TW201529588A - Near infrared absorptive composition, near infrared cut filter and method for manufacturing near infrared cut filter, and camera module and method for manufacturing camera module - Google Patents

Abstract

The invention provides a near infrared absorptive composition, a near infrared cut filter and a method for manufacturing the near infrared cut filter, and a camera module and a method for manufacturing the camera module. The near infrared absorptive composition has high transmittance in a visible light region and high shielding performance in a near infrared region when made into a cured film. The near infrared absorptive composition of the invention includes a copper complex. The copper complex is fromed by reacting a compound (A) with a copper component. The compound (A) has a coordination portion coordinating by an anion, and a coordination atom coordinating by an unshared electron pair.

Description

Near-infrared absorbing composition, near-infrared cut filter and Manufacturing method and camera module and method of manufacturing same

The present invention relates to a near-infrared absorbing composition, a near-infrared cut filter, a method of manufacturing the same, and a camera module and a method of manufacturing the same.

In a video camera, a digital still camera, a camera-equipped mobile phone, etc., a charge-coupled device (CCD) or a complementary image of a solid-state imaging device as a color image is used. Metal oxide semiconductor (Complementary Metal-Oxide-Semiconductor, CMOS). Since these solid-state imaging devices use a silicon photodiode having sensitivity to near-infrared rays in the light receiving portion, it is necessary to perform visibility correction, and a near-infrared cut filter is often used.

As a material for forming such a near-infrared cut filter, for example, a near-infrared absorbing composition using a copper phosphate complex is known (Patent Documents 1 to 3).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-69305

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-52127

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-63814

In the infrared-cut filter using the copper complex described in Patent Document 1 and Patent Document 2, it is understood that the visible light transmittance and the shielding property in the near-infrared range are obtained when the cured film is formed. insufficient. An object of the present invention is to solve the above problems, and to provide a near-infrared absorbing composition having high transmittance in a visible light range and high shielding property in a near-infrared range when a cured film is formed.

The inventors of the present invention conducted diligent research based on the above conditions, and as a result, found that the problem can be solved by a specific copper complex.

Specifically, the above problem is solved by the following means <1>, preferably means <2>~ means <26>.

<1> A near-infrared absorbing composition containing a copper complex which is a coordination atom having a coordination site coordinated by an anion and a coordination atom having a non-covalent electron pair The compound (A) is formed by reacting with a copper component.

<2> A near-infrared absorbing composition containing a copper complex which has copper as a central metal and which has a coordination with an anion The compound (A) having a coordinating atom coordinated to a non-covalent electron pair serves as a ligand.

<3> The near-infrared absorbing composition according to <1> or <2>, wherein the copper complex is a 5-membered ring and/or a 6-membered ring formed by copper and the compound (A).

The near-infrared absorbing composition according to any one of <1> to <3> wherein the anion in the compound (A) is an oxyanion, a nitrogen anion or a sulfur anion, and is carried out by a non-covalent electron pair. The coordinating atom of the coordination is an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom.

The near-infrared absorbing composition according to any one of <1> to <4> wherein the number of atoms linking an anion to a coordinating atom coordinated by a non-covalent electron pair is 1 to 3 .

The near-infrared absorbing composition according to any one of <1> to <5> wherein the compound (A) has a molecular weight of 50 to 1,000.

The near-infrared absorbing composition according to any one of <1> to <6> wherein the compound (A) is a compound containing a 5-membered ring or a 6-membered ring, and is carried out by a non-covalent electron pair. The coordinating atom of the coordination is an atom constituting a 5-membered ring or a 6-membered ring.

The near-infrared absorbing composition according to any one of <1> to <7> wherein the coordinating atom coordinated by the non-covalent electron pair is a nitrogen atom.

<9> The near-infrared absorbing composition according to <8>, wherein the atom adjacent to the nitrogen atom is a carbon atom, and the carbon atom has a substituent.

The near-infrared absorbing composition as described in any one of <1> to <7>, wherein the compound (A) is represented by the formula (I);

In the formula (I), X ¹ represents a group containing a coordination site coordinated by an anion; Y ¹ represents a nitrogen atom or a phosphorus atom, and together with adjacent carbon atoms constitutes a 4-membered ring to a 7-membered ring; R ^X1 represents The substituent, n1 represents an integer from 0 to 6.

<11> The near-infrared absorbing composition according to <10>, wherein in the formula (I), a ring formed by Y ¹ together with an adjacent carbon atom is an aromatic ring.

The near-infrared absorbing composition according to any one of the above-mentioned group, wherein the coordination site coordinated by the anion is at least one selected from the group consisting of the following groups (AN), the group Group (AN)

A coordinating atom coordinated with a non-covalent electron pair is contained in a ring or is contained in at least one partial structure selected from the group consisting of (UE), a group (UE)

The wavy line is a bonding position with the atomic group constituting the compound (A),

X represents N or CR, and R and R ¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. , aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkylthio, arylthio, heteroarylthio, amine or fluorenyl.

<12-1> The near-infrared absorbing composition according to <12>, wherein the coordination site coordinated by the anion is at least one selected from the group consisting of AN-11; X and R and the group The X and R of the group (AN) have the same meaning, group (AN-11)

The near-infrared absorbing composition according to any one of <1> to <6> wherein the compound (A) is represented by the following formula (IV); X ¹ -L ¹ -Y ^{1 is} passed Formula (IV)

In the formula (IV), X ¹ represents a coordination site selected from at least one of the following groups (AN), which is coordinated by an anion, and the group (AN)

Y ¹ represents a ring containing a coordinating atom coordinated by a non-covalent electron pair, or a partial structure containing at least one coordinating atom coordinated by a non-covalent electron pair selected from the following group (UE) Group (UE)

The wavy line is a bonding position with the atomic group constituting the compound (A), X represents N or CR, and R and R ¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, R ² independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl 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, Amine or a thiol group, and L ¹ represents a single bond or a divalent linking group.

<13> The near-infrared absorbing composition according to <13>, wherein X ¹ is at least one selected from the group consisting of (AN-11); X and R and X of the group (AN) R is the same meaning, group (AN-11)

The near-infrared absorbing composition according to any one of <1> to <13> further comprising a curable compound and a solvent.

<15> A near-infrared ray-cutting filter which is obtained by hardening the near-infrared absorbing composition according to any one of <1> to <14>.

<16> A method of manufacturing a near-infrared cut filter, comprising: coating the light-receiving side of the solid-state image sensor with a coating as described in any one of <1> to <14> An infrared absorbing composition, whereby a film is formed.

<17> A camera module having a solid-state image sensor and a near-infrared cut filter disposed on a light receiving side of the solid-state image sensor, and a near-infrared cut filter for causing any one of <1> to <14> The near-infrared cut filter in which the near-infrared absorbing composition described above is cured.

<18> A method of manufacturing a camera module, comprising: a camera module having a solid-state image sensor and a near-infrared cut filter disposed on a light receiving side of the solid-state image sensor; and the method of manufacturing the camera module includes: In the light-receiving side of the solid-state image sensor, the near-infrared ray absorbing composition described in any one of <1> to <14> is applied to form a near-infrared cut filter.

<19> The near-infrared absorbing composition according to <1>, wherein the compound (A) is represented by the formula (1);

In the formula (1), R ¹ represents a hydrocarbon group; and R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group; and R ¹ and R ² or R ³ may be bonded to each other to form a ring.

<20> The near-infrared absorbing composition according to <19>, wherein R ¹ in the formula (1) represents an alkyl group or an aryl group.

<21> The near-infrared absorbing composition according to <19> or <20>, wherein R ¹ in the formula (1) represents an alkyl group, and R ² and R ³ each independently represent a hydrogen atom, a halogen atom, or a Base, ethyl or propyl.

<22> The near-infrared absorbing composition according to <19>, wherein R ¹ and R ² in the formula (1) are bonded to each other to form a 5-membered ring or a 6-membered ring containing an oxygen atom. And R ³ is a hydrogen atom.

<23> The near-infrared absorbing composition according to <19> or <20>, wherein the compound represented by the formula (1) is represented by the formula (2);

In the formula (2), R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group; L represents an n-valent hydrocarbon group, or an n-valent group containing a combination of a hydrocarbon group and -O-; n represents 2 An integer of ~6.

The near-infrared absorbing composition of any one of the above-mentioned <1>, wherein at least one of R ² and R ³ in the formula (1) represents a halogen atom or a monovalent organic group.

<25> A method of using a copper complex as an infrared absorbing agent, wherein the copper complex is obtained by reacting a compound (A) represented by the formula (1) with a copper component;

In the formula (1), R ¹ represents a hydrocarbon group; and R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group; and R ¹ and R ² or R ³ may be bonded to each other to form a ring.

According to the present invention, it is possible to provide a near-infrared absorbing composition having high transmittance in the visible light range and high hiding property in the near-infrared range when the cured film is formed.

10‧‧‧ camera module

11‧‧‧ Solid-state imaging components

12‧‧ ‧ flattening layer

13‧‧‧Near-infrared cut-off filter

14‧‧‧ camera lens

15‧‧‧Lens Holder

16‧‧‧Photographic Components Division

17‧‧‧Color Filter

18‧‧‧Microlens

19‧‧‧UV. Infrared light reflecting film

20‧‧‧Transparent substrate

21‧‧‧Near infrared absorption layer

22‧‧‧Anti-reflective layer

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.

2 is a schematic cross-sectional view showing an example of a peripheral portion of a near-infrared cut filter in a camera module.

3 is a schematic cross-sectional view showing an example of a peripheral portion of a near-infrared cut filter in a camera module.

4 is a schematic cross-sectional view showing an example of a peripheral portion of a near-infrared cut filter in a camera module.

Hereinafter, the contents of the present invention will be described in detail.

In the present specification, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

In the expression of the group (atomic group) of the present specification, no substitution or The expression of the substitution includes a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means acrylonitrile group and Methyl methacrylate.

In addition, in this specification, "single quantity" and "monomer" have the same meaning. The singly is a compound which is different from the oligomer and the polymer and has a weight average molecular weight of 2,000 or less.

In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

The method for measuring the weight average molecular weight and the number average molecular weight of the compound used in the present invention can be determined by gel permeation chromatography (GPC), and the molecular weight is defined as the measurement by GPC. Polystyrene converted value. For example, it can be obtained by using HLC-8220 (manufactured by Tosoh Corporation), using TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) as a column, and using 10 mmol. /L lithium bromide N-methyl pyrrolidinone (NMP) solution as a solution.

The so-called near infrared, the maximum absorption wavelength range is 700nm ~ 2500nm Light (electromagnetic waves).

In the present specification, the term "total solid content" means the total mass of the components obtained by removing the solvent from the total composition of the composition. The solid content in the present invention means a solid component at 25 °C.

<Near infrared absorbing composition>

The near-infrared absorbing composition of the present invention (hereinafter also referred to as the composition of the present invention) contains a copper complex which has at least one coordination site each having an anion coordinated The compound (A) in which the coordinating atom of the coordination is coordinated with a non-covalent electron pair is formed by reacting with a copper component. Further, the composition of the present invention may further contain a copper complex compound in which copper is used as a central metal and each of which has at least one coordination site coordinated by an anion and is coordinated with a non-covalent electron pair. The compound (A) of the coordinating atom (hereinafter also referred to as the compound (A)) serves as a copper complex of the ligand.

According to the composition of the present invention, it is possible to obtain a high transmittance in the visible range, A near-infrared cut filter with high near-infrared shielding properties can be realized. Further, according to the present invention, the film thickness of the near-infrared cut filter can be made thin, which contributes to downsizing of the camera module.

The reason for obtaining the effect of the invention of the present application is not certain, but it can be presumed as follows. The compound (A) having a copper component and a coordinating site each having at least one anion-coordinating ligand and a coordinating atom coordinated by a non-covalent electron pair, the compound (A) is used as a chelate with respect to the copper component. The complexing body functions. That is, it is considered that the coordination site of the compound (A) coordinated by an anion and the non-covalent electron pair The coordinating coordination atom and the copper in the copper component are chelate-coordinated, whereby the structure of the copper complex is skewed, high transmittance in the visible light range is obtained, the light absorption capability of the near infrared ray is improved, and the color value is also increased. Big.

The copper complex compound used in the present invention has the compound (A) A form of a copper complex (copper compound) in which a coordinating atom coordinated by a non-covalent electron pair is chelate-coordinated with a coordination site coordinated by an anion. The copper in the copper complex used in the present invention is usually divalent copper, and can be obtained, for example, by mixing and reacting the compound (A) with a copper component (copper or a compound containing copper).

Further, the copper complex compound used in the present invention may be exemplified by 4 coordination, 5 coordination, and 6 coordination, more preferably 4 coordination and 5 coordination.

Here, when the structure of copper and the compound (A) can be detected from the composition of the present invention, a copper complex compound containing the compound (A) as a ligand can be formed in the composition of the present invention. The method for detecting copper and the compound (A) from the composition of the present invention is, for example, an inductively coupled plasma (ICP) luminescence analysis.

The copper complex used in the present invention preferably has a maximum absorption wavelength (λ _max ) in the near-infrared wavelength range of 700 nm to 2500 nm, more preferably a maximum absorption wavelength in the range of 720 nm to 890 nm, and more preferably from 730 nm to 880 nm. It has the largest absorption wavelength inside. The maximum absorption wavelength can be measured, for example, using a Cary 5000 Ultra-Vibration-Near-Infrared (UV-Vis-NIR) (spectrophotometer, manufactured by Agilent Technologies, Inc.). .

<<Compound (A) having at least one coordination site coordinated by an anion and a coordination atom coordinated by a non-covalent electron pair, respectively>>

The compound (A) may have at least one coordination site coordinated by an anion in one molecule, or may have two. In the compound (A), the total number of the coordination sites coordinated by the anions in one molecule and the coordination atoms coordinated by the non-covalent electron pair may be two or more, or three. It can also be four.

The total value of the coordination site coordinated by the anion and the coordination atom coordinated by the non-covalent electron pair is three, and there are two coordination sites having an anion coordination and one In the case of a coordinating atom coordinated by a non-covalent electron pair, there is a case where one coordinating site coordinated by an anion and two coordinating atoms coordinated by a non-covalent electron pair.

The total value of the coordination site coordinated by the anion and the coordination atom coordinated by the non-covalent electron pair is four, and there are two coordination sites having two anions coordinated. In the case of a coordinating atom coordinated by a non-covalent electron pair, there is a case where one coordinating site coordinated by an anion and three coordinating atoms coordinated by a non-covalent electron pair.

The maximum absorption wavelength (λ _max ) of the compound (A) is preferably 420 nm or less, more preferably 400 nm or less, and still more preferably 350 nm or less. Further, the maximum absorption wavelength of the compound (A) is preferably 10 nm or more, more preferably 50 nm or more. Further, the maximum absorption wavelength of the compound (A) is preferably not present at 430 nm or more.

The compound (A) may be used alone or in combination of two or more.

In compound (A), anion is coordinated with a pair of non-covalent electrons The number of atoms to which the coordination atom is bonded is preferably from 1 to 6, more preferably from 1 to 3. By setting such a configuration, the structure of the copper complex is more likely to be skewed, so that the color value can be further increased.

The atom to which the anion is bonded to the coordinating atom coordinated by the non-covalent electron pair may be one type or two or more types. The atom linking the anion to the coordinating atom coordinated by the non-covalent electron pair is preferably a carbon atom.

In the following exemplified compounds, the anion is an oxyanion, the coordinating atom coordinated by a non-covalent electron pair is a nitrogen atom, and the atom linking the anion to a coordinating atom coordinated by a non-covalent electron pair is carbon. atom. Further, the number of atoms linking an anion to a coordinating atom coordinated by a non-covalent electron pair is two.

The molecular weight of the compound (A) is preferably from 50 to 1,000, more preferably from 50 to 600.

In the compound (A), the anion may be provided on the copper atom in the copper component, and is preferably an oxyanion, a nitrogen anion or a sulfur anion.

The coordination site coordinated by the anion is preferably at least one selected from the group consisting of the following groups (AN). Further, the wavy line in the following structural formula is a bonding position with the atomic group constituting the compound (A).

Group (AN)

Further, the coordination site coordinated by an anion is also preferably the following group (AN-11). Further, the wavy line in the following structural formula is a bonding position with the atomic group constituting the compound (A).

Group (AN-11)

In the coordination site coordinated by an anion, X represents N or CR, R preferably each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

The alkyl group may be linear, branched or cyclic, and is preferably linear. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 4. An example of the alkyl group is 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 a monocyclic ring or a polycyclic ring, and may be aromatic or non-aromatic. The number of the hetero atoms constituting the hetero ring is preferably from 1 to 3, preferably from 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom. In the case where the alkyl group has a substituent, it may have a more substituent.

The number of carbon atoms of the alkenyl group is preferably from 1 to 10, more preferably from 1 to 6.

The alkynyl group preferably has a carbon number of from 1 to 10, more preferably from 1 to 6.

The aryl group may be a single ring or a polycyclic ring, preferably a single ring. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6.

The heteroaryl group may be a single ring or a polycyclic ring. The number of the hetero atoms constituting the heteroaryl group is preferably from 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom. The carbon number of the heteroaryl group is preferably from 6 to 18, more preferably from 6 to 12.

In the compound (A), the coordinating atom coordinated by the non-covalent electron pair is preferably 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, and further preferably Nitrogen atom. In the case where the coordinating atom coordinated by the non-covalent electron pair is a nitrogen atom, it is preferred that the atom adjacent to the nitrogen atom is a carbon atom, and the carbon atom has a substituent.

Coordination atoms coordinated by non-covalent electron pairs are preferably contained in the ring Or in at least one partial structure selected from the group consisting of (UE). Further, the wavy line in the following structural formula is a bonding position with the atomic group constituting the compound (A).

Group (UE)

In the group (UE), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. Alkoxy, aryloxy, heteroaryloxy, alkylthio, arylthio, heteroarylthio, amine or fluorenyl.

In the case where a coordinating atom coordinated by a non-covalent electron pair is contained in a ring, the ring containing a coordinating atom coordinated by a non-covalent electron pair may be a single ring or a polycyclic ring, and It can be aromatic or non-aromatic. The ring containing a coordinating atom coordinated by a non-covalent electron pair is preferably a 5-membered ring to a 12-membered ring, more preferably a 5-membered ring to a 7-membered ring.

The ring containing a coordinating atom coordinated by a non-covalent electron pair may have a substituent, and the substituent may be a hydrocarbon group (for example, a carbon number of 1 to 30 (preferably, a carbon number of 1 to 10). a linear, branched or cyclic alkyl group, an aryl group having 6 to 30 carbon atoms (preferably 6 to 12 carbon atoms), a halogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, A fluorenyl group having 2 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, and a carboxyl group. In the case where the substituent is a hydrocarbon group, a group containing a combination of a hydrocarbon group and -O- is also preferred.

In the case where the ring containing a coordinating atom coordinated by a non-covalent electron pair has a substituent, it may have a more substituent, and may include a coordinating atom containing a coordinate group coordinated by a non-covalent electron. a group of a ring, a group containing at least one partial structure selected from the group (UE), an alkyl group having 1 to 12 carbon atoms, a fluorenyl group having 2 to 12 carbon atoms, and a hydroxyl group.

In the case where the ring containing a coordinating atom coordinated by a non-covalent electron pair has a substituent, it is preferred that the substituent is bonded to an atom bonded to a coordinating atom coordinated by a non-covalent electron pair. .

When a coordinating atom coordinated by a non-covalent electron pair is contained in a partial structure represented by a group (UE), it represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl 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 amine. Base or thiol.

The alkyl group, the alkenyl group, the alkynyl group, the aryl group and the heteroaryl group have the same meanings as the alkyl group, alkynyl group, aryl group and heteroaryl group described in the coordination site where the anion is coordinated, and the preferred range is also the same.

The alkoxy group preferably has 1 to 12 carbon atoms, more preferably 3 to 9 carbon atoms.

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

The heteroaryloxy group may be a single ring or a polycyclic ring. The heteroaryl group constituting the heteroaryloxy group has the same meaning as the heteroaryl group described in the coordination site where the anion is coordinated, and the preferred range is also the same.

The carbon number of the alkylthio group is preferably from 1 to 12, more preferably from 1 to 9.

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

The heteroarylthio group may be a single ring or a polycyclic ring. The heteroaryl group constituting the heteroarylthio group has the same meaning as the heteroaryl group described in the coordination site where the anion is coordinated, and the preferred range is also the same.

The carbon number of the fluorenyl group is preferably from 2 to 12, more preferably from 2 to 9.

The compound (A) is also preferably represented by the following formula (IV).

X ¹ -L ¹ -Y ¹ Formula (IV)

In the general formula (IV), X ¹ represents a coordination site represented by a group (AN) or the group (AN-11). Y ¹ represents a ring containing a coordinating atom coordinated by a non-covalent electron pair, or a partial structure represented by a group (UE). L ¹ represents a single bond or a divalent linking group.

In the general formula (IV), X ¹ has the same meaning as the coordination site coordinated by the anion, and the preferred range is also the same.

In the formula (IV), the partial structure of Y ¹ with the ring containing a coordinating atom coordinated by a non-covalent electron pair or the coordinate atom containing a coordinating atom with a non-covalent electron pair is The same meaning, the preferred range is also the same.

In the general formula (IV), when L ¹ represents a divalent linking group, an alkylene group having 1 to 12 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -SO, and -O- are preferred. And -SO ₂ - or a group containing the combination of these, preferably an alkylene group having a carbon number of 1 to 3, a phenyl group or a -SO ₂ - group.

More specific examples of the compound (A) include the compounds represented by the following formula (IV-1) to formula (IV-8).

In the general formulae (IV-1) to (IV-8), X ² to X ⁴ , X ⁸ and X ⁹ each independently represent a group selected from the group (AN) or the group (AN-11). At least one of them. Further, X ⁵ , X ⁷ , and X ¹⁰ to X ¹² are each independently at least one selected from the group consisting of the following group (AN-1) or group (AN-12). X in the group (AN-1) and the group (AN-12) represents N or CR, and R has the same meaning as R described by CR in the group (AN). The wavy line is a bonding position with the atomic group constituting the compound (A).

Group (AN-1)

Group (AN-12)

In the general formulae (IV-1) to (IV-8), Y ³ , Y ⁵ to Y ⁷ , and Y ¹² to Y ¹⁵ each independently represent a coordinating atom coordinated by a non-covalent electron pair. A ring, or at least one partial structure selected from the group (UE). Further, Y ² , Y ⁴ , Y ⁸ to Y ¹¹ , and Y ¹⁶ are each independently a ring containing a coordinating atom coordinated by a non-covalent electron pair, or selected from the following group (UE-1) At least one. R in the group (UE-1) is identical to R in the case where the coordinating atom coordinated by the non-covalent electron pair is contained in the partial structure represented by the group (UE). The wavy line is a bonding position with the atomic group constituting the compound (A).

Group (UE-1)

In the general formulae (IV-1) to (IV-8), L ² to L ²⁰ each independently represent a single bond or a divalent linking group. The divalent linking group has the same meaning as the case where L ¹ in the formula (IV) represents a divalent linking group, and the preferred range is also the same.

The compound (A) is also preferably a compound represented by the following formula (IV-11) to formula (IV-20).

In the general formulae (IV-11) to (IV-20), Z ¹ to Z ³⁴ , Z ¹⁰¹ to Z ¹⁰⁸ , and Z ²⁰¹ to Z ²⁰³ each independently represent a coordination site, and L ¹¹ to L ²⁵ are independently independently The single bond or the divalent linking group is represented, and L ²⁶ to L ³² each independently represent a trivalent linking group, and L ³³ to L ³⁴ each independently represent a tetravalent linking group.

Z ¹ to Z ³⁴ preferably each independently represent a group comprising a ring containing a coordinating atom coordinated by a non-covalent electron pair, and is selected from the group (AN-11) or group (UE). At least one of them.

Z ¹⁰¹ to Z ¹⁰⁸ preferably each independently represent a group comprising a ring containing a coordinating atom coordinated by a non-covalent electron pair, selected from the group (AN-12) or a group (UE- At least one of 1).

Z ²⁰¹ to Z ²⁰³ preferably each independently represent at least one selected from the group consisting of UE-2.

L ¹¹ to L ²⁵ each independently represent a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group having 1 to 12 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -SO-, -O-, -SO ₂ - or a group containing the combination thereof. More preferably, it is an alkyl group having 1 to 3 carbon atoms, a phenyl group, a -SO ₂ - group or a group containing the combination.

L ²⁶ to L ³² each independently represent a trivalent linking group. Examples of the trivalent linking group include a group obtained by removing one hydrogen atom from the divalent linking group.

L ³³ to L ³⁴ each independently represent a tetravalent linking group. Examples of the tetravalent linking group include a group obtained by removing two hydrogen atoms from the divalent linking group.

Group (UE-2)

Further, in order to improve the visible light transmittance, the compound (A) is preferably a continuous π-conjugated system other than an aromatic group and a plurality of bonds.

The compound (A) is also preferably a compound having a 5-membered ring or a 6-membered ring. Further, the coordinating atom coordinated by the covalent electron pair preferably also constitutes a 5-membered ring or a 6-membered ring.

The coordinating atom which the compound (A) has coordinated with a non-covalent electron pair is also preferably a nitrogen atom. Further, it is also preferred that the atom adjacent to the nitrogen atom of the coordinating atom coordinated by the non-covalent electron pair of the compound (A) is a carbon atom, and the carbon atom has a substituent. By setting such a configuration, the structure of the copper complex is more likely to be skewed, so that the color value can be further increased. The substituent may have the same meaning as the substituent having a coordinating atom coordinated by a non-covalent electron pair, and is preferably a hydrocarbon group having 1 to 30 carbon atoms (for example, a carbon number of 1 to 30) An alkyl group (preferably an alkyl group having 1 to 12 carbon atoms), an aryl group having 6 to 30 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms), a carboxyl group, and an alkoxy group having 1 to 12 carbon atoms. A fluorenyl group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, and a halogen atom. More preferably, it is an alkyl group, an aryl group, a carboxyl group, or a halogen atom.

The compound (A) is also preferably represented by the formula (II) or the formula (III).

In the formula (II), X ² represents a group containing a coordination site coordinated by an anion. Y ² represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ¹ and A ⁵ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ² to A ⁴ each independently 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 from 0 to 3. In the formula (III), X ³ represents a group containing the coordination site coordinated by the anion. Y ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ⁶ and A ⁹ each independently 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. N3 represents an integer from 0 to 2.

In the formula (II), X ² may include, for example, only a group containing a coordination site coordinated by an anion, or a group having a coordination site coordinated by an anion may have a substituent. Examples of the substituent which the group having a coordination site coordinated by an anion may have a halogen atom, a carboxyl group, or a heterocyclic group. The heterocyclic group as a substituent may be a monocyclic ring or a polycyclic ring, and may be aromatic or non-aromatic. The number of the hetero atoms constituting the hetero ring is preferably from 1 to 3, preferably from 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom.

In the formula (II), Y ² represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom, and further preferably a nitrogen atom.

In the formula (II), A ¹ and A ⁵ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom, and preferably a carbon atom.

In the formula (II), A ² to A ⁴ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ² and A ³ preferably represent a carbon atom. A ⁴ preferably represents a carbon atom or a nitrogen atom.

In the formula (II), R ¹ represents a substituent, and when the adjacent atom of the nitrogen atom which is a coordinating atom coordinated by the non-covalent electron pair of the compound (A) is a carbon atom, The substituents possessed by the carbon atoms have the same meanings, and the preferred ranges are also the same. Further, from the viewpoint of water absorbability, R ^{1 is} also preferably a hydrophobic substituent, more preferably a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 30 carbon atoms. The aryl group having a carbon number of 6 to 30 is particularly preferably an alkyl group having 1 to 10 carbon atoms. In the case where R ¹ represents an alkyl group, it is preferably a primary alkyl group or a secondary alkyl group, more preferably a primary alkyl group.

In the formula (II), R ^X2 represents a substituent, and the substituent which the ring containing a coordinating atom coordinated by a non-covalent electron pair may have the same meaning, and the preferred range is also the same. R ^{X2 is} preferably any one of A ² to A ⁴ in the formula (II), and further preferably unsubstituted on Y ² .

In the formula (II), n2 represents an integer of 0 to 3, preferably 0 or 1, more preferably 0.

When the compound (A) is represented by the formula (II), the hetero ring containing Y ² in the formula (II) may have a monocyclic structure or a polycyclic structure. Specific examples of the case where the hetero ring containing Y ² has a monocyclic structure include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyran ring, and the like. Specific examples of the case where the hetero ring containing Y ^{2 has} a polycyclic structure include a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring and the like.

When the compound (A) is a pyridine ring-containing compound and has a primary alkyl group or a secondary alkyl group at the 6-position of the pyridine ring, the transmittance in the visible light range can be further improved. In the specification of the present application, the compound 6 (A) is a 6-position of a pyridine ring in the case of a compound containing a pyridine ring, and means that Y ² in the formula (II) represents a nitrogen atom, and A ¹ to A ⁵ represent a carbon atom. The position of R ¹ in place of substitution. The alkyl group in the case where the compound (A) has a primary alkyl group or a secondary alkyl group at the 6-position of the pyridine ring has a carbon number of preferably 1 to 10, more preferably 1 to 6, more preferably 1 to 3. The alkyl group in the case where the compound (A) has a primary alkyl group or a secondary alkyl group at the 6-position of the pyridine ring is also preferably a group containing a combination with -O-. The alkyl group of the compound (A) at the 6-position of the pyridine ring is preferably a primary alkyl group.

In the formula (III), X ³ represents a group containing a coordination site coordinated by an anion, and has the same meaning as X ² in the formula (II), and the preferred range is also the same.

In the formula (III), Y ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom.

In the formula (III), A ⁶ and A ⁹ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ^{6 is} preferably a carbon atom or a nitrogen atom. A ^{9 is} preferably a carbon atom.

In the formula (III), A ⁷ and A ⁸ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ^{7 is} preferably a carbon atom. A ^{8 is} preferably a carbon atom, a nitrogen atom or a sulfur atom.

In the formula (III), R ² represents a substituent and has the same meaning as R ¹ in the formula (II). Further, from the viewpoint of water absorbability, R ^{2 is} preferably a hydrophobic substituent, more preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 30 carbon atoms, and a carbon number of 6 to 30. The aryl group is particularly preferably an alkyl group having 3 to 15 carbon atoms. In the case where R ² represents an alkyl group, a secondary alkyl group or a tertiary alkyl group is preferred.

In the formula (III), R ^X3 represents a substituent, and has the same meaning as R ^X2 in the formula (II), and the preferred range is also the same.

In the formula (III), n3 represents an integer of 0 to 2, preferably 0 or 1, more preferably 0.

Further, in order to improve the visible light transmittance, R ^X1 and R ^{X2 are} preferably a substituent which is not a π-conjugated system but a plurality of bonds.

When the compound (A) is represented by the formula (III), the hetero ring containing Y ³ in the formula (III) may have a single ring structure or a polycyclic structure. Specific examples of the case where the hetero ring containing Y ³ has a 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 case where the hetero ring containing Y ^{3 has} a polycyclic structure include an anthracene ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring and the like.

When the compound (A) is a compound containing a pyrazole ring and has a secondary alkyl group or a tertiary alkyl group at the 5-position of the pyrazole ring, the transmittance in the visible light range can be further improved. In the specification of the present application, the compound 5 (A) is a 5-position of a pyrazole ring in the case of a pyrazole ring-containing compound, and means that Y ³ and A ⁶ in the formula (III) represent a nitrogen atom and A ⁷ ~. A ⁹ represents the substitution position of R ² in the case of a carbon atom. The alkyl group in the case where the compound (A) has a secondary alkyl group or a tertiary alkyl group at the 5-position of the pyrazole ring has a carbon number of preferably 3 to 15, more preferably 3 to 12.

The compound (A) is also preferably represented by the following formula (I). By setting such a configuration, heat resistance can be further improved.

In the formula (I), X ¹ represents a group containing a coordination site coordinated by an anion. Y ¹ represents a nitrogen atom or a phosphorus atom, and together with adjacent carbon atoms constitutes a 4-membered ring to a 7-membered ring. R ^X1 represents a substituent, and n1 represents an integer of 0-6.

In the formula (I), X ¹ represents a group containing a coordination site coordinated by an anion, and has the same meaning as X ² in the formula (II), and the preferred range is also the same.

In the formula (I), Y ¹ represents a nitrogen atom or a phosphorus atom, and together with adjacent carbon atoms constitutes a 4-membered ring to a 7-membered ring. More preferably, Y ¹ in the formula (I) represents a nitrogen atom and constitutes a 5-membered ring or a 6-membered ring together with an adjacent carbon atom. In the formula (I), R ^X1 represents a substituent, and the substituent which may be contained in the ring in the case where the coordination atom coordinated by the non-covalent electron pair is contained in the ring has the same meaning, and the preferred range is also the same.

Further, in order to improve the visible light transmittance, R ^{X1 is} preferably a substituent which is not continuous with a π-conjugated system but a plurality of bonds.

In the formula (I), n1 represents an integer of 0 to 6, preferably 0 to 2, more preferably 0 or 1.

Further, the compound (A) is also preferably represented by the formula (1).

In the formula (1), R ¹ represents a hydrocarbon group. R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. R ¹ and R ² or R ³ may also be bonded to each other to form a ring.

By using the composition of the present invention, the transmittance in the visible light range can be reduced when the cured film is formed, and the near-infrared shielding property can be improved.

In the formula (1), R ¹ represents a hydrocarbon group, preferably an alkyl group or an aryl group.

In the case where R ¹ in the formula (1) represents an alkyl group, the alkyl group may be any of a linear chain, a branched chain or a cyclic chain. The carbon number of the alkyl group is preferably from 1 to 12, more preferably from 1 to 10, and still more preferably from 1 to 5. Specifically, the alkyl group is preferably a methyl group, an ethyl group or a propyl group. When R ¹ in the formula (1) represents an alkyl group, it may have a more substituent. The substituent which the alkyl group may have is exemplified by an alkoxy group, an alkylcarbonyl group, a fluorenyl group, an alkoxycarbonyl group, a halogen atom (for example, a fluorine atom), a heterocyclic group (for example, an oxolane ring, an evil). An alkane ring, a dioxolane ring, a furan ring, a dioxane ring, a pyran ring), a polymerizable group (for example, a vinyl group, a (meth)acryl fluorenyl group), or the like. The alkyl group having a substituent may also have a substituent.

In the case where R ¹ in the formula (1) represents an aryl group, the carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12. The aryl group is preferably a phenyl group. In the case where R ¹ in the formula (1) represents an aryl group, it may have a more substituent. The substituent which the alkyl group may have has the same meaning as the case where R ¹ in the formula (1) represents an alkyl group.

In the formula (1), R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group.

A first aspect of the embodiment of the present invention is a mode in which both R ² and R ³ in the formula (1) are hydrogen atoms, and the second aspect of the embodiment of the present invention is R ² and R in the formula (1). At least one of ³ represents a halogen atom or a monovalent organic group, and is preferred.

When R ² and R ³ in the formula (1) represent a halogen atom, a fluorine atom is preferred.

In the case where R ² and R ³ in the formula (1) represent a monovalent organic group, an alkyl group or an aryl group is preferred, and an alkyl group is more preferred. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The carbon number of the alkyl group is preferably from 1 to 8, more preferably from 1 to 5. Particularly, the alkyl group is preferably a methyl group, an ethyl group or a propyl group. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12. The aryl group is preferably a phenyl group.

In the formula (1), it is also preferred that R ¹ and R ² are bonded to each other to form a 5-membered or 6-membered ring containing an oxygen atom, and R ³ is a hydrogen atom.

The 5-membered or 6-membered ring containing an oxygen atom may be an aromatic ring or a non-aromatic ring, preferably a non-aromatic ring. The atom constituting the 5-membered ring or the 6-membered ring containing an oxygen atom is preferably an oxygen atom and a carbon atom. The number of oxygen atoms in the 5-membered ring or the 6-membered ring containing an oxygen atom is preferably from 1 to 3, more preferably 1 or 2, and still more preferably 1. The number of carbon atoms in the 5-membered or 6-membered ring containing an oxygen atom is preferably from 1 to 5, more preferably 4 or 5. Specific examples of the 5-membered or 6-membered ring containing an oxygen atom include an oxolane ring, an oxane ring, a dioxolane ring, a furan ring, a dioxane ring, and a pyran ring.

The compound represented by the formula (1) is also preferably represented by the formula (2).

Formula (2)

In the formula (2), R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. L represents an n-valent hydrocarbon group or an n-valent group containing a combination of a hydrocarbon group and -O-. n represents an integer from 2 to 6.

In the formula (2), R ¹² and R ¹³ have the same meanings as R ² and R ³ in the formula (1), and preferably all represent a hydrogen atom.

In the formula (2), L represents an n-valent hydrocarbon group or an n-valent group containing a combination of a hydrocarbon group and -O-. The hydrocarbon group may be any of a linear chain, a branched chain or a cyclic chain. When the hydrocarbon group is linear, the carbon number is preferably from 2 to 12, more preferably from 2 to 5. The carbon number in the case where the hydrocarbon group is branched is preferably from 3 to 12, more preferably from 6 to 10. The carbon number in the case where the hydrocarbon group is cyclic is preferably from 3 to 12, more preferably from 6 to 12, and still more preferably 6. When the hydrocarbon group is cyclic, it may be an aromatic ring or a non-aromatic ring, preferably a non-aromatic ring.

In the formula (2), n represents an integer of 2 to 6, preferably an integer of 2 to 4, more preferably 2 or 3, and still more preferably 2.

The compound represented by the formula (1) preferably has a carboxyl group equivalent of from 1 to 3, more preferably from 1 to 2.

Specific examples of the compound (A) include the following compounds and salts of the following compounds (for example, metal salts (alkali metal salts) such as sodium), but are not limited thereto.

<<Single tooth ligand>>

The copper complex used in the present invention may also have an anionic or non-covalent A single tooth ligand that coordinates the electron pair. Examples of the ligand coordinated by an anion include a halide anion, a hydroxide anion, an alkoxide anion, a phenoxide anion, a guanamine anion (a guanamine substituted with a mercapto group or a sulfonyl group), and an anthracene. Imine anion (containing fluorenyl or sulfonyl substituted quinone), aniline anion (containing sulfhydryl or sulfonyl substituted anilide), thiolate anion, bicarbonate anion, carboxylate anion , thiocarboxylate anion, dithiocarboxylate anion, hydrogen sulfate anion, sulfonate anion, dihydrogen phosphate anion, phosphodiester anion, phosphonate monoester anion, phosphonate anion, phosphinate anion , nitrogen-containing heterocyclic anion, nitrate anion, hypochlorite anion, cyanidation Anion, cyanate anion, isocyanate anion, thiocyanate anion, isothiocyanate anion, azide anion, and the like. The monodentate ligands coordinated by non-covalent electron pairs include water, alcohol, phenol, ether, amine, aniline, decylamine, quinone imine, imine, nitrile, isonitrile, thiol, thioether. A carbonyl compound, a thiocarbonyl compound, an anthracene, a heterocyclic ring or a carbonic acid, a carboxylic acid, a sulfuric acid, a sulfonic acid, a phosphoric acid, a phosphonic acid, a phosphinic acid, nitric acid, or an ester thereof. The type and the number of the monodentate ligands can be appropriately selected depending on the compound (A) to be placed in the copper complex. Specific examples of the single-dental ligand include the following, but are not limited to these specific examples.

The copper complex used in the present invention corresponds to the number of coordination sites coordinated by an anion, and may be a cation complex or an anion complex in addition to a neutral complex which is not charged. In this case, a counter ion is present as needed to neutralize the charge of the copper complex.

In the case where the counter ion is a negative counter ion, for example, it may be inorganic anion It can also be an organic anion. Specific examples thereof include hydroxide ions, halogen anions (for example, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted or unsubstituted alkyl carboxylate ions (acetate ions). , trifluoroacetic acid, etc.), substituted or unsubstituted aryl carboxylate ion (benzoate ion, etc.), substituted or unsubstituted alkylsulfonate ion (methanesulfonic acid, trifluoromethanesulfonate ion Etc., substituted or unsubstituted aryl sulfonate ion (eg p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), aryl disulfonate ion (eg 1,3-benzenedisulfonate ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion, etc.), alkylsulfate ion (for example, methylsulfate ion, etc.), sulfate ion, thiocyanate ion, nitrate ion, Perchlorate ion, tetrafluoroborate ion, tetraarylborate ion, hexafluorophosphate ion, picrate ion, guanamine ion (containing decyl or sulfonyl substituted guanamine), methylate ion (comprising a methyl group substituted with a mercapto or sulfonyl group), preferably Halogen anion, substituted or unsubstituted alkyl carboxylate ion, sulfate ion, nitrate ion, tetrafluoroborate ion, tetraarylborate ion, hexafluorophosphate ion, guanamine ion (including warp a sulfonyl-substituted indoleamine), a methide ion (containing a thiol- or sulfonyl-substituted methylate).

In the case where the counter ion is a positive counter ion, for example, an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion such as a tetrabutylammonium ion, a triethylbenzylammonium ion, a pyridinium ion or the like), Helium ions (for example, tetraalkylphosphonium ions such as tetrabutylphosphonium ions, alkyltriphenylphosphonium ions, triethylphenylphosphonium ions, etc.), alkali metal ions or protons.

Further, the counter ion may be a metal complex ion, and particularly the counter ion may be a copper complex, that is, a salt of a cationic copper complex and an anionic copper complex.

<<Bronze ingredients>>

As the copper component used in the present invention, copper or a compound containing copper can be used. As the copper-containing compound, for example, copper oxide or a copper salt can be used. The copper salt is preferably monovalent copper or divalent copper, more preferably divalent copper. The copper salt is more preferably copper acetate, copper chloride, copper formate, copper hydroxide, copper stearate, copper benzoate, copper ethyl acetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate. , copper sulfate, copper carbonate, copper chlorate, copper (meth)acrylate, copper perchlorate, and thus preferably copper acetate, copper chloride, copper sulfate, copper hydroxide, copper benzoate, copper (meth)acrylate .

The amount of the copper component to be reacted with the compound (A) is preferably from 1:0.5 to 1:8, more preferably from 1:0.5 to 1: in terms of the molar ratio (compound (A): copper component). 4.

Further, for example, the reaction conditions when the copper component is reacted with the compound (A) are preferably set to be reacted at 20 ° C to 50 ° C for 0.5 hour or longer.

Specific examples of the copper complex compound include the examples shown in the following tables, but are not limited thereto. Further, the compound (A) in the table represents the compounds described above and below. Furthermore, the monodentate ligands in the table represent the above.

Further, in the copper complex compound used in the present invention, components other than the copper complex of the composition of the present invention (solvent, various additives, etc.) may be further coordinated, and the coordination of the copper complex may also be used. A part of the body is replaced with a component other than the copper complex. For the case of d ⁹ having variable copper (II) complexes of the electronic configuration is general in nature.

[Table 2]

Composition of the present invention relative to the composition of the present invention (also including a solvent) The content of the copper complex (the same as the copper complex obtained by reacting the compound (A) with the copper component) is preferably 1% by mass or more, and more preferably 5% by mass or more. Further, the content of the copper complex in the composition of the present invention is preferably from 1% by mass to 60% by mass, more preferably from 5% by mass to 40% by mass, based on the composition of the present invention (including a solvent). Further preferably, it is 5 mass% to 20 mass%.

The content of the copper complex in the composition of the present invention is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more based on the total solid content of the composition of the present invention. Further, the content of the copper complex in the composition of the present invention is preferably 15% by mass to 60% by mass, more preferably 20% by mass to 50% by mass, based on the total solid content of the composition of the present invention, and further Good is 25% by mass to 45% by mass.

The copper complex in the composition of the present invention relative to the composition of the present invention The content of the other copper complex (near-infrared absorbing material) other than that is preferably from 0% by mass to 20% by mass, more preferably from 0% by mass to 10% by mass, even more preferably from 0% by mass to 5% by mass.

In the near-infrared absorbing material contained in the composition of the present invention, the ratio of the compound obtained by reacting the compound (A) with the copper component is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.

The content of copper in the composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 5% by mass or more based on the total solid content of the composition. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

The total solid content of the near-infrared absorbing composition of the present invention is preferably 1% by mass or more, and more preferably 10% by mass or more based on the composition. Further, the total solid content of the near-infrared absorbing composition of the present invention is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 40% by mass, even more preferably from 10% by mass to 35% by mass based on the composition. quality%.

The composition of the present invention may be used alone or in combination of two or more kinds of the copper complexes used in the present invention. In the case where two or more of the copper complexes used in the present invention are used, the total amount thereof is preferably within the above range.

The near-infrared absorbing composition of the present invention may contain any of the copper complex compounds, and may further blend other near-infrared absorbing compounds, solvents, curable compounds, binder polymers, surfactants, and polymerization initiators as needed. And other ingredients.

<<Other near infrared absorption compounds>>

As the other near-infrared absorbing compound which can be used in the present invention, a copper compound obtained by reacting a compound having a coordination site with a copper component having a low molecular weight (for example, a molecular weight of 1,000 or less) or a polymerization containing a coordination site can be used. A copper compound obtained by the reaction of a body with a copper component. Examples of the coordination site include a coordination site coordinated by an anion such as an acid group or an acid group salt, or a coordination atom coordinated by a non-covalent electron pair.

When the composition of the present invention contains another near-infrared absorbing compound, the content of the other near-infrared absorbing compound is preferably 0.01% by mass or more, more preferably 1%, based on the total solid content of the composition of the present invention. % or more, and further preferably 5% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less. Furthermore, the present invention may also be a composition which does not contain other near-infrared absorbing compounds.

(low molecular type)

As the compound which can be used in the present invention and which is obtained by reacting a compound containing a coordination site with a copper component, a copper complex represented by the following formula (i) can be used.

Cu(L) _n1 . (X) _n2 (i)

In the formula (i), L represents a ligand coordinated to copper, and X does not exist or represents a halogen atom, H ₂ O, NO ₃ , ClO ₄ , SO ₄ , CN, SCN, BF ₄ , PF ₆ , BPh ₄ (Ph represents phenyl) or alcohol. N1 and n2 each independently represent an integer of 1 to 4.

Ligand L has C, N, O, S as atoms that can be coordinated to copper. The substituent is more preferably a group having an isolated electron pair having N or O, S or the like. The group which can be coordinated is not limited to one type in the molecule, and may contain two or more types, and may be dissociated or non-dissociated. In the case of non-dissociation, X does not exist.

The copper complex is a copper compound in which the ligand is coordinated to the copper of the central metal, and the copper is usually divalent copper. For example, the copper complex can be obtained by mixing a compound which is a ligand or a salt thereof with a copper component, and performing a reaction or the like.

The compound to be a ligand or a salt thereof is not particularly limited, and examples thereof include a compound containing at least one selected from the group (AN), and preferably an organic acid compound (for example, a sulfonic acid compound) A carboxylic acid compound, a phosphoric acid compound) or a salt thereof.

The compound to be a ligand or a salt thereof can be represented by the following formula (ii).

(In the formula (ii), R ¹ represents an n-valent organic group, X ¹ represents an acid group, and n3 represents an integer of 1 to 6)

In the formula (ii), the n-valent organic group is preferably a hydrocarbon group or an oxygen alkyl group, more preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom (preferably a fluorine atom), a (meth) acrylonitrile group, and a group having an unsaturated double bond. Further, examples of the substituent include an alkyl group, a polymerizable group (e.g., a vinyl group, an epoxy group, an oxetanyl group, etc.), a sulfonic acid group, a carboxylic acid group, an acid group containing a phosphorus atom, and a carboxylate. a group (e.g., -CO ₂ CH ₃ ), a hydroxyl group, an alkoxy group (e.g., a methoxy group), an amine group, an amine carbaryl group, an amine methyl methoxy group, a halogenated alkyl group (e.g., a fluoroalkyl group, a chloroalkyl group), etc. . When the hydrocarbon group has a substituent, the substituent may be further substituted, and examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.

In the case where the hydrocarbon group is monovalent, it is preferably an alkyl group or an aryl group, more preferably an aryl group. Further, when the hydrocarbon group is monovalent, it may be an alkenyl group. In the case where the hydrocarbon group is divalent, it is preferably an alkyl group, an aryl group, an alkyl group, and more preferably an aryl group. Further, when the hydrocarbon group is trivalent or higher, a group corresponding to the monovalent hydrocarbon group or the divalent hydrocarbon group is preferred.

The carbon number of the alkyl group and the alkylene group is preferably from 1 to 20, more preferably from 1 to 10. The alkyl group and the alkylene group may be any of a linear chain, a branched chain or a cyclic chain. The carbon number of the linear alkyl group and the alkyl group is preferably from 1 to 20, more preferably from 1 to 12, and still more preferably from 1 to 8. The carbon number of the branched alkyl group and the 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 the alkylene group may be either a single ring or a polycyclic ring. The carbon number of 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 is preferably from 2 to 10, more preferably from 2 to 8, more preferably from 2 to 4.

The carbon number of the aryl group and the aryl group is preferably from 6 to 18, more preferably from 6 to 14, more preferably from 6 to 12, and particularly preferably from 6 to 10.

In the general formula (ii), X ¹ may, for example, be an acid group (phosphoric acid diester group, phosphonic acid monoester group or phosphinic acid group) containing a phosphorus atom, a sulfo group, a carboxyl group or a hydroxyl group. X ¹ may be used alone or in combination of two or more, preferably two or more, and preferably has a sulfo group and a carboxyl group.

In the formula (ii), n3 is preferably from 1 to 3, more preferably 2 or 3, and still more preferably 3.

The molecular weight of the compound to be ligand or a salt thereof (compound containing an acid group or a salt thereof) is preferably 1,000 or less, preferably 80 to 750, more preferably 80 to 600.

As an example of a copper compound obtained by a reaction of a low molecular weight compound containing a acid group or a salt thereof with a copper component, a compound having two monoanionic coordination sites or a compound having a salt thereof may be reacted with a copper component. Adult. Here, the monoanionic coordination site is a site that is coordinated to a copper atom via a functional group having a negative charge when coordinated to a copper atom. The structure having such a monoanionic coordination site may, for example, be a structure described by X ¹ in the above formula (i).

The structure having a monoanionic coordination site may, for example, be a structure containing at least one selected from the group (AN). For example, a structure having a monoanionic coordination site is coordinated to a copper atom as shown below, thereby forming a copper complex. For example, a carboxyl-copper complex, a phosphodiester-copper complex, a phosphonate mono-copper complex, a phosphinic acid-copper complex, a sulfo-copper complex, a hydroxyl group are formed. Copper complex.

The compound having two monoanionic coordination sites is exemplified by the compound represented by the following formula (10).

X ¹ -L ¹ -X ² Formula (10)

(In the formula (10), X ¹ and X ² each independently represent the monoanionic coordination site, and L ¹ represents an alkylene group, an alkenyl group, an extended aryl group, a heterocyclic group, -O-, - S-, -NR ^N1 -, -CO-, -CS-, -SO ₂ - or a divalent linking group comprising the combination of the above. Here, R ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. )

In the above formula (10), L ¹ represents an alkylene group, an alkenyl group, an extended aryl group, a heterocyclic group, -O-, -S-, -NR ^N1 -, -CO-, -CS-, - SO ₂ - or a divalent linking group comprising the combination. Here, NR ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

The alkylene group may, for example, be a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon alkyl group having 3 to 20 carbon atoms, and the like. .

The alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. Further, the aryl group is a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 8, more preferably a single ring or a condensed ring having a condensation number of 2 to 4. Specific examples thereof include a phenylene group, a naphthyl group, and the like.

The heterocyclic group may be a group having a hetero atom or an aromatic heterocyclic group in the alicyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Further, the heterocyclic group is a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 4. Specifically, it can be exemplified by at least one containing nitrogen, oxygen and sulfur atoms. a heterocyclic aryl group derived from a monocyclic or polycyclic aromatic ring. Examples of the heterocyclic ring include an oxolane ring, an oxane ring, a thiolane ring, an oxazole ring, a thiophene ring, a thianthrene ring, a furan ring, and a pyridyl group. Anthracene, isobenzofuran ring, chromene ring, xanthene ring, phenoxazine ring, pyrrole ring, pyrazole ring, isothiazole ring, isoxazole ring, pyridyl Azine ring, pyrimidine ring, pyridazine ring, pyridazine ring, isooxazine ring, anthracene ring, indazole ring, anthracene ring, quinazoline ring, isoquinoline ring, phthalazine ring, naphthyridine (naphthyridine) ring, quinazoline ring, cinnoline ring, pteridine ring, indazole ring, carboline ring, phenanthrene ring, acridine ring, perimidine Ring, phenanthroline ring, pyridazine ring, phenarsazine ring, phenoxazine ring, furazan ring, and the like.

In -NR ^N1 -, R ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

The alkyl group of R ^N1 may be in the form of a chain, a branch or a ring. The linear or branched alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. The cyclic alkyl group may be either a single ring or a polycyclic ring. The cyclic alkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, more preferably a substituted or unsubstituted cycloalkyl group having 4 to 14 carbon atoms.

The aryl group of R ^N1 is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and thus preferably unsubstituted. An aryl group having 6 to 14 carbon atoms. Specifically, a phenyl group, a naphthyl group, etc. are illustrated.

The aralkyl group of R ^N1 is preferably a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, more preferably an unsubstituted aralkyl group having 7 to 15 carbon atoms.

The substituent which the group may have is exemplified by a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group, Carboxylic acid ester group, halogenated alkyl group, alkoxy group, methacryloxy group, acryloxy group, ether group, sulfonyl group, thioether group, decylamino group, fluorenyl group, hydroxyl group, carboxyl group, aralkyl group , -Si-(OR ^N22 ) ₃ and the like.

Further, the substituent which the group may have may be a group containing at least one of the substituents in combination with at least one of -O-, -CO-, -COO-, and -COOR'. Here, R' is preferably a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms.

Examples of the polymerizable group include a polymerizable group containing a carbon-carbon double bond (preferably a vinyl group, a (meth) propylene fluorenyl group), a (meth) acryl fluorenyl group, an epoxy group, or an aziridine group. (aziridinyl) and so on.

The alkyl group may be any of a chain, a branch, and a ring. The linear or branched alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The cyclic alkyl group may be either a single ring or a polycyclic ring. The cyclic alkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 10 carbon atoms.

The halogenated alkyl group is preferably an alkyl group substituted with a fluorine atom. In particular, an alkyl group having 2 or more carbon atoms and having 1 to 10 carbon atoms is preferable, and may be any of a linear chain, a branched chain, and a cyclic group, and is preferably a linear or branched chain group. group. The carbon number of the alkyl group substituted with a fluorine atom is more preferably from 1 to 10, still more preferably from 1 to 5, still more preferably from 1 to 3. The alkyl group substituted with a fluorine atom preferably has a terminal structure of (-CF ₃ ). The alkyl group substituted with a fluorine atom preferably has a substitution ratio of a fluorine atom of 50% to 100%, more preferably 80% to 100%. Here, the substitution ratio of a fluorine atom means the ratio (%) of the hydrogen atom substituted by a fluorine atom in the alkyl group substituted by a fluorine atom.

Particularly, the halogenated alkyl group is more preferably a perfluoroalkyl group, and more preferably a perfluoroalkyl group having 1 to 10 carbon atoms.

In -Si-(OR ^N22 ) ₃ , R ^N22 is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 1 to 3.

Specifically, in the case of the above formula (10), when L ¹ is a group containing a combination of an exoaryl group and -O-, the substituent which the exoaryl group may have is preferably an alkyl group.

In the specific example of the structure represented by L ¹ in the above formula (10), the following structure is preferred.

In the above formula (10), X ¹ and X ² represent the monoanionic coordination site, and more specifically, a carboxyl group, a phosphodiester group, a phosphonic acid monoester group, a phosphinic acid group, a sulfo group, and a hydroxyl group Wait.

In the above formula (10), X ¹ and X ² may have the same monoanionic coordination sites as each other, or may have mutually different monoanionic coordination sites.

In the above formula (10), X ¹ and X ^{2 are} preferably a structure represented by the following formula (12), formula (13) or formula (13A).

(In the formula (12), R ¹ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. A ¹ and A ² each independently represent an oxygen atom, a sulfur atom or a single bond. Formula (12), general formula (13) and (13A), * indicates a connection portion with the L ¹ )

In the general formula (12), R ¹ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group.

The alkyl group may be any of a chain, a branch, and a ring. The linear or branched alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, more preferably A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. The cyclic alkyl group may be either a single ring or a polycyclic ring. The cyclic alkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, more preferably a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms, particularly preferably Substituted cycloalkyl having 4 to 8 carbon atoms.

The alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. Specifically, a phenyl group, a naphthyl group, etc. are illustrated.

The aralkyl group is preferably a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, more preferably a substituted or unsubstituted aralkyl group having 7 to 16 carbon atoms.

R ¹ in the above formula (12) may have the same substituent as the substituent which L ¹ in the formula (10) may have, and is preferably an alkyl group, an aryl group, an ether group, or Si-(OR ^N22 ) ₃ and the like.

In the above formula (12), A ¹ and A ² each independently represent an oxygen atom, a sulfur atom or a single bond. In particular, it further improved heat resistance of the composition of the present invention is concerned, A ¹ and A ² is preferably a single bond.

In the specific example of the structure represented by R ¹ in the above formula (12), the following structure is preferred.

(polymer type)

The copper compound obtained by the reaction of the polymer containing the coordination site and the copper component is, for example, a polymer type copper compound containing a polymer and a copper ion, and the polymer has a salt selected from an acid group or an acid group. One or more of the coordination sites in which the anion of the same is coordinated and the coordination atom coordinated by the non-covalent electron pair. Preferably, it is a polymer type copper compound containing a polymer-based ion group as a salt of an acid group or an acid group and a copper ion, and more preferably, the acid-based ion site in the polymer is used as a ligand. A polymeric copper compound. The copper compound of the polymer type usually has a coordination site such as an acid group ion site in a side chain of the polymer, and a coordination site such as an acid group ion site is bonded to copper (for example, a coordination bond is formed), and copper is used as a starting point. A crosslinked structure is formed between the side chains. The polymer type copper complex compound may be a copper complex of a polymer having a carbon-carbon bond in the main chain, a copper complex of a polymer having a carbon-carbon bond in the main chain, and a fluorine atom-containing compound. A copper complex or a copper complex of a polymer having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain (hereinafter referred to as an aromatic group-containing polymer).

The copper component is preferably a compound containing divalent copper. The copper content in the copper component is preferably from 2% by mass to 40% by mass, more preferably from 5% by mass to 40% by mass. The copper component may be used alone or in combination of two or more. As the copper-containing compound, for example, copper oxide or a copper salt can be used. The copper salt is more preferably divalent copper. Copper salts are particularly preferably copper hydroxide, copper acetate and copper sulfate.

The acid group is not particularly limited as long as it can react with the copper component, and it is preferred to form a coordinate bond with the copper component. Specific examples thereof include an acid group having an acid dissociation constant (pKa) of 12 or less, preferably a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, and an anthracene group. An imidate group or the like. The polymer may have only one type of acid group or two or more types.

The atom or the atomic group constituting the salt of the acid group used in the present invention may be an atomic group such as a metal atom such as sodium (particularly an alkali metal atom) or tetrabutylammonium. Further, in the polymer containing an acid group or a salt thereof, the acid group or a salt thereof may be contained in at least one of the main chain and the side chain, and is preferably contained in at least one side chain.

The polymer containing an acid group or a salt thereof is preferably a polymer containing a carboxylic acid group or a salt thereof and/or a sulfonic acid group or a salt thereof, more preferably a polymer containing a sulfonic acid group or a salt thereof.

The coordination site to which the anion is coordinated can be exemplified by the coordination site described in the above compound (A).

<<<The first polymer containing an acid group or a salt thereof>>

A preferred example of the polymer containing an acid group or a salt thereof has a structure in which a main chain has a carbon-carbon bond, and preferably contains a structural unit represented by the following formula (A1-1).

(In the formula (A1-1), R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a single bond or a divalent linking group, and M ¹ represents a hydrogen atom or an atom or a group which forms a salt with a sulfonic acid group)

In the formula (A1-1), R ^{1 is} preferably a hydrogen atom.

In the case of the formula (A1-1), when L ¹ represents a divalent linking group, the divalent linking group is not particularly limited, and examples thereof include a divalent hydrocarbon group, a heteroaryl group, and -O-, -S. -, -CO-, -COO-, -OCO-, -SO ₂ -, -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group comprising such a combination.

The divalent hydrocarbon group may, for example, be a linear or branched or cyclic alkyl group or an extended aryl group. The hydrocarbon group may also have a substituent, preferably unsubstituted.

The carbon number of the linear alkyl group is preferably from 1 to 30, more preferably from 1 to 15, more preferably from 1 to 6. Further, the carbon number of the branched alkyl group is preferably from 3 to 30, more preferably from 3 to 15, more preferably from 3 to 6.

The cyclic alkyl group may be either a single ring or a polycyclic ring. The carbon number of the cyclic alkyl group is preferably from 3 to 20, more preferably from 4 to 10, and still more preferably from 6 to 10.

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

The heteroaryl group is not particularly limited, and is preferably a 5-membered ring or a 6-membered ring. Further, the heteroaryl group may be a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 8, more preferably a single ring or a condensed ring having a condensation number of 2 to 4.

In the formula (A1-1), an atom or a group of a salt constituting a salt of a sulfonic acid group represented by M ¹ and the atom or a group of the salt constituting the acid group have the same meaning, preferably a hydrogen atom or an alkali metal atom. .

Other constituent units other than the constituent unit represented by the formula (A1-1) can be referred to The description of the copolymerization component disclosed in paragraphs 0068 to 0015 of the specification of the corresponding Japanese Patent Application Laid-Open No. 2011/0124824, which is incorporated herein by reference. This content is incorporated into the specification of the present application.

The other constituent unit which is preferable is a structural unit represented by the following formula (A1-2).

In the formula (A1-2), R ³ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

Y ² represents a single bond or a divalent linking group, and the divalent linking group has the same meaning as the divalent linking group of the above formula (A1-1). In particular, Y ^{2 is} preferably -COO-, -CO-, -NH-, a linear or branched alkyl group, or a group containing the combination, or a single bond.

In the formula (A1-2), X ² represents -PO ₃ H, -PO ₃ H ₂ , -OH or -COOH, preferably -COOH.

When the polymer containing the constituent unit represented by the formula (A1-1) contains another constituent unit (preferably, the constituent unit represented by the formula (A1-2)), the formula (A1) 1) Preferably, the constituent unit represented by the formula (A1-2) is 95:5 to 20:80, more preferably 90:10 to 40:60.

<<<The second polymer containing an acid group or a salt thereof>>

The copper compound which can be used in the present invention can also be used: a polymer having an acid group or a salt thereof and having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain (hereinafter referred to as an aromatic group-containing polymer) ), the copper type of the polymer type obtained by the reaction with the copper component Things. The aromatic group-containing polymer may have at least one of an aromatic hydrocarbon group and an aromatic heterocyclic group in the main chain, and may have two or more types. The acid group or a salt thereof and the copper component are the same as those of the copper compound obtained by the reaction of the polymer containing the acid group or the salt thereof with the copper component, and the preferred range is also the same.

The aromatic hydrocarbon group is preferably, for example, an aryl group. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and more preferably from 6 to 12. More preferably, it is a phenyl group, a naphthyl group or a biphenyl group. The aromatic hydrocarbon group may be monocyclic or polycyclic, preferably monocyclic.

As the aromatic heterocyclic group, for example, an aromatic heterocyclic group having 2 to 30 carbon atoms can be used. The aromatic heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Further, the aromatic heterocyclic group is a monocyclic ring or a condensed ring, and examples thereof include a monocyclic ring or a condensed ring having a condensation number of 2 to 8. The hetero atom contained in the hetero ring may be a nitrogen, an oxygen or a sulfur atom, preferably nitrogen or oxygen.

When the aromatic hydrocarbon group and/or the aromatic heterocyclic group has a substituent T, the substituent T may, for example, be an alkyl group or a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond) or a halogen. Atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxylate group, a halogenated alkyl group, an alkoxy group, a methacryloxy group, an acryloxy group, an ether group, a sulfonyl group, a thioether group Amidino group, mercapto group, hydroxyl group, carboxyl group, aralkyl group or the like is preferably an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms).

In particular, the aromatic group-containing polymer is preferably at least one polymer selected from the group consisting of a polyether oxime polymer, a polyfluorene polymer, a polyether ketone polymer, and a polyphenylene ether polymer. Polyimide-based polymer, polybenzimidazole-based polymer, polyphenyl-based polymer, phenol resin-based polymer, polycarbonate-based polymer, polyamine-based polymer, and polyester-based polymer. Examples of the respective polymers are shown below.

Polyether oxime polymer: a polymer having a main chain structure represented by (-O-Ph-SO ₂ -Ph-) (Ph represents a phenyl group, the same applies hereinafter)

Polyfluorene polymer: a polymer having a main chain structure represented by (-O-Ph-Ph-O-Ph-SO ₂ -Ph-)

Polyether ketone polymer: a polymer having a main chain structure represented by (-O-Ph-O-Ph-C(=O)-Ph-)

Polyphenylene ether polymer: a polymer having a main chain structure represented by (-Ph-O-, -Ph-S-)

Polyphenylene polymer: a polymer having a main chain structure represented by (-Ph-)

Phenolic resin-based polymer: a polymer having a main chain structure represented by (-Ph(OH)-CH ₂ -)

Polycarbonate-based polymer: a polymer having a main chain structure represented by (-Ph-O-C(=O)-O-)

The polyamine-based polymer is, for example, a polymer having a main chain structure represented by (-Ph-C(=O)-NH-)

The polyester-based polymer is, for example, a polymer having a main chain structure represented by (-Ph-C(=O)O-)

For example, the polyether oxime polymer, the polyfluorene polymer, and the polyether ketone polymer can be referred to, for example, in paragraph 0022 of JP-A-2006-310068 and paragraph 0028 of JP-A-2008-27890. The main chain structure, which is incorporated into the specification of the present application.

The polyimine-based polymer can be referred to Japanese Patent Laid-Open Publication No. 2002-367627 The main chain structure described in paragraphs 0047 to 0058 of the paragraphs and paragraphs 0018 to 0019 of JP-A-2004-35891, the contents of which are incorporated herein by reference.

A preferred example of the aromatic group-containing polymer preferably contains a structural unit represented by the following formula (A1-3).

(In the formula (A1-3), Ar ¹ represents an aromatic hydrocarbon group and/or an aromatic heterocyclic group, Y ¹ represents a single bond or a divalent linking group, and X ¹ represents an acid group or a salt thereof)

In the case of the formula (A1-3), when Ar ¹ represents an aromatic hydrocarbon group, the same meaning as the above-mentioned aromatic hydrocarbon group is used, and the preferred range is also the same. When Ar ¹ represents an aromatic heterocyclic group, it has the same meaning as the above aromatic heterocyclic group, and the preferred range is also the same.

Ar ¹ may have a substituent in addition to -Y ¹ -X ¹ in the formula (A1-3). In the case where Ar ¹ has a substituent, the substituent has the same meaning as the substituent T, and the preferred range is also the same.

In the formula (A1-3), Y ^{1 is} preferably a single bond. In the case where Y ¹ represents a divalent linking group, examples of the divalent linking group include a hydrocarbon group, an aromatic heterocyclic group, -O-, -S-, -SO ₂ -, -CO-, -C(=O). -O-, -OC(=O)-O-, -SO ₂ -, -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), -C(R ^Y1 )(R ^Y2 )- Or a group comprising such combinations. Here, R ^Y1 and R ^Y2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group.

Examples of the hydrocarbon group include a linear alkyl group, a branched chain or a cyclic alkyl group or an extended aryl group. The carbon number of the linear alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 6. The carbon number of the branched alkyl group is preferably from 3 to 20, more preferably from 3 to 10, and still more preferably from 3 to 6. The cyclic alkyl group may be either a single ring or a polycyclic ring. The carbon number of the cyclic alkyl group is preferably from 3 to 20, more preferably from 4 to 10, and still more preferably from 6 to 10. In the linear, branched or cyclic alkyl groups, the hydrogen atom in the alkyl group may be substituted by a fluorine atom.

The aryl group has the same meaning as the case where the divalent linking group of the formula (A1-1) is an exoaryl group.

The aromatic heterocyclic group is not particularly limited, and is preferably a 5-membered ring or a 6-membered ring. Further, the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 4.

In the formula (A1-3), the acid group represented by X ¹ or a salt thereof has the same meaning as the acid group or a salt thereof, and the preferred range is also the same.

The weight average molecular weight of the polymer containing the constituent unit represented by the formula (A1-1), the formula (A1-2) or the formula (A1-3) is preferably 1,000 or more, more preferably from 1,000 to 10,000,000, and further preferably 3000~1 million, especially 4,000~400,000.

Containing the formula (A1-1), formula (A1-2) or formula (A1-3) Specific examples of the polymer of the constituent unit include the following compounds and salts of the following compounds, but are not limited thereto.

(inorganic particles)

The composition of the present invention may contain inorganic fine particles in order to obtain a target near-infrared shielding property. The inorganic fine particles may be used singly or in combination of two or more.

The inorganic fine particles are particles which mainly function to block (absorb) infrared rays. In terms of more excellent infrared ray opacity, the inorganic fine particles are preferably at least one selected from the group consisting of metal oxide particles and metal particles.

Examples of the inorganic fine particles include indium tin oxide (ITO) particles, antimony tin Oxide (ATO) particles, and aluminum-doped zinc oxide (Al-doped ZnO) particles. Metal oxide particles such as fluorine-doped tin dioxide (F-doped SnO ₂ ) particles or erbium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, or silver (Ag) particles, gold (Au) particles, copper (Cu) Metal particles such as particles or nickel (Ni) particles. Further, in order to have both infrared ray blocking property and photo lithography, it is preferable that the transmittance at the exposure wavelength (365 nm to 405 nm) is high, and indium tin oxide (ITO) particles or strontium tin oxide (ATO) particles are preferable.

The shape of the inorganic fine particles is not particularly limited, and may of course be spherical or non-spherical, and may be in the form of a sheet, a wire or a tube.

In addition, a tungsten oxide-based compound can be used as the inorganic fine particles, and specifically, a tungsten oxide-based compound represented by the following general formula (composition formula) (I) is more preferable.

M _x W _y O _z ...(I)

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

0.001≦x/y≦1.1

2.2≦z/y≦3.0

Examples of the metal of M include alkali metal, alkaline earth metal, magnesium (Mg), zirconium (Zr), chromium (Cr), manganese (Mn), iron (Fe), ruthenium (Ru), cobalt (Co), and rhodium (Rh). ),iridium

(Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), aluminum (Al), gallium (Ga), indium (In), tantalum (Tl), tin (Sn), lead (Pb), titanium (Ti), niobium (Nb), vanadium (V), molybdenum (Mo), tantalum (Ta), tantalum (Re), beryllium (Be), hafnium (Hf), osmium (Os), bismuth (Bi), preferably an alkali metal, and preferably Rb or Cs, more preferably Cs. The metal of M may be one type or two or more types.

When x/y is 0.001 or more, infrared rays can be sufficiently shielded, and when x/y is 1.1 or less, it is possible to more reliably prevent the formation of an impurity phase in the tungsten oxide-based compound.

By having z/y of 2.2 or more, the chemical stability of the material can be further improved, and by z/y being 3.0 or less, infrared rays can be sufficiently shielded.

The metal oxide is preferably tungsten oxide.

Specific examples of the tungsten oxide-based compound represented by the above formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 ,} etc., preferably Cs _0.33 WO ₃ or Rb _0.33. WO _{3 is more} preferably Cs _0.33 WO ₃ .

The metal oxide is preferably a microparticle. The average particle diameter of the metal oxide is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. Since the average particle diameter is in such a range, the metal oxide is less likely to block visible light by light scattering, so that light transmittance in the visible light range can be made more reliable. In view of avoiding photo-acidity, the average particle diameter is preferably as small as possible, but the average particle diameter of the metal oxide is usually 1 nm or more for reasons such as ease of handling during production.

The tungsten oxide-based compound can be, for example, a tungsten fine particle such as YMF-02, YMF-02A, YMS-01A-2, or YMF-10A-1 manufactured by Sumitomo Metal Mining Co., Ltd. Obtained from the dispersion.

The content of the metal oxide is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, even more preferably from 1% by mass to 10% by mass based on the total solid content of the metal oxide-containing composition. quality%.

The composition of the present invention can also be used in Japanese Patent Laid-Open No. 2013-195480 The phthalocyanine compound described in paragraphs 0013 to 0029 of the gazette is used as another near-infrared absorbing compound, and the content thereof is incorporated into the specification of the present application.

<solvent>

The composition of the present invention may also contain a solvent.

The solvent to be used in the present invention is not particularly limited as long as the components of the composition of the present invention can be uniformly dissolved or dispersed, and can be appropriately selected according to the purpose. For example, water or an organic solvent can be used. Since the compound (A) is used as the composition of the present invention, when an organic solvent is used as the solvent, the influence on the spectral characteristics can be reduced.

The solvent is, for example, preferably exemplified by alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, and dimethylformamide, dimethylacetamide, dimethyl hydrazine, and cyclobutyl hydrazine. Wait. These may be used alone or in combination of two or more. In this case, a mixed solution composed of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve is particularly preferred. Acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Kikabi alcohol acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

Specific examples of the alcohol, the aromatic hydrocarbon, and the halogenated hydrocarbon include Japanese Patent Laid-Open The contents described in paragraph 0136 of the Japanese Patent Publication No. 2012-194534, the contents of which are incorporated herein by reference. Further, specific examples of the esters, the ketones, and the ethers can be described in paragraph 0497 of the Japanese Patent Application Laid-Open No. 2012-208494 (the corresponding Japanese Patent Application Publication No. 2012/0235099 [0609]). Listed: n-amyl acetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate Wait.

The content of the solvent is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and still more preferably 40% by mass or more based on the composition of the present invention. Further, the content of the solvent is preferably contained in a proportion of 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass based on the composition of the present invention, and particularly preferably 30% by mass or more. 70% by mass of solvent. The solvent may be one type or two or more types. In the case of two or more types, the total amount is in the above range.

<hardening compound>

The composition of the present invention may also contain a curable compound. The curable compound may be a polymerizable compound or a non-polymerizable compound such as a binder. Further, the curable compound may be a thermosetting compound or a photocurable compound, and in the case of a thermosetting composition, it is preferred because the reaction rate is high.

<Compound having a polymerizable group>

The curable composition preferably contains a compound having a polymerizable group (hereinafter sometimes referred to as "polymerizable compound"). Such a compound group is widely known in the industrial field, and the present invention can be used without any particular limitation. These compounds can be, for example It is any of chemical forms such as monomers, oligomers, prepolymers, and polymers.

The polymerizable compound may be monofunctional or polyfunctional, preferably polyfunctional. By containing a polyfunctional compound, near-infrared shielding properties and heat resistance can be further improved. The number of functional groups is not particularly limited, but is preferably a bifunctional to an octafunctional, more preferably a trifunctional to a hexafunctional.

In the case where the copper complex is contained in the composition of the present invention and the curable compound is contained, preferred examples of the curable compound include the following compounds. The present invention is not limited to the following aspects. Examples of the curable compound include a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate (preferably a trifunctional to hexafunctional (meth) acrylate), and a polybasic acid-modified acrylic oligo. Polymer, epoxy resin, or polyfunctional epoxy resin.

<<Polymerizable monomer and polymerizable oligomer>>

The first preferred embodiment of the composition of the present invention contains a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (hereinafter, polymerizability is sometimes used) The monomer and the polymerizable oligomer are collectively referred to as a "polymerizable monomer or the like" as a polymerizable compound.

Examples of the polymerizable monomer and the like include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof, guanamines, and preferably no. An ester of a saturated carboxylic acid and an aliphatic polyol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, it is also preferred to use the following reactants: an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition of a monofunctional or polyfunctional isocyanate or epoxy group. reaction Or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid, and the like. Further, the following reactants are also preferred: an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. The reactants further include a substituted carboxylic acid ester of a detachable substituent such as a halogen group or a tosyloxy group, or a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as another example, a compound group of a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used instead of the unsaturated carboxylic acid.

For the specific compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 is preferably used in the present invention.

In addition, the polymerizable monomer or the like is also preferably one having at least one An ethylenically unsaturated group-containing compound having an added vinyl group and a boiling point of 100 ° C or higher at normal pressure, and preferably a monofunctional (meth) acrylate or a difunctional (meth) acrylate. A trifunctional or higher (meth) acrylate (for example, a trifunctional-6 functional (meth) acrylate).

Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(a) Acrylate, dipentaerythritol penta (meth) acrylate, dipenta Tetraol hexa(meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene methoxy propyl) ether, isomeric cyanuric acid tris(propylene oxy oxyethyl) An ester, a polyfunctional alcohol such as glycerin or trimethylolethane, which is added with ethylene oxide or propylene oxide and then (meth)acrylated; Japanese Patent Publication No. Sho 48-41708, Japanese Patent (Meth)acrylic acid urethanes as described in each of the Japanese Patent Laid-Open Publication No. SHO-51-37193, Japanese Patent Laid-Open Publication No. SHO-48-64183, Japanese Patent Publication No. Sho 49-43191 A polyester acrylate described in each of Japanese Patent Publication No. Sho 52-30490, a polyfunctional acrylate or methyl group such as an epoxy acrylate which is a reaction product of an epoxy polymer and (meth)acrylic acid. Acrylate and mixtures of these.

Among them, the polymerizable compound is preferably an ethoxylated modified pentaerythritol tetraacrylate (commercially available as NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (commercially available) KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercial product is Kaya) KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and the structure of these (meth)acryloyl group-separated ethylene glycol residues and propylene glycol residues. In addition, these oligomer types can also be used.

Examples of the polymerizable compound include a polyfunctional (meth) acrylate having a cyclic ether group such as glycidyl (meth)acrylate and the like. A compound of an ethylenically unsaturated group is obtained by reacting with a polyfunctional carboxylic acid.

In addition, other preferred polymerizable monomers and the like may be used in an ethylene polymerization having an anthracene ring and having a difunctional or higher content as described in JP-A-2010-160418, JP-A-2010-129825, and Japanese Patent No. 4,364,216. A compound based on a cardo polymer.

Further, a compound having a boiling point of 100 ° C or higher and having at least one ethylenically unsaturated group capable of undergoing addition polymerization under normal pressure is also preferably a paragraph number [0254] of JP-A-2008-292970. The compound described in paragraph No. [0257].

In addition, in the case of adding an ethylene oxide or a propylene oxide to the polyfunctional alcohol described in the general formula (1) and the general formula (2) together with the specific examples, Japanese Patent Publication No. Hei 10-62986 A compound obtained by esterifying (meth) acrylate can also be used as a polymerizable monomer.

The polymerizable monomer used in the present invention is more preferably a polymerizable monomer represented by the following formula (MO-1) to formula (MO-6).

(wherein, n is 0~14, respectively, and m is 1~8. A plurality of R, T, and Z in one molecule may be the same or different. When T is an oxygen-extended alkyl group, The end of the carbon atom side is bonded to R. At least one of R is a polymerizable group)

n is preferably 0 to 5, more preferably 1 to 3.

m is preferably from 1 to 5, more preferably from 1 to 3.

R is preferably the following four structures.

R is preferably the following two of the four structures.

Specific examples of the radical polymerizable monomer represented by the above formula (MO-1) to (MO-6) may be given in paragraph number 0248 to paragraph number of JP-A-2007-269779. The compound described in 0251 is preferably used in the present invention.

Among them, polymerizable monomers and the like can be cited as Japanese Patent Laid-Open No. 2012-208494 Polymerizable monomers and the like described in Paragraph 0477 (corresponding to U.S. Patent Application Publication No. 2012/0235099, the entire disclosure of which is incorporated herein by reference). Further, Ethylene Oxide (EO) modified (meth) acrylate (commercially available as M-460; manufactured by Toago Seisakusho Co., Ltd.) is preferred. Also preferred is pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA). These oligomer types can also be used.

For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) or the like can be mentioned.

The polymerizable monomer or the like may also be a polyfunctional monomer, and may also have a carboxyl group or a sulfonate. An acid group such as an acid group or a phosphoric acid group. Therefore, the ethylene compound may be used as it is in the case of a mixture as described above, and may be used as it is, and if necessary, a non-aromatic carboxylic anhydride may be reacted with a hydroxyl group of the ethylenic compound to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated six. Hydrogen phthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an aliphatic polyhydroxy compound and The ester of an unsaturated carboxylic acid is preferably a polyfunctional monomer having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and particularly preferably an aliphatic polyhydroxy group in the ester thereof. The compound is pentaerythritol and/or dipentaerythritol. For example, M-305, M-510, M-520, etc. of the Aronix series which are polybasic acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned.

The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, and more preferably from 5 mg-KOH/g to 30 mg-KOH/g. In the case where a polyfunctional monomer having two or more acid groups is used in combination, or a combination of a polyfunctional monomer having no acid group, it is preferred that the acid value of the entire polyfunctional monomer is within the range Method of preparation.

Further, a polyfunctional monolith having a modified structure of caprolactone is preferably used as a polymerizable monomer or the like.

The polyfunctional monomer having a modified structure of caprolactone is not particularly limited as long as it has a caprolactone-modified structure in its molecule. For example, a polyfunctional monolith having a modified structure of caprolactone may be exemplified by ε-caprolactone-modified polyfunctional (meth) acrylate, which ε- Caprolactone modified polyfunctional (meth) acrylate by trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, two Polyols such as pentaerythritol, tripentaerythritol, glycerine, diglycerol, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a polyfunctional mono-weight having a caprolactone modified structure represented by the following formula (20) is preferred.

(In the formula, all of the six R groups are groups represented by the following formula (21), or one to five of the six R groups are groups represented by the following formula (21), and the rest are the following formulas; (22) the group indicated)

(wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond)

(wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond)

Such a polyfunctional monolith having a modified structure of caprolactone is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (the formula ( 20), where m = 1 in the formula (22), the number of groups represented by the formula (21) = 2, and all compounds in which R ¹ is a hydrogen atom), DPCA-30 (the formula (20) to the formula (20) 22) m = 1, the number of groups represented by the formula (21) = 3, a compound in which all R ¹ are a hydrogen atom), DPCA-60 (m = in the formula (20) to the formula (22) 1. The number of groups represented by the formula (21) = 6, the compound in which all of R ¹ is a hydrogen atom), DPCA-120 (m=2 in the formula (20) to the formula (22), and the formula (21) The number of groups represented by the formula = 6 and the compound in which all of R ¹ is a hydrogen atom).

In the present invention, the polyfunctional monothomer having a modified structure of caprolactone may be used alone or in combination of two or more.

A commercially available product such as a polymerizable monomer is, for example, a tetrafunctional acrylate SR-494 having four ethylene glycol chains manufactured by Sartomer Co., Ltd., and six extensions manufactured by Nippon Kayaku Co., Ltd. A pentyloxy chain hexafunctional acrylate DPCA-60, a trifunctional acrylate TPA-330 having three isobutoxy chain extensions, and the like.

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

A third preferred embodiment of the present invention is a form containing a compound having an epoxy group or an oxetanyl group as a polymerizable compound. The compound having an epoxy group or an oxetanyl group specifically has a polymer having an epoxy group in a side chain and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule. Listed: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin, and the like. Further, a monofunctional or polyfunctional glycidyl ether compound is preferred, and a polyfunctional aliphatic glycidyl ether compound is preferred.

These compounds can be used as a commercial product, and can also be obtained by introducing an epoxy group to a side chain of a polymer.

For the commercial product, for example, the description of Japanese Patent Laid-Open Publication No. 2012-155288, paragraph 0191, and the like can be incorporated into the specification of the present application.

Further, commercially available products include: Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, and Denacol EX- 321L, a polyfunctional aliphatic glycidyl ether compound such as Denacol EX-850L (above, manufactured by Nagase Chemtex). These compounds are low-chlorine products, and Denacol EX-212, Denacol EX-214, and Denacol EX-216 which are not low-chlorine products can be similarly used. , Denacol EX-321, Denacol EX-850, etc.

In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, Adeco resin (ADEKA) RESIN) EP-4011S (above is made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above ADEKA) (share) manufacturing), JER1031S, etc.

Further, commercially available products of the phenol novolac type epoxy resin include JER-157S65, JER-152, JER-154, and JER-157S70 (the above are manufactured by Mitsubishi Chemical Corporation).

a polymer having an oxetanyl group in a side chain, and having the intramolecular Specific examples of the polymerizable monomer or oligomer of two or more oxetanyl groups can be used: Aron Oxetane OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.).

The molecular weight is from 500 to 5,000,000, more preferably from 1,000 to 500,000 on a weight basis.

As the epoxy unsaturated compound, a compound having a glycidyl group as an epoxy group such as glycidyl (meth)acrylate or allyl glycidyl ether may be used, and an unsaturated compound having an alicyclic epoxy group is preferred. Such a compound can be referred to, for example, the description of Japanese Patent Laid-Open Publication No. 2009-265518, paragraph 0045, and the like.

The composition of the present invention may also contain a polymer having a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group. Specifically, a polymer (interpolymer) containing the following repeating unit can be mentioned. The polymer having the following repeating unit is preferably an epoxy group. Polymer.

<<Compound having partial structure represented by formula (30)>>

The curable compound used in the present invention may have a partial structure represented by the following formula (30). The curable compound may have a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group.

(In the formula (30), R ¹ represents a hydrogen atom or an organic group)

In the formula (30), R ¹ represents a hydrogen atom or an organic group. The organic group may, for example, be a hydrocarbon group, specifically an alkyl group or an aryl group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a group containing the divalent linking group. The group of the combination.

Specific examples of such an organic group are preferably -OR', -SR', or a ring containing the group and -(CH ₂ ) _m - (m is an integer of 1 to 10) and having a carbon number of 5 to 10. a group of a combination of at least one of an alkyl group, -O-, -CO-, -COO-, and -NH-. Here, R' is preferably a hydrogen atom, a linear chain having a carbon number of 1 to 10, a branched or cyclic alkyl group having 3 to 10 carbon atoms (preferably a linear alkyl group having 1 to 7 carbon atoms). a combination of a branched or cyclic alkyl group having 3 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms Group.

Further, in the formula (30), R ¹ and C may be bonded to each other to form a ring structure (heterocyclic structure). The hetero atom in the heterocyclic structure is the nitrogen atom in the formula (30). The heterocyclic structure is preferably a 5-membered ring or a 6-membered ring structure, more preferably a 5-membered ring structure. The heterocyclic structure may also be a condensed ring, preferably a single ring.

Specific examples of the preferable R ¹ include a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and -OR'(R' is a linear alkyl group having 1 to 5 carbon atoms) and -(CH ₂ ) _m a group in which (m is an integer of 1 to 10, preferably m is an integer of 1 to 5), and R ¹ and C in the formula (30) are bonded to each other to form a heterocyclic ring structure (preferably a 5-membered ring structure).

The compound having the partial structure represented by the formula (30) is preferably represented by (the main chain structure of the polymer - the partial structure of the (30) - R ¹ ), or by (A-the (30) Part of the structure - B). Here, A is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms. Further, B is a group containing -(CH ₂ ) _m - (m is an integer of 1 to 10, preferably m is an integer of 1 to 5), a combination of the partial structure (30) and a polymerizable group. .

In addition, the compound having a partial structure represented by the above formula (30) may have a structure represented by any one of the following formulas (1-1) to (1-5).

(In the formula (1-1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. In the formula (1-2), R ⁷ represents a hydrogen atom or a methyl group. In the formula (1-3), L ¹ represents a divalent linking group, and R ⁸ represents a hydrogen atom or an organic group. In the formula (1-4), L ² and L ³ each independently represent a divalent linking group, and R ⁹ and R ¹⁰ each independently represents a hydrogen atom or an organic group. In the formula (1-5), L ⁴ represents a divalent linking group, and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or an organic group)

In the formula (1-1), R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. The organic group has the same meaning as R ¹ in the formula (30), and the preferred range is also the same.

In the formulae (1-3) to (1-5), L ¹ to L ⁴ represent a divalent linking group. The divalent linking group preferably comprises -(CH ₂ ) _m - (m is an integer of 1 to 10), a cyclic alkyl group having 5 to 10 carbon atoms, and -O-, -CO-, -COO- and A combination group of at least one of -NH- is more preferably -(CH ₂ ) _m - (m is an integer of from 1 to 8).

In the formulae (1-3) to (1-5), R ⁸ to R ¹⁴ each independently represent a hydrogen atom or an organic group. The organic group is preferably a hydrocarbon group, specifically an alkyl group or an alkenyl group.

Alkyl groups can also be substituted. Further, the alkyl group may be in the form of a chain, a branch or a ring, and is preferably a linear or cyclic alkyl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

Alkenyl groups can also be substituted. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 1 to 4 carbon atoms, and particularly preferably a vinyl group.

The substituent may, for example, be a polymerizable group, a halogen atom, an alkyl group, a carboxylate group, a halogenated alkyl group, an alkoxy group, a methacryloxy group, an acryloxy group, an ether group, a sulfonyl group, a thioether. Base, guanamine, sulfhydryl, hydroxy, carboxyl, and the like. Among these substituents, a polymerizable group (e.g., a vinyl group, a (meth) propylene fluorenyloxy group), a (meth) acryl fluorenyl group, an epoxy group, an aziridine group or the like is preferable, and a vinyl group is more preferable. .

In addition, the compound having the partial structure represented by the formula (30) may The monomer may also be a polymer, preferably a polymer. That is, the compound having the partial structure represented by the formula (30) is preferably a compound represented by the above formula (1-1) or the formula (1-2).

Further, in the case where the compound having the partial structure represented by the formula (30) is a polymer, it is preferred to contain the partial structure in the side chain of the polymer.

Molecular weight of a compound having a partial structure represented by the formula (30) It is preferably 50 to 1,000,000, more preferably 500 to 500,000. By setting such a molecular weight, the effects of the present invention can be more effectively achieved.

In the composition of the present invention, the content of the compound having the partial structure represented by the above (30) is preferably from 5% by mass to 80% by mass, more preferably from 10% by mass to 60% by mass.

Specific examples of the compound having the partial structure represented by the formula (30) The compound having the following structure or the following exemplified compound may be mentioned, but it is not limited to these compounds. In the present invention, a compound having a partial structure represented by the above formula (30) is preferably a polyacrylamide.

Further, a compound having a partial structure represented by the formula (30) Specific examples thereof include water-soluble polymers, and preferred main chain structures include polyvinylpyrrolidone, poly(meth)acrylamide, polyamine, polyvinylpyrrolidone, and polyamine. Carbamate, polyurea. The water soluble polymer may also be a copolymer, and the interpolymer may also be a random interpolymer.

As the polyvinylpyrrolidone, trade names K-30, K-85, K-90, K-30W, K-85W, and K-90W (manufactured by Nippon Shokubai Co., Ltd.) can be used.

The poly(meth) acrylamide may, for example, be a polymer of (meth) acrylamide. Polymer. Specific examples of the acrylamide include acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-butyl acrylamide, N-benzyl propylene. Indoleamine, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-tolyl acrylamide, N-(hydroxyphenyl) acrylamide, N-(amine sulfonylphenyl) propylene Indoleamine, N-(phenylsulfonyl) acrylamide, N-(methylsulfonyl) acrylamide, N,N-dimethyl decylamine, N-methyl-N-phenyl propylene Indoleamine, N-hydroxyethyl-N-methylpropenylamine, and the like. Further, methacrylamide corresponding to these compounds can also be used in the same manner.

The water-soluble polyamine resin may, for example, be a compound obtained by copolymerizing a polyamine resin with a hydrophilic compound. The derivative of the water-soluble polyamine resin means, for example, a water-soluble polyamine resin as a raw material, and a hydrogen atom of a guanamine bond (-CONH-) is substituted by a methoxymethyl group (-CH ₂ OCH ₃ ). A compound obtained by changing the structure of a guanamine bond by substitution or addition reaction of an atom in a water-soluble polyamine resin molecule.

The polyamine resin may, for example, be a so-called "n-nylon" synthesized by polymerization of an ω-amino acid or a so-called "n, m-nylon" synthesized by copolymerization of a diamine and a dicarboxylic acid. Among them, from the viewpoint of imparting hydrophilicity, a copolymer of a diamine and a dicarboxylic acid is preferred, and a reaction product of ε-caprolactam and a dicarboxylic acid is more preferred.

Examples of the hydrophilic compound include a hydrophilic nitrogen-containing cyclic compound, a polyalkylene glycol, and the like.

Here, the hydrophilic nitrogen-containing cyclic compound means a compound having a tertiary amine component in a side chain or a main chain, and examples thereof include an aminoethyl piperazine, a bisaminopropyl piperazine, and α. -Dimethylamino-ε-caprolactam and the like.

On the other hand, in the compound obtained by copolymerizing a polyamine resin with a hydrophilic compound, for example, a copolymerization of a polyamine-containing resin has a hydrophilic nitrogen-containing cyclic compound and a polyalkylene group. At least one of the groups consisting of alcohols, the hydrogen bond ability of the guanamine bond of the polyamide resin is greater than that of the N-methoxymethylated nylon.

Among the compounds obtained by copolymerizing a polyamine resin with a hydrophilic compound, 1) is a reaction product of ε-caprolactam with a hydrophilic nitrogen-containing cyclic compound and a dicarboxylic acid, and 2) ε- The reaction product of caprolactam and a polyalkylene glycol with a dicarboxylic acid.

These compounds are commercially available, for example, from Toray Finetech Co., Ltd. under the trademark "AQ Nylon". The reaction product of ε-caprolactam and a hydrophilic nitrogen-containing cyclic compound and a dicarboxylic acid can be obtained as AQ nylon A-90 manufactured by Toray Finetech Co., Ltd., ε-caprolactam The reaction product with the polyalkylene glycol and the dicarboxylic acid can be obtained as AQ nylon P-70 manufactured by Toray Finetech Co., Ltd. AQ nylon A-90, AQ nylon P-70, AQ nylon P-95, and AQ nylon T-70 (manufactured by Toray Industries, Inc.) can be used.

The molar containing the repeating unit having the partial structure represented by the formula (30) and the repeating unit having an epoxy group is preferably from 10/90 to 90/10, more preferably from 30/70 to 70/. 30. The weight average molecular weight of the copolymer is preferably 3,000. ~1,000,000, more preferably 5,000~200,000.

The content of the polymerizable compound in the composition of the present invention is preferably from 1% by mass to 90% by mass, more preferably from 15% by mass to 80% by mass, even more preferably 40% by mass, based on the total solid content other than the solvent. ~75% by mass.

In the case where a polymer containing a repeating unit having a crosslinking group is used as the polymerizable compound, it is preferably 10% by mass to 75% by mass based on the total solid content of the composition of the present invention other than the solvent. More preferably, it is 20% by mass to 65% by mass, and particularly preferably 20% by mass to 60% by mass.

The number of the polymerizable compounds may be one or two or more. When two or more types are used, the total amount is in the above range.

<adhesive polymer>

In order to improve film properties and the like, the composition of the present invention may further contain a binder polymer in addition to the polymerizable compound. As the binder polymer, an alkali-soluble resin can be preferably used. By containing an alkali-soluble resin, it is effective in the improvement of heat resistance, etc., or the fine adjustment of a coating.

The content of the alkali-soluble resin can be referred to in the following paragraphs 0558 to 5571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to U.S. Patent Application Publication No. 2012/0235099; Incorporated into the specification of the present application.

When the composition of the present invention contains a binder polymer, the content of the binder polymer is preferably from 1% by mass to 80% by mass, more preferably from 5% by mass to 50% by mass, based on the total solid content of the composition. Further preferably, it is 7 mass% to 30 mass%.

<Surfactant>

The composition of the present invention may also contain a surfactant. The surfactant may be used alone or in combination of two or more. The amount of the surfactant added is preferably 0.0001% by mass to 2% by mass, more preferably 0.005% by mass to 1.0% by mass, even more preferably 0.01% by mass to 0.1% by mass based on the solid content of the composition of the present invention.

As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

In particular, the composition of the present invention contains a fluorine-based surfactant and an anthrone. At least one of the surfactants is further improved in solution characteristics (particularly fluidity) when it is prepared as a coating liquid. Thereby, the uniformity of the coating thickness or the liquid-saving property is further improved.

In other words, when a film is formed by using a coating liquid containing a composition containing at least one of a fluorine-based surfactant and an anthrone-based surfactant, the interface between the surface to be coated and the coating liquid is used. The tension is reduced, the wettability to the surface to be coated is improved, and the coatability to the surface to be coated is improved. Therefore, even when a film having a thickness of about several micrometers (μm) is formed with a small amount of liquid, it is possible to more preferably form a film having a uniform thickness having a small thickness unevenness, which is effective in this respect.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass. % is more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. The fluorine-containing surfactant is effective in the uniformity of the thickness of the coating film or the liquid-saving property in the fluorine-based surfactant, and the solubility in the colored photosensitive composition is also good.

Specific examples of the fluorine-based surfactant include those described in JP-A-2012-208494, paragraph 0552 (corresponding to U.S. Patent Application Publication No. 2012/0235099, the disclosure of Enter the specification of this application.

Examples of the nonionic surfactant include polyoxyethylene ethyl ether, polyoxyethylene ethyl allylate, polyoxyethyl alcohol ester, sorbitan fatty acid ester, and polyoxyethyl ether. Sorbitan fatty acid ester, polyoxyethylene ethylamine, glycerin fatty acid ester, oxygen ethoxylated propyl block copolymer, acetylene glycol surfactant, acetylene polyoxyethylene oxide, etc. . These nonionic surfactants may be used alone or in combination of two or more.

Specific trade names can be listed as: Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Sophino (Surfynol) 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 104S, Suffolk (Surfynol) 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol 504, Surfynol CT-111, Sophino (Surfynol) CT-121, Surfynol CT-131, Surfynol CT-136, Surfynol CT-141, Surfynol CT-151, Suffolk (Surfynol) CT-171, Surfynol CT-324, Surfynol DF-37, Surfynol DF-58, Surfynol DF-75, Suffino (Surfynol) DF-110D, Sofino (Surfynol) DF-210, Surfynol GA, Surfynol OP-340, Surfynol PSA-204, Surfynol PSA-216, Surfynol ) PSA-336, Surfynol SE, Surfynol SE-F, Surfynol TG, Surfynol GA, Dynol 604 (above) Chemicals and Air Products & Chemicals), Olfine A, Olfine B, Olfine AK-02, Olfine CT -151W, Olfine E1004, Olfine E1010, Olfine P, Olfine SPC, Olfine STG, Olfine Y , Olfine 32W, Olfine PD-001, Olfine PD-002W, Olfine PD-003, Olfine PD-004, Austria Olfine EXP.4001, Olfine EXP.4036, Olfine EXP. 4051, Olfine AF-103, Olfine AF-104, Austria Olfine SK-14, Olfine AE-3 (above is Nisshin Chemical Co., Ltd.), Acetylenol E00, Acetylenol E13T, Arcedi (Acetylenol) E40, Acetylenol E60, Acetylenol E81, Acetylenol E100, Acetylenol E200 (all above are trade names, Chuanyanjing (manufactured by the company) and so on. Among them, Olfine E1010 is preferred.

Further, the nonionic surfactant may specifically be described in paragraph 0553 of Japanese Patent Laid-Open Publication No. 2012-208494 (corresponding U.S. Patent Application Publication No. The nonionic surfactant described in [0679] of the specification of 2012/0235099, etc., is incorporated in the specification of the present application.

Specific examples of the cation-based surfactant include the cationic surfactant described in paragraph 0554 of the Japanese Patent Application Laid-Open No. 2012-208494 (the corresponding US Patent Application Publication No. 2012/0235099 [0680]). The content is incorporated into the specification of the present application.

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

Examples of the anthrone-based surfactants include Japanese Patent Laid-Open The anthrone-based surfactant described in paragraph 0556 of the Japanese Patent Application Laid-Open No. 2012/0235099, the entire disclosure of which is incorporated herein by reference. In addition, it can also be illustrated: Toray. "Toray Silicone SF8410", "Toray Silicone SF8427", "Toray Silicone SH8400", "East" manufactured by Toray-Dow Corning Co., Ltd. Toray Silicone ST80PA, Toray Silicone ST83PA, Toray Silicone ST86PA, and TSF-400 manufactured by Momentive Performance Materials ""TSF-401", "TSF-410", "TSF-4446", "KP321", "KP323", "KP324", "KP340" manufactured by Shin-Etsu Chemical Co., Ltd., etc.

<Polymerization initiator>

The composition of the present invention may also contain a polymerization initiator. The polymerization initiator has only The ability to initiate polymerization of the polymerizable compound by either light or heat or both is not particularly limited, and may be appropriately selected depending on the intended purpose, and is preferably a photopolymerizable compound. In the case where light is used to initiate polymerization, it is preferred to have a sensitivity to ultraviolet light to visible light.

Further, in the case where polymerization is initiated by heat, a polymerization initiator which decomposes at 150 ° C to 250 ° C is preferred.

The polymerization initiator which can be used in the present invention preferably has at least an aromatic Examples of the compound of the group include a mercaptophosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound, a thioxanthone compound, and an anthracene. a compound, a hexaarylbiimidazole compound, a trihalomethyl compound, an azo compound, an organic peroxide, a diazo compound, an anthraquinone compound, an anthraquinone compound, an oxazine compound, a benzoin ether compound, a ketal derivative compound, An onium salt compound such as a metallocene compound, an organic boron salt compound, a diterpene compound, a thiol compound, or the like.

The acetophenone-based compound, the trihalomethyl compound, the hexaarylbiimidazole compound, and the hydrazine compound can be specifically referred to the paragraph 0506 to paragraph 0510 of the Japanese Patent Laid-Open Publication No. 2012-208494 (corresponding U.S. Patent Application Publication No. 2012/0235099 The contents of the specification [0622 to 0628] and the like are incorporated in the specification of the present application.

In addition, a cyclic ruthenium compound described in Japanese Patent Laid-Open Publication No. 2007-231000 (the corresponding U.S. Patent Application Publication No. 2011/0123929) and the Japanese Patent Publication No. 2007-322744.

In addition, an antimony compound having a specific substituent as shown in Japanese Patent Laid-Open Publication No. Hei. No. 2007-269779 (corresponding U.S. Patent Application Publication No. 2010/0104976), or Japanese Patent Laid-Open Publication No. 2009-191061 An antimony compound having a thioaryl group as shown in the corresponding U.S. Patent Application Publication No. 2009/023085.

Reference may be made to the formula (OX-1), the formula (OX-2) or the formula (After the [0632] of the specification of the corresponding US Patent Application Publication No. 2012/235099) of JP-A-2012-208494. The description of the compounds represented by OX-3) is incorporated into the specification of the present application.

Further, a specific example of the ruthenium compound which is preferably used can be referred to paragraph 0090 to paragraph 0106 of the Japanese Patent Laid-Open Publication No. 2009-191061 (paragraph 0039 of the specification of the corresponding US Patent Application Publication No. 2009/023085), Japanese Patent Laid-Open The description of paragraph 0054 of JP-A-2012-032556, paragraph 0054 of JP-A-2012-122045, and the like is incorporated herein by reference.

The photopolymerization initiator is preferably an anthracene compound, an acetophenone-based compound or a mercaptophosphine compound. More specifically, for example, an amino acetophenone-based initiator described in JP-A-10-291969, and a mercaptophosphine oxide-based initiator described in Japanese Patent No. 4,258,899 can be used. Further, the oxime-based initiator and the oxime-based initiator may be those described in JP-A-2001-233842.

The hydrazine compound can be used as a commercially available product (IRGACURE)-OXE 01 (manufactured by BASF), IRGACURE-OXE 02 (bar) Made by BASF). As the acetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names, all of which are BASF Japan) can be used as a commercial product. Japan) manufactured by the company). Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name, all manufactured by BASF Japan Co., Ltd.) can be used as a commercial product.

The content of the polymerization initiator is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, even more preferably 0.1% by mass to 15% by mass based on the solid content of the composition of the present invention. The polymerization initiator may be used alone or in combination of two or more. In the case of two or more types, the total amount is in the above range.

<Other ingredients>

Examples of other components which can be used in combination in the composition of the present invention include a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and the like. And use the adhesion promoter on the surface of the substrate and other additives (such as conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chains Transfer agent, etc.).

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

For the components, for example, paragraph number 0183~ of Japanese Patent Laid-Open Publication No. 2012-003225 (corresponding U.S. Patent Application Publication No. 2013/0034812), paragraph number 0101 to paragraph number 0102 of Japanese Patent Laid-Open Publication No. 2008-250074 , paragraph number 0103 ~ paragraph number 0104 and paragraph number 0107 ~ paragraph The description of paragraph number 0159 to paragraph number 0184 of Japanese Patent Laid-Open No. Hei. No. 2013-195480 is incorporated herein by reference.

<Preparation and use of near-infrared absorbing composition>

The near-infrared absorbing composition of the present invention can be prepared by mixing the above components.

In the preparation of the composition, the components constituting the composition may be formulated at once, or the components may be dissolved in an organic solvent and dispersed to be successively formulated. In addition, the order of input or the working conditions at the time of preparation are not particularly limited.

In the present invention, it is preferred to perform filtration using a filter to remove foreign matter or to reduce defects and the like. The filter can be used without particular limitation as long as it has been used for filtration purposes or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamine resin such as nylon-6 or nylon-6,6, or a polyolefin resin such as polyethylene or polypropylene (PP) may be mentioned ( A filter containing high density, ultra high molecular weight, etc. Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably from 0.1 μm to 7.0 μm, more preferably from 0.2 μm to 2.5 μm, still more preferably from 0.2 μm to 1.5 μm, still more preferably from 0.3 μm to 0.7 μm. By setting it as this range, it is possible to suppress clogging of the filter, and it is possible to reliably remove fine foreign matter such as impurities or aggregates contained in the composition.

Different filters can also be combined when using filters. At this time, the filtration by the first filter may be performed only once or twice or more. In the case where two or more filters are combined by using different filters, it is preferred that the second filter is The subsequent pore size is equal to the pore size of the first filtration or larger than the pore diameter of the first filtration. Further, it is also possible to combine the first filters having different pore diameters within the above range. The aperture here can be referred to the nominal value of the filter maker. Commercially available filters are available, for example, from Pall Co., Ltd., Advantec Toyo Co., Ltd., and Entegris Co., Ltd. (formerly Japan's Mykrolis). )))) or various filters provided by KITZ Micro Filter Co., Ltd., etc.

The second filter can be formed of the same material or the like as the first filter. The pore diameter of the second filter is preferably 0.2 μm to 10.0 μm, more preferably 0.2 μm to 7.0 μm, still more preferably 0.3 μm to 6.0 μm. By setting it as this range, a foreign material can be removed in the state of the component particle contained in the residual composition.

The use of the near-infrared absorbing composition of the present invention is not particularly limited The near-infrared cut filter (for example, a near-infrared cut filter for a wafer level lens) on the light receiving side of the solid-state image sensor, and the back side of the solid-state image sensor (opposite to the light receiving side) The near-infrared cut filter or the like is preferably a near-infrared cut filter on the light receiving side of the solid-state image sensor. Further, it is preferred that the near-infrared absorbing composition of the present invention is directly applied onto a solid-state image sensor to form a coating film.

When the infrared cut-off layer is formed by coating, the viscosity of the near-infrared absorbing composition of the present invention is preferably 1 mPa. Above s, 3000mPa. Within the range of s below, more preferably 10mPa. Above s, 2000mPa. s below the range, and thus better It is 100mPa. Above s, 1500mPa. s the following range.

Since the composition of the present invention can be supplied in a coatable state, a near-infrared cut filter can be easily formed on a desired member or position of the solid-state image sensor.

The near-infrared cut filter obtained by using the composition of the present invention preferably has a light transmittance satisfying at least one of the following (1) to (9), and more preferably satisfying all of the following conditions (1) to (8). And then it satisfies all the conditions of (1)~(9).

(1) The light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, further 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, further 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, further 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, further preferably 92% or more, and particularly preferably 95% or more.

(5) The light transmittance at a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

(6) The light transmittance at a wavelength of 750 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

(7) The light transmittance at a wavelength of 800 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

(8) The light transmittance at a wavelength of 850 nm is preferably 20% or less, more preferably 15%. Hereinafter, it is preferably 10% or less, and particularly preferably 5% or less.

(9) The light transmittance at a wavelength of 900 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

Further, the light transmittance of the near-infrared cut filter is preferably 95% or more in the entire range of wavelengths of 450 nm to 500 nm.

The near-infrared cut filter can be appropriately selected depending on the purpose, and is preferably set to have a film thickness of 300 μm or less, more preferably set to 250 μm or less, further preferably set to 200 μm or less, and more preferably set to 100 μm or less. The lower limit of the film thickness is, for example, preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 20 μm or more. According to the composition of the present invention, since the near-infrared shielding property is high, the film thickness of the near-infrared cut filter can be made thin.

The near-infrared cut filter preferably has a light transmittance of 85% or more, and more preferably 90% or more in the entire range of a film thickness of 300 μm or less and a wavelength of 400 nm to 550 nm. Further, it is preferable that the light transmittance at at least one wavelength in the range of 700 nm to 800 nm is 20% or less, and preferably the light transmittance in the entire range of 700 nm to 800 nm is 20% or less. According to the present invention, it is possible to ensure a wide range of visible light with high transmittance, and it is possible to provide a near-infrared cut filter having high near-infrared shielding properties.

A near-infrared cut-off filter can be used to have absorption. A lens that cuts off the function of near-infrared rays (a digital camera, a camera lens such as a mobile phone or a car camera, an optical lens such as an f-θ lens or a pickup-up lens), and an optical filter for a semiconductor light-receiving element. Near-infrared absorption filter for energy-saving blocking hot line Or a near-infrared absorbing plate, an agricultural coating agent for selectively utilizing sunlight, a recording medium that absorbs heat by using near-infrared rays, a near-infrared filter for electronic equipment or photos, and safety goggles. Sunglasses, hot wire blocking film, optical text reading and recording, confidential document anti-photocopying, electronic photoreceptor, laser welding, etc. In addition, it is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

The invention also relates to a manufacturer of a near-infrared cut filter The method comprises the steps of: applying (preferably dropping, coating or printing) the near-infrared absorbing composition of the present invention to the light-receiving side of the solid-state image sensor, thereby forming a film; and performing a drying step. The film thickness, the laminate structure, and the like can be appropriately selected depending on the purpose.

The support to which the composition of the present invention is applied may be a transparent substrate including glass or the like, or may be a solid-state image sensor, or may be another substrate provided on the light-receiving side of the solid-state image sensor, or may be received by a solid-state image sensor. A layer of a flattening layer on the side.

The method of forming the near-infrared cut filter can be performed, for example, by using a drop method (drop cast), a spin coater, a slit spin coater, a slit coater, screen printing, applicator coating, or the like. Implementation. In the case of a dropping method (drop casting), it is preferred to form a dropping region of a near-infrared absorbing composition having a barrier as a partition wall on a glass substrate so as to obtain a uniform film with a predetermined film thickness. Further, regarding the film thickness, the amount of the composition to be dropped, the solid content concentration, and the area of the dropping region can be adjusted.

In addition, the drying conditions of the coating film vary depending on the components, the type of the solvent, the ratio of use, etc., and are usually dried at a temperature of 60 ° C to 150 ° C for 30 seconds to 15 minutes. right.

Using the near-infrared absorbing composition of the present invention to form near infrared rays The method of cutting off the filter can also include other steps. The other steps are not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a surface treatment step of a substrate, a pre-heating step (pre-baking step), a hardening treatment step, a post-heating step (post-baking step), and the like.

<Preheating step. Post heating step >

The heating temperature in the pre-heating step and the post-heating step is usually from 80 ° C to 200 ° C, preferably from 90 ° C to 150 ° C. The heating time in the pre-heating step and the post-heating step is usually from 30 seconds to 240 seconds, preferably from 60 seconds to 180 seconds.

<hardening treatment step>

The hardening treatment step is a step of hardening the formed film as needed, and by performing this treatment, the mechanical strength of the near-infrared cut filter is improved.

The hardening treatment step is not particularly limited and may be appropriately selected depending on the purpose. For example, a full-surface exposure treatment, a full-surface heat treatment, or the like can be preferably exemplified. Here, the "exposure" in the present invention is intended to include not only light of various wavelengths but also irradiation of radiation such as electron beams and X-rays.

The exposure is preferably performed by irradiation of radiation, and ultraviolet rays or visible light such as an electron beam, KrF, ArF, g-ray, h-ray, or i-ray may be preferably used, particularly for radiation that can be used for exposure.

The exposure method may be, for example, a stepper exposure or an exposure using a high pressure mercury lamp.

The exposure amount is preferably ⁵ mJ/cm ² to 3000 mJ/cm ² , more preferably 10 mJ/cm ² to 2000 mJ/cm ² , and particularly preferably 50 mJ/cm ² to 1000 mJ/cm ² .

The method of the entire surface exposure treatment may, for example, be a method of exposing the entire surface of the formed film. When the near-infrared absorbing composition contains a polymerizable compound, the curing of the polymer component in the film formed by the composition is promoted by the entire surface exposure, and the hardening of the film proceeds further, mechanical strength, Durability is improved.

The apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected depending on the purpose. For example, a UV exposure machine such as an ultrahigh pressure mercury lamp can be preferably used.

Further, the method of heat treatment of the entire surface may be a method of heating the entire surface of the formed film. The film strength of the pattern can be increased by heating over the entire surface.

The heating temperature for the entire surface heating is preferably from 120 ° C to 250 ° C, more preferably from 160 ° C to 220 ° C. When the heating temperature is 120° C. or more, the film strength is improved by heat treatment, and when it is 250° C. or lower, the components in the film are prevented from being decomposed and the film quality is weak and brittle.

The heating time for the entire surface heating is preferably from 3 minutes to 180 minutes, more preferably from 5 minutes to 120 minutes.

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

The camera module of the present invention has a solid-state imaging element and is disposed on a solid A near-infrared cut filter on the light receiving side of the image pickup element, and a near infrared cut filter is the near infrared cut filter described above.

Further, in the method of manufacturing a camera module of the present invention, a camera module having a solid-state image sensor and a near-infrared cut filter disposed on a light receiving side of the solid-state image sensor is manufactured, and the method of manufacturing the camera module includes the following steps: The near-infrared absorbing composition of the present invention is applied to the light-receiving side of the solid-state image sensor to form a film.

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, for example, a solid-state imaging device 11 , a planarization layer 12 provided on the solid-state imaging device 11 , a near-infrared cut filter 13 , and an upper portion of the near-infrared cut filter, and an imaging lens 14 in the internal space. Lens holder 15.

In the camera module 10, the incident light hν from the outside is sequentially transmitted through the imaging lens 14, the near-infrared cut filter 13, and the planarization layer 12, and then reaches the imaging element portion 16 of the solid-state imaging device 11.

The solid-state imaging device 11 includes, for example, an imaging element portion 16, an interlayer insulating film (not shown), a substrate layer (not shown), a color filter 17, and an overcoat layer on the main surface of the ruthenium substrate as a substrate. Shown), microlens 18. The color filter 17 (a red color filter, a green color filter, a blue color filter) or the microlens 18 is disposed so as to correspond to the imaging element unit 16 .

Alternatively, the near-infrared cut filter 13 may be provided instead of the surface of the planarization layer 12, between the surface of the microlens 18, the matrix layer and the color filter 17, or the color filter 17 and the outside. Near-infrared cutoff between coatings Filter 13. For example, the near-infrared cut filter 13 may be disposed at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens. When it is installed in this position, the step of forming the near-infrared cut filter can be simplified, and the unnecessary near-infrared rays to the microlens can be sufficiently cut off, so that the near-infrared shielding property can be further improved.

The near-infrared cut filter of the present invention is available for a reflow soldering step. By manufacturing the camera module by the reflow step, it is possible to automatically mount the electronic component mounting board or the like which must be soldered, and it is possible to particularly improve productivity without using the reflow step. Further, since it can be automatically performed, cost reduction can be achieved. In the case of the reflow step, it is exposed to a temperature of about 250 ° C to 270 ° C, so the infrared cut filter preferably has heat resistance that can withstand the reflow step (hereinafter also referred to as "reflow-resistant soldering" Sex").

In the specification of the present application, "having resistance to reflow resistance" means maintaining the characteristics as an infrared cut filter before and after heating at 200 ° C for 10 minutes. More preferably, the characteristics are maintained before and after heating at 230 ° C for 10 minutes. Further, it is preferable to maintain the characteristics before and after heating at 250 ° C for 3 minutes. In the case where the reflow resistance is not exhibited, the infrared ray absorbing ability of the infrared cut filter may be lowered or the function as a film may be insufficient when held under the above conditions.

Further, the present invention is also directed to a method of manufacturing a camera module including the steps of performing a reflow process. The near-infrared cut filter of the present invention maintains the near-infrared absorption capability even if it has a reflow step, so that it does not damage the small size and light weight. The characteristics of a high-performance camera module.

Figures 2 to 4 show the near-infrared cut-off filter week of the camera module. A schematic cross-sectional view of an example of a side portion.

As shown in FIG. 2, the camera module sequentially has a solid-state imaging element 11, a planarization layer 12, and ultraviolet light. The infrared light reflecting film 19, the transparent substrate 20, the near infrared ray absorbing layer 21, and the antireflection layer 22.

UV. The infrared light reflecting film 19 has an effect of imparting or improving the function of the near-infrared cut filter. For example, the paragraphs 0033 to 0039 of Japanese Patent Laid-Open Publication No. 2013-68688, the contents of which are incorporated herein by reference.

The transparent substrate 20 transmits light of a wavelength in the visible range. For example, reference is made to paragraph 0026 to paragraph 0032 of JP-A-2013-68688, the contents of which are incorporated herein by reference.

The near-infrared absorbing layer 21 can be formed by coating the near-infrared absorbing composition of the present invention.

The anti-reflection layer 22 has a function of preventing reflection of light incident into the near-infrared cut filter, thereby increasing transmittance and efficiently utilizing incident light, for example, refer to paragraph 0040 of Japanese Patent Laid-Open Publication No. 2013-68688, The content thereof is incorporated into the specification of the present application.

As shown in FIG. 3, the camera module may also have a solid-state imaging element 11, a near-infrared absorbing layer 21, an anti-reflection layer 22, a planarization layer 12, an anti-reflection layer 22, a transparent substrate 20, and ultraviolet light. Infrared light reflecting film 19.

As shown in FIG. 4, the camera module may also have a solid-state imaging element 11, a near-infrared absorbing layer 21, and an ultraviolet ray in sequence. The infrared light reflecting film 19, the planarizing layer 12, the antireflection layer 22, the transparent substrate 20, and the antireflection layer 22.

In addition, the solid-state imaging device may be configured as the imaging element in the first to fourteenth embodiments described in the 0049 column of the International Publication No. WO14/061188.

[Examples]

The invention is more specifically illustrated by the following examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "%" and "parts" are quality standards unless otherwise specified.

<Synthesis Example>

Compound A1-1~Compound A1-3, Compound A1-6, Compound A1-7, Compound A1-9, Compound A1-15, Compound A1-26 and Compound A2-1, Compound A2-33, Compound A2-35, Compound A2-37 was commercially available as a reagent from Tokyo Chemical Co., Ltd., Wako Pure Chemical Industries, or Aldrich, and was used without further purification.

Synthesis example of compound A1-4

Introduced 2,6-dibromopyridine 14.24g, iodine in a three-necked flask under nitrogen atmosphere Copper (I) 0.61 g, tetrahydrofuran (commercially available dehydration solvent) 180 mL, and cooled to 0 °C. 70 mL of a 1.0 M tetrahydrofuran solution of tributylmagnesium chloride was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Add 100 mL of saturated ammonium chloride aqueous solution and 100 mL of ethyl acetate by extraction. The organic layer obtained by liquid separation was concentrated, and the obtained crude product was purified by silica gel column chromatography (solvent: hexane) to obtain 10 g of 2-bromo-6-t-butylpyridine.

Then, in a three-necked flask, 3.65 g of 2-bromo-6-tert-butylpyridine synthesized above and 50 mL of tetrahydrofuran (a commercially available dehydrating solvent) were introduced under a nitrogen atmosphere, and the mixture was cooled to -78 °C. 10.0 mL of a 1.6 M hexane solution of n-butyllithium was added dropwise thereto, and the mixture was stirred at -78 ° C for 30 minutes. A large excess amount of the pulverized dry ice was slowly added thereto, and stirred at room temperature for 2 hours. Add 100 mL of water and 50 mL of ethyl acetate by extraction. The liquid layer was separated by liquid separation (the pH was adjusted to 11). The aqueous layer was gradually added with a small amount of concentrated hydrochloric acid to adjust the pH to 2, and extracted three times with 50 mL of ethyl acetate. The obtained organic layer was concentrated to obtain 2 g of Compound A1-4.

Synthesis Example of Compound A1-5

Instead of chlorinated tert-butylmagnesium chloride, 2-ethylhexylmagnesium bromide was used, and the synthesis was carried out in the same manner as in the compound A1-4.

Synthesis Example of Compound A1-8

0.10 g of 2-cyanopyrimidine and 13 mL of a 12% by mass aqueous sodium hydroxide solution were added to the flask, and the mixture was stirred at 70 ° C for 30 minutes. 1N dilute hydrochloric acid was added in small portions, and the pH was adjusted to 3, and extraction was performed three times with 10 mL of ethyl acetate, and the obtained organic layer was concentrated, whereby 0.10 g of Compound A1-8 was obtained.

Synthesis Example of Compound A1-10

In a three-necked flask, 8.5 g of thiazole and 150 mL of tetrahydrofuran (a commercially available dehydrating solvent) were introduced under a nitrogen atmosphere, and the mixture was cooled to -78 °C. 60 mL of a 1.6 M hexane solution of n-butyllithium was added dropwise thereto, and the mixture was stirred at -78 ° C for 30 minutes. A large excess amount of the pulverized dry ice was slowly added thereto, and stirred at room temperature for 2 hours. Add 100 mL of water and 50 mL of ethyl acetate by extraction. The liquid layer was separated by liquid separation (the pH was adjusted to 11). To the aqueous layer, concentrated hydrochloric acid was added in small portions to adjust the pH to 2, and extracted three times with 50 mL of ethyl acetate, and the obtained organic layer was concentrated to obtain 12 g of Compound A1-10.

Synthesis Example of Compound A1-11

In a three-necked flask, 3.0 g of pyrazole-3-carboxylic acid ethyl ester and iodine were added under a nitrogen atmosphere. 3.55 g of potassium, 4.44 g of potassium carbonate, 4.40 g of 1-bromobutane, and 48 mL of acetone were heated under reflux for 10 hours. After cooling to room temperature, the insoluble matter was removed by filtration, the filtrate was concentrated, and the obtained crude product was purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to thereby obtain 2.8 g of 1- Ethyl butyl pyrazole-3-carboxylate.

0.39 g of the product and 3 mL of ethanol were added to the flask, and 0.05 g of water and 0.22 g of potassium t-butoxide were added thereto while stirring at room temperature, followed by stirring at 70 ° C for 30 minutes. The solid obtained by concentration under reduced pressure was the corresponding potassium carboxylate, which was directly used for copper complexation.

Synthesis example of compound A1-12

In a three-necked flask, 3.0 g of pyrazole-3-carboxylic acid ethyl ester, 2.40 g of 2-bromo-2-methylpropane, and 48 mL of dimethylformamide were added under a nitrogen atmosphere, and the mixture was heated under reflux for 72 hours. After cooling to room temperature, the insoluble matter was removed by filtration, and the filtrate was concentrated, and the obtained crude product was purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to obtain 0.8 g of 1- Ethyl tert-butyl-pyrazole-3-carboxylate.

The ester was hydrolyzed by the same method as the compound A1-11 to give the compound A1-12.

Synthesis Example of Compound A1-13

In a three-necked flask, 5.5 g of pyrazole-3-carboxylic acid, 7.5 g of 1-adamantanol, 100 mL of phosphoric acid, and 25 mL of acetic acid were added under a nitrogen atmosphere, and the mixture was stirred at 60 ° C for 7.5 hours. After cooling to room temperature, 200 mL of water was added, and the precipitated white solid was collected by filtration. To the white solid, 300 mL of water and 100 mL of ethyl acetate were added, and while stirring at room temperature, a 50% by mass aqueous sodium hydroxide solution was added until the pH became 12. By extraction. The aqueous layer was separated by liquid separation, and washed with 100 mL of ethyl acetate for 4 times. When a small amount of concentrated hydrochloric acid was added to the aqueous layer in a small amount to adjust the pH to 2, a white solid precipitated, and the white solid was filtered and washed with water to obtain 3.9 g of 1-(1-adamantyl)pyridinium. Oxazole-3-carboxylic acid.

Synthesis Example of Compound A1-14

In a three-necked flask, 4.4 g of pyruvic acid and 10 mL of cyclopentyl methyl ether were added under a nitrogen atmosphere, and the mixture was stirred at room temperature. 4.7 g of aniline was added dropwise thereto, and the mixture was stirred for 10 minutes, and then cooled to 0 ° C, and the precipitated solid was collected by filtration to obtain 3.6 g. Compound A1-14.

Synthesis Example of Compound A1-16

Into a three-necked flask, 16.3 g of 2,6-diethylpyridinium and 160 mL of tetrahydrofuran (a commercially available dehydrating solvent) were introduced under a nitrogen atmosphere, and the mixture was cooled to 0 °C. 33 mL of a 3 M diethyl ether solution of methyl magnesium bromide n-butyllithium was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. Add 100 mL of saturated ammonium chloride aqueous solution and 100 mL of ethyl acetate by extraction. The organic layer obtained by liquid separation was concentrated, whereby 19.5 g of Compound A1-16 was obtained.

Synthesis Example of Compound A1-17

In a three-necked flask, 2.46 g of picolinic acid, 3.0 g of trifluoromethanesulfonamide, 3.66 g of N,N-dimethylaminopyridine (DMAP), and 150 mL of dimethylformamide were added in a nitrogen atmosphere. Stir under temperature. Thereto was added 5.73 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), and the mixture was stirred at room temperature for 4 hours. Add 100 mL of water and 100 mL of ethyl acetate by extraction. The aqueous layer was separated by liquid separation, and concentrated hydrochloric acid was added thereto in small portions to adjust the pH to 2. Add ethyl acetate 100 mL, will be extracted by extraction. The organic layer obtained by liquid separation was concentrated, whereby 1.56 g of Compound A1-17 was obtained.

Synthesis example of compound A1-18

In a three-necked flask, 11.20 g of potassium t-butoxide and 100 mL of toluene were added under a nitrogen atmosphere, and the mixture was cooled to 0 °C. After 5.30 g of ethyl acetate was added dropwise thereto, 9.75 g of dimethyl dipicolinate was introduced, and the mixture was stirred at room temperature for 2 hours. Add 200 mL of saturated ammonium chloride solution, which will be extracted by extraction. The organic layer obtained by liquid separation was concentrated, and 50 mL of 2N diluted hydrochloric acid was added, and the mixture was stirred at 80 ° C for 2 hours. Add ethyl acetate 50mL, which will be extracted by extraction. The organic layer obtained by liquid separation was concentrated, and the obtained crude product was recrystallized twice with hot water, whereby 10 g of compound A1-18 was obtained.

Synthesis Example of Compound A1-19

In a three-necked flask, 5.6 g of 2,2-bis(6-bromo-2-pyridyl)propane synthesized by the method described in WO2006098505, tetrahydrogen was introduced under a nitrogen atmosphere. Furan (a commercially available dehydration solvent) 150 mL, cooled to -78 °C. 20 mL of a 1.6 M hexane solution of n-butyllithium was added dropwise thereto, and the mixture was stirred at -78 ° C for 30 minutes. A large excess amount of the pulverized dry ice was slowly added thereto, and stirred at room temperature for 2 hours. Add 100 mL of water and 50 mL of ethyl acetate by extraction. The liquid layer was separated by liquid separation (the pH was adjusted to 11). To the aqueous layer, concentrated hydrochloric acid was added in small portions, and the pH was adjusted to 2, and extracted three times with ethyl acetate (50 mL), and the obtained organic layer was concentrated to obtain 4.2 g of Compound A1-19.

Synthesis Example of Compound A1-20

The synthesis was carried out by the method described in "J. Org. Chem." (1970, 35, 4114).

Synthesis Example of Compound A1-21

Instead of pyrazole-3-carboxylic acid ethyl ester, diethyl pyrazole-3-carboxylate synthesized by the method described in "Tetrahedron" (1999, 55, 14791), and p-toluenesulfonic acid was used. The methyl ester was replaced by 1-bromobutane, and the synthesis was carried out in the same manner as in the compound A1-14.

Synthesis example of compound A1-22

3-bromopentane was used instead of 1-bromobutane, and cesium carbonate was used instead of potassium carbonate, and the synthesis was carried out in the same manner as in the compound A1-11.

Synthesis Example of Compound A1-23

In a three-necked flask, 20 g of 2,6-dimethyl-4-heptanol and 50 mL of pyridine were introduced under a nitrogen atmosphere, and the mixture was stirred at room temperature. 55 g of p-toluenesulfonyl chloride was introduced thereinto, and stirred at room temperature overnight. Add 2 equivalents of dilute hydrochloric acid 100 mL, ethyl acetate 100 mL, and extract. Liquid separation. Further, 100 mL of ethyl acetate was added to the aqueous phase, and extraction was carried out twice. The liquid separation operation was carried out, and the organic phases obtained by the liquid separation operation for a total of 3 times were combined, and 2 equivalents of dilute hydrochloric acid 100 mL was added thereto for 2 extractions. The operation of liquid separation. Further, 100 mL of a saturated aqueous solution of sodium chloride is added to the organic phase, which is extracted by extraction. The organic phase obtained by liquid separation was concentrated, whereby 42 g of the corresponding tosylate salt was obtained.

This tosylate was used instead of 3-bromopentane, whereby Compound A1-23 was synthesized by the same method as Compound A1-22.

Synthesis Example of Compound A1-24

The synthesis was carried out in the same manner as in the compound A1-23, using 2,6,8-trimethyl-4-nonanol instead of 2,6-dimethyl-4-heptanol.

Synthesis Example of Compound A1-27

The synthesis was carried out in the same manner as in the compound A1-10 using 4,5-dimethylthiazole in place of the thiazole.

Synthesis Example of Compound A1-28

Into a three-necked flask, 1.00 g of phenylboronic acid, 1.00 g of 6-bromopyridine-2-carboxylic acid, 1.38 g of potassium carbonate, and a mixed solvent of 5:1 of tetrahydrofuran and water were introduced under a nitrogen atmosphere, and the mixture was cooled at room temperature. 0.55 g of tetrakis(triphenylphosphine)palladium was introduced thereinto, and the mixture was heated under reflux for 4 hours. After cooling to room temperature, 40 mL of water and 40 mL of ethyl acetate were introduced by extraction. 20 mL of ethyl acetate was introduced into the aqueous phase obtained by liquid separation, and extraction and liquid separation were carried out. Dilute hydrochloric acid was introduced into the obtained aqueous phase (pH 11) until the pH became 4. The precipitated solid was recovered by filtration, whereby 0.07 g of Compound A1-28 was obtained.

Synthesis Example of Compound A1-29

In a three-necked flask, 0.90 g of 2,6-dimethylphenylboronic acid, 0.92 g of methyl 6-bromopyridine-2-carboxylate, 1.92 g of potassium phosphate, and 30 mL of toluene were introduced under a nitrogen atmosphere, and the mixture was cooled at room temperature. 0.13 g of tricyclohexylphosphine and 0.10 g of palladium acetate were introduced thereto, and stirred at 100 °C overnight. After cooling to room temperature, 30 mL of a saturated aqueous ammonium chloride solution and 40 mL of ethyl acetate were introduced and extracted. Liquid separation. The organic phase thus obtained was concentrated, and the obtained crude product was purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to thereby obtain 0.45 g of the methyl ester of compound A1-29.

The ester was hydrolyzed in the same manner as in the compound A1-11 to obtain a compound. A1-29.

Synthesis Example of Compound A1-30

Into a three-necked flask, 13.2 g of diisopropylamine and 200 mL of tetrahydrofuran (a commercially available dehydrating solvent) were introduced under a nitrogen atmosphere, and the mixture was cooled to -78 °C. 64.0 mL of a 1.6 M hexane solution of n-butyllithium was added dropwise thereto, and the mixture was stirred at -78 ° C for 10 minutes. 6.0 g of 2-bromo-6-methylpyridine was added dropwise thereto, and the mixture was stirred at -78 ° C for 30 minutes. After 15.97 g of ethyl iodide was added dropwise thereto, the temperature was slowly raised to room temperature. After stirring at room temperature for 1 hour, 100 mL of a saturated aqueous solution of ammonium chloride was introduced and extracted. Liquid separation. 100 mL of ethyl acetate was introduced into the aqueous phase and extracted twice. For the liquid separation operation, the organic phase obtained by the three-time liquid separation operation including the initial liquid separation is combined and concentrated, and the obtained product is obtained by a silica gel column chromatography (solvent: hexane/ethyl acetate). The crude product was purified, whereby 7.2 g of 2-bromo-6-(3-pentyl)pyridine was obtained. This compound was converted into the compound A1-30 by the same method as the synthesis of the compound A1-4.

Synthesis Example of Compound A1-31

Into a three-necked flask, 13.0 g of diisopropylamine and 200 mL of tetrahydrofuran (a commercially available dehydrating solvent) were introduced under a nitrogen atmosphere, and the mixture was cooled to -78 °C. 80.0 mL of a 1.6 M hexane solution of n-butyllithium was added dropwise thereto, and the mixture was stirred at -78 ° C for 15 minutes. 20 g of 2-bromo-6-methylpyridine was added dropwise thereto, and the mixture was stirred at -78 ° C for 30 minutes. After 17.7 g of 1-bromo-2-methylpropane was added dropwise thereto, the temperature was slowly raised to room temperature. After stirring at room temperature for 1 hour, 100 mL of a saturated aqueous solution of ammonium chloride was introduced and extracted. Liquid separation. 150 mL of ethyl acetate was introduced into the aqueous phase and extracted. Liquid separation. The organic phase obtained by the liquid separation operation of the total of 2 times was combined and concentrated, and the obtained crude product was purified by a silica gel column chromatography (solvent: hexane / ethyl acetate), whereby 18.8 g of 2 was obtained. -Bromo-6-(3-methylbutyl)pyridine. This compound was converted into the compound A1-31 by the same method as the synthesis of the compound A1-4.

Synthesis Example of Compound A1-32

2,6-Dibromo-4-trifluoromethylpyridine was synthesized by the method described in International Publication WO 2007/148738. 1.73 g of this compound was introduced into a three-necked flask, and 0.40 g of iron(III) chloride and 30 mL of tetrahydrofuran were introduced under a nitrogen atmosphere, and the mixture was stirred at room temperature. 2 mL of a 3 M diethyl ether solution of methylmagnesium bromide was added dropwise thereto, and the mixture was stirred at room temperature for 1.5 hours. Add saturated aqueous ammonium chloride solution 30mL, ethyl acetate 30mL, will be extracted by. The organic layer obtained by liquid separation was concentrated, and the obtained crude product was purified by silica gel column chromatography (solvent: hexane) to obtain 0.18 g of 2-bromo-6-methyl-4-trifluoromethylpyridine. . This compound was converted into the compound A1-32 by the same method as the synthesis of the compound A1-4.

Synthesis Example of Compound A1-33

In a three-necked flask, 1.44 g of compound A1-31, 1.11 g of trifluoromethanesulfonamide, 1.37 g of 4-dimethylaminopyridine, and 20 mL of dimethylformamide were introduced under a nitrogen atmosphere at room temperature. Stir in the night. 100 mL of water was introduced thereto, and while stirring at room temperature, concentrated hydrochloric acid was added until the pH became 1. The precipitated solid was recovered by filtration, and recrystallized from methanol, whereby 1.5 g of Compound A1-33 was obtained.

Synthesis Example of Compound A1-34

According to the procedure, the synthesis was carried out in the same manner as in the compound A1-33.

Synthesis Example of Compound A1-35

Perfluorobutsulfonamide synthesized by the method described in the literature of "Eur. J. Med. Chem." (2010, 45, 1225), using the compound A1 according to the procedure -33 The same method was used for the synthesis.

Synthesis Example of Compound A1-36

The compound A1-30 was used instead of the compound A1-31, and the synthesis was carried out in the same manner as the compound A1-33.

Synthesis Example of Compound A1-37

The compound A1-11 was used instead of the compound A1-31, and the synthesis was carried out in the same manner as the compound A1-33.

Synthesis Example of Compound A1-38

The compound A1-22 was used instead of the compound A1-31, and the synthesis was carried out in the same manner as the compound A1-33.

Synthesis Example of Compound A1-39

The compound A1-12 was used instead of the compound A1-31, and the synthesis was carried out in the same manner as in the compound A1-33.

Synthesis Example of Compound A1-40

Use mesalamine instead of trifluoromethanesulfonamide, using the same as compound A1-38 The method of synthesis.

Synthesis Example of Compound A1-41

The synthesis was carried out in the same manner as in the compound A1-38, using o-toluenesulfonamide instead of trifluoromethanesulfonamide.

Synthesis Example of Compound A1-42

The compound A1-27 was used instead of the compound A1-31, and the synthesis was carried out in the same manner as in the compound A1-33.

Synthesis example of compound A2-3

In a three-necked flask, 13.0 g of 2-ethylhexanol and 200 mL of tetrahydrofuran (a commercially available dehydrating solvent) were introduced under a nitrogen atmosphere, and the mixture was cooled to 0 °C. 4.0 g of sodium hydride (60% dispersion) was introduced thereto, and stirred at 0 ° C for 30 minutes. 15.0 g of bromoacetic acid was added dropwise thereto, and the mixture was stirred at room temperature for 5 hours. Add 200 mL of saturated ammonium chloride and 100 mL of ethyl acetate to extract. The organic layer obtained by liquid separation was concentrated, whereby 18.4 g of Compound A2-3 was obtained.

Synthesis example of compound A2-4

The synthesis was carried out in the same manner as in the compound A2-3 using a third butanol instead of 2-ethylhexanol.

Synthesis example of compound A2-7

The synthesis was carried out in the same manner as in the compound A2-3 using diethylene glycol monoethyl ether instead of 2-ethylhexanol.

Synthesis example of compound A2-10

2-(2-methyl-1,3-dioxan-2-yl)ethanol synthesized by the method described in J. Org. Chem. (1989, 54, 3625), The obtained product was reacted with bromoacetic acid in the same manner as in the compound A2-3, and the obtained product was heated under reflux at 80 ° C for 2 hours in concentrated hydrochloric acid, whereby acetal deprotection was carried out. The deprotection reaction solution was added to a saturated aqueous solution of sodium hydrogencarbonate for neutralization, and extracted with ethyl acetate. The liquid layer was separated, and the obtained organic layer was concentrated, whereby Compound A2-10 was obtained.

Synthesis example of compound A2-12

Into a three-necked flask, 7.2 g of β-propiolactone and 100 mL of methanol were introduced, and while stirring at room temperature, 19.3 g of sodium methoxide (28% methanol solution) was added dropwise thereto, and the mixture was heated under reflux at 50° C. for 2 hours. After cooling to room temperature, 13.9 g of bromoacetic acid was added dropwise, and the mixture was heated under reflux for 5 hours. Add 200 mL of saturated ammonium chloride and 100 mL of ethyl acetate to extract. The organic layer obtained by liquid separation was concentrated, whereby 12.4 g of Compound A2-12 was obtained.

Synthesis example of compound A2-13

Use 2,2,2-trifluoroethanol instead of 2-ethylhexanol, using phase with compound A2-3 The same method is used for the synthesis.

Synthesis example of compound A2-18

The synthesis was carried out in the same manner as in the compound A2-3 using methyl salicylate instead of 2-ethylhexanol.

Synthesis example of compound A2-19

The synthesis was carried out in the same manner as in the compound A2-3 using tetrahydropyran-2-methanol instead of 2-ethylhexanol.

Synthesis example of compound A2-21

The synthesis was carried out in the same manner as in the compound A2-3 using tetrahydrofurfuryl alcohol instead of 2-ethylhexanol.

Synthesis example of compound A2-22

The synthesis was carried out in the same manner as in the compound A2-3 using decyl alcohol instead of 2-ethylhexanol.

Synthesis example of compound A2-23

The synthesis was carried out by the method described in "Polymer" (2013, 54, 2924).

Synthesis example of compound A2-24

The synthesis was carried out in the same manner as in the compound A2-3 using 3-buten-1-ol in place of 2-ethylhexanol.

Synthesis Example of Compound A2-28

The synthesis was carried out in the same manner as in the compound A2-3 using 1,6-heptadien-4-ol in place of 2-ethylhexanol.

Synthesis example of compound A2-29

Into a three-necked flask, 15.3 g of 2-bromopropionic acid and 100 mL of methanol were introduced, and while stirring at room temperature, 19.3 g of sodium methoxide (28% methanol solution) was added dropwise thereto, and the mixture was heated under reflux at 50 ° C for 12 hours. The reaction solution was concentrated under reduced pressure, and then 1N diluted hydrochloric acid (100 mL) and ethyl acetate (100 mL) were added to extract. The organic layer obtained by liquid separation was concentrated, whereby 10.4 g of Compound A2-12 was obtained.

Synthesis Example of Compound A2-31

The synthesis was carried out by the method described in "J. Am. Chem. Soc." (1948, 70, 1157).

Synthesis example of compound A2-34

The synthesis was carried out in the same manner as in the compound A2-29 by using bromofluoroacetic acid synthesized by the method described in J. Org. Chem. (1957, 23, 1785.) instead of 2-bromopropionic acid. .

Synthesis example of compound A2-36

In a three-necked flask, 25.0 g of tetrahydropyran-2-methanol and 375 g of acetonitrile were introduced under a nitrogen atmosphere, and while stirring at room temperature, 2,2,6,6-tetramethylperazine was sequentially introduced. There were 2.4 g of pyridine-1-oxyl (TEMPO), 375 g of a phosphate buffer having a pH of 6.8, and 38.9 g of sodium chlorite. After 200.3 g of a 4% by mass aqueous solution of sodium hypochlorite was slowly added dropwise thereto, the mixture was stirred at 40 ° C for 6 hours. After cooling to room temperature, 700 mL of a saturated aqueous sodium hydrogencarbonate solution and 68 g of sodium sulfite were introduced. The mixture was washed three times with ethyl acetate (400 mL, 300 mL, 300 mL), and concentrated hydrochloric acid was slowly added until the pH was adjusted to 2. 3 extractions with ethyl acetate. The obtained organic layer was washed with 300 mL of water, followed by 300 mL of a saturated aqueous sodium chloride solution, and concentrated under reduced pressure to obtain 22.3 g of Compound 2-36.

Synthesis example of compound A2-40

Into a three-necked flask, 12.4 g of ethylene glycol and 200 mL of tetrahydrofuran (a commercially available dehydrating solvent) were introduced under a nitrogen atmosphere, and the mixture was cooled to 0 °C. 16.0 g of sodium hydride (60% dispersion) was introduced thereinto, and the mixture was stirred at 0 ° C for 30 minutes. 55.6 g of bromoacetic acid was added dropwise thereto, and the mixture was stirred at room temperature for 5 hours. Add 200 mL of saturated ammonium chloride and 100 mL of ethyl acetate to extract. The organic layer obtained by liquid separation was concentrated, whereby 32.4 g of Compound A2-3 was obtained.

Synthesis Example of Compound A2-41

The synthesis was carried out in the same manner as in the case of the compound A2-40, using diethylene glycol instead of ethylene glycol.

Synthesis Example of Compound A2-42

The synthesis was carried out in the same manner as in the compound A2-40 using 2,2-diethyl-1,3-propanediol in place of ethylene glycol.

Synthesis example of compound A2-44

The synthesis was carried out in the same manner as in the compound A2-40, using cis-1,2-cyclohexanediol instead of ethylene glycol.

In the present embodiment, the following abbreviation is employed.

<compound (A)>

Compound A1-1 to Compound A1-42: represents the compound A1-1 to the compound A1-42.

Compound A2-1 to Compound A2-44: represent the following compounds.

<hardening compound>

KAYARAD DPHA: (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.)

JER157S65: (manufactured by Mitsubishi Chemical Corporation, special novolak type epoxy resin)

KAYARAD D-320: (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol tetraacrylate)

M-510: (manufactured by Toagosei Co., Ltd., polyacid-modified acrylic oligomer)

M-520: (manufactured by Toagosei Co., Ltd., polyacid-modified acrylic oligomer)

DPCA-60: (manufactured by Nippon Kagaku Co., Ltd., hexafunctional acrylate with 6 pentyloxy chains)

<solvent>

PGMEA: propylene glycol monomethyl ether acetate

<Synthesis of copper complexes> <Synthesis of Copper Complex 1-1>

The sodium salt of Compound A1-1 (814 mg, 2.97 mmol) was dissolved in 50 ml of water. After the solution was heated to 50 ° C, an aqueous solution (50 ml) of copper sulfate pentahydrate (739 mg, 2.97 mmol) was added dropwise, and the mixture was reacted at 50 ° C for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, and the precipitated solid was recovered by filtration, whereby copper complex 1-1 (1.00 g) was obtained.

(Synthesis of copper complex 1-2~copper complex 1-55)

The copper complex 1-2 to copper complex 1-55 was obtained by a method according to the synthesis method of the copper complex 1-1.

(Synthesis of Copper Complex 2-1)

Compound A2-1 (886 mg, 9.84 mmol) was dissolved in 20 mL of methanol. After the temperature of the solution was raised to 50 ° C, a solution of copper hydroxide (449 mg, 4.60 mmol) in methanol (160 ml) was added dropwise, and the mixture was reacted at 50 ° C for 2 hours. After completion of the reaction, the produced water and solvent were distilled off by an evaporator, whereby copper complex 2-1 (1.00 g) was obtained.

(Synthesis of Copper Complex 2-2~ Copper Complex 2-26)

Copper complex 2-2~copper complex 2-26 is utilized according to the copper complex 2-1 Obtained by the method of synthesis.

(Synthesis of copper complex 2-27)

The sodium salt of the compound A2-3 (1.00 g, 4.76 mmol) was dissolved in 20 ml of methanol, and the mixture was heated to 50 ° C, and then a solution of copper sulfate pentahydrate (0.73 g, 2.92 mmol) in methanol (20 ml) was added dropwise. After heating at 50 ° C for 1 hour, the reaction solution was cooled to 5 ° C in an ice water bath, and the reaction mixture was filtered. The filtrate was concentrated using an evaporator, whereby copper complex 2-27 (1.14 g) was obtained.

(Synthesis Example of Copper Complex Cu4-36a)

Into a 100 mL flask, 1.99 g of copper (II) acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 1.67 g of a compound A3-59 (manufactured by Wako Pure Chemical Industries, Ltd.), and 20 mL of methanol were introduced, and the mixture was heated under reflux for 10 minutes. 1.84 g of a compound AA2-15 (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and further heated under reflux for 10 minutes. The solvent was concentrated under reduced pressure to about 5 mL, and the precipitated solid was filtered by adding 20 mL of water, thereby being modified, and the copper complex Cu4-36a was obtained as a blue solid.

(Synthesis Example of Copper Complex Cu4-39a)

To a 200 mL flask, 5.0 g of 4-methylthiazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.83 g of copper acetate (anhydrous) (manufactured by Wako Pure Chemical Industries, Ltd.), and 100 mL of toluene were added, and the mixture was heated under reflux for 12 hours. After cooling to room temperature, water was added and the precipitate was separated by filtration, and then the filtrate was separated by adding ethyl acetate. extraction. The obtained organic phase was pre-dried with anhydrous magnesium sulfate, and the crude brown product (containing a trace amount of the material) obtained by concentration under reduced pressure with methanol was recrystallized, whereby Compound AA-2-22 was obtained as a pale yellow solid. This compound was used for the complexation by the same method as the copper complex Cu4-36a.

(Synthesis Example of Copper Complex Cu4-45a)

In a 500 mL three-necked flask, 10 g of 3,5-dimethylpyrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 mL of dimethyl hydrazine were added and stirred under a nitrogen atmosphere. 23.3 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added in small portions, and the mixture was stirred at 60 ° C for 1 hour. 9 g of dibromomethane (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 40 mL of dimethyl hydrazine was added dropwise thereto, and the mixture was stirred at 60 ° C for 4 hours. After cooling to room temperature, add water After extracting with chloroform, 200 mL of the organic phase obtained by washing with water and saturated brine was concentrated under reduced pressure to obtain Compound AA2-32 as a white solid. This compound was used for the complexation by the same method as the copper complex Cu4-36a.

(Synthesis Example of Copper Complex Cu4-49a)

To a 100 mL flask, 0.20 g of compound AA2-32, 0.19 g of copper (II) acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), and 10 mL of methanol were added, and the mixture was heated from room temperature to 40 °C while stirring, and stirred for 30 minutes. After slowly dissolving and forming a blue solution, 10 mL of a methanol solution in which 0.15 g of a compound A3-96 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.16 g of a 50% by weight aqueous sodium hydroxide solution were dissolved was added dropwise. It was recovered by filtering a slowly precipitated blue-white solid to obtain 0.16 g of a copper complex Cu4-49a.

(Synthesis Example of Copper Complex Cu4-52a)

The synthesis was carried out by the same method as the copper complex Cu4-49a using a compound A3-103 commercially available from Tokyo Chemical Co., Ltd. as a chelatemic acid monohydrate.

<Evaluation of Near Infrared Absorbing Composition> <<Preparation of near-infrared absorbing composition>> (Example 1-1)

The near-infrared absorbing composition of Example 1-1 was prepared by mixing the following compounds.

The near-infrared absorption of each of the examples was prepared except that the copper complex 1-1 was changed to the copper complex 1-2 to the copper complex 1-55, and the same composition as in Example 1-1 was set. Sexual composition.

(Example 2-1)

The near-infrared absorbing composition of Example 2-1 was prepared by mixing the following compounds.

The examples were prepared in the same manner as in Example 2-1 except that the copper complex 2-1 was changed to the copper complex 2-2 to the copper complex 2-27 or copper acetate. The near-infrared absorbing composition of the comparative example.

<<Making of near infrared cutoff filter>>

A photoresist is applied onto the glass substrate, and patterned by lithography to form a partition wall of the photoresist, thereby forming a dropping region of the near-infrared absorbing composition. 3 ml of the near-infrared absorbing composition prepared in the examples and the comparative examples were added dropwise. The substrate with the coating film was allowed to stand at room temperature for 24 hours, and after drying, the coating film thickness was evaluated, and as a result, the film thickness was 192 μm.

<<Near infrared shielding evaluation>>

The transmittance of the obtained near-infrared cut filter at a wavelength of 800 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Co., Ltd.). The near-infrared shielding property was evaluated in accordance with the following criteria.

A: Transmittance at 800 nm ≦5%

B: 5% <800 nm transmittance ≦7%

C: transmittance of 7% < 800 nm ≦ 10%

D: transmittance of 10% < 800 nm

<<Heat resistance evaluation>>

The obtained near-infrared cut filter was allowed to stand at 200 ° C for 5 minutes. Before the heat resistance test and the heat resistance test, the maximum absorbance at a wavelength of 700 nm to 1400 nm of the near-infrared cut filter (Absλmax) was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-technologies Co., Ltd.). And the minimum absorbance (Absλmin) at a wavelength of 400 nm to 700 nm, and the absorbance ratio expressed by "Absλmax/Absλmin" is obtained.

Evaluation according to the following criteria|((absorbance ratio before test - absorbance after test) The ratio of the absorbance ratio expressed by the ratio of absorbance before the test to the ratio of ×100|(%). The results are shown in the table below.

A: Absorbance ratio change rate ≦2%

B: 2% < absorbance ratio change rate ≦ 4%

C: 4% < absorbance ratio change rate ≦ 7%

D: 7% < absorbance ratio change rate

It is clear from the table that the near-infrared absorbing composition of the examples is When the cured film is formed, the shielding property in the near-infrared range can also be improved. Further, it is understood that the near-infrared cut-off filters of the examples have a light transmittance of 80% or more at a wavelength of 550 nm, and can improve transmittance in the visible light range and shielding properties in the near-infrared range. Further, it was also confirmed that the near-infrared cut filter of the example has a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm and a light transmittance of 20% or less in a wavelength range of 800 nm to 900 nm. Further, it is also known that the near-infrared cut filter of the embodiment can ensure a wide visible light range with high transmittance and excellent spectral characteristics.

Example 1-1, Example 1-2, Example 1-12, Example 1-13, Example 1-22 to Example 1-24, Example 1-26, Example 1-30, Example In Examples 1-31, Examples 1-35, Examples 1-36, and Examples 1-38, the transmittance in the visible light range in a solution state was particularly good.

It can be seen that the embodiment 1-1, the embodiment 1-2, the embodiment 1-12, the embodiment 1-13, the embodiment 1-22 to the embodiment 1-24, the embodiment 1-26, the embodiment 1-30, The near-infrared absorbing composition of Example 1-31, Example 1-35, Example 1-36, and Example 1-38 was particularly excellent in light transmittance at 400 nm to 500 nm, and the light transmittance was 90% or more.

It was found that the near-infrared cut filter obtained by using the near-infrared absorbing compositions of Examples 1-13, 1-22 and 1-23 was particularly excellent in transmittance in the visible light range.

On the other hand, it is found that the near-infrared absorbing composition of the comparative example is less likely to have both the transmittance in the visible light range and the shielding property in the near-infrared range when the cured film is formed as compared with the examples.

In addition, in Examples 1-1 to 1-55 and Example 2-1~ In the near-infrared absorbing composition of Example 2-27, 20 parts by mass of a polymerizable compound (KAYARAD DPHA) was changed to an equivalent amount of KAYARAD D-320, Kayad A near-infrared cut filter can be obtained in the same manner as in the above embodiments except for M-510, KAYARAD M-520 or KAYARAD DPCA-60. The near-infrared cut-off filters can also be improved in the visible light range when the cured film is formed. Shedding in the range of irradiance and near infrared.

In addition, in Examples 1-1 to 1-55 and Example 2-1~ In the near-infrared absorbing composition of Example 2-27, 20 parts by mass of a polymerizable compound (KAYARAD DPHA) was changed to an equivalent amount of KAYARAD D-310, Kayad (KAYARAD) D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-120 (above manufactured by Nippon Kayaku Co., Ltd.) , M-305, M-460 (made in East Asia), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR-494 (manufactured by Sartomer), and Denacol EX-212L (long A near-infrared cut filter can be obtained in the same manner as in the above examples, except that Nagase Chemtex (manufactured by Nagase Chemtex) or JER-157S65 (manufactured by Mitsubishi Chemical Corporation). These near-infrared cut filters also have excellent effects similarly to the near-infrared cut filter of the embodiment 2-1.

Further, even in the near-infrared absorbing compositions of Examples 1-1 to 1-55 and Examples 2-1 to 2-27, the copper complex was added to the total solid content of the composition. When the content is set to 15% by mass, 20% by mass, 30% by mass or 40% by mass, excellent near-infrared light-shielding ability can be obtained in the same manner as in the above examples.

Further, even in the near-infrared absorbing compositions of Examples 1-1 to 1-55 and Examples 2-1 to 2-27, the content of the solvent (PGMEA) was set to 10% by mass and 20%. In the case of % by mass, 30% by mass or 40% by mass, excellent coating properties can be obtained similarly to the near-infrared absorbing compositions.

Further, in the near-infrared absorbing compositions of Examples 1-1 to 1-55 and Examples 2-1 to 2-27, DFA421NXEY (0.45 manufactured by Pall Japan) was used after preparing each composition. When the μm nylon filter is used for filtration, the same effect can be obtained.

(Example 3-1)

The near-infrared absorbing composition of Example 3-1 was prepared by mixing the following compounds.

Except that the copper complex Cu4-36a was changed to the copper complex Cu4-39a, the copper complex Cu4-45a, the copper complex Cu4-49a, and the copper complex Cu4-52a, it was set as in Example 3. The same composition of -1 was used, whereby the near-infrared absorbing composition of each example was prepared.

<Production of near-infrared cut filter>

A near-infrared cut filter is fabricated using the near-infrared absorbing composition.

A photoresist is applied onto the glass substrate, and patterned by lithography to form a partition wall of the photoresist, thereby forming a dropping region of the near-infrared absorbing composition. 3 ml of each near-infrared absorbing composition was dropped on the dropping area on the glass substrate, and left at room temperature for 24 hours to be dried. Evaluation of the film thickness of the coated film after drying, As a result, the film thickness was 100 μm.

<Measurement of Maximum Absorption Wavelength, Molar Absorption Coefficient, and Gram Absorption Coefficient of Copper Complexes>

A solution having a concentration of 1 g/L was prepared by dissolving various copper complexes in the solvent described in the table. Next, the absorption spectrum of the solution in which the copper complex was dissolved was measured using UV-1800 manufactured by Shimadzu Corporation, and the maximum absorption wavelength, the molar absorption coefficient at the maximum absorption wavelength, the gram absorption coefficient, and the molar absorption coefficient at 800 nm were measured. And gram absorption coefficient. Further, in the table, DMF represents N,N-dimethylformamide, and MFG represents propylene glycol monomethyl ether.

<<Near infrared shielding evaluation>>

The transmittance of the near-infrared cut filter obtained as described above at a wavelength of 800 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Co., Ltd.). The near-infrared shielding property was evaluated in accordance with the following criteria. The results are shown in the table below.

A: Transmittance at 800 nm ≦5%

B: 5% <800 nm transmittance ≦ 25%

C: transmittance of 25% <800 nm

<<visible light transmittance evaluation>>

The transmittance of the near-infrared cut filter obtained as described above at a wavelength of 550 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Co., Ltd.). The visible light transmittance was evaluated in accordance with the following criteria. The results are shown in the table below.

A: 85% 透射 wavelength 550nm transmittance

B: 45% ≦ wavelength 550nm transmittance <85%

C: transmittance at a wavelength of 550 nm <45%

As is apparent from the above table, the near-infrared absorbing composition of the example can also improve the shielding property in the near-infrared range when the cured film is formed. Further, the visible light transmittance is also good.

Further, in the near-infrared absorbing composition of Example 3-1 to Example 3-5, 20 parts by mass of a polymerizable compound (KAYARAD DPHA) was changed to an equivalent amount of Kayarad ( KAYARAD) D-320, KAYARAD M-510, KAYARAD M-520 or KAYARAD DPCA-60, except for these embodiments A near-infrared cut filter is obtained. These near-infrared cut filters can also improve the transmittance in the visible light range and the shielding property in the near-infrared range when the cured film is formed.

Further, in the near-infrared absorbing composition of Example 3-1 to Example 3-5, 20 parts by mass of a polymerizable compound (KAYARAD DPHA) was changed to an equivalent amount of Kayarad ( KAYARAD) D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-120 ( The above is manufactured by Nippon Kayaku Co., Ltd.), M-305, M-460 (made in East Asia), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR-494 (manufactured by Sartomer Co., Ltd.), Daina In addition to the above, the near-infrared cutoff can be obtained in the same manner as the above examples, except that Denacol EX-212L (manufactured by Nagase Chemtex Co., Ltd.) or JER-157S65 (manufactured by Mitsubishi Chemical Corporation). filter.

Further, even in the near-infrared absorbing composition of Examples 3-1 to 3-5, the content of the copper complex with respect to the total solid content of the composition was set to 15% by mass, 20% by mass, and 30%. In the case of % by mass or 40% by mass, excellent near-infrared light-shielding ability can be obtained in the same manner as in the above embodiments.

Further, even in the near-infrared absorbing composition of Examples 3-1 to 3-5, the content of the solvent (PGMEA) was set to 10% by mass, 20% by mass, 30% by mass or 40% by mass. In the same manner, excellent coating properties can be obtained similarly to the near-infrared absorbing compositions.

Further, in the near-infrared absorbing composition of Examples 3-1 to 3-5, when each composition was prepared and then filtered using DFA421NXEY (0.45 μm nylon filter) manufactured by Pall Japan, The same effect can be obtained.

Claims (18)

A near-infrared absorbing composition containing a copper complex which is a compound having a coordination site coordinated by an anion and a coordination atom coordinated by a non-covalent electron pair ( A) It is formed by reacting with copper components. A near-infrared absorbing composition containing a copper complex which has copper as a central metal and has a coordination site coordinated by an anion and coordinated with a non-covalent electron pair The compound (A) of the coordinating atom serves as a ligand. The near-infrared absorbing composition according to claim 1 or 2, wherein the copper complex is formed by copper and the compound (A) to form a 5-membered ring and/or a 6-membered ring. . The near-infrared absorbing composition according to claim 1 or 2, wherein the anion in the compound (A) is an oxyanion, a nitrogen anion or a sulfur anion, and the non-covalent electron The coordinating atom to be coordinated is an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. The near-infrared absorbing composition according to claim 1 or 2, wherein the number of atoms linking the anion to the coordinating atom coordinated by the non-covalent electron pair is 1 to 3 . The near-infrared absorbing composition according to the first or second aspect of the invention, wherein the compound (A) has a molecular weight of 50 to 1,000. The near-infrared absorbing composition according to claim 1 or 2, wherein the compound (A) is a compound having a 5-membered ring or a 6-membered ring, and The coordinating atom coordinated by a non-covalent electron pair is an atom constituting a 5-membered ring or a 6-membered ring. The near-infrared absorbing composition according to claim 1 or 2, wherein the coordinating atom coordinated by the non-covalent electron pair is a nitrogen atom. The near-infrared absorbing composition according to claim 8, wherein an atom adjacent to the nitrogen atom is a carbon atom, and the carbon atom has a substituent. The near-infrared absorbing composition according to claim 1 or 2, wherein the compound (A) is represented by the formula (I); In the formula (I), X ¹ represents a group containing the coordination site coordinated by an anion; Y ¹ represents a nitrogen atom or a phosphorus atom, and together with adjacent carbon atoms constitutes a 4-membered ring to a 7-membered ring; ^X1 represents a substituent, and n1 represents an integer of 0-6. The near-infrared absorbing composition according to claim 10, wherein in the formula (I), a ring formed by Y ¹ together with an adjacent carbon atom is an aromatic ring. The near-infrared absorbing composition according to claim 1 or 2, wherein the coordination site coordinated by the anion is at least one selected from the group consisting of (AN), a group ( AN) The coordinating atom coordinated by a non-covalent electron pair is contained in a ring or contained in at least one partial structure selected from the group consisting of (UE), group (UE) The wavy line is a bonding position with the atomic group constituting the compound (A), X represents N or CR, and R and R ¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. R ² independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group or a heteroaromatic sulfur. Base, amine or sulfhydryl. The near-infrared absorbing composition according to claim 1 or 2, wherein the compound (A) is represented by the following general formula (IV); and the X ¹ -L ¹ -Y ¹ formula ( IV) In the general formula (IV), X ¹ represents a coordination site selected from at least one of the following groups (AN), which is coordinated by an anion, group (AN) Y ¹ represents a ring containing the coordinating atom coordinated by a non-covalent electron pair, or at least one selected from the group consisting of a coordinating atom coordinated by a non-covalent electron pair Partial structure, group (UE) The wavy line is a bonding position with the atomic group constituting the compound (A), X represents N or CR, and R and R ¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. R ² independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group or a heteroaromatic sulfur. A group, an amine group or a thiol group, and L ¹ represents a single bond or a divalent linking group. The near-infrared absorbing composition according to the first or second aspect of the invention, further comprising a curable compound and a solvent. A near-infrared ray-cutting filter which is obtained by hardening a near-infrared absorbing composition according to any one of claims 1 to 14. A method of manufacturing a near-infrared ray-cut filter, comprising: coating a near-infrared absorbing composition according to any one of claims 1 to 14 on the light-receiving side of the solid-state imaging device, whereby The step of forming a film. A camera module having a solid-state imaging element and a near-infrared cut filter disposed on a light receiving side of the solid-state imaging element, and the near infrared ray The cut-off filter is a near-infrared cut filter obtained by hardening the near-infrared absorbing composition according to any one of the first to fourteenth aspects of the invention. A method of manufacturing a camera module, comprising: a solid-state image sensor; and a camera module disposed on a light-receiving side near-infrared cut filter of the solid-state image sensor; and the method of manufacturing the camera module includes: The step of forming the near-infrared cut filter by applying the near-infrared absorbing composition according to any one of claims 1 to 14 to the light-receiving side of the solid-state image sensor.