KR20150143675A - Near-infrared absorbing composition, near-infrared blocking filter using same, method for producing said near-infrared blocking filter, camera module, and method for manufacturing said camera module - Google Patents

Abstract

A near infrared ray absorbing composition capable of forming a cured film excellent in heat resistance while maintaining a high near infrared ray shielding property, a near infrared ray shielding filter using the same, a camera module, and a manufacturing method thereof. A near infrared absorbing composition comprising a compound obtained by reacting a fluorine atom-containing polymer (A) with a copper component, wherein the blending amount of the polymer (A) relative to the total solid content in the composition is 10 mass% or more.

Description

[0001] The present invention relates to a near infrared ray absorbing composition, a near infrared ray absorbing composition using the same, a manufacturing method thereof, and a camera module and a manufacturing method thereof. BACKGROUND OF THE INVENTION METHOD FOR MANUFACTURING SAID CAMERA MODULE}

The present invention relates to a near-infrared light absorbing composition, a near-infrared ray blocking filter using the same, a method of manufacturing the same, a camera module, and a manufacturing method thereof.

2. Description of the Related Art A CCD or CMOS image sensor, which is a solid-state image pickup device for a color image, is used for a video camera, a digital still camera, or a mobile phone having a camera function. Since the solid-state image pickup device uses 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 cutoff filter (hereinafter also referred to as an IR cutoff filter) is often used.

As a material of the near-infrared ray cut filter, Patent Document 1 discloses a material for infrared blocking property which is obtained by adding a metal compound to a copolymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof and a compound having an ethylenic unsaturated bond Discloses an infrared shielding film comprising a resin.

Patent Document 1: JP-A-2010-134457

Here, the infrared shielding resin disclosed in Patent Document 1 is considered to have insufficient heat resistance.

An object of the present invention is to provide a near infrared absorbing composition capable of forming a cured film excellent in heat resistance while maintaining a high near infrared ray shielding property.

Concretely, the above problems are solved by the following means <1>, preferably by <2> to <18>.

<1> A near-infrared light absorbing composition comprising a compound obtained by reacting a fluorine atom-containing polymer (A) with a copper component, wherein a blending amount of the polymer (A) relative to the total solid content in the composition is 10 mass% or more.

<2> A near infrared absorbing composition comprising a fluorine atom-containing polymer (A) and at least one of copper ion and copper compound, wherein the blend amount of the polymer (A) relative to the total solid content in the composition is 10% Composition.

(3) The near-infrared absorbing composition according to (1) or (2), wherein the polymer (A) is a polymer (A2) further comprising an acid group or a salt thereof.

<4> The near infrared absorbing composition according to <3>, wherein the acid group or a salt thereof is at least one selected from a carboxylic acid group and a salt thereof, a phosphoric acid group and a salt thereof, and a sulfonic acid group and a salt thereof.

<5> The polymer composition according to any one of <1> to <4>, wherein the polymer (A) comprises at least one of the structural units represented by the following formulas (A2-1), (A2-2) A near-infrared absorbing composition as described;

[Chemical Formula 1]

Formula (A2-1) of, R ¹ is an aliphatic hydrocarbon, Y ¹ denotes a single bond or a divalent linking group, X ¹ is a group or an salt thereof, R ¹ and Y ¹ is a fluorine atom, at least one of &Lt; / RTI &gt;

Formula (A2-2) of, R ² is an aliphatic hydrocarbon, R ³ represents an hydrocarbon, Y ² denotes a single bond or a divalent connecting group, R ^2, R ³ and Y ² at least one of a fluorine- Substituted by an atom;

In formula (A2-3), Ar ¹ represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, R ⁴ represents an organic group, Y ³ represents a single bond or a divalent linking group, X ² represents an acid group or a salt thereof , And at least one of Ar ¹ , R ⁴ and Y ³ is substituted with a fluorine atom.

&Lt; 6 > The polymer according to any one of < 1 > to < 5 >, wherein the polymer comprises at least one member selected from the structural units represented by the following formulas (A2-1-1), (A2-2-1) A near infrared absorbing composition according to any one of claims 1 to 5;

(2)

Equation (A2-1-1) of, R ⁵ and R ⁶ each independently represents a hydrogen atom, a methyl group or a fluorine atom, Y ⁴ represents a single bond or a divalent linking group, X ³ represents a group or a salt thereof ;

In formula (A2-2-1), R ⁷ and R ⁸ each independently represent a hydrogen atom, a methyl group or a fluorine atom, Y ⁵ represents a single bond or a divalent linking group, R ⁹ represents an alkyl group or an aryl group, At least one of R ⁷ , R ⁸ , Y ⁵ and R ⁹ is substituted with a fluorine atom;

In formula (A2-3), Ar ¹ represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, R ⁴ represents an organic group, Y ³ represents a single bond or a divalent linking group, X ² represents an acid group or a salt thereof , And at least one of Ar ¹ , R ⁴ and Y ³ is substituted with a fluorine atom.

&Lt; 7 >, wherein the polymer (A) is at least one selected from the group consisting of (A2-1-1-1), (A2-1-1-2), (A2-3-1) The near infrared absorbing composition according to any one of < 1 > to < 6 >, wherein the near infrared absorbing composition has at least one member selected from constituent units;

(3)

(In the formula (A2-1-1-1), L ¹ represents a single bond or a linking group of (n 2 + 1), n 2 represents an integer of 1 to 5, and X ⁴ represents an acid group or a salt thereof;

Equation (A2-1-1-2) of, Y ⁶ is a straight chain, branched or cyclic alkylene group, arylene group, -C (= O) O-, -O-, or -C (= O) - NR '- (R' is a hydrogen atom or an alkyl group), or a combination thereof, Rf ¹ represents a divalent linking group containing a fluorine atom, and X ⁵ represents an acid group or a salt thereof;

In formula (A2-3-1), Ar ² represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Rf ² represents an alkyl group substituted by a fluorine atom or a fluorine atom, and X ⁶ represents an acid group or a salt thereof;

Equation (A2-2-1-1) of, Y ⁷ represents a single bond, a straight chain, branched or cyclic alkylene group, -C (= O) O-, -O-, or represents a group composed of a combination thereof , And Rf ³ represents an alkyl group or aryl group substituted with a fluorine atom.

The acid generator or salt thereof according to any one of <5> to <7>, wherein the acid generator or salt thereof is selected from at least one selected from a carboxylic acid group and a salt thereof, a phosphoric acid group and a salt thereof, Near infrared absorptive composition.

<9> The near infrared absorbing composition according to <8>, wherein the acid group or a salt thereof is a sulfonic acid group or a salt thereof, respectively.

<10> The near IR absorptive composition according to any one of <1> to <9>, wherein the polymer does not contain a C-H bond.

<11> The near infrared ray absorbing composition according to any one of <1> to <10>, wherein the polymer (A) contains fluorine atoms in a proportion of 10 mass% or more.

<12> The near infrared absorbing composition according to any one of <1> to <11>, further containing water.

&Lt; 13 > The near infrared ray absorbing composition according to < 2 >, wherein the polymer (A) is a polymer (A3) containing an acid group ion and the acid group ion contains a copper complex to be added to the copper ion.

<14> A near infrared ray blocking filter obtained by using the near infrared absorbing composition according to any one of <1> to <13>.

<15> The near infrared ray blocking filter according to <14>, wherein the rate of change of the absorbance ratio obtained by the following equation before and after heating at 200 ° C for 5 minutes is 5% or less.

[(Absorbance ratio before heating - Absorbance ratio after heating) / Absorbance ratio before heating]

Here, the term "absorbance ratio" refers to a value obtained by dividing the maximum absorbance at a wavelength of 700 to 1400 nm by the minimum absorbance at a wavelength of 400 to 700 nm.

<16> A manufacturing method of a near-infrared light blocking filter, comprising a step of forming a film by applying a near infrared absorbing composition described in <1> to <13> on a light receiving side of a solid-state imaging element substrate.

<17> A camera module having a solid-state imaging element substrate and a near-infrared ray blocking filter disposed on a light receiving side of the solid-state imaging element substrate, wherein the near-infrared ray blocking filter is a near-infrared ray blocking filter described in <14> or <15>.

<18> A manufacturing method of a camera module having a solid-state imaging element substrate and a near-IR blocking filter disposed on a light-receiving side of the solid-state imaging element substrate, A method for manufacturing a camera module, comprising the step of forming a film by applying the near infrared absorbing composition according to claim 1.

According to the present invention, it becomes possible to provide a cured film excellent in heat resistance while maintaining a high near infrared ray shielding property.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an image diagram showing an example of a polymer complex state with a polymer (A1) according to a first embodiment of the present invention. FIG.
2 is an image diagram showing an example of a compound containing a polymer (A2) and a copper ion according to the second embodiment of the present invention.
3 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image pickup device according to an embodiment of the present invention.
4 is a schematic cross-sectional view of a solid-state imaging element substrate according to an embodiment of the present invention.

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

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

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acrylic and methacryl, "(meth) acryloyl" Represents &lt; / RTI &gt;

As used herein, "monomer" and "monomer" are synonyms, and "polymer" and "polymer" are synonyms.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent.

The near infrared ray in the present invention means the maximum absorption wavelength region of 700 to 2500 nm, particularly 700 to 1000 nm.

The near infrared ray absorbency in the present invention means that the near infrared ray region has the maximum absorption wavelength.

The main chain of the polymer in the present invention refers to an atom or an atomic group necessary for forming a skeleton (long chain) of a polymer. When a part or the whole of the skeleton is a cyclic group (for example, an aryl group) As part of the prayer chain. The atom directly bonded to the main chain is also part of the main chain. The side chain of the polymer in the present invention refers to a portion other than the main chain. However, the side chain is also a functional group directly bonded to the main chain (for example, an acid group or salt thereof described later).

<Near infrared absorptive composition of the present invention>

The near infrared absorbing composition of the present invention is a near infrared absorbing composition comprising a compound obtained by reacting a fluorine atom-containing polymer (A) with a copper component, wherein the blending amount of the polymer (A) relative to the total solid content in the composition is 10% Or more. The near infrared absorbing composition of the present invention is a near infrared absorbing composition comprising a polymer (A) containing a fluorine atom and at least one of a copper ion and a copper compound, wherein the blending amount of the polymer (A) relative to the total solid content in the composition Is not less than 10% by mass. By using the fluorine atom-containing polymer (A), a cured film having excellent heat resistance can be formed.

Hereinafter, specific embodiments of the near infrared absorbing composition will be described.

<First Embodiment of Near IR Absorbent Composition of the Present Invention>

The first embodiment of the composition of the present invention is an embodiment in which a copper compound is contained separately from the polymer (A) containing a fluorine atom. In the present embodiment, the polymer (A) containing a fluorine atom is usually a polymer which does not contain an acid group or a salt thereof, and hereinafter may be referred to as a polymer (A1).

In this embodiment, apart from the polymer (A1), a copper compound, preferably a copper complex, is included. 1A is a schematic diagram showing the polymer A1, 2A is a copper complex, and 3A is a main chain of the polymer (A1). Fig. 1 is an image showing an example of the polymer A1 and the copper complex state in the first embodiment. , And 4A represents the side chain of the polymer (A1). In the present embodiment, as shown in Fig. 1, it can be considered that part or all of the copper complex 2A is present in the polymer A1. The polymer (A2) described later may also contain a compound obtained by reacting a copper component within a range not deviating from the object of the present invention.

<< Polymer (A1) Containing Fluorine Atoms >>

The fluorine atom-containing polymer (A1) used in the present invention is preferably 10 mass% or more of the fluorine atom, more preferably 20 mass% or more, and 40 mass% or more. By setting the ratio of fluorine atoms in the polymer (A1) to 10% by mass or more, a cured film having excellent heat resistance can be obtained. The upper limit of the amount of fluorine atoms in the polymer (A1) is not particularly limited, but may be, for example, 60 mass% or less. As the polymer (A1), only one type may be used, but two or more types may be used.

Here, the polymer (A1) used in the present invention can be applied to any polymer other than a surfactant containing a fluorine atom.

The polymer (A1) preferably has no C-H bond. That is, it is preferable that not all carbon atoms contained in the polymer (A1) are bonded to hydrogen atoms. Specifically, the fluorine atom substitution ratio of the polymer (A1) is preferably 30% or more, more preferably 50% or more, and even more preferably 100%. Here, the fluorine atom substitution ratio is defined as CF / (CF + CH) when the total number of C-F bonds contained in the polymer (A1) is CF and the total number of C-H bonds contained in the polymer (A1) is CH.

The weight average molecular weight of the polymer (A1) used in the present invention is preferably 1,000 or more, more preferably 1,500 to 2,000, and still more preferably 5,000 to 400,000.

The blending amount of the polymer (A1) relative to the total solid content in the composition of the present invention is 10 mass% or more, preferably 50 mass% or more, and more preferably 65 mass% or more. The upper limit of the amount of the polymer (A1) to be added to the total solid content in the composition of the present invention is not particularly limited, but is preferably 95% by mass or less.

<< Copper compounds >>

In the first embodiment of the composition of the present invention, usually, a copper compound is included. The copper compound is not particularly limited as long as the maximum absorption wavelength region has a maximum absorption wavelength in the range of 700 to 2500 nm, preferably 700 to 1000 nm (near-infrared region). As the copper compound used in the present embodiment, only one species may be used, or two or more species may be used. The copper compound used in the present embodiment is preferably a copper complex. Copper complexes are copper compounds for ligands in the copper of the central metal, and copper is usually bivalent copper. For example, by mixing and reacting a compound or salt thereof as a ligand with respect to a copper component. As the copper component, a copper component described in the second embodiment to be described later can be preferably employed.

In the copper complex, the ligand L coordinated to the copper is not particularly limited as long as it is capable of coordinating with the copper ion. Examples of the ligand L include a sulfonic acid, a carboxylic acid, a carbonyl (ester, ketone), an amine, an amide, Phosphorus, urea, alcohol, thiol, and the like. Of these, phosphoric acid, phosphoric acid ester, phosphonic acid, phosphonic acid ester, phosphinic acid, substituted phosphinic acid, carboxylic acid and sulfonic acid are preferable, and sulfonic acid is more preferable.

Specific examples of the copper complexes include a phosphorus-containing copper compound, a copper sulfonate compound, or a copper compound represented by the following formula (A). Specific examples of the phosphorus-containing copper compound include compounds described in WO2005 / 030898, page 5, line 27 to page 7, line 20, the contents of which are incorporated herein by reference.

Examples of the copper complexes include copper complexes represented by the following formula (A).

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

In the formula (A), L represents a ligand to be coordinated to copper, X is absent, or a halogen atom, H ₂ O, NO ₃ , ClO ₄ , SO ₄ , CN, SCN, BF ₄ , PF 6 , BPh ₄ (Ph represents a phenyl group), or an alcohol. n1 and n2 each independently represent an integer of 1 to 4;

The ligand L has a substituent containing C, N, O, S as an atom capable of coordinating to copper, more preferably a group having a lone pair of electrons such as N, O, S or the like. The group capable of coordination is not limited to one species within the molecule, and may include two or more species, may be dissociated, or may be resent. In contrast, X does not exist.

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

The compound or salt thereof to be a ligand is not particularly limited, and examples thereof include an organic acid compound (for example, a sulfonic acid compound, a carboxylic acid compound, a phosphate compound) or a salt thereof.

The compound or its salt as the ligand is preferably a compound containing an acid group or a salt thereof, and is preferably represented by the following general formula (i).

In general formula (i)

[Chemical Formula 4]

(In the general formula (i), R ¹ represents an organic group of n, X ¹ represents an acid group, and n represents an integer of 1 to 6.)

In the general formula (i), the n-valent organic group is preferably a hydrocarbon group or an oxyalkylene group, more preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent. Examples of the substituent include a group having a halogen atom (preferably a fluorine atom), a (meth) acryloyl group or an unsaturated double bond.

When the hydrocarbon group is monovalent, an alkyl group or an aryl group is preferable, and an aryl group is more preferable. When divalent, an alkylene group, an arylene group and an oxyalkylene group are preferable, and an arylene group is more preferable. When the trivalent or more is present, it is preferable that the hydrocarbon groups correspond to the hydrocarbon groups.

The alkyl group and the alkylene group preferably have 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

The number of carbon atoms of the aryl group and the arylene group is preferably 6 to 18, more preferably 6 to 12.

In the general formula (i), X ¹ is preferably at least one of a sulfonic acid group, a carboxylic acid group and an acid group containing a phosphorus atom. X ¹ may be a single species or two or more species, but preferably two or more species.

In the general formula (i), n is preferably 1 to 3, more preferably 2 or 3, and more preferably 3.

The molecular weight of the compound or the salt thereof (acid group or a salt thereof) as the ligand is preferably 1,000 or less, more preferably 70 to 1,000, and still more preferably 70 to 500.

Preferred examples of the compound containing an acid group or a salt thereof include (1) a compound having at least one of a sulfonic acid group, a carboxylic acid group and an acid group containing a phosphorus atom, more preferably (2) (3) an embodiment having a sulfonic acid group and a carboxylic acid group. In these embodiments, the infrared absorbing ability is more effectively exerted. Further, by using a compound having a sulfonic acid group and a carboxylic acid group, the color value can be further improved.

(1) Specific examples of the compound having at least one of a sulfonic acid group, a carboxylic acid group and an acid group containing a phosphorus atom include the following. Specific examples of the sulfonic acid compound having a sulfonic acid group include specific examples of the sulfonic acid compound represented by the formula (I) described later. Among the compounds described in the following embodiments (2) and (3), the compounds corresponding to this embodiment are also preferable.

[Chemical Formula 5]

(2) Specific examples of the compound having at least two acid groups include the following. Among the compounds described in the later-described embodiment (3), preferred examples include compounds corresponding to this embodiment.

[Chemical Formula 6]

(3) Specific examples of the compound having a sulfonic acid group and a carboxylic acid group include the following. Specific examples of the compound having a sulfonic acid group and a carboxylic acid group represented by the formula (I) described later are also exemplified.

(7)

As another copper complex which can be used in the present invention, a copper complex obtained by reacting a sulfonic acid compound represented by the following formula (I) or a salt thereof with a copper component is also preferable.

In formula (I)

[Chemical Formula 8]

(In the formula (I), R ⁷ represents a monovalent organic group.)

Specific examples of monovalent organic groups include, but are not limited to, linear, branched or cyclic alkyl groups, alkenyl groups and aryl groups. Here, these groups may be substituted with a divalent linking group (e.g., an alkylene group, a cycloalkylene group, an arylene group, -O-, -S-, -CO-, -C (= O) O-, -OCO-, SO ₂ -, -NR- (R is a hydrogen atom or an alkyl group), etc.). The monovalent organic group may have a substituent.

As the straight-chain or branched alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.

The cyclic alkyl group may be monocyclic or polycyclic. 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, and still more preferably a cycloalkyl group having 6 to 10 carbon atoms. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, an alkenyl group having 2 to 8 carbon atoms is more preferable, and an alkenyl group having 2 to 4 carbon atoms is more preferable.

The aryl group is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.

Examples of the divalent linking group alkylene group, cycloalkylene group and arylene group include divalent linking groups derived by removing one hydrogen atom from the above-mentioned alkyl group, cycloalkyl group and aryl group.

Examples of the substituent which the monovalent organic group may have include an alkyl group and a polymerizable group such as a vinyl group, a (meth) acryloyl group, an epoxy group, an oxetane group and the like), a halogen atom, a carboxyl group, (For example, -CO ₂ CH ₃ ), a hydroxyl group, an amide group, a halogenated alkyl group (for example, a fluoroalkyl group, a chloroalkyl group) and the like.

The molecular weight of the sulfonic acid compound represented by the following formula (I) or its salt is preferably 80 to 750, more preferably 80 to 600, and even more preferably 80 to 450.

Specific examples of the sulfonic acid compound represented by the formula (I) are shown below, but the present invention is not limited thereto.

[Chemical Formula 9]

[Chemical formula 10]

The sulfonic acid compound that can be used in the present invention may be a commercially available sulfonic acid or may be synthesized by referring to a known method.

Examples of the salt of the sulfonic acid compound that can be used in the present invention include a metal salt, and specific examples thereof include a sodium salt and a potassium salt.

In addition to the above, a copper complex having a carboxylic acid as a ligand is also preferably used. As the carboxylic acid used for the copper complex having a carboxylic acid as a ligand, for example, a compound represented by the following formula (K) can be used.

(11)

(In the formula (K), R ¹ represents a monovalent organic group.)

In the formula (K), R ¹ represents a monovalent organic group. The monovalent organic group is not particularly limited, but is, for example, the same as the monovalent organic group in the above-mentioned formula (I).

The copper content in the copper compound used in the present invention is preferably 2 to 40 mass%, more preferably 5 to 40 mass%, of the total solid content. When a copper complex is used as the copper component, the content of the copper complex is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, based on the total solid content of the composition of the present invention.

<Second Embodiment of Near IR Absorbent Composition of the Present Invention>

The second embodiment of the near infrared absorbing composition of the present invention is an embodiment wherein the polymer (A) containing a fluorine atom contains an acid group or a salt thereof and a fluorine atom. Hereinafter, the polymer containing an acid group or a salt thereof and a fluorine atom may be referred to as polymer (A2). In the present embodiment, the polymer A2 includes a compound obtained by reacting a copper component, and the blending amount of the polymer (A2) relative to the total solid content in the composition is 10% by mass or more. The polymer (A2) may contain only one acid group or a salt thereof, or may contain two or more acid groups or salts thereof.

By using the compound obtained by reacting the polymer (A2) with the copper component, a cured film having excellent heat resistance can be formed while maintaining a high near infrared ray shielding property.

Here, when the polymer (A2) is reacted with the copper component, for example, a compound containing a polymer (A3) containing an acid group ion and a fluorine atom and a copper ion is obtained.

Fig. 2 is an image showing an example of a compound (A3) containing an acid group ion and a fluorine atom and a compound containing a copper ion, wherein 1B is a polymer (A3) containing an acid group ion and a fluorine atom, 2B represents a copper ion, 3B represents a main chain of the polymer (A3), 4B represents a side chain of the polymer (A3), and 5 represents an acid group ionic site (5) derived from an acid group or a salt thereof. In the present invention, the acid ion site 5 is bonded (e.g., coordinately bonded) to the copper ion 2B to form a bridge between the side chains 4 of the polymer A3 with the copper ion 2B as a starting point. Structure. With such a constitution, even when heated, it is presumed that the structure of the compound (1) is hardly collapsed and, as a result, a cured film excellent in heat resistance is obtained. In addition, in the present embodiment, since the polymer can be coordinately bound with copper, the content of copper in the composition can be increased. As a result, the infrared shielding property tends to be further improved.

The near infrared absorbing composition of the second embodiment of the present invention contains 20 mass% or more of the polymer (A2) in a proportion of 10 mass% or more of the total solid content of the composition, % Or more.

The content of the compound obtained by the reaction of the polymer (A2) with the copper component is preferably 60 to 100 mass%, more preferably 70 to 100 mass%, of the total solid content of the composition of the present invention.

When the near infrared absorbing composition of the present invention contains a low molecular weight compound containing a compound obtained by the reaction of the polymer (A2) and a copper component and a later-described acid group or a salt thereof and a copper complex obtained by a reaction of a copper component, (A2) and the copper component is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, still more preferably 15 to 70% by mass, with respect to the total solid content in the composition , And still more preferably from 20 to 70 mass%.

<< Copper Ingredients >>

As the copper component, a compound containing divalent copper is preferable. The copper content in the copper component used in the present invention is preferably 2 to 90 mass%, and more preferably 10 to 70 mass%. The copper component may be used alone, or two or more copper components may be used.

As the copper component, for example, a compound containing copper or copper can be used. As the compound containing copper, for example, copper oxide or copper salt can be used. The copper salt is preferably a monovalent or divalent copper, and more preferably a divalent copper. Examples of the copper salts include copper salts such as copper hydroxide, copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethylacetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate, (Meth) acrylate and copper perchlorate are exemplified, and copper hydroxide, copper acetate, copper chloride, copper sulfate, copper benzoate and copper (meth) acrylate are more preferable, and copper hydroxide, copper acetate and copper sulfate Is particularly preferable.

The amount of the copper component to be reacted with the polymer (A2) is preferably 0.01 to 1 equivalent, more preferably 0.1 to 0.6 equivalent, more preferably 0.4 to 0.5 equivalent, per 1 equivalent of the acid group or the salt thereof of the polymer (A2) Do. With such a range, a cured film having a higher near-infrared ray shielding property tends to be obtained.

<< Polymers containing an acid group or a salt thereof and a fluorine atom (A2) >>

The polymer (A2) contains an acid group or a salt thereof, but such an acid group or a salt thereof may be one kind or two or more kinds.

The acid group of the polymer (A2) is not particularly limited as long as it is capable of reacting with the above-mentioned copper component, but it is preferably coordinated with the copper component. For example, an acid group having an acid dissociation constant (pKa) of 5 or less can be mentioned, and a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group and an imidic acid group are preferable.

Examples of the atoms or atomic groups constituting the acid group salt used in the present invention include atomic groups such as metal atoms (particularly alkali metal atoms) such as sodium, tetrabutylammonium and the like, preferably metal atoms and more preferably alkali metal atoms .

Among the acid groups or salts thereof, those containing at least one member selected from, for example, carboxylic acid groups and salts thereof, phosphoric acid groups and salts thereof, sulfonic acid groups and salts thereof are preferable.

In the polymer (A2), 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 at least in the side chain.

The acid value of the polymer (A2) is preferably 1.0 meq / g or more, more preferably 1.7 to 4.5 meq / g.

It is also preferable that 99 mol% or more of the total acid groups in the polymer (A2) is at least one selected from a carboxylic acid group and a salt thereof, a phosphoric acid group and a salt thereof, and a sulfonic acid group and a salt thereof. Particularly, it is preferable that 80 mol% or more of the total acid groups in the polymer (A2) is a sulfonic acid group and a salt thereof.

The polymer (A2) preferably contains a constitutional unit represented by at least any one of the following formulas (A2-1), (A2-2) and (A2-3) (A2-1-1-1), (A2-1-1), (A2-2-1), (A2-2-1) or (A2-3), or a combination thereof. 1-2), (A2-3-1), or (A2-2-1-1), or a combination thereof.

[Chemical Formula 12]

(Formula (A2-1) of, R ¹ is an aliphatic hydrocarbon, Y ¹ denotes a single bond or a divalent linking group, X ¹ is a group or an salt thereof, R ¹ and Y ¹ is at least one of fluorine Substituted with an atom.

Formula (A2-2) of, R ² is an aliphatic hydrocarbon, R ³ represents an hydrocarbon, Y ² denotes a single bond or a divalent connecting group, R ^2, R ³ and Y ² at least one of a fluorine- Substituted with an atom.

In formula (A2-3), Ar ¹ represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, R ⁴ represents an organic group, Y ³ represents a single bond or a divalent linking group, X ² represents an acid group or a salt thereof And at least one of Ar ¹ , R ⁴ and Y ³ is substituted with a fluorine atom.)

Equation (A2-1-1) of, R ⁵ and R ⁶ each independently represents a hydrogen atom, a methyl group or a fluorine atom, Y ⁴ represents a single bond or a divalent linking group, X ³ represents a group or a salt thereof .

In formula (A2-2-1), R ⁷ and R ⁸ each independently represent a hydrogen atom, a methyl group or a fluorine atom, Y ⁵ represents a single bond or a divalent linking group, R ⁹ represents an alkyl group or an aryl group, At least one of R ⁷ , R ⁸ , Y ⁵ and R ⁹ is substituted with a fluorine atom.

In formula (A2-1-1-1), L ¹ represents a single bond or a linking group of (n 2 + 1), n 2 represents an integer of 1 to 5, and X ⁴ represents an acid group or a salt thereof.

In formula (A2-1-1-2), Y ⁶ represents a linear, branched or cyclic alkylene group, an arylene group, -C (= O) O-, -O-, or -C (= O) - NR '- (wherein R' represents a hydrogen atom or an alkyl group), or a combination thereof, Rf ¹ represents a divalent linking group substituted with a fluorine atom, and X ⁵ represents an acid group or a salt thereof.

In formula (A2-3-1), Ar ² represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Rf ² represents an alkyl group substituted by a fluorine atom or a fluorine atom, and X ⁶ represents an acid group or a salt thereof.

Equation (A2-2-1-1) of, Y ⁷ represents a single bond, a straight chain, branched or cyclic alkylene group, -C (= O) O-, -O-, or represents a group composed of a combination thereof , And Rf ³ represents an alkyl group or an aryl group substituted with a fluorine atom.

In the formulas (A2-1) and (A2-2), R ¹ and R ² each independently represent an aliphatic hydrocarbon group, and examples thereof include a linear, branched or cyclic alkyl group. As the straight-chain alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. The branched alkyl group is preferably an alkyl group having 3 to 20 carbon atoms, more preferably an alkyl group having 3 to 10 carbon atoms, and more preferably an alkyl group having 3 to 6 carbon atoms. The cyclic alkyl group may be monocyclic or polycyclic. 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, and still more preferably a cycloalkyl group having 6 to 10 carbon atoms.

When R ¹ and R ² have a substituent, the substituent is not particularly limited, and examples thereof include a polymerizable group (preferably a polymerizable group having a carbon-carbon double bond), a halogen atom (a fluorine atom, a chlorine atom An acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, A hydroxyl group, a carboxyl group, an aralkyl group, -Si- (OR ^N22 ) ₃ and the like are exemplified, and a fluorine atom is particularly preferable. (R ^N22 represents an alkyl group, and preferably has 1 to 3 carbon atoms.)

Y ¹ to Y ⁵ of the formula (A2-1), the formula (A2-2), the formula (A2-3), the formula (A2-1-1) and the formula (A2-2-1) -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO-, -SO ₂ -, -NX-, -NH-, (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a combination thereof.

Examples of the hydrocarbon group include linear, branched or cyclic alkylene groups and arylene groups. The straight chain alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms. The branched alkylene group is preferably an alkylene group having 3 to 20 carbon atoms, more preferably an alkylene group having 3 to 10 carbon atoms, and still more preferably an alkylene group having 3 to 6 carbon atoms. The cyclic alkylene group may be either monocyclic or polycyclic. The cyclic alkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 4 to 10 carbon atoms, and still more preferably a cycloalkylene group having 6 to 10 carbon atoms.

The arylene group is preferably an arylene group having 6 to 18 carbon atoms, more preferably an arylene group having 6 to 14 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and particularly preferably a phenylene group.

The heteroarylene group is not particularly limited, but a 5-membered ring or a 6-membered ring is preferable. The heteroarylene group may be a monocyclic or condensed ring, preferably a monocyclic or condensed ring having 2 to 8 condensed rings, and more preferably a monocyclic or condensed ring having 2 to 4 condensed rings.

Particularly, when Y ¹ represents a divalent connecting group, -COO-, -CO-, -O-, -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), a hydrocarbon group , An alkylene group having 1 to 30 carbon atoms or an arylene group), or a combination thereof.

In formula (A2-1-1-2), Y ⁶ represents a linear, branched or cyclic alkylene group, an arylene group, -C (= O) O-, -O-, or -C (= O) - NR '- (R' is a hydrogen atom or an alkyl group), or a combination thereof, and is preferably an arylene group or a group formed by a combination of an arylene group and -O-.

Equation (A2-2-1-1) of, Y ⁷ represents a single bond, a straight chain, branched or cyclic alkylene group, -C (= O) O-, -O-, or represents a group composed of a combination thereof , -C (= O) O- and an alkylene group having 1 to 6 carbon atoms.

The formula (A2-1), the formula (A2-3-1), the formula (A2-1-1-2), the formula (A2-1-1-1), the formula (A2-1-1) -3), X ¹ to X ⁶ each independently represents an acid group or a salt thereof, and is synonymous with the above-mentioned acid group or a salt thereof, and the preferable range thereof is also the same.

In formula (A2-1), at least one of R ¹ and Y ¹ is substituted with a fluorine atom. Here, among R ¹ and Y ¹ , the substitution of Y ¹ by a fluorine atom means, for example, that at least one of the hydrogen atoms constituting R ¹ is substituted by a fluorine atom. It is preferable that at least one of R ¹ and Y ¹ is a perfluoro group. Of R ¹ and Y ¹ , it is preferable that Y ¹ is substituted with a fluorine atom.

In the formula (A2-2), R ³ represents a hydrocarbon group, and includes an alkyl group and an aryl group described for R ¹ in the formula (A2-1). The alkyl group is synonymous with the alkyl group described for R &^lt; ¹ &gt; in formula (A2-1), and the preferred range is also the same. The aryl group is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. When R ³ has a substituent, the substituent is not particularly limited, but a fluorine atom is preferable.

At least one of R ² , R ³ and Y ² in formula (A2-2) has a fluorine atom, and at least one of R ² , R ³ and Y ² is preferably a perfluoro group.

In the formulas (A2-3) and (A2-3-1), it is preferable that Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group. As the aromatic hydrocarbon group, an aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group or a biphenyl group is more preferable. The aromatic heterocyclic group is not particularly limited, and for example, an aromatic heterocyclic group having 2 to 30 carbon atoms can be used.

In formula (A2-3), R ⁴ represents an organic group, and includes an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 1 to 6 carbon atoms, -O-, -SO ₂ -, -CO-, -NR _N - R _N is a hydrogen atom or an alkyl group), and combinations thereof. R ₄ as an alkylene group is preferably an alkylene group having 1 carbon atom, and among them, -C (R ^4A ) (R ^4B ) - is preferable. Here, R ^4A and R ^4B each independently represent a fluorine atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms), and the alkyl group may be substituted with a fluorine atom. When R ⁴ includes -C (R ^4A ) (R ^4B ) -, one R ^4A and one R ^4B may be bonded to each other to form a ring.

R ⁴ as the cycloalkylene group is preferably a cycloalkylene group having 4 carbon atoms, and among these, a perfluorocyclobutylene group is preferable.

Preferable examples of R ⁴ include -C (R ^4A ) (R ^4B ) -, -O-, -CO-, and -SO ₂ -.

At least one of Ar ¹ , R ⁴ and Y ³ in formula (A2-3) has a fluorine atom, and at least one of Ar ¹ , R ⁴ and Y ³ is preferably a perfluoro group.

The structural unit represented by the formula (A2-3) may contain at least one Ar ¹ and at least one R ⁴ in the structural unit, or may contain two or more.

Equation (A2-1-1) and formula (A2-2-1) of, R ⁵ and R ^6, and R ⁷ and R ⁸ are each independently a hydrogen atom, methyl group or fluorine atom, and each represents a fluorine atom .

In formula (A2-1-1), at least one of R ⁵ , R ⁶ and Y ⁴ may have a fluorine atom. When at least one of R ⁵ , R ⁶ and Y ⁴ has a fluorine atom, it is preferable that at least one of R ⁵ , R ⁶ and Y ⁴ is a perfluoro group.

In the formula (A2-2-1), R ⁹ is the formula (A2-2) an alkyl group as described above agrees with R ³ in, is also the same preferable range. When R ⁹ has a substituent, the substituent is preferably a fluorine atom.

In formula (A2-2-1), at least one of R ⁷ , R ⁸ , Y ⁵ and R ⁹ is substituted with a fluorine atom. In particular, it is preferable that at least one of R ⁷ , R ⁸ , Y ⁵ and R ⁹ is a perfluoro group, more preferably R ⁷ and R ⁸ are fluorine atoms.

In the formula (A2-1-1-1), n2 is particularly preferably 1. if n2 is 1, (n2 + 1) valent connecting group (a divalent connecting group), the formula (A2-1) is a divalent linking group as described in agreement of Y ^1, arylene groups resulting from a preparation of -O- is desirable.

In the formula (A2-1-1-2), Rf ¹ represents a divalent linking group substituted with a fluorine atom. The divalent linking group is the same as the divalent linking group described for Y ¹ in formula (A2-1), and is preferably an arylene group having 6 to 12 carbon atoms substituted with a fluorine atom or an alkylene group having 1 to 5 carbon atoms substituted with a fluorine atom. Particularly, when Rf ¹ represents an alkylene group having 1 to 5 carbon atoms substituted with a fluorine atom, it is preferably an alkylene group having 3 to 5 carbon atoms containing 4 or more fluorine atoms. When Rf ¹ represents an arylene group having 6 to 12 carbon atoms substituted with a fluorine atom, it is more preferably a phenylene group containing 2 to 4 fluorine atoms, particularly preferably a phenylene group containing 4 fluorine atoms Do.

Equation (A2-3-1) of, Rf ² represents an alkyl group substituted with a fluorine atom or a fluorine atom.

Of, Rf ³ is a fluorine atom-substituted alkyl group having 6-12 aryl groups of 1 to 5 carbon atoms (especially fluorine atoms are a phenyl group optionally substituted) or a fluorine atom is preferred in formula (A2-2-1-1) . In particular, when Rf ³ represents an alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, it is preferably an alkyl group having 3 to 5 carbon atoms and containing 4 or more fluorine atoms. When Rf ³ is a phenyl group substituted with a fluorine atom, it is preferable that four or more fluorine atoms are contained, and it is particularly preferable that the fluorine atom is a perfluorophenyl group.

The weight average molecular weight of the polymer (A2) is preferably 2000 or more, more preferably 2,000 to 2,000, and still more preferably 5,000 to 400,000. By setting the weight average molecular weight of the polymer (A2) within such a range, it is possible to provide a near infrared absorbing composition capable of forming a cured film excellent in moisture resistance.

Specific examples of the polymer (A2) used in the present invention include, but are not limited to, the following compounds and salts of the following acid groups. In addition, a perfluorocarbon sulfonic acid polymer represented by Nafion (registered trademark) may also be used.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

The polymer (A2) is obtained by polymerizing monomers constituting the above-mentioned constituent units. As the polymerization reaction, a known polymerization reaction such as a radical polymerization reaction, a polycondensation reaction, a coordination polymerization and the like can be used. For example, in a radical polymerization reaction, a known polymerization initiator can be used for the reaction. As the polymerization initiator, an azo polymerization initiator can be used. Specific examples thereof include a water-soluble azo polymerization initiator, an oil-soluble azo polymerization initiator, and a polymeric polymerization initiator. The polymerization initiator may be used alone or in combination of two or more.

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

The near infrared absorbing composition of the present invention may contain a compound obtained by reacting the polymer (A2) with a copper component, but may contain other near infrared absorbing compound, solvent, curing compound, binder polymer, surfactant, May be contained.

In addition, the near infrared absorbing composition of the present invention may contain a compound containing the above-mentioned acid group or its salt used for obtaining other near infrared absorbing compound.

&Lt; Other near infrared absorbing compound >

The composition of the present invention may be blended with a near infrared absorbing compound other than the compound obtained by the reaction of the polymer (A2) with the copper component, for the purpose of further improving the near infrared absorbing ability. The other near infrared absorbing compound used in the present invention is not particularly limited as long as it has a maximum absorption wavelength in a range of 700 to 2500 nm, preferably 700 to 1000 nm (near infrared region), in the maximum absorption wavelength region.

As the other near infrared absorbing compound, a copper compound is preferable, and a copper complex is more preferable. As the copper complex, the copper compound (preferably a copper complex) described in the first embodiment can be used.

When other near infrared absorbing compounds are compounded, the ratio (mass ratio) of the compound obtained by the reaction of the polymer (A2) with the copper component to another near infrared absorbing compound is preferably 10:90 to 95: 5, more preferably 20:80 To 90:10, and more preferably from 20:80 to 80:20.

(Inorganic fine particles)

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

The inorganic fine particles are mainly particles that act to shield (absorb) infrared rays. The inorganic fine particles are preferably at least one selected from the group consisting of metal oxide particles and metal particles because of their superior infrared ray shielding properties.

Examples of the inorganic fine particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO that is doped with Al) particles which may be doped with aluminum, fluorine doped tin dioxide Doped SnO ₂ ) particles or niobium-doped titanium dioxide (Nb doped TiO ₂ ) particles, silver (Ag) particles, gold (Au) particles, copper (Cu) And the like. In order to achieve both infrared light shielding property and photolithography property, a high transmittance of an exposure wavelength (365 to 405 nm) is preferable, and indium tin oxide (ITO) particles or antimony tin oxide (ATO) particles are preferable.

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

As the inorganic fine particles, tungsten oxide-based compounds can be used, and more specifically, tungsten oxide-based compounds represented by the following general formula (composition formula) (I).

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

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

0.001? X / y?

2.2? Z / y? 3.0

As the metal of M, an alkali metal, an alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, But it is preferably an alkali metal and is preferably Rb or Cs, and it is preferably Cs, and more preferably, Cs is at least one selected from the group consisting of In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os and Bi. More preferable. The metal of M may be one kind or two kinds or more.

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

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

The metal oxide is preferably tungsten oxide cesium.

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

The metal oxide is preferably fine particles. The average particle diameter of the metal oxide is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. Since the average particle diameter is within this range, the metal oxide is less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be more surely obtained. From the viewpoint of avoiding light scattering, the smaller the average particle diameter is, the better, but the average particle diameter of the metal oxide is usually 1 nm or more for ease of handling at the time of production.

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

The content of the metal oxide is preferably 0.01 to 30 mass%, more preferably 0.1 to 20 mass%, and further preferably 1 to 10 mass% with respect to the total solid content of the composition containing the metal oxide .

<Solvent>

The solvent used in the present invention is not particularly limited and may be appropriately selected depending on the purpose so long as each component of the composition of the present invention can be uniformly dissolved or dispersed. Examples of the solvent include water-based solvents such as water and alcohols . In addition, the solvent used in the present invention may be an organic solvent, a ketone, an ether, an ester, an aromatic hydrocarbon, a halogenated hydrocarbon, and dimethylformamide, dimethylacetamide, dimethylsulfoxide , Sulfolane, and the like. These may be used alone, or two or more kinds may be used in combination.

Specific examples of alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in Japanese Laid-Open Patent Publication No. 2012-194534, paragraph 0136, the contents of which are incorporated herein by reference. Specific examples of the esters, ketones and ethers are those described in Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0497 (corresponding to United States Patent Application Publication No. 2012/0235099 [0609]), and acetic acid- n-amyl, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether and ethylene glycol monobutyl ether acetate.

It is particularly preferable that the composition of the present invention contains water. Water is preferably contained in an amount of 40 to 95 mass% with respect to the composition of the present invention, and more preferably 50 to 85 mass% with respect to the composition of the present invention.

The solvent may be a single kind or two or more types. The solvent may be contained in an amount of 40 to 90% by mass relative to the composition of the present invention.

<Curable compound>

The composition of the present invention may further contain a curable compound. The curable compound may be a polymerizable compound or a non-polymerizable compound such as a binder. In addition, a thermosetting compound or a photo-curing compound may be used, but a thermosetting composition is preferable because of a high reaction rate.

<< Compounds having polymerizable groups >>

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

<< Polymerizable Monomers and Polymerizable Oligomers >>

The composition of the present invention is a composition comprising a monomer having a polymerizable group (a polymerizable monomer) or an oligomer having a polymerizable group (a polymerizable oligomer) (hereinafter, a polymerizable monomer or the like, May be included).

Examples of the polymerizable monomer and the like include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof and amides, An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

As specific compounds of these, compounds described in paragraph [0095] to [0108] of Japanese Laid-Open Patent Publication No. 2009-288705 can be suitably used in the present invention.

The polymerizable monomer may also be a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 under normal pressure, and may be a monofunctional (meth) acrylate, a bifunctional (meth) Acrylate, and trifunctional or more (meth) acrylate (for example, (meth) acrylate having 3 to 6 functionalities).

Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate;

(Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, and then (meth) acrylate.

As the polymerizable compound, ethyleneoxy-modified pentaerythritol tetraacrylate (NK Ester ATM-35E, Shin Nakamura Kagaku Co., Ltd., a commercial product), dipentaerythritol triacrylate (KAYARAD D-330, Nippon Kayaku Kabushiki (KAYARAD D-320 manufactured by Nippon Kayaku Kabushiki Kaisha), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310, manufactured by Nippon Kayaku Kabushiki Kaisha), dipentaerythritol tetraacrylate (Trade name, manufactured by KAYARAD DPHA, manufactured by Nippon Kayaku K.K.), and these (meth) acryloyl groups include ethylene glycol and propylene glycol moieties An intervening structure can be used. These oligomer types can also be used. The compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779 can also be used in the present invention.

Polymerizable monomers and the like include polymerizable monomers described in Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0477 (corresponding to United States Patent Application Publication No. 2012/0235099 [0585]), Is used. Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (M-460, commercially available from Toagosei Co., Ltd.) can be used. Pentaerythritol tetraacrylate (Shin-Nakamura Kagaku Co., A-TMMT) and 1,6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.) can also be used. These oligomer types can also be used.

For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like.

In the present invention, examples of the monomer having an acid group include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which are obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride to give an acid group Can be used. Commercially available products include, for example, M-305, M-510, and M-520 of Aronix series as a polybasic acid-modified acrylic oligomer made by Toagosei Co.,

The acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, particularly preferably 5 to 30 mg-KOH / g. When two or more polyfunctional monomers having different acid groups are used in combination or when polyfunctional monomers having no acid group are used in combination, it is essential to prepare the polyfunctional monomers so that the total acid value of the polyfunctional monomer falls within the above range.

<< Polymer having polymerizable group in side chain >>

The second aspect of the composition of the present invention may be a mode in which the polymerizable compound includes a polymer having a polymerizable group in its side chain. Examples of the polymerizable group include an ethylenically unsaturated double bond group, an epoxy group and an oxetanyl group.

&Lt; Compound having an epoxy group or oxetanyl group &gt;

The third aspect of the present invention may be a mode in which a compound having an epoxy group or an oxetanyl group is contained as the polymerizable compound. Specific examples of the compound having an epoxy group or an oxetanyl group include a polymer having an epoxy group in the side chain and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule. Examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, Novolak type epoxy resins, cresol novolak type epoxy resins, and aliphatic epoxy resins. Also included are monofunctional or polyfunctional glycidyl ether compounds.

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

As a commercial product, for example, Japanese Laid-Open Patent Publication No. 2012-155288, paragraph 0191 and the like can be taken into consideration, and these contents are incorporated herein by reference.

As a commercial product, polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L and EX-850L (manufactured by Nagase ChemteX Corporation) . These are low-salt small articles, but EX-212, EX-214, EX-216, EX-321, EX-850 and the like can be used in the same manner.

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- -501, EPPN-502 (manufactured by ADEKA Corporation), JER1031S, and the like.

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

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

In the case of synthesizing by introduction into the side chain of the polymer, the introduction reaction is carried out, for example, by using a tertiary amine such as triethylamine or benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride , Pyridine, triphenylphosphine or the like as a catalyst in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several hours. The introduction amount of the alicyclic epoxy unsaturated compound can be controlled so that the acid value of the obtained polymer is in the range satisfying 5 to 200 KOH · mg / g. The weight average molecular weight may be in the range of 500 to 5000000, more preferably 1000 to 500000.

As the epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether can also be used. For example, Japanese Patent Application Laid-Open No. 2009-265518, paragraph 0045, and the like can be taken into consideration, and these contents are incorporated herein by reference.

In the present invention, it is preferable to include a polymer having a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetane group. This makes it possible to improve film formability (suppression of cracking and warping) and moisture resistance when the film is formed into a cured film. Specifically, a polymer having the following repeating unit can be mentioned. As the polymer having the following repeating unit, a polymer having an epoxy group is preferable.

[Chemical Formula 17]

<< Compounds having a partial structure represented by the formula (1) >>

The curable compound used in the present invention preferably has a partial structure represented by the following formula (1), and the curable compound may have a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group.

[Chemical Formula 18]

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

By containing such a compound, when the near infrared absorbing composition of the present invention is used as a cured film, the near infrared ray shielding property can be further improved and the moisture resistance can be further improved.

In the formula (1), R ¹ represents a hydrogen atom or an organic group. The organic group is preferably 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 combination of these groups and a divalent linking group .

Specific examples of such an organic group include -OR ', -SR', or a group of these groups and - (CH ₂ ) _m - (m is an integer of 1 to 10), a cyclic alkylene group having 5 to 10 carbon atoms, -O-, CO-, -COO-, and -NH-. Here, R 'represents a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms (preferably a straight chain having 1 to 7 carbon atoms, a branched or cyclic alkyl group having 3 to 7 carbon atoms ), An aryl group having 6 to 10 carbon atoms, or a combination of an aryl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms.

In formula (1), R ¹ and C may be bonded to form a ring structure (heterocyclic structure). The hetero atom in the heterocyclic structure is a nitrogen atom in formula (1). The heterocyclic structure is preferably a 5- or 6-membered ring structure, and more preferably a 5-membered ring structure. The heterocyclic structure may be a condensed ring, but monocyclic ring is preferred.

Specific examples of the preferable R ¹ include a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, -OR '(R' is a straight chain alkyl group having 1 to 5 carbon atoms) and - (CH ₂ ) _m - (Preferably an integer of 1 to 5), and a group formed by combining R ¹ and C in formula (1) to form a heterocyclic structure (preferably a 5-membered ring structure).

The compound having a partial structure represented by the formula (1) may be represented by (a main chain structure of the polymer - a partial structure of formula (1) - R ¹ ), or a compound represented by the following formula desirable. Here, A is a straight chain, a branched chain having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, having 1 to 10 carbon atoms. B is a group consisting of a partial structure of the formula (1) and a polymerizable group in combination with - (CH ₂ ) _m - (m is an integer of 1 to 10, preferably m is an integer of 1 to 5) to be.

The compound having a partial structure represented by the formula (1) preferably has a structure represented by any one of the following formulas (1-1) to (1-5).

[Chemical Formula 19]

(In formula (1-1) of, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ and R ⁶ represents a hydrogen atom or an organic each independently formula (1-2) of, R ⁷ is a hydrogen atom or a methyl group represents the equation (1-3) of the, L ¹ represents a divalent connecting group, R ⁸ represents a hydrogen atom or an organic group. Eq. (1-4) of the, L ² and L ³ each independently represents a divalent linking group (1-5), L ⁴ represents a divalent linking group, R ¹¹ to R ¹⁴ each independently represents a hydrogen atom or an organic group, and R ⁹ and R ¹⁰ 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 agrees with R ¹ in formula (1), and the preferable range is also the same.

In formulas (1-3) to (1-5), L ¹ to L ⁴ represent a divalent linking group. As the divalent linking group, at least one of - (CH ₂ ) _m - (m is an integer of 1 to 10), a cyclic alkylene group having 5 to 10 carbon atoms, -O-, -CO-, -COO- and -NH- , And more preferably - (CH ₂ ) _m - (m is an integer of 1 to 8).

In formulas (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.

The alkyl group may be substituted. The alkyl group may be any of chain, branched, and cyclic, but is preferably straight-chain or cyclic. 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, and more preferably an alkyl group having 1 to 6 carbon atoms.

The alkenyl group may be substituted. As the alkenyl group, an alkenyl group having 1 to 10 carbon atoms is preferable, an alkenyl group having 1 to 4 carbon atoms is more preferable, and a vinyl group is particularly preferable.

Examples of the substituent include a polymerizable group, a halogen atom, an alkyl group, a carboxylic acid ester group, a halogenated alkyl group, an alkoxy group, a methacryloyloxy group, an acryloyloxy group, an ether group, a sulfonyl group, a sulfide group, An acyl group, a hydroxyl group, a carboxyl group and the like. Among these substituents, a polymerizable group (e.g., a vinyl group, a (meth) acryloyloxy group, a (meth) acryloyl group, an epoxy group, an aziridinyl group, etc.) is preferable and a vinyl group is more preferable.

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

When the compound having a partial structure represented by the formula (1) is a polymer, it is preferable that the side chain of the polymer contains the partial structure.

The molecular weight of the compound having the partial structure represented by the formula (1) is preferably 50 to 1000000, more preferably 500 to 500000. By using such a molecular weight, the effect of the present invention can be achieved more effectively.

The content of the compound having a partial structure represented by the formula (1) is preferably 5 to 80% by mass, more preferably 10 to 60% by mass in the composition of the present invention.

Specific examples of the compound having a partial structure represented by the formula (1) include a compound having the following structure or the following exemplified compounds, but are not limited thereto. In the present invention, it is particularly preferable that the compound having a partial structure represented by the formula (1) is a polyacrylamide.

[Chemical Formula 20]

Specific examples of the compound having a partial structure represented by the formula (1) include water-soluble polymers. Preferred examples of the main chain structure include polyvinylpyrrolidone, poly (meth) acrylamide, polyamide, polyvinylpyrrolidone , Polyurethane, and polyurea. The water-soluble polymer may be a copolymer, and the copolymer may be a random copolymer.

As the polyvinylpyrrolidone, a trade name KW-30 (manufactured by Nippon Shokubai Co., Ltd.) may be used.

Examples of the poly (meth) acrylamide include polymers and copolymers of (meth) acrylamide. Specific examples of acrylamide include acrylamide, N-methylacrylamide, N-ethyl acrylamide, N-propylacrylamide, N-butyl acrylamide, N-benzyl acrylamide, N-hydroxyethyl acrylamide, (Phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N (hydroxyphenyl) acrylamide, N- , N-dimethyl acrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like. The corresponding methacrylamides can also be used as such.

The water-soluble polyamide resin may particularly be a compound obtained by copolymerizing a polyamide resin with a hydrophilic compound. Derivatives of the water-soluble polyamide resin include derivatives of a water-soluble polyamide resin such as water-soluble polyamide resin as a raw material and a compound obtained by substituting hydrogen (- atom of the --CONH-) with methoxymethyl group (CH ₂ OCH ₃ ) Refers to a compound in which the atom in the amide resin molecule is substituted or the structure of the amide bond is changed by an addition reaction.

As the polyamide resin, there may be mentioned, for example, so-called "n-nylon" synthesized by polymerization of ω-amino acid or so-called "n, m-nylon" synthesized by copolymerization of diamine and dicarboxylic acid. Among them, a copolymer of a diamine and a dicarboxylic acid is preferable from the viewpoint of imparting hydrophilicity, and a reaction product of? -Caprolactam and a dicarboxylic acid is more preferable.

Examples of the hydrophilic compound include hydrophilic nitrogen-containing cyclic compounds and polyalkyleneglycols.

Here, the hydrophilic nitrogen ring cyclic compound is a compound having a tertiary amine component in the side chain or the main chain, and examples thereof include aminoethylpiperazine, bisaminopropylpiperazine,? -Dimethylamino? Caprolactam, and the like. have.

On the other hand, in the compound in which the polyamide resin and the hydrophilic compound are copolymerized, at least one selected from the group consisting of a hydrophilic cyclic nitrogen compound and a polyalkyleneglycol is copolymerized with the main chain of the polyamide resin, The hydrogen bonding ability of the amide bond portion of the resin is larger than that of N-methoxymethylated nylon.

Among the compounds in which a polyamide resin and a hydrophilic compound are copolymerized, 1) a reaction product of? -Caprolactam and a hydrophilic cyclic nitrogen compound and a dicarboxylic acid and 2) a reaction between? -Caprolactam and a polyalkylene glycol and a dicarboxylic acid The product is preferred.

These are commercially available under the trademark "AQ nylon ", for example, from Toray Fine Tech Co., Ltd. The reaction product of? -caprolactam and a hydrophilic nitrogen-containing cyclic compound and a dicarboxylic acid is available as AQ Nylon A-90 manufactured by Toray Fine Chemicals Co., Ltd., and? -caprolactam, polyalkyleneglycol and dicarboxylic acid Is available as AQ Nylon P-70 manufactured by Toray Fine Chemicals Co., Ltd. AQ nylon A-90, P-70, P-95, and T-70 (manufactured by Toray Industries, Inc.).

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

Details of the structure, the use of the polymerizable compound, whether it is used alone or in combination with the polymerizable compound, and the like can be arbitrarily set in accordance with the final performance design of the near infrared absorbing composition. For example, from the viewpoint of sensitivity, a structure having a large number of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. From the viewpoint of enhancing the strength of the near-IR blocking filter, it is preferable to use a trifunctional or higher functional group, and a combination of other functional groups and other polymerizable groups (for example, acrylate ester, methacrylate ester, styrene group compound, vinyl ether group compound) A method of adjusting both the sensitivity and the intensity is also effective. In addition, regarding the compatibility and dispersibility with other components (for example, metal oxides, pigments, polymerization initiators) contained in the near-infrared absorbing composition, selection and use of polymerizable compounds are important factors. For example, May be used, or the compatibility may be improved by combining two or more species. In addition, a specific structure may be selected from the viewpoint of improving adhesion with a hard surface such as a support.

The amount of the polymerizable compound to be added in the composition of the present invention is in the range of 1 to 50 mass%, more preferably 1 to 30 mass%, and particularly preferably 1 to 10 mass% with respect to the total solid content excluding the solvent .

When a polymer containing a repeating unit having a crosslinking group is used as the polymerizable compound, the amount of the polymer is preferably 10 to 75% by mass, more preferably 20 to 65% by mass, particularly preferably 20 to 80% by mass relative to the total solid content of the composition of the present invention, By mass to 20% by mass to 60% by mass.

The polymerizable compound may be a single kind or two or more kinds, and when two or more kinds are used, the total amount is in the above range.

&Lt; Binder polymer &

In the present invention, for the purpose of improving the film properties, etc., a binder polymer may be further included if necessary. As the binder polymer, an alkali-soluble resin can be used.

As alkali-soluble resins, mention may be made of the description in Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to United States Patent Application Publication No. 2012/0235099 [0685] to [0700]), Quot;

The content of the binder polymer in the present invention may be 0 to 80% by mass, 0 to 50% by mass, 0 to 30% by mass, or 0% by mass, based on the total solid content of the composition. %.

<Surfactant>

The composition of the present invention may contain a surfactant. Only one surfactant may be used, or two or more surfactants may be combined. The addition amount of the surfactant may be from 0.0001 to 2% by mass, preferably from 0.005 to 1.0% by mass, more preferably from 0.01 to 0.1% by mass, and most preferably from 0% by mass to the solid content of the composition of the present invention It is possible.

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

Particularly, since the composition of the present invention contains at least any one of a fluorine-based surfactant and a silicone-based surfactant, the liquid property (particularly, fluidity) when the composition is prepared as a coating liquid is further improved, The liquid-storing property can be further improved.

That is, when a film is formed using a coating liquid to which a composition containing at least one of a fluorine-based surfactant and a silicone-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, So that the coating property to the surface to be coated is improved. Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine-based surfactant may be, for example, 3 to 40% by mass.

Examples of the fluorine-based surfactant include Megapac F171, copper F172, copper F173, copper F176, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437, copper F479, copper F482, copper F554 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, S-141, and S-141 (all manufactured by DIC Corporation) (Above), SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and K- (Manufactured by OMNOVA), EF Top EF301, EF303, EF351 and EF352 (manufactured by Zemko Co., Ltd.), PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA).

As the fluorine-based surfactant, a polymer having a fluoroaliphatic group can be used. Examples of the polymer having a fluoroaliphatic group include a fluoroaliphatic group and the fluoroaliphatic group is a fluoroaliphatic group produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method) A fluorinated surfactant obtained from a compound is exemplified.

Here, the "telomerization method" means a method of synthesizing a compound having one or two active groups in the molecule by polymerizing a substance having a low molecular weight. Further, the "oligomerization method" means a method of converting a monomer or a mixture of monomers into an oligomer.

Examples of the fluoroaliphatic group in the present invention include -CF ₃ group, -C ₂ F ₅ group, -C ₃ F ₇ group, -C ₄ F ₉ group, -C ₅ F ₁₁ group, -C ₆ F ₁₃ group, -C ₇ F ₁₅ group, -C ₈ F ₁₇ group, C ₉ F ₁₉ group and C ₁₀ F ₂₁ group, and from the viewpoint of compatibility and application property, -C ₂ F ₅ group, -C ₃ F ₇ group, -C ₄ F ₉ group, -C ₅ F ₁₁ group, -C ₆ F ₁₃ group, -C ₇ F ₁₅ group and -C ₈ F ₁₇ group can be used.

The fluoroaliphatic compound in the present invention can be synthesized according to the method described in JP-A-2002-90991.

Examples of the polymer having a fluoroaliphatic group in the present invention include a fluoroaliphatic group-containing monomer and a (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate May be used. These copolymers may be irregularly distributed or may be subjected to block copolymerization. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group and a poly (oxybutylene) group. Block linking group) or poly (block linking group of oxyethylene and oxypropylene) group, or may be a unit having other chain alkylene in the same chain. Further, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) may be a monomer having two or more different fluoroaliphatic groups, (Poly (oxyalkylene)) acrylate (or methacrylate) or the like may be copolymerized at the same time.

As a commercially available surfactant containing a polymer having a fluoroaliphatic group in the present invention, for example, Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0552 (corresponding to United States Patent Application Publication No. 2012/0235099 [0678]), And the like, the content of which is incorporated herein by reference. (Methacrylate) having a C ₆ F ₁₃ group and (poly (oxyethylene)) acrylate (or methacrylate (meth) acrylate having a C ₆ F ₁₃ group) ) And (poly (oxypropylene)) acrylate (or methacrylate), copolymers of acrylate (or methacrylate) having C ₈ F ₁₇ groups with (poly (oxyalkylene) (Meth) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group, Rate) may be used.

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

Concrete product names include Surfynol 61, 82, 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, 504, CT- DF-75, DF-110, DF-210, GA, OP-340, PSA-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF- A-B, AK-02, CT-151W, and DYNOL 604 (all manufactured by Nisshin Chemical Industries, Ltd. and AirProducts & Chemicals), PSA-216, PSA-216, PSA-336, SE, SE- PD-001, PD-002W, PD-003, PD-004, EXP, SP, STG, Y, 32W, E1004, E1010, 4001, EXP. 4036, EXP. E51, E40, E60, E81, E100, and E200 (all trade names, Kawaken Co., (Manufactured by Fine Chemical Co., Ltd.). Of these, Olfin E1010 is suitable.

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

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

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

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

<Polymerization Initiator>

The composition of the present invention may contain a polymerization initiator. The polymerization initiator may be used singly or in combination of two or more, and in the case of two or more types, the total amount is in the above range. For example, the amount is preferably 0.01 to 30 mass%, more preferably 0.1 to 20 mass%, still more preferably 0.1 to 15 mass%. The addition amount of the polymerization initiator is preferably 0.05 to 2.0 mol%, more preferably 0.1 to 1.0 mol%, relative to the monomer for synthesizing the polymer.

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by either or both of light and heat, and may be appropriately selected depending on the purpose, but it is preferably a photopolymerizable compound. In the case of initiating polymerization by light, it is preferable to have photosensitivity to visible light from the ultraviolet region.

When heat polymerization is initiated, a polymerization initiator which decomposes at 150 to 250 캜 is preferable.

The polymerization initiator usable in the present invention is preferably a compound having at least an aromatic group, and examples thereof include acylphosphine compounds, acetophenone compounds,? -Amino ketone compounds, benzophenone compounds, benzoin ether compounds, An azo compound, an organic peroxide, a diazonium compound, an iodonium compound, a sulfonium compound, an azinium compound, a benzoin compound, a benzoin compound, An onium salt compound such as an ether-based compound, a ketal derivative compound, and a metallocene compound, an organic boron salt compound, and a disulfone compound.

From the viewpoint of sensitivity, oxime compounds, acetophenone compounds,? -Amino ketone compounds, trihalomethyl compounds, hexaarylbaimidazole compounds and thiol compounds are preferable.

Specific examples of the acetophenone compound, the trihalomethyl compound, the hexaarylbaimidazole compound and the oxime compound are described in Japanese Laid-Open Patent Publication No. 2012-208494, paragraphs 0506 to 0510 (corresponding US Patent Application Publication No. 2012/0235099 [0622] to [0628]), the contents of which are incorporated herein by reference.

As the photopolymerization initiator, a compound selected from the group consisting of oxime compounds, acetophenone compounds and acylphosphine compounds is more preferable. More specifically, for example, an aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969, an acylphosphine oxide-based initiator disclosed in Japanese Patent Publication No. 4225898, a oxime-based initiator described above, , Compounds described in Japanese Patent Application Laid-Open No. 2001-233842 may also be used.

As the oxime compounds, commercially available IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be used. As the acetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369 and IRGACURE-379 (all trade names, all manufactured by BASF Japan) can be used. As the acylphosphine-based initiator, commercial products IRGACURE-819 and DAROCUR-TPO (all trade names, all manufactured by BASF Japan) can be used.

<Other ingredients>

To the composition of the present invention, other components may be appropriately selected and used depending on the purpose, in addition to the essential components and additives described above, so long as the effect of the present invention is not impaired.

Examples of other components that can be used in combination include a binder polymer, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermal curing accelerator, a thermal polymerization inhibitor and a plasticizer. A conductive agent, a filler, a defoaming agent, a flame retardant, a leveling agent, a release promoter, an antioxidant, a flavor, a surface tension adjuster, a chain transfer agent, etc. may be used in combination.

By suitably containing these components, it is possible to adjust properties such as stability and film physical properties of the objective near-infrared absorbing filter.

These components are described, for example, in Japanese Patent Laid-Open Publication No. 2012-003225, paragraphs 0183 and 2013 (corresponding to [0237] of U.S. Patent Application Publication No. 2013/0034812), Japanese Patent Application Publication No. 2008-250074 0101 to 0102, paragraph numbers 0103 to 0104, and paragraph numbers 0107 to 0109 can be taken into consideration, and these contents are incorporated herein by reference.

Since the composition of the present invention can be in the form of a liquid, for example, the composition of the present invention can be directly applied and dried, thereby making it possible to easily manufacture a near-infrared cutoff filter. In addition, The manufacturing aptitude can be improved.

The near infrared ray shielding filter of the present invention preferably has a rate of change of the absorbance ratio determined by the following equation before and after heating at 200 ° C for 5 minutes, preferably 5% or less, more preferably 2% or less .

[(Absorbance ratio before heating - Absorbance ratio after heating) / Absorbance ratio before heating]

Here, the term "absorbance ratio" refers to (the maximum absorbance at a wavelength of 700 to 1400 nm / the minimum absorbance at a wavelength of 400 to 700 nm).

The near infrared ray shielding filter of the present invention preferably has a change ratio of the absorbance ratio determined by the following equation before and after being left under high temperature and high humidity of 85 캜 / 95% RH for 3 hours, preferably 7% or less, more preferably 5% , And more preferably 2% or less.

[(Absorbance ratio before test - Absorbance ratio after test) / Absorbance ratio before test]

Here, the term "absorbance ratio" refers to (the maximum absorbance at a wavelength of 700 to 1400 nm / the minimum absorbance at a wavelength of 400 to 700 nm).

The thickness of the near infrared ray shielding filter of the present invention is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably 1 to 500 μm, more preferably 1 to 300 μm, and particularly preferably 1 to 200 μm. In the present invention, even in the case of such a thin film, high near infrared ray shielding property can be maintained.

The use of the near infrared ray absorbent composition of the present invention is not particularly limited, but the use of the near infrared ray absorbing composition for the near infrared ray shielding filter (for example, for a near-infrared ray filter for a wafer level lens) on the light receiving side of the solid- For the near-infrared ray blocking filter on the back side (the side opposite to the light receiving side) of the solid-state imaging element substrate, and is preferably for the light-shielding film on the light receiving side of the solid-state imaging element substrate. In particular, it is preferable that the near infrared absorbing composition of the present invention is directly applied on an image sensor for a solid-state imaging element to form a coating film.

In particular, it is preferable that the near infrared ray absorbing composition of the present invention comprises a copper compound and a near infrared ray shielding filter containing the structure of formula (1) and having a film thickness of 200 μm or less and a visible light transmittance of 90% or more.

The viscosity of the near infrared absorbing composition of the present invention is preferably in the range of 1 mPa · s to 3000 mPa · s, more preferably in the range of 10 mPa · s to 2000 mPa · s in the case of forming the infrared ray blocking layer by coating s or less, more preferably in the range of 100 mPa · s or more and 1500 mPa · s or less.

When the near infrared absorbing composition of the present invention is used for a near infrared ray shielding filter on the light receiving side of the solid-state imaging element substrate, when forming the infrared ray blocking layer by coating, from 10 mPa · s to 3,000 mPa · s s or less, more preferably 500 mPa · s or more and 1,500 mPa · s or less, and most preferably 700 mPa · s or more and 1,400 mPa · s or less.

The total solid content of the near infrared absorbing composition of the present invention varies depending on the application method, but is preferably 1 to 50 mass%, more preferably 1 to 30 mass%, and more preferably 10 to 30 mass% desirable.

The present invention may be a laminate having a near infrared ray blocking layer and a dielectric multilayer film obtained by curing the near infrared absorbing composition. For example, there are embodiments in which (i) a transparent support, a near-infrared ray blocking layer, and a dielectric multilayer film are provided in this order, (ii) a near-infrared ray blocking layer, a transparent support, and a dielectric multilayer film are provided in this order. The transparent support may be a glass substrate or a transparent resin substrate.

The dielectric multilayer film is a film having an ability to reflect and / or absorb near-infrared rays.

As a material of the dielectric multilayer film, for example, a ceramic can be used. Alternatively, the noble metal film having absorption in the near infrared region may be used in consideration of the thickness and the number of layers so as not to affect the transmittance of the visible light of the near-IR cut filter.

Specifically, as the dielectric multilayer film, a structure in which a high refractive index material layer and a low refractive index material layer are alternately laminated can be suitably used.

As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of usually 1.7 to 2.5 is selected.

Examples of the material include titanium oxide (titania), zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, Titanium, tin oxide and / or cerium oxide in a small amount. Of these, titanium oxide (titania) is preferable.

As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of usually 1.2 to 1.6 is selected.

Examples of the material include silica, alumina, lanthanum fluoride, magnesium fluoride, and aluminum sodium hexafluoride. Of these, silica is preferable.

The thicknesses of the respective layers of the high refractive index material layer and the low refractive index material layer are generally 0.1λ to 0.5λ of the infrared wavelength λ (nm) to be blocked. When the thickness is out of the above range, the product (nxd) of the refractive index (n) and the film thickness (d) greatly differs from the optical film thickness calculated by? / 4, It tends to be difficult to control blocking and transmission of a specific wavelength.

The number of laminated layers in the dielectric multilayer film is preferably 5 to 50 layers, and more preferably 10 to 45 layers.

In addition, the present invention relates to a method for manufacturing a solid-state imaging element substrate having a step of forming a film by applying (preferably applying or printing, and more preferably, applying an applicator) the near infrared absorbing composition of the present invention on a light receiving side of a solid- , And a manufacturing method of a near-infrared cut filter. The film thickness, the lamination structure, and the like can be appropriately selected depending on the purpose.

The support may be a transparent substrate made of glass or the like, a solid-state imaging element substrate, or another substrate provided on the light-receiving side of the solid-state imaging element substrate (for example, a glass substrate 30 described later) Or a planarization layer or the like provided on the light receiving side.

The method of applying the near infrared absorbing composition (coating liquid) on a support can be carried out by using, for example, a spin coater, a slit spin coater, a slit coater, a screen printing, an applicator coating or the like.

The drying condition of the coating film is usually from 60 to 200 DEG C for about 30 seconds to 15 minutes, though it depends on the components, the type of solvent, and the usage ratio.

The method for forming the near infrared ray shielding filter using the near infrared absorbing composition of the present invention may include other steps. The other processes are not particularly limited and can be appropriately selected according to the purpose. For example, the surface treatment process of the substrate, the preheating process (prebake process), the curing process process, the postheating process (postbake process) .

&Lt; Preheating process & Post-heating process &gt;

The heating temperature in the preheating step and the post-heating step is usually 80 to 200 占 폚, preferably 90 to 180 占 폚.

The heating time in the preheating step and the post-heating step is usually 30 seconds to 400 seconds, preferably 60 seconds to 300 seconds.

<Curing Treatment Step>

The curing treatment step is a step of performing a curing treatment for the film formed as necessary, and by performing this treatment, the mechanical strength of the near-infrared blocking filter is improved.

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

The exposure is preferably performed by irradiation with radiation, and ultraviolet rays or visible rays such as electron beam, KrF, ArF, g line, h line, i line and the like are preferably used as the radiation usable in exposure. Preferably, KrF, g line, h line, and i line are preferred.

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

Exposure dose, and 5 ~ 3000mJ / cm ² are preferred and more preferably ^{10 ~ 2000mJ / cm 2, 50} ~ 1000mJ / cm 2 is particularly preferred.

As a method of the entire surface exposure treatment, for example, there is a method of exposing the entire surface of the formed film. In the case where the near infrared absorbing composition contains a polymerizable compound, the curing of the polymerization component in the film formed of the composition is promoted by the entire surface exposure, and the curing of the film progresses further, thereby improving the mechanical strength and durability.

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

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

The heating temperature in the whole surface heating is preferably 120 ° C to 250 ° C, more preferably 120 ° C to 250 ° C. When the heating temperature is 120 ° C or higher, the film strength is improved by the heat treatment. When the heating temperature is 250 ° C or lower, the components in the film are decomposed to prevent the film quality from becoming fragile.

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

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

The present invention also relates to a camera module having a solid-state imaging element substrate and a near infrared ray blocking filter disposed on a light receiving side of the solid-state imaging element substrate, wherein the near infrared ray blocking filter is a near-infrared blocking filter of the present invention .

Hereinafter, a camera module according to an embodiment of the present invention will be described with reference to Figs. 3 and 4. However, the present invention is not limited to the following specific examples.

3 and 4, common reference numerals are given to common parts.

Quot; lower ", " lower ", and "lower side" refer to the side farther from the silicon substrate 10 than to the silicon substrate 10, To the nearest side.

3 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image pickup device.

The camera module 200 shown in Fig. 3 is connected to a circuit board 70, which is a mounting board, via a solder ball 60, which is a connecting member.

Specifically, the camera module 200 includes a solid-state imaging element substrate 100 having an imaging element portion on a first main surface of a silicon substrate, and a plurality of pixel electrodes (not shown) provided on the first main surface side A planarization layer (not shown in FIG. 3), a near-infrared cut filter 42 provided on the planarization layer, a lens holder 50 disposed above the near-infrared cut filter 42 and having an image pickup lens 40 in the inner space, And a light shielding and electronic shield 44 arranged so as to surround the periphery of the solid-state imaging element substrate 100 and the glass substrate 30. Further, a glass substrate 30 (light-transmitting substrate) may be provided on the planarizing layer. Each member is adhered by an adhesive 45.

The present invention is a method of manufacturing a camera module having a solid-state imaging element substrate (100) and a near-infrared cutoff filter (42) disposed on the light receiving side of the solid-state imaging element substrate, Infrared absorbing composition according to the present invention. In the camera module according to the present embodiment, the near infrared ray blocking filter 42 can be formed by forming a film by applying the near infrared ray absorbing composition of the present invention on a planarizing layer, for example. The method of applying the near-infrared cutoff filter is as described above.

In the camera module 200, incident light hν from the outside sequentially passes through the imaging lens 40, the near-infrared ray blocking filter 42, the glass substrate 30, and the flattening layer, And reaches the element portion.

The camera module 200 is provided with a near infrared ray cut filter directly on the planarization layer. However, the planarization layer may be omitted and a near infrared ray cut filter may be provided directly on the microlens. A near infrared ray cut filter Or a glass substrate 30 provided with a near-infrared cutoff filter may be applied.

4 is an enlarged cross-sectional view of the solid-state imaging element substrate 100 in Fig.

The solid-state imaging element substrate 100 includes an imaging element 12, an interlayer insulating film 13, a base layer 14, a color filter 15, an overcoat 16 ), And a microlens 17 in this order. The red color filter 15R, the green color filter 15G and the blue color filter 15B (hereinafter collectively referred to as "color filter 15" ) And the microlenses 17 are arranged, respectively. A light shielding film 18, an insulating film 22, a metal electrode 23, a solder resist layer 24, an internal electrode 26, and an element surface electrode (not shown) are formed on a second main surface of the silicon substrate 10 opposite to the first main surface. 27). Each member is bonded by an adhesive 20.

On the microlens 17, a planarization layer 46 and a near-IR cut filter 42 are provided. The near infrared ray blocking filter 42 may be provided on the microlens 17, between the base layer 14 and the color filter 15 or between the color filter 15 and the overcoat 16 may be provided with a near-infrared cutoff filter. Particularly, it is preferable that it is provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens 17. It is possible to simplify the step of forming the near-IR blocking filter and to sufficiently block the unnecessary near-infrared rays to the microlens, so that the near-IR blocking property can be further improved.

As for the solid-state imaging element substrate 100, the following description of the solid-state imaging element substrate 100 after paragraph 0245 (corresponding to [0407] of U.S. Patent Application Publication No. 2012/068292) , The contents of which are incorporated herein by reference.

As described above, one embodiment of the camera module has been described with reference to Figs. 3 and 4. However, the above embodiment is not limited to the configurations of Figs. 3 and 4. Fig.

Example

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

<Synthesis Example>

&Lt; Synthesis of polymer A >

&Lt; Synthesis of Polymer A-1 &gt;

In a three-necked flask, 9.33 g of N-methylpyrrolidone was added, and the temperature was raised to 60 占 폚 under a nitrogen stream. To this flask, Solution A and Solution B shown below were simultaneously added dropwise at the same time for 2 hours and stirred at 60 캜 for 2 hours. Thereafter, the temperature was raised to 80 DEG C, and the mixture was stirred for 2 hours, and then the reaction solution was returned to room temperature. The reaction solution was added dropwise to 1 L of ethyl acetate to obtain a precipitate, which was collected by filtration. The obtained precipitate was dissolved in methanol, and the solution was added dropwise to 1 L of ethyl acetate. The obtained precipitate was dried under reduced pressure to obtain 13.7 g of polymer A-1. ^The composition (shown below) was determined by ¹³ C NMR, and the sulfonic acid group content (2.99 meq / g) in the polymer was calculated by neutralization titration. The fluorine content (17.3 wt%) in the polymer was calculated by elemental analysis.

(Solution A) 0.66 g of acrylic acid, 12.42 g of acrylamide-2-methylpropanesulfonic acid, 6.92 g of 1H, 1H, 5H-octafluoropentyl methacrylate, 24.89 g of N-methylpyrrolidone

(Solution B) 11.4 mg of 2,2'-azobis (2,4-dimethylvaleronitrile) (V-65: manufactured by Wako Pure Chemical Industries, Ltd.) and 12.44 g

[Chemical Formula 21]

<< Synthesis of Polymers A-2 to A-6 >>

A precursor (sulfonate) of Polymers A-2 to A-6 was obtained in the same manner as in the synthesis of Polymer A-1, except that the ratio of monomer species and monomer species used was changed as shown in Table 1 below. Next, Polymer A-2 to A-6 were obtained by salt exchange of the resulting precursor polymer with a proton type by Amberlyst 15 (hydrogen form) (manufactured by aldrich). The compositions (shown below) of the polymers A-2 to A-6 were determined by ¹³ C NMR, and the content of sulfonic acid groups in the polymer was calculated by neutralization titration. The fluorine content in the polymer was calculated by elemental analysis.

[Table 1]

[Chemical Formula 22]

(23)

<< Synthesis of polymer A-7 >>

3.42 g of hexafluorobisphenol A, 5.00 g of dipotassium sulfone-4,4'-dichloro-3,3'-disulfonic acid disodium and 1.69 g of potassium carbonate were placed in a three-necked flask equipped with a Dean- 10 g of toluene and 25 g of N-methylpyrrolidone were added and the mixture was refluxed for 4 hours under a nitrogen stream. After toluene in the system was removed, the temperature was raised to 180 캜 and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered through a Kiriyama-rohto funnel on the whole surface of celite, and the filtrate was added dropwise to 300 ml of a saturated aqueous solution of sodium chloride. The resulting precipitate was filtered, dissolved in methanol, and then added dropwise in 500 ml of acetone. The obtained precipitate was filtered and dissolved in methanol, and then the salt was converted into a proton type by Amberlyst 15 (hydrogen form) (manufactured by aldrich) to obtain 6.4 g of polymer A-7. The content of sulfonic acid group (2.8 meq / g) in the polymer was calculated for Polymer A-7 by neutralization titration. The fluorine content (16.0 mass%) in the polymer was calculated by elemental analysis.

&Lt; EMI ID =

<< Synthesis of Polymer A-8 >>

Polymer A-8 shown below was obtained in accordance with the method described in U.S. Patent No. 5602185. The polymer A-8 was subjected to ¹³ C NMR to give a composition (shown below), and the sulfonic acid group content (3.6 meq / g) in the polymer was calculated by neutralization titration. The fluorine content (25.7 mass%) in the polymer was calculated by elemental analysis.

(25)

&Lt; Synthesis of polymer A-9 &gt;

J. New Mater. Electrochem. Syst. 2000, 3 (1), and 43-, Polymer A-9 shown below was obtained. The polymer A-9 was subjected to neutralization titration to calculate the sulfonic acid group content (3.9 meq / g) in the polymer. The fluorine content (23.9 mass%) in the polymer was calculated by elemental analysis.

(26)

<< Synthesis of polymer A-10 >>

Polymer A-10 shown below was obtained in accordance with the method described in Fuel Cells 2005, 5, No. 3, 383-. The composition (shown below) was determined for polymer A-10 by ¹³ C NMR, and the sulfonic acid group content (1.72 meq / g) in the polymer was calculated by neutralization titration. The fluorine content (44.6 mass%) in the polymer was calculated by elemental analysis.

(27)

<< Synthesis of polymer A-11 >>

J. Membr. Sci. 325, 2008, and 989 to obtain Polymer A-11 shown below. Composition (shown below) was determined for polymer A-11 by ¹³ C NMR, and the content of sulfonic acid group (1.9 meq / g) in the polymer was calculated by neutralization titration. Further, the fluorine content (20.3 mass%) in the polymer was calculated by elemental analysis.

(28)

<Synthesis of Copper Complex>

<< Synthesis of Copper Complex Cu-1 >>

554 mg of copper hydroxide was added to 20 g of a 20% aqueous solution of the polymer A-1, and the mixture was stirred at room temperature for 3 hours to dissolve the copper hydroxide. Thus, an aqueous solution of copper complex Cu-1 was obtained.

<< Synthesis of copper complexes Cu-2 to Cu-14 >>

Copper complexes Cu-2 to Cu-14 were synthesized in the same manner as in the synthesis of the copper complex Cu-1, except that the mass ratio of the acid groups of the polymer A to the equivalent amounts of the copper atoms was changed as shown in Table 2 . Nafion (registered trademark) (DE1021 CS type, made by Wako Pure Chemical Industries, Ltd., the following structure) was used as the polymer A for the synthesis of the copper complex Cu-12.

[Chemical Formula 29]

[Table 2]

<< Synthesis of Copper Complex Cu-15 >>

3.00 g of ethanesulfonic acid and 3.76 g of butanesulfonic acid were diluted with 100 ml of methanol, 2.66 g of copper hydroxide was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was concentrated, and the obtained solid was vacuum dried to obtain copper complex Cu-15.

<< Synthesis of Copper Complex Cu-16 >>

6.00 g of ethanesulfonic acid was diluted with 100 ml of methanol, 2.66 g of copper hydroxide was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was concentrated, and the resulting solid was dried under reduced pressure to obtain a copper complex Cu-16.

<< Synthesis of Copper Complex Cu-17 >>

1.05 g of copper acetate was added to 20 g of a 20% aqueous solution of Polymer A-5, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated with an evaporator, and the resulting acetic acid was removed. Then, water was added to the residue to obtain a 20% aqueous solution, whereby an aqueous solution of copper complex Cu-17 was obtained.

<< Synthesis of Copper Complex Cu-18 (Comparative Synthesis Example 1) >>

A copper complex Cu-18 was synthesized in the same manner as in the method described in Example 1 of JP-A-2011-227528. In the following formulas, "Ac " represents an acetyl group.

(30)

&Lt; Preparation of near infrared absorbing composition >

&Lt; Example 1 &gt;

&Lt; Adjustment of near infrared absorbing composition 1 >

The near infrared absorptive compositions of Examples 1 to 21 and Comparative Example 1 were prepared by mixing the copper complex and the solvent so that the blend amounts shown in Table 3 were obtained.

(II) hydrate (Wako Pure Chemical Industries, Ltd.) was used as the copper complex Cu-19 in Table 3, and solvent EG was dissolved in ethylene glycol (Wako Pure Chemical Industries Co., Ltd. Manufactured by Wako Pure Chemical Industries, Ltd.) was used, and methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the solvent MeOH.

[Table 3]

<Fabrication of near-infrared ray cut filter>

Each of the near infrared absorbing compositions prepared in Examples and Comparative Examples was applied to a glass substrate using an applicator application method (Baker applicator, YBA-3 type, manufactured by YOSHIMITS SEIKI, adjusted to a slit width of 250 mu m) (Prebaked) at 100 DEG C for 120 seconds. Thereafter, all the samples were heated at 180 DEG C for 180 seconds on a hot plate to obtain a near infrared ray blocking filter.

<Evaluation>

<<< Evaluation of Near Infrared Shielding >>>

The transmittance at a wavelength of 800 nm in the near-infrared cut filter obtained as described above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The near infrared ray shielding property was evaluated by the following criteria.

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

B: 5% <transmittance of 800 nm wavelength ≤7%

C: 7% <transmittance of 800 nm wavelength ≤10%

D: 10% <transmittance of 800 nm wavelength

<<< Evaluation of moisture resistance >>>

The near-infrared cut filter obtained as described above was allowed to stand under high temperature and high humidity of 85 占 폚 / 95% RH for 3 hours. (Abs λmax) at a wavelength of 700 to 1400 nm and a minimum absorbance (Absλmin) at a wavelength of 400 to 700 nm of the near infrared ray blocking filter were measured with a spectrophotometer U-4100 Manufactured by Hitachi High-Technologies Corporation), and the absorbance ratio represented by "Absλmax / Absλmin" was obtained. | Absorbance ratio before test (Absorbance ratio before test - Absorbance ratio after test) / Absorbance ratio before test 占 100 (%) The rate of change in absorbance was expressed by the following criteria.

A: Absorption ratio change rate ≤ 2%

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

C: 4% <change in absorbance ratio ≤7%

D: 7% <change in absorbance ratio

<<< Heat resistance evaluation 1 >>>

The near-infrared cut filter thus obtained was allowed to stand at 200 占 폚 for 5 minutes. (Abs λmax) at a wavelength of 700 to 1400 nm and a minimum absorbance (Absλmin) at a wavelength of 400 to 700 nm of the near infrared ray blocking filter were measured with a spectrophotometer U-4100 (Hitachi High- Manufactured by Technologies Inc.), and the absorbance ratio represented by "Absλmax / Absλmin" was obtained.

(Absorbance ratio before test / Absorbance ratio before test / Absorbance ratio before test) x 100 (%) was evaluated by the following criteria. The results are shown in Table 4 below.

A: Absorption ratio change rate ≤ 2%

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

C: 4% <change in absorbance ratio ≤7%

D: 7% <change in absorbance ratio

<< Heat resistance evaluation 2 >>

Evaluation was carried out in the same manner as in the heat resistance evaluation 1 except that the heating temperature was changed from 200 캜 to 265 캜.

[Table 4]

As can be seen from Table 4, the near infrared absorbing composition of the Example was able to form a cured film having excellent heat resistance while maintaining a high near infrared ray shielding property. In addition, the near infrared absorbing composition of the Examples was able to form a cured film having excellent moisture resistance.

On the other hand, the near infrared absorbing composition of the comparative example had poor heat resistance as a cured film as compared with the examples. In addition, the near infrared absorbing composition of the comparative example did not have good moisture resistance when it was used as a cured film, as compared with the examples.

1A polymer (A1)
1B A polymer (A3) containing an acid group ion and a fluorine atom and a compound containing a copper ion
2A copper complex
2B copper ion
3A, 3B main chain
4A, 4B side chain
Pentasaccharide ion site
10 silicon substrate
12 image pickup element
13 interlayer insulating film
14 base layer
15 Color filters
16 Overcoat
17 microlens
18 Light-shielding film
20 Adhesive
22 insulating film
23 metal electrode
24 solder resist layer
26 internal electrode
27 Element surface electrode
30 glass substrate
40 imaging lens
42 NIR filter
44 Shielded electronic shield
45 Adhesive
46 planarization layer
50 Lens Holder
60 solder balls
70 circuit board
100 solid-state imaging element substrate

Claims (17)

A near-infrared absorbing composition comprising a compound obtained by reacting a polymer (A) containing a fluorine atom with a copper component, wherein the blending amount of the polymer (A) relative to the total solid content in the composition is 10% by mass or more. A near infrared absorbing composition comprising a fluorine atom-containing polymer (A) and at least one of a copper ion and a copper compound, wherein the blend amount of the polymer (A) relative to the total solid content in the composition is at least 10 mass% . The method according to claim 1 or 2,
Wherein the polymer (A) is a polymer (A2) further comprising an acid group or a salt thereof. The method of claim 3,
Wherein the acid group or a salt thereof is at least one selected from a carboxylic acid group and a salt thereof, a phosphoric acid group and a salt thereof, and a sulfonic acid group and a salt thereof. The method of claim 4,
Wherein the acid group or a salt thereof is a sulfonic acid group or a salt thereof, respectively. The method according to any one of claims 1 to 5,
Wherein the polymer (A) comprises at least one of the structural units represented by the following formulas (A2-1), (A2-2) and (A2-3);
[Chemical Formula 1]

Formula (A2-1) of, R ¹ is an aliphatic hydrocarbon, Y ¹ denotes a single bond or a divalent linking group, X ¹ is a group or an salt thereof, R ¹ and Y ¹ is a fluorine atom, at least one of &Lt; / RTI &gt;
Formula (A2-2) of, R ² is an aliphatic hydrocarbon, R ³ represents an hydrocarbon, Y ² denotes a single bond or a divalent connecting group, R ^2, R ³ and Y ² at least one of a fluorine- Substituted by an atom;
In formula (A2-3), Ar ¹ represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, R ⁴ represents an organic group, Y ³ represents a single bond or a divalent linking group, X ² represents an acid group or a salt thereof , And at least one of Ar ¹ , R ⁴ and Y ³ is substituted with a fluorine atom. The method according to any one of claims 1 to 6,
Wherein the polymer comprises at least one member selected from the constituent units represented by the following formulas (A2-1-1), (A2-2-1) and (A2-3);
(2)

Equation (A2-1-1) of, R ⁵ and R ⁶ each independently represents a hydrogen atom, a methyl group or a fluorine atom, Y ⁴ represents a single bond or a divalent linking group, X ³ represents a group or a salt thereof ;
In formula (A2-2-1), R ⁷ and R ⁸ each independently represent a hydrogen atom, a methyl group or a fluorine atom, Y ⁵ represents a single bond or a divalent linking group, R ⁹ represents an alkyl group or an aryl group, At least one of R ⁷ , R ⁸ , Y ⁵ and R ⁹ is substituted with a fluorine atom;
In formula (A2-3), Ar ¹ represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, R ⁴ represents an organic group, Y ³ represents a single bond or a divalent linking group, X ² represents an acid group or a salt thereof , And at least one of Ar ¹ , R ⁴ and Y ³ is substituted with a fluorine atom. The method according to any one of claims 1 to 7,
Wherein the polymer (A) is at least one kind selected from the group consisting of structural units represented by the following formulas (A2-1-1-1), (A2-1-1-2), (A2-3-1) and (A2-2-1-1) A near-infrared absorbing composition having at least one species selected from the group consisting of
(3)

In formula (A2-1-1-1), L ¹ represents a single bond or a linking group of (n 2 + 1), n 2 represents an integer of 1 to 5, and X ⁴ represents an acid group or a salt thereof;
Equation (A2-1-1-2) of, Y ⁶ is a straight chain, branched or cyclic alkylene group, arylene group, -C (= O) O-, -O-, or -C (= O) - NR '- (R' is a hydrogen atom or an alkyl group), or a combination thereof, Rf ¹ represents a divalent linking group containing a fluorine atom, and X ⁵ represents an acid group or a salt thereof;
In formula (A2-3-1), Ar ² represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Rf ² represents an alkyl group substituted by a fluorine atom or a fluorine atom, and X ⁶ represents an acid group or a salt thereof;
Equation (A2-2-1-1) of, Y ⁷ represents a single bond, a straight chain, branched or cyclic alkylene group, -C (= O) O-, -O-, or represents a group composed of a combination thereof , And Rf ³ represents an alkyl group or aryl group substituted with a fluorine atom. The method according to any one of claims 1 to 8,
Wherein the polymer does not comprise a CH bond. The method according to any one of claims 1 to 9,
Wherein the polymer (A) contains fluorine atoms in a proportion of 10 mass% or more. The method according to any one of claims 1 to 10,
Further comprising water. The method according to claim 1 or 2,
Wherein the polymer (A) is a polymer (A3) containing an acid group ion, and the acid group ion contains a copper complex to be added to the copper ion. A near infrared ray blocking filter obtained by using the near infrared absorbing composition according to any one of claims 1 to 12. 14. The method of claim 13,
Wherein the rate of change of the absorbance ratio obtained by the following equation before and after heating at 200 占 폚 for 5 minutes is 5% or less.
[(Absorbance ratio before heating - Absorbance ratio after heating) / Absorbance ratio before heating]
Here, the term "absorbance ratio" refers to a value obtained by dividing the maximum absorbance at a wavelength of 700 to 1400 nm by the minimum absorbance at a wavelength of 400 to 700 nm. A method for manufacturing a near-infrared light blocking filter, comprising the step of forming a film on the light receiving side of a solid-state imaging element substrate by applying the near infrared absorbing composition according to any one of claims 1 to 12. Wherein the solid-state imaging element substrate and the near infrared ray blocking filter disposed on the light receiving side of the solid-state imaging element substrate, wherein the near infrared ray blocking filter is the near infrared ray blocking filter according to claim 13 or claim 14. 1. A manufacturing method of a camera module having a solid-state imaging element substrate and a near-infrared cut-off filter disposed on a light-receiving side of the solid-state imaging element substrate, characterized in that, on the light receiving side of the solid- And a step of forming a film by applying the near infrared absorbing composition.

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