrared Absorbing Compound >>

The near infrared absorbing composition of the present invention may be blended with a near infrared absorbing compound (hereinafter also referred to as another near infrared absorbing compound) other than the above-mentioned polymer copper compound for the purpose of further improving the near infrared ray shielding property.

The near infrared absorbing compound used in the present invention is not particularly limited as long as it has a maximum absorption wavelength region within 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, more preferably a copper complex.

The ratio of the polymer copper compound to other near infrared absorbing compound (mass ratio) is preferably from 10:90 to 95: 5, more preferably from 20:80 to 90:10, even more preferably from 20: 80 to 80:20 is more preferable.

Examples of other near infrared absorbing compounds include copper compounds obtained by the reaction of a low molecular weight compound having a coordination site coordinated with an anion (for example, a molecular weight of 1000 or less) and a copper component, low molecular weight compounds having coordination atoms coordinated by a non- , A molecular weight of 1000 or less) and a copper component.

As the copper compound, for example, a copper complex represented by the following formula (B) can be used.

Cu (L) _n1 (X) _n2 ????? (B)

In the formula (B), L represents a ligand to be coordinated to copper, X does not exist, or a halogen atom, H ₂ O, NO ₃ , ClO ₄ , SO ₄ , CN, SCN, BF ₄ , PF ₆ , BPh ₄ (Ph represents a phenyl group), or an alcohol. n1 and n2 each independently represent an integer of 1 to 4;

The ligand L is a group having at least one selected from a coordination site coordinated with an anion for copper and a coordination atom coordinated with a non-covalent electron pair with respect to copper. The coordination site coordinated with the anion may be dissociated or compared. In contrast, X does not exist.

The copper complex is a copper compound for ligating the ligand to the copper of the central metal, and the copper is usually bivalent copper. For example, by compounding or reacting a compound or salt thereof as a ligand with respect to a copper component.

The compound or salt thereof to be a ligand is not particularly limited, but a compound represented by the following general formula (i) is preferable.

R¹⁰⁰- (X¹⁰⁰)_n3 ... (i)

(In the general formula (i), X ¹⁰⁰ represents a coordination site, n 3 represents an integer of 1 to 6, and R ¹⁰⁰ represents a single bond or an n-valent group.)

In the general formula (i), X ¹⁰⁰ is preferably at least one selected from a coordination site coordinated with an anion and a coordination atom coordinated with a non-covalent electron pair, more preferably at least one coordination site coordinated with an anion Do.

The anion is preferably an oxygen anion, a nitrogen anion or a sulfur anion so long as it can coordinate to a copper atom in the copper component.

The coordination moiety coordinated with the anion is preferably at least one selected from the above-mentioned group (AN), for example.

Examples of coordination sites coordinated with anions include monoanionic coordination sites. The monoanionic coordination site represents a moiety coordinating with a copper atom via a functional group having one negatively charged moiety. For example, an acid group having a acid dissociation constant (pKa) of 12 or less can be mentioned. Specific examples thereof include acid groups (phosphoric acid diastereoisomeric groups, phosphonic acid monoester groups and phosphinic acid groups) containing a phosphorus atom, sulfo groups, carboxyl groups, imidic acid groups and the like, and a sulfo group and a carboxyl group are preferable , And a carboxyl group is more preferable.

The coordinating atom coordinated with a non-covalent electron pair preferably contains an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably a nitrogen atom desirable. It is also preferable that the coordination atom coordinated with the unshared electron pair is a nitrogen atom and the atom adjacent to the nitrogen atom is a carbon atom, and such a carbon atom preferably has a substituent. With this structure, the structure of the copper complex is more easily deformed, so that the color value can be further improved. The substituent is the same as the substituent which the ring containing the coordinating atom coordinated by a non-covalent electron pair described below may have and includes an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a carboxyl group, an alkoxy group having 1 to 12 carbon atoms, An acyl group having 2 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, and a halogen atom are preferable.

The coordinating atoms coordinated with a non-covalent electron pair may be contained in the ring or may be contained in at least one partial structure selected from the group UE described above.

When the coordinating atoms coordinated with the unshared electron pair are included in the ring, the ring containing the coordinating atom may be monocyclic or polycyclic, and may be aromatic or non-aromatic. Is preferably a 5- to 12-membered ring, more preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring.

A ring containing a coordinating atom coordinated with a non-covalent electron pair may have a substituent. Examples of the substituent include a linear, branched or cyclic alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms, a halogen atom, a silicon atom, an alkoxy group of 1 to 12 carbon atoms, an acyl group of 1 to 12 carbon atoms, An alkylthio group having 1 to 12 carbon atoms, and a carboxyl group.

The substituent may further have a substituent. Examples of such a substituent include a group comprising a ring containing a coordinating atom coordinated with a non-covalent electron pair, a group containing at least one partial structure selected from the above-mentioned group (UE), an alkyl group having 1 to 12 carbon atoms, An acyl group having 1 to 12 carbon atoms, and a hydroxyl group.

In the general formula (i), n3 represents an integer of 1 to 6, preferably 1 to 3, more preferably 2 or 3, and further preferably 3.

In the general formula (i), R ¹⁰⁰ represents a single bond or an n-valent group. The n-valent group is preferably an n-valent organic group or a group formed by a combination of an n-valent organic group and -O-, -SO-, -SO ₂ -, -NR ^{N 1} -, -CO-, and -CS-. The n-valent organic group includes a hydrocarbon group, an oxyalkylene group, and a heterocyclic group. The n-valent group includes at least one group selected from the above-mentioned group (AN-1), a ring containing coordinating atoms coordinated to a pair of non-covalent electrons, or a group containing at least A contribution including one species may also be made.

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 (e.g., a vinyl group, a (meth) acryloyl group, an epoxy group, (For example, -CO ₂ CH ₃ ), a hydroxyl group, an alkoxy group (for example, methoxy group), an amino group, a carbamoyl group, a carbamoyl group, a carboxyl group, A halogenated alkyl group (e.g., a fluoroalkyl group, a chloroalkyl group), (meth) acryloyloxy group, and the like. When the hydrocarbon group has a substituent, it may further have a substituent. Examples of the substituent include an alkyl group, a 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 more, it is preferable that the hydrocarbon group corresponds to the monovalent hydrocarbon group or the divalent hydrocarbon group.

The alkyl group and the alkylene group may be any of linear, branched or cyclic. The straight-chain alkyl group and the alkylene group preferably have 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms. The number of carbon atoms in the branched alkyl group and alkylene group is preferably from 3 to 20, more preferably from 3 to 12, and still more preferably from 3 to 8. The cyclic alkyl group and alkylene group may be monocyclic or polycyclic. The number of carbon atoms in the cyclic alkyl group and the alkylene group is preferably from 3 to 20, more preferably from 4 to 10, and still more preferably from 6 to 10.

The number of carbon atoms of the alkenyl group and the alkenylene group is preferably from 2 to 10, more preferably from 2 to 8, and even more preferably from 2 to 4.

The carbon number of the aryl group and the arylene group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

The heterocyclic group may be one having a hetero atom in the vicinal group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group is preferably a monocyclic or condensed ring, preferably a monocyclic or condensed ring having 2 to 8 condensed rings, more preferably a monocyclic or condensed ring having 2 to 4 condensed rings. The heterocyclic group may have a substituent, and the substituent is the same as the above-mentioned substituent which may have a hydrocarbon group.

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 chain, branched, and cyclic. The number of carbon atoms of the linear or branched alkyl group is preferably from 1 to 20, more preferably from 1 to 12. The cyclic alkyl group may be monocyclic or polycyclic. The number of carbon atoms of the cyclic alkyl group is preferably from 3 to 20, more preferably from 4 to 14.

The carbon number of the aryl group in R ^N1 is preferably 6 to 18, more preferably 6 to 14. Specific examples thereof include a phenyl group and a naphthyl group. As the aralkyl group in R ^N1 , an aralkyl group having 7 to 20 carbon atoms is preferable, and an unsubstituted aralkyl group having 7 to 15 carbon atoms is more preferable.

As a specific form of the compound to be a ligand, a compound having at least two coordination sites is preferable. Specifically, a compound (hereinafter also referred to as a compound (B1)) containing at least one coordination atom coordinated with an anion and at least one coordination atom coordinating to a non-covalent electron pair, a coordination atom coordinated with a non- (Hereinafter also referred to as a compound (B2)), and a compound containing two coordination sites coordinated to an anion (hereinafter also referred to as a compound (B3)). These compounds may be used independently or in combination of two or more.

The compound to be a ligand may be a compound having only one coordination site.

&Lt; Compound (B1) &gt;

The total of the coordination sites coordinated with the anions in one molecule and coordination atoms coordinated with the non-covalent electron pair may be two or more, three or 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 above-mentioned group (AN).

Y ¹¹ represents a partial structure represented by a ring or a group (UE) containing coordination atoms coordinated to the above-described non-covalent electron pair.

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 combination thereof.

As a more specific example 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 the 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 above-mentioned group (AN). Each of X ¹⁵ , X ¹⁷ and X ²⁰ to X ²² independently represents a coordination site represented by the aforementioned group (AN-1).

In the general formulas (i-2) to (i-9), L ¹² to L ³¹ each independently represent a single bond or a divalent linking group. The divalent linking group is synonymous with the case where L ¹ in the general formula (i-1) represents a divalent linking group.

As the compound (B1), a compound represented by the formula (i-10) or (i-11) is preferable.

[Chemical Formula 15]

In the formula (i-10), X ² represents a group including a coordination site coordinated with 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 represent 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 the formula (i-10), X ² may be composed only of a group including a coordination site coordinated with the anion, and the group including a coordination site coordinated with the anion may have a substituent. Examples of the substituent which the group containing the coordination site coordinated to the 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 from 1 to 3. The hetero atom constituting the heterocycle 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 more preferably a nitrogen atom.

In the formula (i-10), A ¹ and A ⁵ are preferably carbon atoms.

In the formula (i-10), A ² and A ³ preferably represent a carbon atom. A ⁴ is preferably a carbon atom or a nitrogen atom.

In the formula (i-10), R ¹ is the same as the substituent which the ring containing the coordinating atom coordinated with the above-described non-covalent electron pair may have.

In the formula (i-10), R ^X2 is synonymous with the substituent group which the ring containing coordination atoms coordinated with the above-described non-covalent electron pair may have, and the preferable range is also the same.

In the formula (i-10), n2 represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.

The compound represented by the formula (i-10) may be a monocyclic structure or a polycyclic structure with a hetero ring containing Y ² . Specific examples of the heterocyclic ring containing Y ² in the monocyclic structure include a pyridine ring, a pyridazin ring, a pyrimidine ring, a pyrazine ring, a triazin ring, and a pyran ring. Specific examples of the heterocyclic ring containing Y ² include a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, and the like.

In the formula (i-11), X ³ represents a group including a coordination site coordinated with 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 represent 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. and n3 represents an integer of 0 to 2.

In the formula (i-11), X ³ is the same as X ² in the formula (i-10), and the preferable range is also the same.

In the 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 the formula (i-11), A ⁶ is preferably a carbon atom or a nitrogen atom. A ⁹ is preferably a carbon atom.

In the 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 the formula (i-11), R ² is preferably a hydrophobic substituent, more preferably a hydrocarbon group of 1 to 30 carbon atoms, more preferably an alkyl group of 3 to 30 carbon atoms or an aryl group of 6 to 30 carbon atoms, An alkyl group of 3 to 15 is particularly preferred.

In the formula (i-11), R ^X3 is synonymous with R ^X2 in the formula (i-10), and the preferable range is also the same.

In the formula (i-11), n3 is preferably 0 or 1, and more preferably 0.

As the compound represented by the formula (i-11), the heterocycle containing Y ³ may be a monocyclic structure or a polycyclic structure. Specific examples of the heterocyclic ring containing Y ³ in the monocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring and an isothiazole ring. Specific examples of the heterocyclic ring containing Y ³ include a polycyclic structure include an indole ring, an isoindole ring, a benzofuran ring, and an isobenzofuran ring.

In particular, it is preferable that the compound represented by the formula (i-11) has a secondary or tertiary alkyl group at the 5th position of the pyrazole ring as a compound containing a pyrazole ring. In the present specification, the 5th position of the pyrazole ring in the case where the compound represented by the formula (i-11) is a compound containing a pyrazole ring, Y ³ and A ⁶ in the above-mentioned (i-3) ⁷ ~ ⁹ a refers to the substitution position of R ² cases showing a carbon atom. The carbon number of the secondary or tertiary alkyl group at the 5th position of the pyrazole ring is preferably 3 to 15, more preferably 3 to 12.

The molecular weight of the compound (B1) is preferably 1000 or less, more preferably 750 or less, and still more preferably 600 or less. The molecular weight of the compound (B1) is preferably 50 or more, more preferably 80 or more.

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, potassium and the like. Examples of the alkaline earth metal atom include calcium, magnesium and the like.

[Chemical Formula 16]

&Lt; Compound (B2) &gt;

The compound (B2) may contain two or more coordination atoms coordinated with a pair of non-covalent electrons in one molecule, or may have three or more coordination atoms and preferably have 2 to 4 coordination atoms.

The compound (B2) is, for example, a compound represented by the following 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 partial structure represented by a ring or a group (UE) containing coordinating atoms coordinated to a non-covalent electron pair.

In the general formula (ii-1), L ⁴⁰ represents a single bond or a divalent linking group. When L ¹ represents a divalent linking group, 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 is preferable, An alkylene group having 1 to 3 carbon atoms, a phenylene group or -SO ₂ -.

As a more specific example of the compound (B2), a compound represented by the following formula (ii-2) or (ii-3) is also exemplified.

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)

Y ⁴² , Y ⁴⁴ , Y ⁴⁵ and Y ⁴⁸ in the general formulas (ii-2) and (ii-3) are each independently a ring containing a coordinating atom coordinated to a non-covalent electron pair, Represents a partial structure.

Y ⁴³ , Y ⁴⁶ and Y ⁴⁷ each independently represent a ring containing a coordinating atom coordinated with a non-covalent electron pair, or a partial structure represented by the group (UE-1) described above.

In the general formula (ii-2) and ^{(ii-3), L 41} ~ L 48 represents a single bond or a divalent connecting group independently. The divalent linking group is synonymous with the case where L ⁴⁰ in the general formula (ii-1) represents a divalent linking group, and the preferable range is also the same.

The molecular weight of the compound (B2) is preferably 1000 or less, more preferably 750 or less, and still more preferably 600 or less. The molecular weight of the compound (B2) is preferably 50 or more, more preferably 80 or more.

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

[Chemical Formula 17]

&Lt; Compound (B3) &gt;

The compound (B3) has two coordination sites coordinated with anions. The coordination site coordinated with the anion is in agreement with the coordination site coordinated with the above-mentioned anion.

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), each of X ⁵⁰ and X ⁵¹ independently represents a coordination site coordinated with an anion, agrees with a coordination site coordinated with the above-mentioned anion, and is preferably a monoanionic coordination site.

In the 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-, -NR ^N1 -, - -CS-, -SO ₂ -, or a combination thereof. 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 at least one member selected from the group consisting of a sulfo group and a carboxyl group, more preferably a group containing a sulfo group and a carboxyl group. By using a compound having at least one kind 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 still more preferably 600 or less. The molecular weight of the compound (B3) is preferably 50 or more, more preferably 80 or more.

Specific examples of the compound (B3) include the following compounds and salts thereof. The atoms constituting the salt are the same as those described above, and the preferable range thereof is also the same.

[Chemical Formula 18]

The near infrared absorbing composition of the present invention can be used as the near infrared absorbing compound as a near infrared absorbing compound such as a pyrrolopyrrole compound, a cyanide compound, a phthalocyanine compound, a naphthalocyanine compound, an iminium compound, a thiol complex compound, A metal oxide-based compound, a squarylium-based compound, a quaternary-based compound, a dithiol metal complex compound, a chromium-based compound, and the like.

The pyrrolopyrrole compound may be a pigment or a dye but is preferably a pigment because a coloring composition capable of forming a film having excellent heat resistance tends to be obtained. Examples of the pyrrolopyrrole compound include the pyrrolopyrrole compounds described in paragraphs 0016 to 0058 of JP-A No. 2009-263614.

The compounds described in paragraphs 0010 to 0081 of Japanese Laid-Open Patent Publication No. 2010-111750 may be used as the cyanide compound, the phthalocyanine compound, the iminium compound, the squarylium compound and the croconium compound, Which is incorporated herein by reference. The cyanine compound can be referred to, for example, as "functional coloring matter, Makawa Ogawa / Masaru Matsuoka / Kitao Daiziro / Hirashimatsuaki Aichi, Kodansha Scientific" Is used. The phthalocyanine-based compound can be referred to the description of paragraphs 0013 to 0029 of JP-A-2013-195480, the content of which is incorporated herein by reference.

<< Inorganic Particles >>

The near infrared absorbing composition of the present invention may contain inorganic fine particles. The inorganic fine particles may be used alone, or two or more kinds may be used.

The inorganic fine particles are mainly particles that act to shield (absorb) infrared rays. The inorganic fine particles are preferably metal oxide fine particles or metal fine particles because they are more excellent in infrared ray shielding property.

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, SnO ₂ ) particles, and niobium doped titanium dioxide (Nb doped TiO ₂ ) particles.

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 property and photolithographic property, it is preferable that the transmittance of the exposure wavelength (365-405 nm) is high, 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 shape or non-spherical shape.

As the inorganic fine particles, a tungsten oxide-based compound can be used. Specifically, it is more preferably a tungsten oxide-based compound represented by the following general formula (composition formula) (I).

M_xW_yO_z ... (I)

M represents a metal, W represents tungsten, and O represents oxygen.

0.001? X / y?

2.2? Z / y? 3.0

As the metal represented by M, an alkali metal, an alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os and Bi are preferable. Rb or Cs is more preferable, desirable. The metal of M may be one kind or two kinds or more.

When x / y is 0.001 or more, infrared rays can be shielded sufficiently, and when it is 1.1 or less, generation of an impurity phase in the tungsten oxide compound can be more reliably avoided.

When z / y is 2.2 or more, the chemical stability as a material can be further improved, and the infrared ray can be sufficiently shielded by having 3.0 or less.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _{0 . 33 WO 3, Rb 0.33 WO 3} , K 0. 33 WO 3, Ba 0. ₃₃ WO ₃ and the like, and Cs _{0 . 33} WO ₃ or Rb _{0 . 33} WO ₃ , and Cs _{0 . 33} WO ₃ is more preferable.

The tungsten oxide-based compound is available, for example, as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Chemical Co., Ltd.

The average particle diameter of the inorganic fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average particle diameter of the inorganic fine particles is in this range, the light transmittance in the visible light region can be more surely obtained. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the better, but the average particle size of the inorganic fine particles is usually 1 nm or more for ease of handling at the time of production.

The content of the inorganic fine particles is preferably from 0.01 to 30% by mass relative to the total solid content of the near infrared absorptive composition. The lower limit is preferably 0.1 mass% or more, more preferably 1 mass% or more. The upper limit is preferably 20 mass% or less, more preferably 10 mass% or less.

<< Solvent >>

The near infrared 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 if it is capable of dissolving or dispersing each component uniformly. For example, water and an organic solvent can be used.

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 two or more kinds may be used in combination.

Specific examples of alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in Japanese Laid-Open Patent Publication No. 2012-194534, paragraph 0136, the contents of which are incorporated herein by reference.

Specific examples of esters, ketones and ethers include those described in Japanese Laid-Open Patent Publication No. 2012-208494, paragraph 0497 (corresponding US Patent Application Publication No. 2012/0235099 [0609]). In addition, examples include n-amyl acetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether and ethylene glycol monobutyl ether acetate.

Examples of the solvent include 1-methoxy-2-propanol, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, ethyl lactate and propylene glycol And at least one selected from monomethyl ether is preferably used.

The content 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 mass% or less.

The solvent may be one kind or two kinds or more, and in the case of two or more types, the total amount is preferably in the above range.

<< Curing compound >>

The near infrared absorbing composition of the present invention may contain a curable compound. The curable compound may be a compound having a polymerizable group (hereinafter may be referred to as a "polymerizable compound"), or may be a non-polymerizable compound such as a binder. The curable compound may be any of chemical forms such as monomers, oligomers, prepolymers, polymers, and the like. As curable compounds, for example, Japanese Patent Laid-Open Publication No. 2014-41318, paragraphs 0070 to 0191 (Corresponding International Publication Pamphlet WO2014 / 017669, paragraphs 0071 to 0192), Japanese Laid-Open Patent Publication No. 2014-32380, paragraphs 0045 to 0216 , The contents of which are incorporated herein by reference.

As the curable compound, a polymerizable compound is preferable. Examples of the polymerizable compound include compounds containing polymerizable groups such as ethylenic unsaturated bonds and cyclic ethers (epoxy, oxetane). The ethylenically unsaturated bond is preferably a vinyl group, a styryl group, a (meth) acryloyl group or an allyl group. 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. The heat resistance of the near infrared absorbing composition can be further improved by containing a polyfunctional compound.

Examples of the curable compound include monofunctional (meth) acrylates, polyfunctional (meth) acrylates (preferably trifunctional to hexafunctional (meth) acrylates), polybasic acid modified acrylic oligomers, epoxy resins, polyfunctional epoxy resins And the like.

<<< Compounds Containing Ethylenically Unsaturated Bonds >>>

In the present invention, as the curing compound, a compound containing an ethylenic unsaturated bond can be used. As an example of the compound containing an ethylenic unsaturated bond, reference can be made to the description of paragraphs 0033 to 0034 of Japanese Laid-Open Patent Publication No. 2013-253224, the content of which is incorporated herein by reference.

Examples of the compound containing an ethylenic unsaturated bond include ethyleneoxy-modified pentaerythritol tetraacrylate (NK Ester ATM-35E, Shin Nakamura Kagaku Co., Ltd.) and dipentaerythritol triacrylate (a commercial product, KAYARAD D- 330 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320, manufactured by Nippon Kayaku K.K.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310 manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA, A-DPH-12E, manufactured by Nippon Kayaku Co., ), And a structure in which the (meth) acryloyl group intervenes between ethylene glycol and propylene glycol moieties. These oligomer types can also be used.

Reference can also be made to the description of polymerizable compounds in paragraphs 0034 to 0038 of Japanese Laid-Open Patent Publication No. 2013-253224, the content of which is incorporated herein by reference.

The polymerizable monomers described in Japanese Patent Application Laid-Open Publication No. 2012-208494, paragraph 0477 (corresponding to United States Patent Application Publication No. 2012/0235099 [0585]), and the contents thereof are herein incorporated by reference.

Further, diglycerin EO (ethylene oxide) -substituted (meth) acrylate (M-460, a commercially available product) is preferred. Pentaerythritol tetraacrylate (Shin-Nakamura Kagaku Co., A-TMMT) and 1,6-hexanediol diacrylate (KAYARAD HDDA manufactured by Nippon Kayaku Co., Ltd.) are also preferable. These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like.

The compound containing an ethylenically unsaturated bond may have an acid group such as a carboxyl group, a sulfo group or a phosphoric acid group.

Examples of the compound containing an acid group and an ethylenic unsaturated bond include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A compound in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a nonaromatic carboxylic acid anhydride to have an acid group is preferable, and particularly preferred is a compound wherein the aliphatic polyhydroxy compound is pentaerythritol and / / &Lt; / RTI &gt; or dipentaerythritol. Commercially available products include, for example, M-305, M-510, and M-520 of Aronix series as a polybasic acid-modified acrylic oligomer made by Toagosei Co.,

The acid value of the compound containing an acid group and an ethylenic unsaturated bond is preferably 0.1 to 40 mg KOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

<<< Compound having an epoxy group or an oxetanyl group >>>

In the present invention, as the curable compound, a compound having an epoxy group or an oxetanyl group can be used. Examples of the compound having an epoxy group or an oxetanyl group include a polymer having an epoxy group in the side chain, a monomer or oligomer having two or more epoxy groups in the molecule, and the like. Examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, aliphatic epoxy resins and the like. A monofunctional or polyfunctional glycidyl ether compound may also be used, and a polyfunctional aliphatic glycidyl ether compound is preferable.

The weight average molecular weight is preferably 500 to 5,000,000, more preferably 1,000 to 500,000.

These compounds may be commercially available products, or may be obtained by introducing an epoxy group into the side chain of the polymer.

As a commercially available product, reference can be made, for example, to Japanese Laid-Open Patent Publication No. 2012-155288, paragraph 0191, which are incorporated herein by reference.

Further, 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. These are low-salt small articles, but EX-212, EX-214, EX-216, EX-321, EX-850 and the like can be used in the same manner.

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- -501, EPPN-502 (manufactured by ADEKA), JER1031S, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, (Manufactured by Daicel Chemical Industries, Ltd.), cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300 and ACA Z320 (manufactured by Daicel Chemical Industries, Ltd.).

Examples of commercially available phenol novolac epoxy resins include JER-157S65, JER-152, JER-154 and JER-157S70 (manufactured by Mitsubishi Kagaku Co., Ltd.).

Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having at least two oxetane groups in the molecule include AOXT-121, OXT-221, OX-SQ and PNOX Available from Kosei Co., Ltd.) can be used.

As the compound having an epoxy group, a compound having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether may be used, but an unsaturated compound having an alicyclic epoxy group is preferable. As such, reference may be made to, for example, Japanese Laid-Open Patent Publication No. 2009-265518, paragraph 0045, the contents of which are incorporated herein by reference.

The compound containing an epoxy group or an oxetanyl group may contain a polymer having an epoxy group or an oxetanyl group as a repeating unit. Specifically, a polymer (copolymer) having the following repeating units can be mentioned.

[Chemical Formula 19]

<<< Other Curable Compounds >>>

As the curable compound, a polymerizable compound having a caprolactone-modified structure can be used.

As a polymerizable compound having a caprolactone-modified structure, reference can be made to the description of paragraphs 0042 to 0045 of Japanese Laid-Open Patent Publication No. 2013-253224, the content of which is incorporated herein by reference.

Examples of the polymerizable compound having a caprolactone-modified structure include DPCA-20, DPCA-30, DPCA-60 and DPCA-120, which are commercially available from Nippon Kayaku KAYARAD DPCA series SR-494, which is a tetrafunctional acrylate having four ethylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

The content of the curable compound is preferably 1 to 90% by mass based on the total solid content of the near infrared absorbing 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 mass% or less, and more preferably 75 mass% or less.

When a polymer containing a repeating unit having a polymerizable group is used as the curable compound, the content of the curable compound is preferably 10 to 75% by mass relative to the total solid content of the near infrared absorptive composition. The lower limit is preferably 20% by mass or more. The upper limit is preferably 65 mass% or less, more preferably 60 mass% or less.

The curing compound may be either one type or two or more kinds. In the case of two or more kinds, it is preferable that the total amount falls within the above range.

<< Binder Polymer >>

The near infrared absorbing composition of the present invention may contain a binder polymer for the purpose of improving film properties and the like. As the binder polymer, an alkali-soluble resin is preferably used. By containing the alkali-soluble resin, it is effective in improving the heat resistance and the like and fine adjustment of the application suitability. As the alkali-soluble resin, reference can be made to the description of Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to US Patent Application Publication No. 2012/0235099 [0685] to [0700]), Quot;

The content of the binder polymer is preferably 1 to 80% by mass based on the total solid content of the near infrared absorbing 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 mass% or less, and more preferably 30 mass% or less.

<< Surfactant >>

The near infrared absorbing composition of the present invention may contain a surfactant. Only one surfactant may be used, or two or more surfactants may be combined. The content of the surfactant is preferably 0.0001 to 2% by mass based on the total solid content of the near infrared absorbing composition. The lower limit is preferably 0.005 mass% or more, and more preferably 0.01 mass% or more. The upper limit is preferably 1.0 mass% or less, more preferably 0.1 mass% or less.

As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The near infrared absorbing composition of the present invention preferably contains at least one of a fluorinated surfactant and a silicone surfactant. According to this, the interfacial tension between the surface to be coated and the coating liquid is lowered, and the wettability to the surface to be coated is improved. This improves the liquid property (in particular, the fluidity) of the near-infrared absorbing composition and further improves the uniformity and liquid-repellency after application. As a result, even when a thin film of about several micrometers is formed in a small amount of liquid, film formation with a uniform thickness with a small thickness deviation can be more suitably performed.

The fluorine content of the fluorine surfactant 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 mass% or less, more preferably 25 mass% or less. When the fluorine content is within the above range, it is effective from the viewpoint of the uniformity of the thickness of the coating film and the lyophobic property, and the solubility in the near infrared absorbing composition is also good.

Specific examples of the fluorine-based surfactant include surfactants described in Japanese Patent Laid-Open Publication No. 2014-41318, paragraphs 0060 to 0064 (paragraphs 0060 to 0064 of corresponding international publication publication WO2014 / 17669 pamphlet) Quot;

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamine, glycerin fatty acid esters , Oxyethylene oxypropylene block copolymer, acetylene glycol surfactant, and acetylene-based polyoxyethylene oxide. These may be used alone or in combination of two or more.

Concrete product names include Surfynol 61, 82, 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, 504, CT- DF-75, DF-110, DF-210, GA, OP-340, PSA-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF- B, AK-02, CT-151W (manufactured by Nisshin Kagaku Co., Ltd. and Air Products & Chemicals), PSA-216, PSA-216, PSA-336, SE, SE- , E1004, E1010, P, SPC, STG, Y, 32W, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. E100, E100, E100, E100, and E200 (all of which are trade names, all of which are trade names, manufactured by Nisshin Chemical Industries, Ltd.), 4051, AF-103, AF-104, SK- (Manufactured by Fine Chemical Co., Ltd.). Of these, Olfin E1010 is suitable.

Other examples of the nonionic surfactant include nonionic surfactants described in Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0553 (corresponding to United States Patent Application Publication No. 2012/0235099 [0679]), etc. , The contents of which are incorporated herein by reference.

Specific examples of the cationic surfactant include cationic surfactants described in Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0554 (corresponding to United States Patent Application Publication No. 2012/0235099 [0680]), Which is incorporated herein by reference.

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

Examples of the silicone surfactants include silicone surfactants described in Japanese Laid-Open Patent Publication No. 2012-208494, paragraph 0556 (corresponding to United States Patent Application Publication No. 2012/0235099 [0682]), . "TSF-400" manufactured by Momentive Performance Materials Co., Ltd., "TORAY Silicone SF8410", "Dong SF8427", "SH8400", "ST80PA", "ST83PA", "ST86PA" manufactured by Toray Dow Corning Co., TSF-401, TSF-410, TSF-4446, KP321, KP323, KP324, and KP340 manufactured by Shin-Etsu Silicones.

<< Polymerization initiator >>

The near infrared absorbing composition of the present invention may contain a polymerization initiator. The polymerization initiator is not particularly limited as long as it has an ability of initiating polymerization of the polymerizable compound by either or both of light and heat, but a photopolymerizable compound (photopolymerization initiator) is preferable. In the case of initiating polymerization by light, it is preferable to have photosensitivity to visible light from the ultraviolet region. When heat polymerization is initiated, a polymerization initiator which decomposes at 150 to 250 캜 is preferable.

As the polymerization initiator, a compound having an aromatic group is preferable. Examples of the compound include acylphosphine compounds, acetophenone compounds,? -Aminoketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thiazonthone compounds, oxime compounds, hexaarylbaimidazole compounds, An onium salt compound such as a chloromethyl compound, an azo compound, an organic peroxide, a diazonium compound, an iodonium compound, a sulfonium compound, an azinium compound and a metallocene compound, an organic boron salt compound, a disulfone compound, .

As the polymerization initiator, reference can be made to the description in paragraphs 0217 to 0228 of Japanese Laid-Open Patent Publication No. 2013-253224, the content of which is incorporated herein by reference.

The polymerization initiator is preferably an oxime compound, acetophenone compound or acylphosphine compound.

IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) , ADEKA ACKLES NCI-831 (manufactured by ADEKA), ADEKA ACKLS NCI-930 (manufactured by ADEKA), and the like.

IRGACURE-907, IRGACURE-369 and IRGACURE-379 (all trade names, manufactured by BASF) can be used as commercially available acetophenone compounds.

As commercially available products of the acylphosphine compounds, IRGACURE-819 and DAROCUR-TPO (all trade names, manufactured by BASF) can be used.

The content of the polymerization initiator is preferably 0.01 to 30% by mass relative to the total solid content of the near infrared absorbing composition. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20 mass% or less, and more preferably 15 mass% or less.

The polymerization initiator may be used singly or in combination of two or more, and in the case of two or more types, the total amount is preferably in 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 dispersants, sensitizers, crosslinking agents, curing accelerators, fillers, thermal curing accelerators, thermal polymerization inhibitors and plasticizers. Adhesion promoters and other auxiliary agents (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, release promoters, antioxidants, flavors, surface tension regulators, chain transfer agents and the like) may be used in combination.

By suitably containing these components, properties such as stability and film physical properties of the objective near-infrared absorption filter can be adjusted.

These components are described, for example, in Japanese Patent Laid-Open Publication No. 2012-003225, paragraphs 0183 and 2013 (corresponding to [0237] of U.S. Patent Application Publication No. 2013/0034812), Japanese Patent Application Publication No. 2008-250074 0101 to 0104, 0107 to 0109, and the like, the content of which is incorporated herein by reference.

<Preparation of Near-Infrared Absorbent Composition>

Since the near infrared absorbing composition of the present invention can be in a liquid form, for example, the near infrared ray shielding filter can be easily manufactured by applying the near infrared absorbing composition of the present invention to a substrate or the like and then drying it.

When the near infrared ray shielding filter is formed by coating, the viscosity of the near infrared ray absorbent composition of the present invention is preferably 1 to 3000 mPa · s. The lower limit is preferably 10 mPa · s or more, more preferably 100 mPa · s or more. The upper limit is preferably 2000 mPa · s or less, more preferably 1500 mPa · s or less.

The total solid content of the near infrared absorbing composition of the present invention is changed depending on the application method, and is preferably 1 to 50% by mass, for example. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 30 mass% or less.

The use of the near infrared absorbing composition of the present invention is not particularly limited, but can be suitably used for forming a near infrared ray shielding filter and the like. (For example, a near-infrared ray filter for a wafer-level lens and the like) on the light-receiving side of the solid-state image sensor, a near-infrared ray filter (for example, A cut filter and the like. In particular, it can be suitably used as a near-infrared ray cut filter on the light receiving side of the solid-state image pickup device.

Further, according to the near infrared ray absorbing composition of the present invention, a near infrared ray shielding filter capable of realizing a high near infrared ray shielding property while maintaining a high transmittance in a visible region can be obtained. Further, the film thickness of the near-infrared cutoff filter can be reduced, contributing to lowering of the height of the camera module.

<Near-infrared ray filter>

Next, the near-IR blocking filter of the present invention will be described.

The near infrared ray blocking filter of the present invention is obtained by curing the above-described near infrared ray absorbing composition of the present invention.

The near-infrared cut filter of the present invention preferably satisfies at least one of the following conditions (1) to (9) and more preferably satisfies all the following conditions (1) to (8) , And 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, 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, 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, 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, more preferably 10% or less, 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, more preferably 10% or less, 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, more preferably 10% or less, 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, more preferably 10% or less, 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, more preferably 10% or less, particularly preferably 5% or less.

The near-infrared cut filter preferably has a light transmittance of 85% or more, more preferably 90% or more, in all the wavelengths of 400 to 550 nm. The higher the transmittance in the visible region, the better, and the higher the transmittance in the wavelength range of 400 to 550 nm. Further, it is preferable that the light transmittance at at least one of the wavelengths in the range of 700 to 800 nm is 20% or less, and the light transmittance in all the wavelengths of 700 to 800 nm is more preferably 20% or less.

The film thickness of the near-infrared cutoff filter can be appropriately selected in accordance with the purpose. For example, it is preferably 500 μm or less, more preferably 300 μm or less, more preferably 250 μm or less, particularly preferably 200 μm or less. The lower limit of the film thickness is, for example, preferably 0.1 占 퐉 or more, more preferably 0.2 占 퐉 or more, and still more preferably 0.5 占 퐉 or more.

According to the near infrared absorbing composition of the present invention, the film thickness of the near infrared ray shielding filter can be made thin in view of high near infrared ray shielding property.

The near infrared ray shielding filter of the present invention preferably has a rate of change of the absorbance ratio determined by the following equation before and after leaving for 1 hour under high temperature and high humidity of 85 캜 / relative humidity of 85%, preferably at most 7% , More preferably not more than 2%. When the rate of change of the absorbance ratio is in the above range, moisture resistance is excellent.

(%) = (Absorbance ratio before test - Absorbance ratio after test) / Absorbance ratio before test 占 100 (%)

Here, the absorbance ratio is a value represented by the following formula.

Absorbance ratio = (maximum absorbance at a wavelength of 700 to 1400 nm / near infrared ray blocking filter / minimum absorbance at a wavelength of 400 to 700 nm of a near infrared ray blocking filter)

The near infrared ray blocking filter of the present invention preferably has a rate of change in absorbance at a wavelength of 400 nm and a rate of change in absorbance at a wavelength of 800 nm both before and after heating at 200 DEG C for 5 minutes, and is particularly preferably 5% or less. When the rate of change of the absorbance is within the above range, the heat resistance is excellent.

The near-IR cut filter of the present invention is a filter for absorbing and blocking near-infrared rays (a lens for a camera such as a digital camera, a camera lens for a mobile phone, a vehicle camera, an optical lens such as an f- A near infrared ray absorbing film for blocking heat rays for energy saving, a near infrared ray absorbing plate, an agricultural coating agent for selective use of sunlight, a recording medium using absorption heat of near infrared rays, a near infrared ray filter for electronic devices or photographs, Protective glasses, sunglasses, heat-ray shielding film, reading of optical characters, prevention of confidential document copying, electrophotographic photosensitive member, laser welding. It is also useful as a noise filter for a CCD camera or as a filter for a CMOS image sensor.

&Lt; Method of manufacturing near-infrared cut filter >

The near infrared ray shielding filter of the present invention can be manufactured by applying a near infrared ray absorbing composition of the present invention to a support to form a film and drying the film. The film thickness, the lamination structure, and the like can be appropriately selected depending on the purpose. Further, a step of forming a pattern may be further performed.

The step of forming the film can be carried out, for example, by using a dropping method, a spin coater, a slit spin coater, a slit coater, a screen printing, an applicator application, or the like on the support in the near infrared ray absorbing composition of the present invention. In the case of the dropping method (droplet casting), it is preferable to form a dropping region of the near infrared absorptive composition having a photoresist as a partition wall on the support so as to obtain a uniform film with a predetermined film thickness. By adjusting the amount of the near infrared absorbing composition to be dropped, the solid content concentration, and the area of the dropping region, a desired film thickness can be obtained. The thickness of the film after drying is not particularly limited and may be appropriately selected depending on the purpose. The thickness of the film is preferably, for example, 1 to 500 μm, more preferably 1 to 300 μm, and particularly preferably 1 to 200 μm. In the present invention, even in the case of such a thin film, the near infrared ray shielding property can be maintained.

The support may be a transparent substrate made of glass or the like. In addition, a solid-state imaging device may be used. Alternatively, it may be a separate substrate provided on the light-receiving side of the solid-state image sensor. A layer such as a planarization layer provided on the light-receiving side of the solid-state imaging element may also be used.

In the step of drying the film, the drying conditions are different depending on the components, the kind of the solvent, the use ratio and the like. For example, at a temperature of 60 to 150 캜 for 30 seconds to 15 minutes.

Examples of the step of forming the pattern include a step of forming a film-like composition layer by applying the near infrared absorbing composition of the present invention on a support, a step of exposing the composition layer in a pattern shape, And a method including a step of forming a pattern. As the step of forming the pattern, a pattern may be formed by a photolithography method, or a pattern may be formed by a dry etching method.

The manufacturing method of the near-infrared cut filter may include other processes. The other processes are not particularly limited and can be appropriately selected depending on the purpose. For example, the surface treatment of the base material, the preheating step (prebaking step), the curing step, and the postheating step (postbake step).

<< Preheating process · Post-heating process >>

The heating temperature in the pre-heating step and the post-heating step is preferably 80 to 200 占 폚. The upper limit is preferably 150 占 폚 or lower. The lower limit is preferably 90 DEG C or higher.

The heating time in the pre-heating step and the post-heating 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 treatment step is a step of performing a curing treatment to the film formed as necessary, and by performing this treatment, the mechanical strength of the near-infrared cut filter is improved.

The curing treatment step is not particularly limited and can be appropriately selected depending on the purpose. For example, the whole surface exposure treatment, the whole surface heating treatment, and the like are suitably exemplified. Here, in the present invention, the term "exposure" is used not only to light of various wavelengths but also to include irradiation with radiation such as electron beams and X-rays.

The exposure is preferably performed by irradiation of radiation. Especially, ultraviolet rays or visible rays such as electron beams, KrF, ArF, g line, h line and i line are preferably used as the radiation usable in exposure.

Examples of the exposure method include stepper exposure and exposure using a high-pressure mercury lamp.

The exposure dose is preferably 5 to 3000 mJ / cm ² . The upper limit is not more than 2000mJ / cm ² are preferred, and more preferably not more than 1000mJ / cm ^2. The lower limit is preferably 10 mJ / cm ² or more, more preferably 50 mJ / cm ² or more.

As a method of the entire surface exposure treatment, for example, a method of exposing the entire surface of the formed film may be mentioned. When the near infrared absorptive composition contains a polymerizable compound, the curing of the polymerizable compound is promoted by the entire surface exposure, and the curing of the film proceeds further, thereby improving the mechanical strength and durability.

The apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected according to the purpose. For example, a UV exposure apparatus such as an ultra-high pressure mercury lamp is suitably used.

As a method of heating the entire surface, there is a method of heating the entire surface of the formed film. By heating the entire surface, the film strength of the pattern can be increased.

The heating temperature in the whole surface heating is preferably 120 to 250 ° C. The lower limit is preferably 160 DEG C or more. The upper limit is preferably 220 DEG C or higher. If the heating temperature is within the above range, a film having excellent strength tends to be obtained.

The heating time for heating the entire surface is preferably 3 to 180 minutes. The lower limit is preferably 5 minutes or longer. The upper limit is preferably 120 minutes or less.

The apparatus for heating the entire surface is not particularly limited and may be appropriately selected from known apparatuses according to the purpose, and examples thereof include a dry oven, a hot plate, and an IR heater.

<Manufacturing Method of Camera Module and Camera Module>

The camera module of the present invention has a solid-state image pickup device and a near-IR cut filter disposed on the light-receiving side of the solid-state image pickup device.

The manufacturing method of the camera module of the present invention has a step of applying the above-mentioned near infrared absorbing composition of the present invention on the light receiving side of the solid state image pickup device.

1 is a schematic cross-sectional view showing a configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention.

The camera module 10 includes a solid-state image pickup device 11, a planarization layer 12 provided on a main surface side (light receiving side) of the solid-state image pickup device, a near-infrared cut filter 13, And a lens holder (15) disposed above the blocking filter and having an imaging lens (14) in an inner space.

In the camera module 10, incident light hν from the outside sequentially passes through the imaging lens 14, the near-IR cut filter 13, and the planarization layer 12, .

The solid-state image pickup device 11 is provided with a photodiode, an interlayer insulating film (not shown), a base layer (not shown), a color filter 17, An overcoat (not shown), and a microlens 18 in this order. The color filters 17 (red color filter, green color filter, and blue color filter) and microlenses 18 are arranged so as to correspond to the solid-state image pickup device 11, respectively.

Instead of providing the near infrared ray blocking 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 near-infrared cut-off filter 13 may be provided between the two filters. For example, the near-infrared cut-off filter 13 may be provided at a position within 2 mm (more preferably, within 1 mm) from the surface of the microlens. It is possible to simplify the step of forming the near-IR cut filter and to sufficiently block the unnecessary near infrared rays to the microlens, thereby further enhancing the near infrared ray shielding property.

The near-infrared cut filter of the present invention can be used in a solder reflow process. By manufacturing the camera module by the solder reflow process, it becomes possible to automatically mount the electronic component mounting board or the like which requires soldering, and the productivity can be remarkably improved as compared with the case where the solder reflow process is not used. In addition, since it can be performed automatically, the cost can be reduced. When the solder reflow process is used, the near-infrared cut filter is also excellent in heat resistance (hereinafter referred to as "resistant solder reflow resistance") that can withstand the solder reflow process ).

In the present specification, "having solder reflow property" means maintaining the characteristic as a near-infrared cutoff filter before and after heating at 200 DEG C for 10 minutes. More preferably, the characteristics are maintained before and after heating at 230 DEG C for 10 minutes. More preferably, the characteristics are maintained before and after heating at 250 DEG C for 3 minutes. In the case where the solder has no solder reflow property, the near infrared ray shielding property of the near-infrared cut filter may be lowered or the function as a film may become insufficient when the condition is maintained under the above conditions.

The present invention also relates to a manufacturing method of a camera module including a reflow process. The near infrared ray shielding filter of the present invention maintains the near infrared ray shielding property even when the reflow process is performed, so that it does not hinder the characteristics of the camera module which is small and lightweight and has high performance.

2 to 4 are schematic sectional views showing an example of a peripheral portion of a near infrared ray blocking filter in a camera module.

2, the camera module includes a solid-state imaging element 11, a planarization layer 12, an ultraviolet / infrared light reflective film 19, a transparent substrate 20, a near infrared absorbing layer (near- An antireflection layer 21, and an antireflection layer 22 in this order.

The ultraviolet / infrared ultraviolet reflective film 19 has an effect of imparting or enhancing the function of the near-infrared cut filter. For example, reference can be made to paragraphs 0033 to 0039 of JP-A-2013-68688, Is used.

The transparent substrate 20 transmits light having a wavelength in the visible region, for example, refer to paragraphs 0026 to 0032 of Japanese Laid-Open Patent Publication No. 2013-68688, the content of which is incorporated herein by reference.

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 the reflection of light incident on the near-infrared cut filter and using the incident light efficiently. For example, refer to paragraph 0040 of JP-A-2013-68688 , The contents of which are incorporated herein by reference.

3, the camera module includes a solid-state imaging element 11, a near-infrared absorbing layer (near infrared ray blocking filter) 21, an antireflection layer 22, a planarization layer 12, an antireflection layer 22, The transparent substrate 20, and the ultraviolet / infrared light reflective film 19 in this order.

4, the camera module includes a solid-state image pickup element 11, a near-infrared absorbing layer (near-infrared ray blocking filter) 21, an ultraviolet / infrared light reflecting film 19, a planarization layer 12, An antireflection layer 22, a transparent substrate 20, and an antireflection layer 22 in this order.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Synthesis Example 1 (Synthesis of Polymers (P-1) to (P-10)

Methoxy-2-propanol (21 g) was charged into a three-necked flask, and the temperature was raised to 85 캜 under a nitrogen atmosphere.

Next, 4-vinylpyridine (11.21 g), benzyl methacrylate (18.79 g), and V-601 (azo type polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd., 1.06 g) were added to 1-methoxy- -Propanol (49 g) was added dropwise over 2 hours.

After completion of the dropwise addition, the mixture was stirred for 4 hours, and the reaction was terminated to obtain a polymer (P-1). The polymer (P-1) had a weight average molecular weight of 20,000.

Polymers (P-2) to (P-10) were also obtained in the same manner as in polymer (P-1). The weight average molecular weight of the polymers (P-2) to (P-9) was 20,000. The weight average molecular weight of the polymer (P-10) was 30,000.

&Lt; Near-infrared absorbing composition >

(Example 1)

2,6-pyridine dicarboxylic acid (17.82 g) and methanol (50 g) were added to a branch flask and dissolved at room temperature. A solution prepared by dissolving copper acetate (19.37 g) in methanol (50 g) and water (20 g) was added and stirred at room temperature for 30 minutes to confirm the formation of the precipitate. Then, a 1-methoxy-2-propanol solution (100 g, 30 mass%) of the polymer (P-1) was added thereto and stirred at room temperature for 1 hour to obtain a polymer copper compound to prepare a near infrared absorbing composition. The solid content concentration (content of the polymeric copper compound) was 21 mass%.

The total coordination portion (the coordination atom coordinated with the unshared electron pair and the coordination site coordinated with the anion) of the polymer (P-1) and the molar ratio of copper were as follows: total coordination portion: copper = 1: 1.

(Examples 2 to 6)

A polymer copper compound was obtained in the same manner as in Example 1 except that Polymers (P-2) to (P-6) were used instead of Polymer (P-1) in Example 1 to prepare a near infrared absorbing composition It was prepared. The solid content concentration (content of the polymeric copper compound) of each near-infrared absorbing composition was 21 mass%.

In Examples 2 to 5, the total coordination portion (the coordination atom coordinated with a non-covalent electron pair and the coordination site coordinated with anion) and the molar ratio of copper in the polymer were as follows: total coordination portion: copper = 1: 1 . In Example 6, the total coordination portion (the coordination atom coordinated with the non-covalent electron pair and the coordination site coordinated with the anion) and the molar ratio of copper in the polymer were as follows: total coordination portion: copper = 2: 1. The amount of methanol was adjusted so that the solid concentration became 21 mass%.

(Example 7)

A polymer copper compound was obtained in the same manner as in Example 6 except that itaconic acid was used instead of 2,6-pyridinedicarboxylic acid in Example 6 to prepare a near infrared absorbing composition. The solid content concentration (content of the polymeric copper compound) of the near infrared absorptive composition was 21 mass%. In Example 7, the total coordination portion (the coordination atom coordinated with the unshared electron pair and the coordination site coordinated with the anion) of the polymer and the molar ratio of copper were as follows: total coordination portion: copper = 2: 1. The amount of methanol was adjusted so that the solid concentration became 21 mass%.

(Example 8)

A polymer copper compound was obtained in the same manner as in Example 6 except that 2,6-pyridinedicarboxylic acid was not used and that 2-ethylhexanoate copper was used instead of copper acetate to obtain a near infrared ray absorbing property A composition was prepared. The solid content concentration (content of the polymeric copper compound) of the near infrared absorptive composition was 21 mass%. In Example 8, the total coordination portion (the coordination atom coordinated with the unshared electron pair and the coordination site coordinated with the anion) and the molar ratio of copper in the polymer were as follows: total coordination portion: copper = 2: 1. The amount of methanol was adjusted so that the solid concentration became 21 mass%.

(Example 9)

A polymer copper compound was obtained in the same manner as in Example 6 except that 2,6-pyridinedicarboxylic acid was not used and copper methanesulfonate was used instead of copper acetate to obtain a near infrared absorbing composition It was prepared. The solid content concentration (content of the polymeric copper compound) of the near infrared absorptive composition was 21 mass%. In Example 9, the total coordination portion (the coordination atom coordinated with the unshared electron pair and the coordination site coordinated with the anion) and the molar ratio of copper were as follows: total coordination portion: copper = 2: 1. The amount of methanol was adjusted so that the solid concentration became 21 mass%.

(Example 10)

A polymer copper compound was obtained in the same manner as in Example 1 except that the polymer (P-7) was used instead of the polymer (P-1) in Example 1 to prepare a near infrared absorbing composition. The solid content concentration (content of the polymeric copper compound) of the near infrared absorptive composition was 21 mass%. In Example 10, the total coordination portion (total coordination atom coordinated with a non-covalent electron pair and the coordination site coordinated with anion) and copper molar ratio of the polymer were as follows: total coordination portion: copper = 2: 1. The amount of methanol was adjusted so that the solid concentration became 21 mass%.

(Example 11)

Except that 2,6-pyridinedicarboxylic acid was not used, polymer (P-8) was used instead of polymer (P-1), copper methanesulfonate was used in place of copper acetate, , The polymer copper compound was obtained in the same manner as in Example 1 to prepare a near infrared absorbing composition. The solid content concentration (content of the polymeric copper compound) of the near infrared absorbing composition was 21 mass%. In Example 11, The total coordination portion: copper = 1: 1. The molar ratio of copper to the coordination portion (the sum of the coordination atoms coordinated with the unshared electron pair and the coordination portion coordinated with the anion) and copper were 1: 1. Of the total amount.

(Example 12)

A polymer copper compound was obtained in the same manner as in Example 1 except that 2,6-pyridinedicarboxylic acid was not used and the polymer (P-9) was used instead of the polymer (P-1) To obtain a near infrared absorbing composition. The solid content concentration (content of the polymeric copper compound) of the near infrared absorptive composition was 21 mass%. In Example 12, the total coordination portion (the coordination atom coordinated with the unshared electron pair and the coordination site coordinated with the anion) and the molar ratio of copper in the polymer were as follows: total coordination portion: copper = 2: 1. The amount of methanol was adjusted so that the solid concentration became 21 mass%.

(Example 13)

Except that 2,6-pyridinedicarboxylic acid was not used in Example 1, polymer (P-10) was used instead of polymer (P-1), copper methanesulfonate was used instead of copper acetate, 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 (content of the polymeric copper compound) of the near infrared absorptive composition was 21 mass%. In Example 13, the total coordination portion (total coordination atom coordinated with a non-covalent electron pair and the coordination site coordinated with anion) and the mole ratio of copper were as follows: the total coordination portion: copper = 1: 1. The amount of methanol was adjusted so that the solid concentration became 21 mass%.

(Comparative Example 1)

A near infrared absorbing composition was prepared in the same manner as in Example 1 of JP-A-2010-134457.

<< Fabrication of NIR filter >>

A near infrared ray shielding filter was produced using each near infrared absorbing composition.

A photoresist was coated on the glass substrate and patterned by lithography to form a partition of the photoresist to form a dropping region of the near infrared absorbing composition. 3 ml of each near infrared absorptive composition was dropped into a dropping area on a glass substrate, and the resultant was left to stand at room temperature for 24 hours. The film thickness of the coated film after drying was evaluated, and the film thickness was 200 m.

<< Evaluation of near infrared ray shielding >>

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). The near infrared ray shielding property was evaluated by the following criteria. The results are shown in the following table.

A: transmittance of 800 nm &lt; = 5%

B: transmittance of 5% &lt; 800 nm &lt; 7%

C: transmittance of 7% &lt; 800 nm &lt; = 10%

D: transmittance of 10% &lt; 800 nm

<< Heat resistance evaluation >>

The near-infrared cut filter thus obtained was allowed to stand at 200 占 폚 for 5 minutes. The absorbance at 800 nm of the near infrared ray shielding filter was measured before and after the heat resistance test and after the heat resistance test, and the absorbance at 800 nm was measured as ((absorbance before test - absorbance after test) / The rate of change of the absorbance at 800 nm was obtained. The absorbance at 400 nm was also measured to determine the rate of change of absorbance at 400 nm, which is expressed as ((absorbance after test - absorbance before test) / absorbance before test) x 100 (%). The heat resistance at each wavelength was evaluated by the following criteria. A spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation) was used for measurement of the absorbance.

A: Rate of change of absorbance? 3%

B: 3% <change rate of absorbance? 6%

C: 6% <change rate of absorbance ≤10%

D: 10% <change in absorbance

<< Evaluation of moisture resistance >>

The near-infrared cut filter thus obtained was allowed to stand under high temperature and high humidity at 85 캜 / 85% relative humidity for 1 hour. (Abs λmax) at a wavelength of 700 to 1400 nm and a minimum absorbance (Abs λmin) at a wavelength of 400 to 700 nm of the near infrared ray blocking filter were measured by a spectrophotometer U- 4100 (manufactured by Hitachi High-Technologies Corporation), and the absorbance ratio represented by "Abs λmax / Abs λmin" was obtained. | Absorbance ratio before test (Absorbance ratio before test - Absorbance ratio after test) / Absorbance ratio before test × 100 | (%) The rate of change in absorbance was expressed by the following criteria.

A: Absorption ratio change rate ≤ 2%

B: 2% <change in absorbance ratio? 4%

C: 4% <change in absorbance ratio ≤7%

D: 7% <change in absorbance ratio

<< Absorption Rate Evaluation >>

The sufficiently dried copper complex (polymer copper complex) powder was allowed to stand at 25 캜 and 95% relative humidity for 5 hours (absorption rate test). Water absorption rate The mass increase rate of the copper complex powder after the water absorption test was calculated on the basis of the mass before the test and evaluated according to the following criteria.

A1: 0? Mass increase rate? 3%

A2: 3% <Mass increase rate ≤10%

B: 10% &lt; mass increase rate &lt; = 25%

C: 25% <Mass increase rate ≤60%

D: 60% <Mass increase rate

[Table 1]

As is apparent from Table 1, the near infrared absorbing composition of the present invention was able to form a cured film having excellent heat resistance while maintaining a high near infrared ray shielding property. In addition, a cured film excellent in moisture resistance could be formed. It is also possible to set the light transmittance in the wavelength range of 450 to 550 nm to 85% or more and the light transmittance in the wavelength range of 800 to 900 nm to 20% or less.

On the other hand, Comparative Example 1 was poor in heat resistance.

In the near infrared absorbing composition of Examples 1 to 13, even when the content of the polymeric copper compound relative to the total solid content of the composition was 15 mass%, 20 mass%, 30 mass% or 40 mass%, excellent near infrared ray shielding .

(Example 20)

Except that the following low-molecular-weight copper complex A was further added to the near infrared absorbing composition of Example 1 to make the ratio of the polymeric copper compound to the low-molecular-weight copper complex A was 7: 3 on the basis of the solid content To thereby obtain the near infrared absorbing composition of Example 20.

(Examples 21 to 24)

Infrared absorptive composition of Examples 21 to 24 was obtained in the same manner as in Example 20 except that the low molecular weight copper complex A was changed to the low molecular weight copper complex B, C, D or E in the near infrared absorbing composition of Example 20, .

(Examples 25 to 28)

The procedure of Example 20 was repeated except that the proportion of the polymeric copper compound and the low molecular weight copper complex A was changed to 5: 5, 6: 4, and 8: 2, respectively, on the basis of the solid content in the near infrared absorbing composition of Example 20 , And the near infrared absorbing compositions of Examples 25 to 28 were obtained.

It was confirmed that these types of mixed types of the polymer copper compound and the low molecular weight copper complex can achieve a higher near infrared ray shielding property.

(Low molecular weight copper complex)

Low molecular copper complex A: Copper complex having (M-1) below as a ligand. The synthesis method will be described later.

Low molecular weight copper complex B: Copper complex having the following compound (B1-21) as a ligand. The synthesis method will be described later.

Low molecular weight copper complex C: monobutyl phthalate, Tokyo Kasei Kogyo Co., Ltd.

Low molecular weight 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: Copper complex having the following compound (B3-18) as a ligand. The synthesis method will be described later.

[Chemical Formula 20]

<Synthesis of low molecular weight copper complex A>

In a three-necked flask, 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 in a nitrogen atmosphere, For 1 hour. After cooling to room temperature, the insoluble material was removed by filtration, and the filtrate was concentrated. The obtained crude product was purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to obtain 1- (3 -Pentyl) pyrazole-3-carboxylate (3.3 g).

0.87 g of the above product and 6 mL of ethanol were added to the flask, and while stirring at room temperature, 0.1 g of water and 0.46 g of tert-butoxy potassium were added, followed by stirring at 70 캜 for 30 minutes. After cooling to room temperature, a solution of 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 weight copper complex A.

<Synthesis of Copper Complex B>

Compound B1-21 (886 mg, 9.84 mmol) was dissolved in 20 ml of methanol. After raising the temperature of the solution to 50 占 폚, a methanol solution (160 ml) of copper hydroxide (449 mg, 4.60 mmol) was added dropwise and reacted at 50 占 폚 for 2 hours. After completion of the reaction, water and solvent generated in the evaporator were distilled off to obtain a low molecular weight copper complex B (1.00 g).

<Synthesis of Copper Complex D>

Compound B2-1 (0.2 g, 1.1 mmol) was dissolved in 5 ml of ethanol. After raising the temperature of the solution to 70 占 폚, an ethanol solution (5 ml) of copper acetate (0.2 g, 1.1 mmol) was added dropwise and the mixture was reacted at 70 占 폚 for 2 hours. After completion of the reaction, water and solvent generated in the evaporator were distilled off to obtain low molecular weight copper complex D (0.6 g).

<Synthesis of Copper Complex E>

An aqueous solution (13.49 g, 29.1 mmol) of 53.1% by mass of the compound B3-18 (sulfophthalic acid) was dissolved in 50 mL of methanol, and the temperature of the solution was raised to 50 캜. Copper hydroxide (2.84 g, 29.1 mmol) For 2 hours. After completion of the reaction, the solvent and the resulting water were distilled off with an evaporator to obtain a low molecular weight copper complex E (8.57 g).

10 Camera module
11 solid-
12 planarization layer
13 NIR filter
14 imaging lens
15 Lens Holder
16 silicon substrate
17 Color filters
18 micro lenses
19 Ultraviolet / infrared reflective film
20 transparent substrate
21 Near infrared absorbing layer
22 Antireflection layer

Claims (11)

And a compound obtained by a reaction of a copper component and a polymer containing coordination atoms coordinated to a copper component by a non-covalent electron pair. The method according to claim 1,
Wherein the coordination atom is at least one element selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom. The method according to claim 1 or 2,
The polymer further has a coordination site coordinated with an anion. The method of claim 3,
Wherein the anion is at least one selected from an oxygen anion, a nitrogen anion and a sulfur anion. The method according to any one of claims 1 to 4,
The polymer contains a group represented by the following formula (1) in the side chain: a near infrared absorbing composition;
-L ¹ -Y ¹ ... (One)
In the general formula (1), L ¹ represents a single bond or a linking group, Y ¹ represents a group having one or more coordination atoms coordinated with a non-covalent electron pair or a coordination atom coordinating to a pair of non- Represents a group having at least one coordination site to be coordinated, and * denotes a link to a polymer. The method according to any one of claims 1 to 5,
The polymer includes a constituent unit represented by the following formula (A1-1): a near infrared absorbing composition;
[Chemical Formula 1]

In the formula (A1-1), R ¹ represents a hydrogen atom or a hydrocarbon group, L ¹ represents a single bond or a linking group, Y ¹ represents a group having one or more coordination atoms coordinated with a pair of non- A group having one or more coordination atoms coordinating to one or more coordination atoms and anions coordinated to anions. The method according to any one of claims 1 to 6,
Wherein the polymer comprises at least one constituent unit selected from the following formulas (A1-1-1) to (A1-1-4): a near infrared absorbing composition;
(2)

In the 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, Y ¹ represents a coordination atom coordinated with a non- Or a group having one or more coordination sites for coordinating one or more coordinating atoms coordinated with a pair of non-covalent electrons and anions. A near infrared ray blocking filter obtained by using the near infrared absorbing composition according to any one of claims 1 to 7. A method for manufacturing a near-infrared light blocking filter, comprising the step of applying a near infrared absorbing composition according to any one of claims 1 to 7 on a light receiving side of a solid-state image pickup device. A solid-state image pickup element having a near-infrared ray blocking filter obtained by using the near infrared absorbing composition according to any one of claims 1 to 7. And a near infrared ray blocking filter disposed on a light receiving side of the solid state image pickup device, wherein the near infrared ray blocking filter is the near infrared ray blocking filter according to claim 8.

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