TW201505854A - Method for manufacturing copper compound-containing film, method for suppressing an increasing of viscosity of composition for film formation, kit for manufacturing composition for film formation, and solid-state image sensing device - Google Patents

Abstract

This invention provides a method for manufacturing a copper compound-containing film with little flaws such as cracks, a method for suppressing an increasing of viscosity of a composition for film formation, a kit for manufacturing the composition for film formation and a solid-state image sensing device. The method for manufacturing the copper compound-containing film includes: a step of mixing a composition containing a copper compound and a curable composition containing a curable compound to produce the composition for film formation, and a step of applying the composition for film formation on a substrate within three days after the production of the composition for film formation.

Description

Method for producing a film containing a copper compound, a method for suppressing adhesion of a film-forming composition, a kit for producing a film-forming composition, and a solid-state image sensor

The present invention relates to a method for producing a film containing a copper compound, a method for suppressing adhesion of a film-forming composition, a kit for producing a film-forming composition, and a solid-state image sensor.

In a camera, a digital still camera, a mobile phone with a camera function, etc., a charge coupled device (CCD) image sensor or a complementary metal oxide semiconductor (Complementary Metal Oxide) is used as a solid-state image sensor of a color image. Semiconductor, CMOS) image sensor. Since the solid-state imaging device uses a silicon photodiode having sensitivity to near-infrared rays in its light receiving portion, it is necessary to perform visual sensitivity correction. A near-infrared cut filter (hereinafter also referred to as an infrared (IR) cut filter) is often used.

As a material of the near-infrared cut filter, Patent Document 1 discloses that a curable compound (epoxy compound) and a copper compound (at least one of a copper phosphate complex and a copper carboxylate complex) are contained. A hardening composition.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-303308

Here, as a result of examining the curable composition disclosed in Patent Document 1, it is found that there is a tendency that it tends to increase in viscosity due to passage of time. The hardenable composition which is thickened as described above is difficult to apply to the substrate in a layer form by coating or the like. Further, there is a tendency that defects such as cracks are likely to occur in the obtained film.

The present invention has been made to solve the above problems, and an object of the invention is to provide a method for producing a copper compound-containing film having few defects such as cracks.

As a result of intensive studies based on the above-mentioned conditions, the present inventors have found that a composition containing a copper compound is used within three days before use by setting a composition containing a copper compound and a curable compound in a different state. The problem can be solved by mixing with a curable composition containing a curable compound.

Specifically, by the following means <1>, it is preferable to use the means <2>~ Means <14> to solve the problem.

<1> A method for producing a film containing a copper compound, comprising: a step of preparing a film-forming composition by mixing a composition containing a copper compound and a curable composition containing a curable compound, and 3 days after preparation The step of applying the film-forming composition to the substrate is carried out.

<2> The method for producing a film containing a copper compound according to <1>, wherein the film forming composition is used within one day after preparation.

<3> The method for producing a film containing a copper compound according to <1> or <2>, wherein the initial viscosity (V0) of the film-forming composition after 10 minutes from the preparation of the film-forming composition is The rate of change of the viscosity (V1) of the film-forming composition when applied at the same temperature is 140% or less, and the rate of change of the viscosity (V1) with respect to the initial viscosity (V0) is represented by the following formula: (( V1-V0)/V0)×100.

The method for producing a copper compound-containing film according to any one of <1> to <3> wherein the curable compound contains an oxygen heterocyclic compound.

The method for producing a copper compound-containing film according to any one of <1> to <3> wherein the curable compound contains an epoxy compound.

The method for producing a copper compound-containing film according to any one of the above aspects, wherein the content of the copper compound relative to the total solid content in the film-forming composition is 10% by mass or more .

The method for producing a copper compound-containing film according to any one of the above aspects, wherein the copper compound contains a copper compound obtained by a reaction of a polymer containing a coordination site and a copper component. .

The method for producing a copper compound-containing film according to any one of the above aspects, wherein the copper compound comprises an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain. Further, a copper compound obtained by a reaction of a polymer (A1) having a coordination site with a copper component; and a copper compound obtained by a reaction of a compound containing a molecular weight of 1,000 or less of a coordination site with a copper component.

The method for producing a film containing a copper compound according to any one of the above aspects, wherein the film forming composition is applied to a substrate within 3 days after preparation, thereby suppressing The composition for film formation is thickened.

The method for producing a film containing a copper compound according to any one of the above aspects, wherein the film-forming composition is applied to a substrate within 3 days after preparation, thereby suppressing The composition for film formation is thickened.

The method for producing a copper compound-containing film according to any one of <1> to <10> wherein the film containing the copper compound is a near-infrared cut filter.

<12> A solid-state image sensor comprising a copper compound-containing film obtained by the method for producing a copper compound-containing film according to any one of <1> to <11>.

<13> A method for inhibiting adhesion of a film-forming composition, which is a suppression package A method for thickening a film-forming composition comprising a composition containing a copper compound and a curable composition containing a curable compound, comprising: a composition containing a copper compound within 3 days before the film forming composition is used The substance is mixed with the curable composition.

<14> A kit for producing a film-forming composition comprising a composition containing a copper compound and a curable composition containing a curable compound, comprising: a composition containing a copper compound and hardening Sexual composition.

According to the invention, a film can be suitably produced using a curable composition. Further, it is possible to further suppress defects such as cracks in the obtained copper compound-containing film.

1‧‧‧ Copper compound containing polymer (A2) containing acid-based ions and copper ions

2‧‧‧ copper

3‧‧‧Main chain

4‧‧‧ side chain

5‧‧‧ Acid-based ion sites

10‧‧‧矽 substrate

12‧‧‧ Camera Components Division

13‧‧‧Interlayer insulating film

14‧‧‧ basal layer

15‧‧‧Color filters

15B‧‧‧Blue color filter

15G‧‧‧Green color filter

15R‧‧‧Red color filter

16‧‧‧Protective layer

17‧‧‧Microlens

18‧‧‧Shade film

20‧‧‧Adhesive

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧ solder resist layer

26‧‧‧Internal electrodes

27‧‧‧ Component surface electrode

30‧‧‧ glass substrate

40‧‧‧ camera lens

42‧‧‧Near-infrared cut-off filter

44‧‧‧Shading and electromagnetic cover

45‧‧‧Adhesive

46‧‧‧Destivation layer

50‧‧‧Lens frame

60‧‧‧ solder balls

70‧‧‧ circuit board

80‧‧‧UV. Infrared light reflecting film

81‧‧‧Transparent substrate

82‧‧‧Near infrared absorption layer

83‧‧‧Anti-reflective layer

100‧‧‧Solid camera components

200‧‧‧ camera module

Hν‧‧‧ incident light

Fig. 1 is a view showing an example of a copper compound used in the present invention.

FIG. 2 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image sensor according to an embodiment of the present invention.

Fig. 3 is a schematic cross-sectional view showing a solid-state image sensor according to an embodiment of the present invention.

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

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

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

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

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

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

In the present specification, "single body" has the same meaning as "monomer", and "polymer" has the same meaning as "polymer".

In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group).

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

The near-infrared absorbing property in the present invention means having a maximum absorption wavelength in the near-infrared region.

The main chain of the polymer in the present invention means an atom or an atom group required to form a skeleton (long chain) of the polymer, and when a part or all of the skeleton is a cyclic group (for example, an aryl group), the ring is also The base is part of the main chain. In addition, atoms directly bonded to the main chain are also included as part of the main chain. The side chain of the polymer in the present invention means a portion other than the main chain. However, the function that is directly bonded to the main chain A group (for example, an acid group or a salt thereof described later) is used as a side chain.

<Method for Producing Film Containing Copper Compound>

The method for producing a copper compound-containing film of the present invention is characterized in that a composition containing a copper compound (hereinafter referred to as a composition containing a copper compound) and a curable composition containing a curable compound are mixed to prepare a film formation. The step of using the composition and the step of applying the film-forming composition to the substrate within 3 days after preparation.

According to the present invention, it is possible to provide a film containing a copper compound having few defects such as cracks. Though the reason for this is estimated, it is considered that the film-forming composition obtained by mixing the composition containing a copper compound and the curable composition containing a curable compound is likely to be sticky due to passage of time. In the present invention, this can be eliminated. In other words, in the prior art, copper contained in the film-forming composition acts as a catalyst to promote hardening of the curable compound. Therefore, it is considered that the composition for forming a film excessively increases in viscosity due to passage of time, and it is difficult to apply it to the substrate in a layered manner, and the obtained film containing the copper compound is cracked.

In the present invention, a composition containing a copper compound and a curable composition are separately prepared, and these compositions are mixed within 3 days before being applied to a substrate to prepare a film-forming composition, thereby successfully succeeding The adhesion of the film forming composition is suppressed. As a result, the film-forming composition can be applied to the substrate in a state where the viscosity is not excessively high, and a film containing a copper compound having less defects such as cracks can be provided.

<<Step of preparing a film-forming composition by mixing a composition containing a copper compound and a curable composition>>

The method for producing a copper compound-containing film of the present invention includes a step of preparing a film-forming composition by mixing a composition containing a copper compound and a curable composition.

The composition containing the copper compound and the curable composition are preferably stored at 40 ° C or lower during the period until the mixing. By storing at 40 ° C or lower, the composition of the copper compound and the curable composition can be further suppressed from increasing, and as a result, the thickening of the film forming composition can be further suppressed. The storage temperature of the composition containing the copper compound and the curable composition is preferably 30° C. or lower, more preferably 25° C. or lower, still more preferably 15° C. or lower, and particularly preferably 10° C. or lower. By setting such a storage temperature, it is possible to more effectively suppress the adhesion of the composition containing the copper compound and the curable composition.

The difference in storage temperature between the composition containing the copper compound and the curable composition is preferably small, and is, for example, preferably 20 ° C or lower, more preferably 10 ° C or lower, and still more preferably 5 ° C or lower.

The details of the composition containing the copper compound and the curable composition will be described later.

<<Step of applying the film-forming composition to the substrate within 3 days after preparation>>

The production method of the present invention includes the step of applying the film-forming composition to the substrate within 3 days after preparation. By applying the film-forming composition to the substrate in a short time after preparation, the film-forming composition can be suppressed from being thickened.

The application to the substrate is within 3 days after the preparation of the film-forming composition, preferably within 1 day, more preferably within 12 hours, further preferably within 6 hours, and even more preferably within 3 hours.

The change rate of the viscosity (V1) of the film-forming composition when applied at the same temperature with respect to the initial viscosity (V0) of the film-forming composition 10 minutes after the preparation of the film-forming composition [((V1-) V0)/V0)×100] is preferably 140% or less, more preferably 120% or less, still more preferably 90% or less, and particularly preferably 50% or less. By satisfying the range of the change rate of the viscosity, it is possible to provide a film containing a copper compound having less defects such as cracks.

The film-forming composition is preferably stored at 40 ° C or lower during the period until it is applied to the substrate. By storing at 40 ° C or lower, the thickening of the film-forming composition can be further suppressed. The storage temperature of the film-forming composition is more preferably 25° C. or lower, more preferably 15° C. or lower, and particularly preferably 10° C. or lower. By setting such a storage temperature, the thickening of the film formation composition can be more effectively suppressed.

The method of applying the film-forming composition to a substrate is preferably coating or printing. Specifically, it is preferably selected from the group consisting of drop casting, applicator coating, dip coating, and slit coating. At least one of screen printing, spray coating and spin coating.

In the case of the dropping method (drop casting), in order to obtain a uniform film with a predetermined film thickness, it is preferable to form a dropping region of a film forming composition using a photoresist as a partition wall on the support. The desired film thickness can be obtained by adjusting the amount of the film forming composition, the solid content concentration, and the area of the dropping region.

The substrate is not particularly limited, and examples thereof include a transparent substrate (glass substrate or plastic substrate) containing glass or the like. Further, when used for a solid-state imaging device, the substrate may be a solid-state imaging device, another substrate provided on the light-receiving side of the solid-state imaging device, or a layer such as a planarization layer.

The amount of the film-forming composition to be applied to the substrate is not particularly limited. However, the film thickness after drying the film-forming composition is preferably 50 μm to 300 μm.

In addition, the drying conditions of the coating film differ depending on the type of each component, the type of the solvent, the ratio of use, and the like, but are usually from 60 ° C to 200 ° C for about 30 seconds to 15 minutes.

The method of forming a film containing a copper compound (near-infrared cut filter) using the film forming composition may also include other steps. Other steps can be appropriately selected depending on the purpose, and examples thereof include a step of drying the composition for forming a film on a substrate, and the like.

The drying conditions vary depending on the components, the type of the solvent, the ratio of use, and the like, but are usually from 60 ° C to 200 ° C for about 30 seconds to 15 minutes.

The heating device is not particularly limited, and may be appropriately selected from known devices depending on the purpose, and examples thereof include a drying oven, a hot plate, and an IR heater.

Hereinafter, the composition for forming a film, the composition containing a copper compound, and the curable composition used in the present invention will be described in detail.

<<Composition for film formation>>

The film-forming composition can be obtained by mixing a composition containing a copper compound and a curable composition, and contains at least a copper compound and a curable compound.

The total content of the copper compound and the curable compound in the film-forming composition is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably more, based on the total solid content in the film-forming composition. 85 mass% or more.

The film forming composition is relative to the total solid content in the film forming composition The content of the copper compound is preferably 10% by mass or more, and more preferably 15% by mass or more. Further, the upper limit is preferably 70% by mass or less. In particular, the content of the copper compound is preferably 10% by mass or more, and more preferably 15% by mass to 70% by mass based on the total solid content in the film-forming composition.

The film-forming composition may further contain a copper compound and other components other than the curable compound. As another component, a solvent (preferably water), a surfactant, etc. are mentioned.

In order to remove foreign matter, reduce defects, and the like, it is preferred to filter the film formation composition by a filter. The filter is not particularly limited as long as it is a filter used for filtration purposes or the like from the past. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon, or a polyolefin resin (including high density, ultrahigh molecular weight) such as polyethylene or polypropylene (polypropylene) may be used. filter. Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred.

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

Different filters can also be combined when using filters. At this time, the filtration by the first type of filter may be performed only once or twice or more. When two or more filters are combined by using different filters, it is preferable that the pore diameter after the second time is equal to or larger than the pore diameter of the first filtration. In addition, it can also be used in In the above range, the first type of filters having different pore diameters are combined. The aperture can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., Japan Nihon Entegris Co., Ltd. (formerly Japan Mico) Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd.

As the second filter, a filter formed of the same material as the first filter or the like can be used. The pore diameter of the second filter is preferably from about 0.2 μm to about 10.0 μm, more preferably from about 0.2 μm to about 7.0 μm, still more preferably from about 0.3 μm to about 6.0 μm. By setting it as this range, the foreign material mixed in the film formation composition can be removed more reliably.

The use of the film-forming composition used in the present invention is not particularly limited, and examples thereof include a near-infrared cut filter for light-receiving side of a solid-state image sensor (for example, a near-infrared cut filter for a wafer-level lens) The use of the near-infrared cut filter or the like on the back side of the solid-state image sensor (opposite to the light-receiving side) is preferably used for the light-shielding film on the light-receiving side of the solid-state image sensor.

In particular, it is preferable to form a coating film by directly applying a film forming composition to an image sensor for a solid-state imaging device.

In addition, when the infrared cut-off layer is formed by coating, the viscosity of the film-forming composition is preferably 1 mPa. Above s, 3000mPa. Below s, more preferably 1mPa. Above s, 2000mPa. s below, and then preferably 1mPa. s~20mPa. s, and more preferably 1 mPa. s~16mPa. s.

The total solid content of the film-forming composition is changed according to the coating method, but is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, and still more preferably 10% by mass based on the composition. %~30% by mass.

<<Composition containing copper compound>>

The copper compound contained in the composition containing a copper compound may be a copper-containing compound, and is preferably a copper complex. The copper compound preferably contains a copper compound obtained by a reaction of a polymer (A1) containing a coordination site and a copper component described later, and a compound having a molecular weight of 1000 or less and a copper component containing a coordination site. At least one of the obtained copper compounds may also contain both of them.

The composition containing a copper compound contains a copper compound obtained by a reaction of the polymer (A1) and a copper component, and a copper compound obtained by a reaction of a compound having a molecular weight of 1000 or less and a copper component containing a coordination site. In the case of the total solid content in the composition containing the copper compound, the content of the copper compound obtained by the reaction of the polymer (A1) and the copper component is preferably 10% by mass or more, and more preferably 15% by mass or more. More preferably, it is 20 mass% or more. In particular, it is preferably 10% by mass to 90% by mass, more preferably 15% by mass to 80% by mass, still more preferably 15% by mass to 70% by mass, still more preferably 20% by mass to 70% by mass.

When the copper compound is a copper complex, the ligand L to be placed on the copper is not particularly limited as long as it can be coordinately bonded to the copper ion, and examples thereof include a sulfonic acid, a carboxylic acid, and a carbonyl group. (Ester, ketone), amine, decylamine, sulfonamide, urethane, urea, alcohol, thiol, and the like. Among these, a carboxylic acid and a sulfonic acid are preferable, and a sulfonic acid is more preferable.

<<<Low Molecular Copper Compound>>>

The copper complex compound is, for example, a copper complex represented by the formula (A).

The copper complex compound represented by the following formula (A) is exemplified as the copper complex.

Cu(X) _n1 formula (A)

In the formula (A), X represents a ligand disposed on copper, and n1 independently represents an integer of 1 to 6.

The ligand X is a coordination site for coordinating to copper, and is, for example, a substituent containing C, N, O, and S as an atom which can be coordinated to copper, and more preferably contains N or O, S, or the like. The base of the lone pair of electrons. In the molecule, the coordination site is not limited to one type, and may be contained in two or more types, and may be dissociated or non-dissociated.

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

The compound to be a ligand or a salt thereof preferably contains a coordination site (for example, a coordination site (specifically, an acid group or a salt thereof) coordinated by an anion, and a coordination using an unshared electron pair The compound of the site is preferably represented by the following formula (i).

General formula (i)

[Chemical 1]

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

In the general formula (i), X ¹ preferably contains one or more kinds of coordination sites selected from the group consisting of a coordination site coordinated by an anion and a group of non-shared electrons, and more preferably one or more. A coordination site that coordinates with an anion. X ¹ may be one type alone or two or more types, and preferably two or more types.

The anion may be an anion containing a copper atom which may be coordinated to the copper component, and for example, preferably contains an oxyanion, a nitrogen anion or a sulfur anion.

The coordination site to be coordinated by an anion is, for example, preferably at least one selected from the group (AN) below.

Group (AN)

In the group (AN), X represents N or CR, and R independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

The alkyl group represented by R may be linear, branched or cyclic, but is preferably linear. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 4. As an example of an alkyl group, a methyl group is mentioned. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, a carboxylic acid group, and a heterocyclic group. The heterocyclic group as a substituent may be a single ring or a polycyclic ring, and may be aromatic or non-aromatic. The number of the hetero atoms constituting the hetero ring is preferably from 1 to 3, more preferably 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom. When the alkyl group has a substituent, it may further have a substituent.

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

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

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

An example of a coordination site coordinated by an anion is a monoanionic coordination site. The monoanionic coordination site represents a site that coordinates with a copper atom via a functional group having one negative charge. For example, an acid group having an acid dissociation constant (pKa) of 12 or less can be cited. Specific examples thereof include an acid group (phosphoric acid diester group, phosphonic acid monoester group, phosphinic acid group, etc.) containing a phosphorus atom, a sulfonic acid group, a carboxylic acid group, a quinone acid group, and the like, and preferably a sulfonate. Acid group, carboxylic acid group and acid group containing phosphorus atom At least one kind is more preferably a sulfonic acid group and a carboxylic acid group, and still more preferably a carboxylic acid group.

The coordination site for coordination by the unshared electron pair preferably contains an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom as a coordinating atom, more preferably an oxygen atom, a nitrogen atom or a sulfur atom as a coordinating atom, and further More preferably, it contains a nitrogen atom as a coordinating atom. Further, it is preferred that the coordinating atom coordinated by the unshared electron pair is a nitrogen atom and the atom adjacent to the nitrogen atom is a carbon atom, and the carbon atom preferably has a substituent. With such a configuration, the structure of the copper complex is more easily deformed, so that the color price can be further improved. The substituent is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a carboxylic acid group, an alkoxy group having 1 to 12 carbon atoms, or a fluorenyl group having 2 to 12 carbon atoms. An alkylthio group having 1 to 12 carbon atoms and a halogen atom.

The coordinating atom coordinated by the non-shared electron pair may be included in the ring or may be included in at least one partial structure selected from the group (UE) below.

Group (UE)

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

The meaning of the alkyl group represented by R ¹ is the same as the alkyl group described in R in the group (AN), and the preferred range is also the same.

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

The alkynyl group represented by R ¹ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

The heteroaryl group represented by R ¹ has the same meaning as the heteroaryl group described in R in the group (AN), and the preferred range is also the same.

The meaning of the alkyl group represented by R ² is the same as the alkyl group described in R ¹ in the group (UE), and the preferred range is also the same.

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

The alkynyl group represented by R ² preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

The meaning of the aryl group represented by R ² is the same as the aryl group described in R ¹ in the group (UE), and the preferred range is also the same.

The heteroaryl group represented by R ² has the same meaning as the heteroaryl group described in R ¹ in the group (UE), and the preferred range is also the same.

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

The aryloxy group represented by R ² preferably has 6 to 18 carbon atoms.

The heteroaryloxy group represented by R ² may be a single ring or a polycyclic ring. The heteroaryl group constituting the heteroaryloxy group has the same meaning as the heteroaryl group described in R ¹ in the group (UE), and the preferred range is also the same.

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

The arylthio group represented by R ² preferably has 6 to 18 carbon atoms.

The heteroarylthio group represented by R ² may be a single ring or a polycyclic ring. The heteroaryl group constituting the heteroarylthio group has the same meaning as the heteroaryl group described in R ¹ , and the preferred range is also the same.

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

When a coordinating atom coordinated by an unshared electron pair is contained in a ring, the ring containing the coordinating atom may be a single ring or a polycyclic ring, and may be aromatic or non-aromatic. The ring containing the coordinating atom is preferably a 5-membered ring to a 12-membered ring, more preferably a 5-membered ring to a 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

A ring comprising a coordinating atom coordinated by a non-shared electron pair may have a substituent. Examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, a halogen atom, and a carbon number of 1 to 12. The alkoxy group is a fluorenyl group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, a carboxylic acid group or the like. The substituent may further have a substituent. Examples of such a substituent include a group containing a ring including a coordinating atom coordinated by a non-shared electron pair, a group containing at least one partial structure selected from the group (UE), and carbon. The number is 1 to 12 alkyl groups, the carbon number is 1 to 12 sulfhydryl groups, hydroxyl groups, and the like.

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

In the formula (i), the n-valent group is preferably an n-valent organic group, or an n-valent organic group and -O-, -SO-, -SO ₂ -, -NR ^N1 -, -CO-, The base of the combination of -CS-.

The n-valent organic group is preferably a hydrocarbon group, an alkylene group, a heterocyclic group or the like, more preferably a fat. An aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the n-valent group may be a group containing at least one selected from the group (AN-1) selected from below, a ring including a coordinating atom coordinated by an unshared electron pair, or a selected from the group consisting of A base of at least one of the groups (UE-1).

The hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom (preferably a fluorine atom) and a polymerizable group (for example, a group having an unsaturated double bond (vinyl group, (meth)acryl fluorenyl group, etc.), or a ring. An oxy group, an oxetane group, etc.), an alkyl group, a sulfonic acid group, a carboxylic acid group, an acid group containing a phosphorus atom, a carboxylate group (for example, -CO ₂ CH ₃ ), a hydroxyl group, an alkoxy group (for example) Methoxy), an amine group, an amine methyl sulfhydryl group, an amine methyl methoxy group, a halogenated alkyl group (for example, a fluoroalkyl group, a chloroalkyl group), a (meth) acryloxy group, and the like. When the hydrocarbon group has a substituent, it may further have a substituent. Examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.

When the hydrocarbon group is monovalent, it is preferably an alkyl group, an alkenyl group or an aryl group, more preferably an aryl group. When the hydrocarbon group is divalent, it is preferably an alkyl group, an aryl group or an alkyl group, more preferably an aryl group. When the hydrocarbon group is trivalent or higher, it preferably corresponds to the monovalent hydrocarbon group or the divalent hydrocarbon group.

The alkyl group and the alkylene group may be any of a linear chain, a branched chain or a cyclic chain. The carbon number of the linear alkyl group and the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 8. The carbon number of the branched alkyl group and the alkyl group is preferably from 3 to 20, more preferably from 3 to 12, and still more preferably from 3 to 8. The cyclic alkyl group and the alkylene group may be either a single ring or a polycyclic ring. The carbon number of the cyclic alkyl group and the alkylene group is preferably from 3 to 20, more preferably from 4 to 10, still more preferably from 6 to 10.

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

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

The heterocyclic group may be a heterocyclic group or an aromatic heterocyclic group in the alicyclic group. As the heterocyclic group, a 5-membered ring or a 6-membered ring is preferred. Further, the heterocyclic group is a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 4. The heterocyclic group may have a substituent, and as a substituent, the meaning is the same as the substituent which the hydrocarbon group may have.

In -NR ^N1 -, R ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. The alkyl group in R ^N1 may be in the form of a chain, a branch, or a ring. The linear or branched alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. The cyclic alkyl group may be either a single ring or a polycyclic ring. The carbon number of the cyclic alkyl group is preferably from 3 to 20, more preferably from 4 to 14.

The carbon number of the aryl group in R ^N1 is preferably from 6 to 18, more preferably from 6 to 14. Specifically, a phenyl group, a naphthyl group, etc. are illustrated. The aralkyl group in R ^N1 is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an unsubstituted aralkyl group having 7 to 15 carbon atoms.

Group (UE-1)

[Chemical 4]

The same group (UE-1) and the meaning of R group (UE) ¹ in R ^1.

Group (AN-1)

X in the group (AN-1) represents N or CR, and the meaning of R is the same as R described in the CR in the group (AN).

The specific form of the compound to be a ligand is preferably a compound having at least two coordination sites. Specifically, a compound having one or more coordination sites coordinated by an anion and one or more coordination atoms coordinated by an unshared electron pair (hereinafter also referred to as a compound (A1) )), a compound containing two or more coordination atoms coordinated by an unshared electron pair (hereinafter also referred to as a compound (A2)), and having two coordination sites coordinated by an anion A compound at a site (hereinafter also referred to as a compound (A3)) or the like. These compounds may be used alone or in combination of two or more.

Further, as the compound to be a ligand, a compound containing one coordination site coordinated by an anion may be used.

<<<<化合物(A1)>>>>

In the compound (A1), the total number of the coordination sites coordinated by the anions in one molecule and the coordination atoms coordinated by the unshared electron pair may be two or more, and may be three or four. One.

The compound (A1) is preferably a compound represented by the following formula (i-1).

X ¹¹ -L ¹¹ -Y ¹¹ (i-1)

X ¹¹ represents a coordination site represented by the group (AN).

Y ¹¹ represents the ring including a coordinating atom coordinated by a non-shared electron pair, or a partial structure represented by a group (UE).

L ¹¹ represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group having 1 to 12 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -SO-, -SO ₂ -, -O-, or the like. The basis of the combination.

Further, as a more detailed example of the compound (A1), a compound represented by the following formula (i-2) to formula (i-9) can also be mentioned.

X ¹² -L ¹² -Y ¹² -L ¹³ -X ¹³ (i-2)

Y ¹³ -L ¹⁴ -Y ¹⁴ -L ¹⁵ -X ¹⁴ (i-3)

Y ¹⁵ -L ¹⁶ -X ¹⁵ -L ¹⁷ -X ¹⁶ (i-4)

Y ¹⁶ -L ¹⁸ -X ¹⁷ -L ¹⁹ -Y ¹⁷ (i-5)

X ¹⁸ -L ²⁰ -Y ¹⁸ -L ²¹ -Y ¹⁹ -L ²² -X ¹⁹ (i-6)

X ²⁰ -L ²³ -Y ²⁰ -L ²⁴ -Y ²¹ -L ²⁵ -Y ²² (i-7)

Y ²³ -L ²⁶ -X ²¹ -L ²⁷ -X ²² -L ²⁸ -Y ²⁴ (i-8)

Y ²⁵ -L ²⁹ -X ²³ -L ³⁰ -Y ²⁶ -L ³¹ -Y ²⁷ (i-9)

In the general formulae (i-2) to (i-9), X ¹² to X ¹⁴ , X ¹⁶ and X ¹⁸ to X ²⁰ each independently represent a coordination site represented by the group (AN). Further, X ¹⁵ , X ¹⁷ , and X ²¹ to X ²³ each independently represent a coordination site represented by the group (AN-1).

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

The compound (A1) is preferably a compound represented by the formula (i-10) or the formula (i-11).

[Chemical 6]

In the formula (i-10), X ² represents a group including a coordination site coordinated by an anion. Y ² represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ¹ and A ⁵ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ² to A ⁴ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. R ¹ represents a substituent. R ^X2 represents a substituent. N2 represents an integer from 0 to 3.

In the formula (i-10), X ² may contain only the group including the coordination site coordinated by the anion, and the group including the coordination site coordinated by the anion may have a substituent. Examples of the substituent which the group including the coordination site coordinated by the anion may have include a halogen atom, a carboxylic acid group, and a heterocyclic group. The heterocyclic group as a substituent may be a single ring or a polycyclic ring, and may be aromatic or non-aromatic. The number of hetero atoms constituting the hetero ring is preferably from 1 to 3. The hetero atom constituting the hetero ring is preferably a nitrogen atom.

In the formula (i-10), Y ^{2 is} preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom, and still more preferably a nitrogen atom.

In the formula (i-10), A ¹ and A ^{5 are} preferably a carbon atom.

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

In the formula (i-10), the meaning of R ^{1 is} the same as the substituent which the ring containing the coordinating atom coordinated by the unshared electron pair may have.

In the formula (i-10), the meaning of R ^{X2 is} the same as the substituent which the ring containing the coordinating atom coordinated by the unshared electron pair may have, and the preferred range is also the same.

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

Among the compounds represented by the formula (i-10), the hetero ring containing Y ² may have a single ring structure or a polycyclic structure. Specific examples of the case where the hetero ring containing Y ² has a monocyclic structure include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a pyran ring. Specific examples of the case where the hetero ring containing Y ^{2 has} a polycyclic structure include a quinoline ring, an isoquinoline ring, a quinoxaline ring, and an acridine ring.

In the formula (i-11), X ³ represents the group including the coordination site coordinated by an anion. Y ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ⁶ and A ⁹ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ⁷ and A ⁸ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. R ² represents a substituent. R ^X3 represents a substituent. N3 represents an integer from 0 to 2.

In the formula (i-11), X ^{3 has} the same meaning as X ² in the formula (i-10), and the preferred range is also the same.

In the formula (i-11), Y ^{3 is} preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom.

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

In the formula (i-11), A ^{7 is} preferably a carbon atom. A ^{8 is} preferably a carbon atom, a nitrogen atom or a sulfur atom.

In the formula (i-11), R ^{2 is} preferably a hydrophobic substituent, more preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 30 carbon atoms or a carbon number of 6~ The aryl group of 30 is particularly preferably an alkyl group having a carbon number of 3 to 15.

In the formula (i-11), R ^{X3 has} the same meaning as R ^X2 in the formula (i-10), and the preferred range is also the same.

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

Among the compounds represented by the formula (i-11), the hetero ring containing Y ³ may have a single ring structure or a polycyclic structure. Specific examples of the case where the hetero ring containing Y ³ is a monocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, and an isothiazole ring. Specific examples of the polycyclic structure in which the hetero ring containing Y ³ is a polycyclic structure include an anthracene ring, an isoindole ring, a benzofuran ring, and an isobenzofuran ring.

In particular, the compound represented by the formula (i-11) is preferably a pyrazole ring-containing compound and has a secondary or tertiary alkyl group at the 5-position of the pyrazole ring. In the specification of the present application, the 5-position of the pyrazole ring in the case where the compound represented by the formula (i-11) is a pyrazole ring-containing compound means Y ³ and A in the above (i-11). ⁶ represents a nitrogen atom, and A ⁷ to A ⁹ represent a substitution position of R ² in the case of a carbon atom. The carbon number of the secondary or tertiary alkyl group at the 5-position of the pyrazole ring is preferably from 3 to 15, more preferably from 3 to 12.

The molecular weight of the compound (A1) is preferably 1,000 or less, more preferably 750 or less, still more preferably 600 or less, and particularly preferably 500 or less. Further, the molecular weight of the compound (A1) is preferably 50 or more, more preferably 70 or more, still more preferably 80 or more.

Specific examples of the compound (A1) include the following.

[Chemistry 7]

<<<<Salt of Compound (A1)>>>>

As the salt of the compound (A1), that is, a compound containing a salt of a coordination site coordinated by an anion, for example, a metal salt is preferable. The metal atom constituting the metal salt is preferably an alkali metal atom or an alkaline earth metal atom. Examples of the alkali metal atom include sodium and potassium. Examples of the alkaline earth metal atom include calcium and magnesium.

<<<<化合物(A2)>>>>

The compound (A2) may have two or more coordination atoms coordinated by an unshared electron pair in one molecule, and may have three or more, and preferably two to four.

The compound (A2) is preferably, for example, a compound represented by the following formula (ii-1).

Y ⁴⁰ -L ⁴⁰ -Y ⁴¹ ...(ii-1)

In the general formula (ii-1), Y ⁴⁰ and Y ⁴¹ each independently represent a ring including a coordinating atom coordinated by an unshared electron pair or a partial structure represented by a group (UE).

In the formula (ii-1), L ⁴⁰ represents a single bond or a divalent linking group. When L ⁴⁰ represents a divalent linking group, it is preferably an alkylene group having 1 to 12 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -SO-, -O-, -SO ₂ - or The combination of these groups is more preferably an alkylene group having a carbon number of 1 to 3, a phenyl group or a -SO ₂ - group.

Further, as a more detailed example of the compound (A2), a compound represented by the following formula (ii-2) or formula (ii-3) can also be mentioned.

Y ⁴² -L ⁴¹ -Y ⁴³ -L ⁴² -Y ⁴⁴ (ii-2)

Y ⁴⁵ -L ⁴³ -Y ⁴⁶ -L ⁴⁴ -Y ⁴⁷ -L ⁴⁵ -Y ⁴⁸ (ii-3)

In the general formula (ii-2) and the general formula (ii-3), Y ⁴² , Y ⁴⁴ , Y ⁴⁵ and Y ⁴⁸ each independently represent a ring including a coordinating atom coordinated by a non-shared electron pair, or Part of the structure represented by the group (UE).

Further, Y ⁴³ , Y ⁴⁶ and Y ⁴⁷ are each independently a ring including a coordinating atom coordinated by an unshared electron pair or a partial structure represented by the group (UE-1).

In the general formula (ii-2) and the general formula (ii-3), L ⁴¹ to L ⁴⁵ each independently represent a single bond or a divalent linking group. The meaning of the divalent linking group is the same as the case where L ⁴⁰ in the formula (ii-1) represents a divalent linking group, and the preferred range is also the same.

The molecular weight of the compound (A2) is preferably 1,000 or less, more preferably 750 or less, still more preferably 600 or less, and particularly preferably 500 or less. Further, the molecular weight of the compound (A2) is preferably 50 or more, more preferably 70 or more, still more preferably 80 or more.

Specific examples of the compound (A2) include the following.

<<<<化合物(A3)>>>>

The compound (A3) has two coordination sites coordinated by an anion. Profit The meaning of the coordination site coordinated by the anion is the same as that of the coordination site coordinated by the anion.

The compound (A3) is preferably a compound represented by the following formula (iii-1).

X ⁵⁰ -L ⁵⁰ -X ⁵¹ (iii-1)

In the formula (iii-1), X ⁵⁰ and X ⁵¹ each independently represent a coordination site coordinated by an anion, and the meaning thereof is the same as that of the coordination site coordinated by the anion, and is preferably monoanionic. Coordination site.

In the formula (iii-1), L ⁵⁰ represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group having 1 to 20 carbon atoms, an extended alkenyl group having 2 to 10 carbon atoms, an extended aryl group having 6 to 18 carbon atoms, a heterocyclic group, and -O-. , -S-, -NR ^N1 -, -CO-, -CS-, -SO ₂ -, or a group comprising a combination of these. R ^{N1 is} preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

The compound (A3) preferably contains one or more selected from the group consisting of a sulfonic acid group and a carboxylic acid group, and more preferably contains a sulfonic acid group and a carboxylic acid group. The color valence can be further enhanced by using a compound containing at least one selected from the group consisting of a sulfonic acid group and a carboxylic acid group.

The molecular weight of the compound (A3) is preferably 1,000 or less, more preferably 750 or less, still more preferably 600 or less, and particularly preferably 500 or less. Further, the molecular weight of the compound (A3) is preferably 50 or more, more preferably 70 or more, still more preferably 80 or more.

Specific examples of the compound (A3) include (1) a sulfonic acid group and a carboxylic acid. The compound having at least one of a group and an acid group containing a phosphorus atom is more preferably (2) having two or more acid groups, and more preferably (3) having a form of a sulfonic acid group and a carboxylic acid group. In these forms, infrared absorption performance is more effectively exhibited. Further, by using a compound having a sulfonic acid group and a carboxylic acid group, the color price can be further improved.

<<<<Compound with one coordination site coordinated by anion>>>>

As the compound to be a ligand, a compound having one coordination site coordinated by an anion can also be used. For example, an organic acid compound (for example, a sulfonic acid compound, a carboxylic acid compound, a phosphoric acid compound) or a salt thereof is preferable, and at least one compound having a sulfonic acid group, a carboxylic acid group, and an acid group containing a phosphorus atom is preferable.

The sulfonic acid compound is preferably a compound represented by the following formula (I).

Formula (I)

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

The specific monovalent organic group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group, an alkenyl group, and an aryl group. Here, the groups may also be divalent linking groups (eg, alkyl, cycloalkyl, aryl, -O-, -S-, -CO-, -COO-, -OCO-). a group between -SO ₂ -, -NR- (R is a hydrogen atom or an alkyl group). Further, the monovalent organic group may have a substituent.

The linear or branched alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms. .

The cyclic alkyl group may be either a single ring or a polycyclic ring. The cyclic alkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 10 carbon atoms, and still more preferably a cycloalkyl group having 6 to 10 carbon atoms. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, and still more preferably an alkenyl group having 2 to 4 carbon atoms.

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 alkylene group, the extended cycloalkyl group, and the extended aryl group which are a divalent linking group include a divalent linking group derived by removing one hydrogen atom from the alkyl group, the cycloalkyl group, and the aryl group.

Examples of the substituent which the monovalent organic group may have include an alkyl group, a polymerizable group (for example, a vinyl group, a (meth)acrylinyl group, an epoxy group, an oxetanyl group, etc.), a halogen atom, A carboxylic acid group, a carboxylate group (for example, -CO ₂ CH ₃ or the like), a hydroxyl group, a decylamino group, a halogenated alkyl group (for example, a fluoroalkyl group, a chloroalkyl group) or the like.

The molecular weight of the sulfonic acid compound represented by the formula (I) or a salt thereof is preferably from 80 to 750, more preferably from 80 to 600, still more preferably from 80 to 450.

Specific examples of the compound (1) having at least one of a sulfonic acid group, a carboxylic acid group, and an acid group containing a phosphorus atom include the following. In addition, as a better In addition, among the compounds described in the forms (2) and (3) to be described later, the compounds corresponding to the present embodiment are also exemplified.

[11]

[化12]

Specific examples of the compound (2) having at least two acid groups include the following. In addition, as a preferable example, among the compounds described in the form (3) to be described later, a compound corresponding to the present embodiment may be mentioned.

[Chemistry 13]

Specific examples of the compound having (3) a sulfonic acid group and a carboxylic acid group include the following. Further, specific examples of the compound having a sulfonic acid group and a carboxylic acid group represented by the formula (I) to be described later are also mentioned.

<<<Polymer type copper compound>>>

The copper compound is preferably a copper compound (polymer type copper compound) obtained by a reaction of a polymer (A1) containing a coordination site with a copper component. It is considered that the polymer type copper compound is coordinated with copper of the copper component by the coordination site to deform the structure of the polymer type copper compound, and high transmittance in the visible light region can be obtained, and the light absorption ability of the near infrared ray is improved. And the price of color has also increased. Further, since the polymer type copper compound has copper as a starting point and forms a crosslinked structure between the side chains of the polymer, a film excellent in heat resistance can be obtained.

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

Relative to the coordination site of the polymer (A1) (preferably an acid group or a salt thereof) The amount of the copper component to be reacted with the polymer (A1) is preferably from 0.05 equivalents to 1 equivalent, more preferably from 0.1 equivalents to 0.8 equivalents, still more preferably from 0.2 equivalents to 0.5 equivalents. By setting the amount of the copper component to such a range, there is a tendency that a cured film having a higher near-infrared ray shielding property can be obtained.

Examples of the coordination site include a coordination site in which a copper component is coordinated by an unshared electron pair, and a coordination site in which a copper component is coordinated by an anion.

The meaning of the coordinating atom for the coordination of the copper component by the unshared electron pair is the same as the coordinating atom for coordinating with the unshared electron pair, and the preferred range is also the same. Specific examples of the coordination site include those described as the ligand.

The meaning of the coordination site in which the copper component is coordinated by the anion is the same as the coordination site in which the anion is coordinated, and an acid group or a salt thereof can be exemplified. The acid group is preferably a coordinate bond with the copper component. Specifically, an acid group having an acid dissociation constant (pKa) of 12 or less is preferable, and a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a guanidinoic acid group, and a methyl group are preferred. An acid group or the like. The acid group is preferably a carboxylic acid group or a sulfonic acid group, more preferably a sulfonic acid group. The acid group may be one type or two or more types. The salt of the acid group may, for example, be a metal salt such as a sodium salt (particularly an alkali metal salt) or a tetrabutylammonium salt.

Further, the coordination site may be included in at least one of the main chain and the side chain, and is preferably contained in at least the side chain.

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

*-L ¹ -Y ¹ ...(1)

In the formula (1), L represents a single bond or a linking group, and Y ¹ represents a coordination site having a ligand selected from an anion coordinated to a copper component and a coordination atom coordinated to a copper component by an unshared electron pair. One or more of the groups, * represents a bond to the main chain of the polymer.

In the general formula (1), Y ¹ represents one or more kinds of a coordinating site selected from the group consisting of a coordinating site which is coordinated by an anion with respect to a copper component, and a coordinating atom which is coordinated by a non-shared electron pair with respect to a copper component.

In the general formula (1), when L ¹ represents a linking group, examples of the divalent linking group include a divalent hydrocarbon group, a heteroaryl group, -O-, -S-, -CO-, -COO. -, -OCO-, -SO ₂ -, -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group comprising a combination of these.

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

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

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

The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 14, and even more preferably from 6 to 6. 10, especially good for stretching phenyl.

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

When L ¹ represents a trivalent or higher linking group, a group in which one or more hydrogen atoms are removed among the groups exemplified as the divalent linking group may be mentioned.

<<<<Bases of Coordinating Atoms Coordinating with Non-Shared Electron Pairs>>>>

In the above formula (1), when Y ¹ represents a group having a coordinating atom coordinated by an unshared electron pair, Y ^{1 is} , for example, a formula (1a1) or a formula (1a2) The base of the representation.

*-L ¹¹ -(Y ¹¹ ) _p ...(1a1)

*-L ¹¹ -(Y ^11a -L ¹² -Y ¹¹ ) _p ...(1a2)

"*" indicates a link to L ¹ of the formula (1).

L ¹¹ represents a single bond or a (p+1)-valent linking group. When L ¹¹ represents a divalent linking group, an alkylene group having 1 to 12 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -CO-, -COO-, -OCO-, -SO are preferred. ₂ -, -O-, -NR ¹⁰ - (R ¹⁰ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group comprising a combination of these.

When L ¹¹ represents a trivalent or higher linking group, a group in which one or more hydrogen atoms are removed among the groups exemplified as the divalent linking group may be mentioned.

L ¹² represents a single bond or a divalent linking group. The divalent linking group described in L ¹¹ is preferably exemplified as the divalent linking group. L ^{12 is more} preferably a single bond, an alkyl group, or a group comprising a combination of -NH- and -CO-.

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

Y ^11a represents a ring including a coordinating atom coordinated by a non-shared electron pair, or at least one selected from the group (UE-1). When p represents an integer of 2 or more, a plurality of Y ^11a may be the same or different.

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

<<<<The base of a coordination site having one or more coordination atoms coordinated by an unshared electron pair and one or more coordination sites using an anion>>>>

In the above formula (1), when Y ¹ represents a group having one or more coordination atoms coordinated by an unshared electron pair and one or more coordination sites coordinated by an anion, Y is represented as Y. ^{1 is} , for example, a group represented by the following formula.

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

*-L ²¹ -(Y ^22a -L ²³ -Y ²¹ ) _q ...(1b2)

*-L ²² -(Y ²¹ ) _q (Y ²² ) _r ...(1b3)

*-L ²² -(Y ^21a -L ²³ -Y ²² ) _q (Y ²¹ ) _r ...(1b4)

*-L ²² -(Y ^22a -L ²³ -Y ²¹ ) _q (Y ²¹ ) _r ...(1b5)

*-L ²² -(Y ^21a -L ²³ -Y ²² ) _q (Y ²² ) _r ...(1b6)

*-L ²² -(Y ^22a -L ²³ -Y ²¹ ) _q (Y ²² ) _r ...(1b7)

"*" indicates a link to L ¹ of the formula (1).

L ²¹ represents a single bond or a (q+1)-valent linking group. The meaning of L ^{21 is} the same as L ^{11 of the} formula (1a1), and the preferred range is also the same.

L ²² represents a single bond or a (q+r+1)-valent linking group. L ^{22 has} the same meaning as L ^{11 of the} formula (1a1), and the preferred range is also the same.

L ²³ represents a single bond or a divalent linking group. As the divalent linking group, a divalent linking group described in L ¹¹ of the formula (1a1) can be preferably mentioned. L ^{23 is more} preferably a single bond, an alkylene group, or a group containing a combination of -NH- and -CO-.

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

Y ^21a represents a ring including a coordinating atom coordinated by a non-shared electron pair, or at least one selected from the group (UE-1). When q and r represent an integer of 2 or more, the plurality of Y ^21a may be the same or different.

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

Y ^22a represents at least one selected from the group (AN-1).

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

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

q+r represents 2 or more, preferably 2 to 5, and particularly preferably 2 to 3.

<<<<Bases of coordination sites with coordination with anions>>>>

In the above formula (1), when Y ¹ represents a group having a coordination site coordinated by an anion, examples of Y ¹ include a group represented by the following formula (1c1) or formula (1c2). .

*-L ³¹ -(Y ³¹ ) _p ...(1c1)

*-L ³¹ -(Y ^31a -L ³² -Y ³¹ ) _p ...(1c2)

"*" indicates a link to L ¹ of the formula (1).

L ³¹ represents a single bond or a (p+1)-valent linking group. L ^{31 has} the same meaning as L ^{11 of the} formula (1a1), and the preferred range is also the same.

L ³² represents a single bond or a divalent linking group. The divalent linking group has the same meaning as L ^{12 of the} formula (1a2), and the preferred range is also the same.

Y ³¹ represents the coordination site in which the anion is coordinated. When p represents an integer of 2 or more, a plurality of Y ³¹ may be the same or different.

Y ^31a represents at least one selected from the group (AN-1). When p represents an integer of 2 or more, the plurality of Y ^31a may be the same or different.

In the formula (1c1) and the formula (1c2), p represents an integer of 1 or more, preferably 2 or more. The upper limit is, for example, preferably 5 or less, more preferably 3 or less.

A preferred form of the copper compound is, for example, a polymer type copper compound containing a polymer containing an acid group ion site and copper ions, and more preferably a polymer type having a acid group ion site in the polymer as a ligand. Copper compound. The polymer type copper compound is a copper compound containing a polymer (A2) containing an acid group ion and a copper ion, and a preferred form is a copper error in which an acid group ion site in the polymer (A2) is used as a ligand. Compound.

1 is an image diagram showing an example of a compound containing a polymer (A2) containing an acid group ion and a copper ion, 1 is a compound containing a polymer (A2) containing an acid group ion and a copper ion, and 2 is a copper ion. 3 denotes a main chain of the polymer (A2), 4 denotes a side chain of the polymer (A2), and 5 denotes an acid group ion site 5 derived from an acid group or a salt thereof. In the polymer type copper compound, the acid-based ion site 5 is bonded (for example, coordinately bonded) to the copper 2, and the copper 2 is used as a starting point to form a crosslinked structure between the side chains 4 of the polymer (A2). . It is estimated that by adopting such a configuration, even if heating is performed, the structure of the compound 1 is not easily damaged, and a cured film excellent in heat resistance can be obtained.

<<<First Embodiment>>

A preferred example of the polymer containing the coordination site has a structure in which the main chain has a carbon-carbon bond, and preferably contains a constituent unit represented by the following formula (A1-0).

[Chemistry 16]

In the formula (A1-0), R ¹ represents a hydrogen atom or a hydrocarbon group, L ¹ represents a single bond or a linking group, and Y ¹ represents a coordination site selected from the group consisting of an anion for copper component and a non-copper component. One or more groups of the coordinating atoms coordinated by the shared electron pair.

In the formula (A1-0), when R ¹ represents a hydrocarbon group, examples of the hydrocarbon group include a linear, branched or cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent, but is preferably unsubstituted. The carbon number of the hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3. The hydrocarbon group is preferably a methyl group. R ^{1 is} preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

In formula (A1-0), L ¹ and the meaning of Y ¹ and Y ¹ L ¹ and the same preferred ranges are also the same as the formula (1).

More preferably, the polymer containing the coordination site contains a constituent unit represented by the following formula (A1-1).

[化17]

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

In the formula (A1-1), R ¹ have the meaning as in the formula (A1-0) R ¹ the same, the preferred ranges are also the same.

In the formula (A1-1), the meaning of L ^{1 is the} same as L ¹ in the formula (A1-0), and the preferred range is also the same.

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

As a constituent unit represented by the formula (A1-0) and other constituent units other than the constituent unit represented by the formula (A1-1), reference may be made to paragraph number 0068 to paragraph number of JP-A-2010-106268. The contents of the copolymerization components disclosed in [0112] to [0118] of the specification of the corresponding US Patent Application Publication No. 2011/0124824, the contents of which are incorporated herein by reference.

As another preferable structural unit, the structural unit represented by the following formula (A1-2) is mentioned.

[化18]

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

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

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

When the polymer (A1) contains another constituent unit (preferably, a constituent unit represented by the formula (A1-2)), the constituent unit represented by the formula (A1-1) The moieties of the constituent units represented by the formula (A1-2) are preferably 95:5 to 20:80, more preferably 90:10 to 40:60.

<<<Second embodiment>>

In the present invention, a polymer having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain (hereinafter referred to as an aromatic group-containing polymer) and a copper component may be used. The polymer type copper compound obtained by the reaction. The aromatic group-containing polymer may have at least one of an aromatic hydrocarbon group and an aromatic heterocyclic group in the main chain, and may have two or more kinds. Regarding the coordination site and copper composition, The meaning is the same as the copper compound obtained by the reaction of the polymer containing the coordination site with the copper component, and the preferred range is also the same.

As the aromatic hydrocarbon group, for example, an aryl group is preferred. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, more preferably from 6 to 12. In particular, a phenyl group, a naphthyl group or a biphenyl group is preferred. The aromatic hydrocarbon group may be monocyclic or polycyclic, but is preferably a single ring.

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

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

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

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

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

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

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

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

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

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

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

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

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

As the polyimine-based polymer, the description of paragraphs 0047 to 0058 of Japanese Patent Laid-Open Publication No. 2002-367627 and Japanese Patent Laid-Open The main chain structure described in 0018 to 0019 of the Japanese Patent Publication No. 2004-35891 can be incorporated into the specification of the present application.

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

(In the formula (A1-3), Ar ¹ represents an aromatic hydrocarbon group and/or an aromatic heterocyclic group, Y ¹ represents a single bond or a divalent linking group, and X ¹ represents a ligand selected from an anion selected from a copper component. The coordination site and one or more of the coordination atoms that are coordinated to the copper component by the unshared electron pair)

In the formula (A1-3), when Ar ¹ represents an aromatic hydrocarbon group, the meaning thereof is the same as that of the aromatic hydrocarbon group, and the preferred range is also the same. When Ar ¹ represents an aromatic heterocyclic group, the meaning is the same as that of the aromatic heterocyclic group, and the preferred range is also the same.

Ar ^1, except in the formula (A1-3) -Y ¹ -X ^1, may have a substituent. When Ar ¹ has a substituent, the meaning of the substituent is the same as that of the substituent T, and the preferred range is also the same.

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

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

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

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

In the formula (A1-3), X ^{1 has} the same meaning as Y ^{1 of} the above formula (1), and is preferably an acid group or a salt thereof.

The weight average molecular weight of the polymer (A1-0) to the polymer (A1-3) is preferably 1,000 or more, more preferably 1,000 to 10,000,000, still more preferably 3,000 to 1,000,000, and particularly preferably 4,000 to 400,000. .

Specific examples of the polymer (A1-0) to the polymer (A1-3) include the compounds described in the following tables and the salts of the following compounds, but are not limited to these specific examples.

[Chemistry 20]

[Chem. 21]

[化23]

[Chem. 26]

The composition containing a copper compound may also contain other components than the copper compound. Examples of other components other than the copper compound include a solvent and a surfactant.

The composition containing a copper compound preferably contains substantially no curable compound. In particular, the content of the curable compound contained in the composition containing the copper compound is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably more, based on the total solid content of the composition containing the copper compound. 1% by mass or less.

Solvent

The solvent is not particularly limited as long as the components of the composition used in the present invention are uniformly dissolved or dispersed, and may be appropriately selected depending on the purpose, for example, An aqueous solvent such as water or an alcohol (for example, ethanol) is suitably used. Further, in addition to the above, the solvent used in the present invention may suitably be exemplified by an organic solvent, a ketone, an ether, an ester, an aromatic hydrocarbon, a halogenated hydrocarbon, and dimethylformamide or dimethyl. Ethyl amide, dimethyl hydrazine, cyclobutyl hydrazine, and the like. These solvents may be used alone or in combination of two or more.

Specific examples of the alcohol, the aromatic hydrocarbon, and the halogenated hydrocarbon include those described in paragraph 0136 of JP-A-2012-194534, and the contents thereof can be incorporated into the specification of the present application. In addition, specific examples of the esters, the ketones, and the ethers are described in paragraph 0497 of the Japanese Patent Application Laid-Open No. 2012-208494 (the corresponding Japanese Patent Application Publication No. 2012/0235099 [0609]). Further, acetic acid-n-amyl ester, ethyl lactate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, Ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, and the like.

The composition containing a copper compound particularly preferably contains water. The composition containing the copper compound preferably contains 40% by mass to 95% by mass of water, more preferably 50% by mass to 85% by mass of water.

When the composition containing a copper compound contains a solvent other than water, it is preferable to contain a solvent other than water in a ratio of 1% by mass to 50% by mass, more preferably 5% by mass, based on the composition containing the copper compound. The proportion of 30% by mass contains a solvent other than water. The solvent other than water may be used alone or in combination of two or more.

In the composition containing a copper compound, as long as the effects of the present invention are not impaired, Other ingredients may be selected as appropriate depending on the purpose.

Examples of other components that can be used together include a binder polymer, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and the like. And use adhesion promoters and other additives for the surface of the substrate (such as conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chains) Transfer agent, etc.).

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

For example, Japanese Patent Application Laid-Open No. Hei. No. 2012-003225, the entire disclosure of which is incorporated herein by reference. The contents of paragraph number 0101 to paragraph number 0102, paragraph number 0103 to paragraph number 0104, and paragraph number 0107 to paragraph number 0109 of the Japanese Patent Publication are incorporated herein by reference.

Surfactant

The composition containing a copper compound may further contain a surfactant. The surfactant may be used alone or in combination of two or more. The amount of the surfactant to be added to the solid content of the composition used in the present invention may be 0.0001% by mass to 2% by mass, may be 0.005% by mass to 1.0% by mass, or may be 0.01% by mass. ~0.1% by mass.

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

In particular, the composition containing a copper compound contains at least one of a fluorine-based surfactant and an anthrone-based surfactant, and the liquid property (particularly fluidity) at the time of preparation as a coating liquid is further improved. The uniformity of the coating thickness or the liquid-saving property can be further improved.

In other words, when a film is formed using a coating liquid containing a composition containing at least one of a fluorine-based surfactant and an anthrone-based surfactant, the interfacial tension between the coated surface and the coating liquid is lowered. Thereby, the wettability to the coated surface is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to form a film having a uniform thickness with a small thickness unevenness.

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

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, and Megafac F479. , Megafac F482, Megafac F554, Megafac F780, Megafac R08 (above, Di Ansheng (DIC) (share) manufacturing), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M (Sumitomo 3M) (shares ))), Surflon S-382, Surflon S-141, Surflon S-145, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Eftop EF301, Eftop EF303, Eftop EF351, Eftop EF352 (above, Mitsubishi Materials Electronics ( Jemco), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

As the fluorine-based surfactant, a polymer having a fluoroaliphatic group can be used. The polymer having a fluoroaliphatic group may be exemplified to have a fluoroaliphatic group, and the fluoroaliphatic group is derived from a short-chain polymerization method (also referred to as a short-chain polymer method) or an oligomerization method (also referred to as an oligo group). A fluorine-based surfactant obtained by a fluoroaliphatic compound produced by a polymer method.

Here, the "short-chain polymerization method" refers to a method of synthesizing a compound having a low molecular weight substance and having one to two active groups in a molecule. In addition, the "oligomerization method" refers to a method of converting a mixture of a single amount or a single amount into an oligomer.

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

As the fluoroaliphatic group-containing polymer in the present invention, the fluoroaliphatic group-containing monomer of the present invention and (poly(oxyalkylene)) acrylate and/or (poly(oxyalkylene) group can be used. )) Copolymer of methacrylate. The copolymer may be irregularly distributed or may be subjected to block copolymerization. Further, examples of the poly(oxyalkylene) group include a poly(oxyethylidene) group, a poly(oxypropyl) group, a poly(oxybutylene) group, and the like, and may also be, for example, poly(( Block linkage of oxy-ethyl and oxy-propyl and oxy-ethyl The group or the poly(oxyalkylene group and the oxypropyl group) group have the same chain length as the alkyl group-like unit in the same chain length. Further, the copolymer of a fluoroaliphatic group-containing monomer and (poly(oxyalkylene)) acrylate (or methacrylate) may be not only a binary copolymer but also two or more different types. A ternary or higher copolymer having a fluoroaliphatic group and a copolymer of two or more kinds of (poly(oxyalkylene)) acrylate (or methacrylate).

As a commercially available surfactant containing a fluoroaliphatic group-containing polymer in the present invention, for example, JP-A-2012-208494, paragraph 0552 (Japanese Patent Application Laid-Open No. 2012/0235099) The surfactants described in [0678] and the like can be incorporated into the specification of the present application. In addition, Megafac F-781 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly(oxyethylidene)) acrylate ( Or a copolymer of (methacrylate) and (poly(oxypropyl)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₈ F ₁₇ group and (poly(oxygen) a copolymer of acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₈ F ₁₇ group and (poly(oxyethylidene)) acrylate (or methyl) Acrylate) and a copolymer of (poly(oxypropyl)) acrylate (or methacrylate).

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan fat. Acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block copolymer, acetylene glycol surfactant, B An alkyne polyoxyethylene oxide or the like. These may be used alone or in combination of two or more.

Specific product names include: Surfynol 61, 82, 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, 504, CT. -111, CT-121, CT-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF-37, DF-58, DF-75, DF-110D, DF-210 , GA, OP-340, PSA-204, PSA-216, PSA-336, SE, SE-F, TG, GA, Dynol 604 (above, Nisshin Chemical (share) and air chemical products ( Air Products & Chemicals), Olfine A, B, AK-02, CT-151W, E1004, E1010, P, SPC, STG, Y, 32W, PD-001, PD-002W, PD- 003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, SK-14, AE-3 (above, Nisshin Chemical (share)), Azerbaijani ( Acetylenol) E00, E13T, E40, E60, E81, E100, and E200 (all of which are trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.). Among them, Olfine E1010 is suitable.

Further, as the non-ionic surfactant, specifically, it is described in paragraph 0553 of the Japanese Patent Application Laid-Open No. 2012-208494 (the [0679] of the corresponding US Patent Application Publication No. 2012/0235099). Nonionic surfactants, the contents of which can be incorporated into the specification of the present application.

The cation-based interface described in JP-A-2012-208494, paragraph 0554 (corresponding to US Patent Application Publication No. 2012/0235099 [0680]), the cation-based interface is exemplified. Active agents, the contents of which can be incorporated into the specification of the present application.

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

Examples of the fluorenone-based surfactants include an anthrone-based interface described in JP-A-2012-208494, paragraph 0556 (corresponding to U.S. Patent Application Publication No. 2012/0235099, No. [0682]). Active agents, the contents of which can be incorporated into the specification of the present application. In addition, it can also be illustrated: Toray. "Toray Silicone SF8410", "Toray Silicone SF8427", "Toray Silicone SH8400", "ST80PA", "ST83PA", "ST86PA" manufactured by Dow Corning (shares), Momentive Performance Materials "TSF-400", "TSF-401", "TSF-410", "TSF-4446" manufactured by the company, "KP321", "KP323", "KP324" manufactured by Shintosu Silicon Co., Ltd. ", "KP340" and so on.

Polymerization initiator

The composition containing a copper compound may contain a polymerization initiator. The polymerization initiator may be one type or two or more types. When two or more types are used, the total amount is in the above range. For example, the content of the polymerization initiator is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, even more preferably 0.1% by mass, based on the solid content of the composition containing the copper compound. 15% by mass.

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound by either light or heat, and may be appropriately selected according to the purpose, but is preferably selected. Photopolymerizable compound. When the polymerization is started by light, it is preferably one which is photosensitive from the ultraviolet region to the visible light.

Further, when the polymerization is started by heat, a polymerization initiator which decomposes at 150 ° C to 250 ° C is preferable.

The polymerization initiator which can be used in the present invention is preferably a compound having at least an aromatic group, and examples thereof include a mercaptophosphine compound, an acetophenone compound, an α-aminoketone compound, and a benzophenone compound. , benzoin ether compound, ketal derivative compound, thioxanthone compound, hydrazine compound, hexaarylbiimidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazonium compound, hydrazine a compound, an anthraquinone compound, an oxazine compound, an onium salt compound such as a metallocene compound, an organic boron salt compound, a diterpene compound or the like.

From the viewpoint of sensitivity, an anthracene compound, an acetophenone-based compound, an α-aminoketone compound, a trihalogenated methyl compound, a hexaarylbiimidazole compound, and a thiol compound are preferable.

As an acetophenone-based compound, a trihalogenated methyl compound, a hexaarylbiimidazole compound, and an anthracene compound, for example, reference is made to Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0506 to paragraph 0510 (corresponding US patent) The contents of [0622 to 0628] and the like of the specification of the publication No. 2012/0235099, the contents of which are incorporated herein by reference.

The photopolymerization initiator is more preferably a compound selected from the group consisting of an anthraquinone compound, an acetophenone-based compound, and a mercaptophosphine compound. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969 and a thiophosphonium oxide-based initiator described in Japanese Patent No. 4,258,899 can be used. And the lanthanide initiator as described above, and further as a lanthanide initiator, The compound described in JP-A-2001-233842 can be used.

As the ruthenium compound, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF Corporation), which are commercially available products, can be used. As the acetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan) can be used as a commercial product. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Corporation of Japan) which is a commercially available product can be used.

Inorganic microparticles

The composition containing a copper compound may further contain inorganic fine particles as a near-infrared absorbing compound other than the copper compound. The inorganic fine particles may be used alone or in combination of two or more.

The inorganic fine particles are particles which mainly function to block (absorb) infrared rays. The inorganic fine particles are preferably at least one selected from the group consisting of metal oxide particles and metal particles from the viewpoint of further excellent infrared light blocking properties.

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

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

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

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

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

0.001≦x/y≦1.1

2.2≦z/y≦3.0

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

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

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

The metal oxide is preferably tungsten oxide.

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

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

The tungsten oxide-based compound can be obtained, for example, as a dispersion of tungsten fine particles such as YMF-02, YMF-02A, YMS-01A-2, and YMF-10A-1 manufactured by Sumitomo Metal Mining Co., Ltd.

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

The viscosity of the composition containing the copper compound is preferably 0.1 mPa. s~3000mPa. s, more preferably 0.1mPa. s~2000mPa. s, and then preferably 1mPa. s~15mPa. s, and more preferably 1 mPa. s~5mPa. s.

The total solid content of the composition containing the copper compound is preferably 1 with respect to the composition. The mass % to 50% by mass, more preferably 1% by mass to 30% by mass, still more preferably 10% by mass to 30% by mass.

<<Sclerosing composition>>

The curable composition contains at least a curable compound. The curable compound may be a polymerizable compound or a non-polymerizable compound such as a binder. Further, the thermosetting compound may be a photocurable compound, but the thermosetting composition has a higher reaction rate, which is preferable.

The curable composition preferably contains an oxygen heterocyclic compound, more preferably a compound having an epoxy group or an oxetanyl group, and still more preferably a compound having an epoxy group (epoxy compound). Further, the curable composition is preferably a polymer containing a crosslinking group having an unsaturated double bond, an epoxy group or an oxetanyl group.

<<Compound with polymerizable group>>

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

<<<Polymerizable monomer and polymerizable oligomer>>>

The curable composition may contain a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (hereinafter, a polymerizable monomer and a polymerizable oligomer may be sometimes used) The polymer is collectively referred to as a "polymerizable monomer or the like" as a polymerizable compound.

Examples of the polymerizable monomer and the like include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or The esters and guanamines are preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and amides of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, an addition reaction of an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group with a monofunctional or polyfunctional isocyanate or epoxy group may be suitably used, or A dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid or the like. Further, an addition reaction of an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and having a halogen A substituted reactant of an unsaturated carboxylic acid ester or a guanamine of a detachable substituent such as a sulfonyloxy group or a monofunctional or polyfunctional alcohol, an amine or a thiol is also suitable. Further, as another example, a compound group of a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used instead of the unsaturated carboxylic acid.

As the specific compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

Further, as the polymerizable monomer or the like, a compound having an ethylenically unsaturated group having at least one vinyl group capable of undergoing addition polymerization and having a boiling point of 100 ° C or higher at normal pressure may be used, or a monofunctional group may be used ( Methyl) acrylate, difunctional (meth) acrylate, trifunctional or higher (meth) acrylate (for example, trifunctional to hexafunctional (meth) acrylate).

Examples thereof include monofunctional acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Methacrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylic acid Ester, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris (propylene hydrazine) After the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol, oxypropyl)ether, tris(propyleneoxyethyl)isocyanurate, glycerin or trimethylolethane (A) Base) Acrylate.

As the polymerizable compound, ethoxylated pentylenetetraol tetraacrylate (commercially available as NK ESTER ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (commercially available as Kayad) can be used. (KAYARAD) D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (produced by Nippon Chemical Co., Ltd.) Commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and The structure in which the acrylonitrile group is between the ethylene glycol residue and the propylene glycol residue. In addition, these oligomer types can also be used. In the present invention, the compound described in Paragraph No. 0248 to Paragraph No. 0251 of JP-A-2007-269779 can also be used.

Examples of the polymerizable monomer and the like include a description of paragraph 0477 of the Japanese Patent Application Publication No. 2012-208494 (corresponding U.S. Patent Application Publication No. 2012/0235099) The polymerizable monomer and the like described in [0585] of the book, the contents of which can be incorporated into the specification of the present application. Further, Ethylene Oxide (EO) modified (meth) acrylate (commercially available as M-460; manufactured by Toago Seisakusho Co., Ltd.) can be used. Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) can also be used. These oligomer types can also be used.

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

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group can be used by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Polyfunctional monomer. As a commercial item, the Aronix series M-305, M-510, M-520, etc. which are the polyacid modified acrylic oligomer manufactured by the East Asia Synthesizing Corporation are mentioned, for example.

The acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, preferably from 5 mg-KOH/g to 30 mg-KOH/g. When two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is necessary to adjust such that the acid value of the entire polyfunctional monomer is within the above range.

<<<Polymer with polymerizable group on side chain>>>

The curable composition may also contain a polymer having a polymerizable group in a side chain as a polymerizable compound. The polymerizable group may, for example, be an ethylenically unsaturated double bond group, an epoxy group or an oxetanyl group.

<<<Compounds with epoxy or oxetanyl group>>>

The curable composition may contain a compound having an epoxy group or an oxetanyl group as a polymerizable compound. Specific examples of the compound having an epoxy group or an oxetanyl group include a polymer having an epoxy group in a side chain and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule. Examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and aliphatic epoxy resin. Further, a monofunctional glycidyl ether compound or a polyfunctional glycidyl ether compound can also be mentioned.

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

As a commercial item, for example, the description of Japanese Patent Laid-Open No. 2012-155288, paragraph 0191, and the like can be referred to, and the contents of the present invention can be incorporated into the specification of the present application.

In addition, as a commercial item, Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, Nagase chemteX (share) manufacturing) a polyfunctional aliphatic glycidyl ether compound. These are low-chlorine products, but EX-212, EX-214, EX-216, EX-321, EX-850, etc. which are not low-chlorine products can also be used similarly.

In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, ADEKA) ), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by Eddie Co., Ltd.), JER1031S, etc.

In addition, as a commercial item of the phenol novolak type epoxy resin, JER-157S65, JER-152, JER-154, JER-157S70 (above, Mitsubishi Chemical (made)), etc. are mentioned.

Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule: aronoxacyclohexane Butane (ARONE OXETANE) OXT-121, OXT-221, OX-SQ, PNOX (above, manufactured by Toagosei Co., Ltd.).

When the synthesis is carried out by introducing into the polymer side chain, the introduction reaction is carried out, for example, by using a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride or tetramethyl chloride. A quaternary ammonium salt such as ammonium chloride or tetraethylammonium chloride, pyridine or triphenylphosphine is used as a catalyst, and the reaction is carried out in an organic solvent at a reaction temperature of 50 ° C to 150 ° C for several hours to several tens of hours. The introduction amount of the alicyclic epoxy unsaturated compound can be such that the acid value of the obtained polymer satisfies 5 KOH. Mg/g~200KOH. The range of mg/g is controlled in a manner. Further, the molecular weight is 500 to 5,000,000 on a weight average basis, and may be in the range of 1,000 to 500,000.

As the epoxy unsaturated compound, a glycidyl group such as glycidyl (meth)acrylate or allyl glycidyl ether can also be used as the epoxy group. As such a compound, for example, the description of paragraphs 0045 of JP-A-2009-265518, and the like can be referred to, and the contents of the present invention can be incorporated into the specification of the present application.

The curable composition is preferably a polymer comprising a crosslinking group having an unsaturated double bond, an epoxy group or an oxetanyl group. Thereby, the film formability (suppression of cracks or warpage) and moisture resistance at the time of forming a cured film can be further improved. Specifically, it can be enumerated A polymer having the repeating unit described below. The polymer having the following repeating unit is preferably a polymer having an epoxy group.

<<<Compound having a partial structure represented by formula (11)>>>

The curable compound contained in the curable composition preferably has a partial structure represented by the following formula (11), and the curable compound may have an unsaturated double bond, an epoxy group or an oxetanyl group. Crosslinking base.

In the formula (11), R ¹ represents a hydrogen atom or an organic group.

When the film-forming composition used in the present invention is formed into a cured film by containing such a compound, the near-infrared ray shielding property can be further improved, and the moisture resistance can be further improved.

In the formula (11), R ¹ represents a hydrogen atom or an organic group. The organic group may, for example, be a hydrocarbon group, and 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 the same The combination of the price of the link.

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

Further, in the formula (11), R ¹ and C may be bonded to form a ring structure (heterocyclic structure). The hetero atom in the heterocyclic structure is the nitrogen atom in the formula (11). The heterocyclic structure is preferably a 5-membered ring structure or a 6-membered ring structure, more preferably a 5-membered ring structure. The heterocyclic structure may also be a condensed ring, but is preferably a single ring.

Specific examples of the particularly preferable R ¹ include a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and -OR'(R' is a linear alkyl group having 1 to 5 carbon atoms) and -( CH ₂ ) _m - (m is an integer of 1 to 10, preferably m is an integer of 1 to 5), and R ¹ and C in the formula (11) are bonded to each other to form a heterocyclic structure ( It is preferably a base of a 5-membered ring structure.

The compound having a partial structure represented by the above formula (11) is preferably represented by (the main chain structure of the polymer - the partial structure of the formula (11) - R ¹ ), or by (A- Partial structure of (11) - B) representation. Here, A is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms. Further, B is a group containing -(CH ₂ ) _m - (m is an integer of 1 to 10, preferably m is an integer of 1 to 5) and a combination of a partial structure and a polymerizable group of the formula (11) .

Further, the compound having a partial structure represented by the above formula (11) preferably has a structure represented by any one of the following formulas (11-1) to (11-5).

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

In the formula (11-1), R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. The organic group has the same meaning as R ¹ in the above formula (11), and the preferred range is also the same.

In the formula (11-3) to the formula (11-5), L ¹ to L ⁴ represent a divalent linking group. The divalent linking group is preferably -(CH ₂ ) _m - (m is an integer of 1 to 10), a cyclic alkyl group having a carbon number of 5 to 10, and contains -O-, -CO- Further, at least one combination of -COO- and -NH- is more preferably -(CH ₂ ) _m - (m is an integer of 1 to 8).

In the formula (11-3) to the formula (11-5), R ⁸ to R ¹⁴ each independently represent a hydrogen atom or an organic group. As the organic group, a hydrocarbon group is preferred, and specifically, an alkyl group or an alkenyl group is preferred.

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

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

The substituent may, for example, be a polymerizable group, a halogen atom, an alkyl group, a carboxylate group, a halogenated alkyl group, an alkoxy group, a methacryloxy group, an acryloxy group, an ether group or a sulfonyl group. A thioether group, a decylamino group, a fluorenyl group, a hydroxyl group, a carboxylic acid group or the like. Among these substituents, a polymerizable group (e.g., a vinyl group, a (meth) propylene fluorenyl group, a (meth) acryl fluorenyl group, an epoxy group, an aziridine group, etc.) is preferred, and ethylene is more preferred. base.

Further, the compound having a partial structure represented by the above formula (11) may be a monomer or a polymer, but is preferably a polymer. That is, the compound having a partial structure represented by the above formula (11) is preferably a compound represented by the above formula (11-1) or the formula (11-2).

Further, when the compound having a partial structure represented by the above formula (11) is a polymer, it is preferred to contain the partial structure in the side chain of the polymer.

The molecular weight of the compound having a partial structure represented by the formula (11) is preferably from 50 to 1,000,000, more preferably from 500 to 500,000. By setting such a molecular weight, the effect of the present invention can be more effectively achieved.

In the composition used in the present invention, the content of the compound having a partial structure represented by the above formula (11) is preferably from 5% by mass to 80% by mass, more preferably from 10% by mass to 60% by mass.

Specific examples of the compound having a partial structure represented by the above formula (11) include a compound having the following structure or the following exemplified compound, but It is not limited to these compounds. In the present invention, a compound particularly having a partial structure represented by the formula (11) is a polyacrylamide.

Further, specific examples of the compound having a partial structure represented by the above formula (11) include a water-soluble polymer, and preferred examples of the main chain structure include polyvinylpyrrolidone and poly(methyl). Acrylamide, polyamine, polyurethane, polyurea. The water soluble polymer may be a copolymer, and the copolymer may also be a random copolymer.

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

Examples of the poly(meth)acrylamide include a polymer or a copolymer of (meth)acrylamide. Specific examples of the acrylamide include acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-butyl acrylamide, and N-benzyl. Acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-tolyl acrylamide, N-(hydroxyphenyl) acrylamide, N-(amine sulfonylphenyl) ) Acrylamide, N-(phenylsulfonyl)propenylamine, N-(methylsulfonyl)propenylamine, N,N-dimethylpropenamide, N-methyl-N-phenyl Acrylamide, N-hydroxyethyl-N-methylpropenylamine, and the like. Further, methacrylamide corresponding to these may be used in the same manner.

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

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

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

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

On the other hand, in the compound obtained by copolymerizing a polyamide resin with a hydrophilic compound, the main chain of the polyamide resin is, for example, selected from the group consisting of a hydrophilic nitrogen-containing cyclic compound and a polyalkylene glycol. At least one of the groups is copolymerized, so In the N-methoxymethylated nylon, the polyamide bond of the polyamide resin has a large hydrogen bonding ability.

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

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

The molar of the polymer comprising a repeating unit having a partial structure represented by the formula (11) and a repeating unit having an epoxy group is preferably from 10/90 to 90/10, more preferably from 30/70 to 70. /30. The weight average molecular weight of the copolymer is preferably from 3,000 to 1,000,000, more preferably from 5,000 to 200,000.

The details of the structure, the use alone or in combination, and the amount of use of the polymerizable compounds can be arbitrarily set in combination with the final performance design of the composition. For example, from the viewpoint of sensitivity, a structure having a large content of an unsaturated group per molecule is preferable, and in many cases, a difunctional or higher is preferable. Moreover, from the viewpoint of improving the strength of the near-infrared cut filter, a trifunctional or higher polymerizable compound is preferable, and the number of functional groups is different by the combination. A polymerizable compound having a different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound) is effective for adjusting both sensitivity and strength. In addition, For the compatibility and dispersibility of other components (such as metal oxides, pigments, polymerization initiators) contained in the composition, the choice of polymerizable compounds. The use method is also an important factor. For example, it is sometimes possible to use a low-purity compound or a combination of two or more types to improve compatibility. Moreover, a specific structure can also be selected from the viewpoint of improving the adhesion to a hard surface such as a support.

The amount of the polymerizable compound to be added to the curable composition can be from 1% by mass to 100% by mass, and more preferably from 10% by mass to 100% by mass, based on the total solid content of the solvent.

In addition, when a polymer containing a repeating unit having a crosslinking group is used as the polymerizable compound, the total solid content of the curable composition other than the solvent is preferably 10% by mass to 100% by mass. The ratio is preferably in the range of 20% by mass to 100% by mass.

The polymerizable compound may be used alone or in combination of two or more kinds. In the case of two or more types, the total amount is in the above range.

The curable composition may contain other components than the curable compound. The other components other than the curable compound have the same meanings as those described for the composition containing the copper compound.

Further, the curable composition preferably contains substantially no copper compound. In particular, the content of the copper compound contained in the curable composition is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less based on the total solid content of the curable composition.

The viscosity of the curable composition is preferably 1 mPa. s~3000mPa. s, better Is 1mPa. s~2000mPa. s, and then preferably 1mPa. s~30mPa. s, and more preferably 10mPa. s~20mPa. s.

The total solid content of the curable composition is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 30% by mass, even more preferably from 10% by mass to 30% by mass, based on the composition.

The present invention provides a method for inhibiting the adhesion of a composition for forming a film containing a copper compound and a curable compound, which comprises: containing the copper compound within 3 days before the film forming composition is used. The composition is mixed with the curable composition.

Moreover, the present invention is a kit for producing the film-forming composition containing the copper compound and the curable compound, and the composition comprising the copper compound and the curable composition.

The storage temperature of the kit for producing a film-forming composition of the present invention is preferably 40 ° C or lower, more preferably 30 ° C or lower, further preferably 25 ° C or lower, more preferably 15 ° C or lower, and particularly preferably 10 Below °C. By setting such a storage temperature, it is possible to more effectively suppress the increase in viscosity when the composition containing the copper compound contained in the kit and the curable composition are mixed.

The film containing a copper compound obtained by the production method of the present invention is preferably a near-infrared cut filter.

The near-infrared cut filter preferably has at least one of the following (1) to (9), and more preferably the light transmittance satisfies all of the following conditions (1) to (8), and further More preferably, the light transmittance satisfies all the conditions of (1) to (9).

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

(2) The light transmittance at a wavelength of 450 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.

(3) The light transmittance at a wavelength of 500 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.

(4) The light transmittance at a wavelength of 550 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.

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

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

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

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

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

The film thickness of the near-infrared cut filter is preferably 500 μm or less, more preferably 300 μm or less, still more preferably 250 μm or less, and particularly preferably 200 μm or less. Further, the film thickness is preferably 1 μm or more, more preferably 20 μm or more, still more preferably 50 μm or more, and particularly preferably 100 μm or more. In particular, the film thickness is preferably from 1 μm to 500 μm, more It is preferably 1 μm to 300 μm, and more preferably 1 μm to 200 μm. In the present invention, even in the case of producing such a film, high near-infrared light shielding properties can be maintained.

In addition, the rate of change in the absorbance ratio obtained by the following formula is preferably 7% or less, preferably more preferably, before the near-infrared cut filter is left at a high temperature and high humidity of 85 ° C / 85% relative humidity for 1 hour. It is 4% or less, and more preferably 2% or less.

Rate of change in absorbance ratio (%) = [(absorbance ratio before test - absorbance ratio after test) / absorbance ratio before test] × 100 (%)

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

The rate of change in absorbance at a wavelength of 400 nm and the rate of change in absorbance at a wavelength of 800 nm before and after heating at 200 ° C for 5 minutes in the near-infrared cut filter are preferably 7% or less, and particularly preferably 5% or less.

<Manufacturing method of camera module and camera module>

Further, the present invention is a camera module having a solid-state imaging element and a near-infrared cut filter disposed on a light receiving side of the solid-state imaging element, wherein the near-infrared cut filter is the near-infrared cut filter The camera module is also preferred.

Hereinafter, the camera module will be described with reference to FIGS. 2 and 3, but the present invention is not limited by the following specific examples.

In addition, in FIGS. 2 and 3, the same portions are denoted by the same reference numerals.

In addition, in the description, "upper", "upper" and "upper side" mean away from the 矽 substrate. On the side of 10, "lower", "lower" and "lower side" refer to the side close to the base substrate 10.

2 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image sensor.

The camera module 200 shown in FIG. 2 is connected to the circuit board 70 as a mounting substrate via a solder ball 60 as a connecting member.

Specifically, the camera module 200 includes a solid-state imaging device (solid-state imaging device substrate) 100, and includes a photodiode on the first main surface of the substrate, and a planarization layer (not shown in FIG. 2). The first main surface side (light receiving side) of the image sensor 100; the near-infrared cut filter 42 is provided on the flattening layer; and the lens frame 50 is disposed above the near-infrared cut filter 42 and has an internal space The imaging lens 40 and the light shielding and electromagnetic cover 44 are disposed to surround the solid image sensor 100 and the periphery of the glass substrate 30. Further, a glass substrate 30 (translucent substrate) may be provided on the planarization layer. Each member is adhered by an adhesive 45.

The present invention is a method of manufacturing a camera module including a solid-state imaging device 100 and a near-infrared cut filter 42 disposed on a light receiving side of the solid-state imaging device, and preferably has a light receiving side application to a solid-state imaging device. The film forming composition, whereby the near-infrared cut filter 42 is formed. In the camera module of the present embodiment, for example, a film forming composition is applied onto a flattening layer to form a film, and a near-infrared cut filter 42 can be formed. The method of coating the film formation composition is as described above.

In the camera module 200, the incident light hv from the outside passes through the imaging lens 40, the near-infrared cut filter 42, the glass substrate 30, and the planarization layer in order to reach the solid state. The imaging element portion of the volume imaging element 100.

The camera module 200 directly sets the near-infrared cut filter on the flattening layer, but the flattening layer may be omitted and the near-infrared cut filter may be directly disposed on the microlens, and the near-infrared cut filter may be disposed on the glass substrate 30. The light sheet or the glass substrate 30 provided with the near-infrared cut filter is bonded.

FIG. 3 is an enlarged cross-sectional view showing the solid-state imaging device 100 of FIG. 2.

The solid-state imaging device 100 includes an imaging element portion 12, an interlayer insulating film 13, an underlayer 14, a color filter 15, a protective layer 16, and a microlens 17 in this order on the first main surface of the substrate 10 as a substrate. The red color filter 15R, the green color filter 15G, and the blue color filter 15B are disposed so as to correspond to the imaging element unit 12 (hereinafter, these may be collectively referred to as "color filters". Light sheet 15") and microlens 17. The light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27 are provided on the second main surface of the ruthenium substrate 10 opposite to the first main surface. Each member is adhered by an adhesive 20.

The microlens 17 is provided with a planarization layer 46 and a near-infrared cut filter 42. Alternatively, a near-infrared cut filter 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 protective layer 16 instead of planarization. A near-infrared cut filter 42 is disposed on the layer 46. In particular, it is preferably provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens 17. When it is provided at this position, the step of forming the near-infrared cut filter can be simplified, and the unnecessary near-infrared rays directed to the microlens can be sufficiently cut off, so that the near-infrared ray-off property can be further improved.

For the solid-state imaging device 100, reference may be made to the following description of the Japanese Patent Application Laid-Open No. Hei. No. 2012-068418, the entire disclosure of which is incorporated by reference. In the specification of the present application.

A near-infrared cut filter is available for the reflow step. By manufacturing the camera module by the reflow process, it is possible to automatically mount the electronic component mounting substrate or the like that needs to be soldered, and it is possible to particularly improve productivity without using a reflow soldering step. Further, since it can be automatically performed, it is also possible to reduce the cost. When it is supplied to the reflow step, since it is exposed to a temperature of about 250 ° C to 270 ° C, the infrared cut filter preferably has heat resistance that can withstand the reflow step (hereinafter, also referred to as "resistance Reflowability").

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

Further, the present invention relates to a method of manufacturing a camera module including the step of performing a reflow process. The near-infrared cut filter maintains the near-infrared absorption performance even if it has a reflow step, so it does not impair the small size and light weight. Features of a high-performance camera module.

4 to 6 show the peripheral portion of the near-infrared cut filter in the camera module. A schematic cross-sectional view of an example of a minute.

As shown in FIG. 4, the camera module may have a solid-state imaging element 100, a planarization layer 46, and ultraviolet light in sequence. The infrared light reflecting film 80, the transparent substrate 81, the near infrared absorbing layer 82, and the antireflection layer 83.

UV. The infrared light reflecting film 80 has an effect of imparting or improving the function of the near-infrared cut filter, and for example, refer to paragraphs 0033 to 0039 of Japanese Patent Laid-Open Publication No. 2013-68688, the contents of which can be incorporated in the specification of the present application. .

The transparent substrate 81 is a light that transmits the wavelength of the visible region. For example, reference is made to paragraph 0026 to paragraph 0032 of JP-A-2013-68688, the contents of which are incorporated herein by reference.

The near-infrared ray absorbing layer 82 is a layer formed by applying the near-infrared absorbing composition of the present invention.

The anti-reflection layer 83 is a layer having a function of increasing the transmittance by preventing reflection of light incident into the near-infrared cut filter, and efficiently utilizing incident light, for example, refer to Japanese Patent Laid-Open Publication No. 2013-68688 Paragraph 0040 of the Gazette, the contents of which can be incorporated into the specification of the present application.

As shown in FIG. 5, the camera module may sequentially have a solid-state imaging element 100, a near-infrared absorbing layer 82, an anti-reflection layer 83, a planarization layer 46, an anti-reflection layer 83, a transparent substrate 81, and ultraviolet light. Infrared light reflecting film 80.

As shown in FIG. 6, the camera module may have a solid-state imaging element 100, a near-infrared absorbing layer 82, and an ultraviolet ray in sequence. The infrared light reflecting film 80, the planarizing layer 46, the antireflection layer 83, the transparent substrate 81, and the antireflection layer 83.

Although an embodiment of the camera module has been described above with reference to FIGS. 2 to 6, the above-described embodiment is not limited to the embodiment of FIGS. 2 to 6.

[Examples]

The invention will be more specifically described below by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<copper compound>

<<Synthesis of Polymer (A1) with Coordination Site>>

<<<Synthesis of Polymer A-1>>>

5.0 g of polyether oxime (manufactured by BASF Corporation, Ultrason E6020P) was dissolved in 46 g of sulfuric acid, and 16.83 g of chlorosulfonic acid was added dropwise at room temperature under a nitrogen stream. After reacting for 48 hours at room temperature, the reaction liquid was added to 1 L of a hexane/ethyl acetate (1/1) mixture which was cooled with ice water. The supernatant was removed, and the obtained precipitate was dissolved in methanol. The obtained solution was added dropwise to 0.5 L of ethyl acetate, and the obtained precipitate was recovered by filtration. The obtained solid was dried under reduced pressure, whereby 4.9 g of polymer A-1 was obtained. The sulfonic acid group content (meq/g) in the polymer was calculated by neutralization titration. The weight average molecular weight (Mw) was determined by gel permeation chromatography.

[化31]

<<Synthesis of Polymer A-2>>

Polymer A-2 was obtained in the same manner as in the synthesis of polymer A-1 except that the amount of chlorosulfonic acid was changed to 25.1 g, and the reaction temperature and time were changed to 70 ° C for 7 hours.

<<Synthesis of Polymer A-3>>

The polymer A-3 was obtained in the same manner as in the synthesis of the polymer A-1 except that the chlorosulfonic acid was changed to 14.4 g of 30% fuming sulfuric acid and the reaction time was changed to 8 hours.

<<Synthesis of Polymer A-4>>

8.0 g of polyfluorene (manufactured by Aldrich Co., Ltd.) was dissolved in 92.0 g of chloroform, and 8.43 g of chlorosulfonic acid was added dropwise at room temperature under a nitrogen stream. After the reaction was carried out for 1 hour at room temperature, a solid precipitated. The supernatant was removed, and the obtained solid was washed with chloroform and dissolved in methanol. This solution was added dropwise to 0.5 L of ethyl acetate, and the obtained precipitate was recovered by filtration. The obtained solid was dried under reduced pressure, whereby 8.3 g of polymer A-4 was obtained.

<<Synthesis of Polymer A-5>>

Add hexafluorobisphenol A 3.42 g, diphenyl sulfonium-4,4'-dichloro-3,3'-disulfonic acid disodium to a three-necked flask equipped with a Dean-Stark tube. 5.00 g, 1.69 g of potassium carbonate, 10 g of toluene, and 25 g of N-methylpyrrolidone were refluxed under a nitrogen stream for 4 hours. After the toluene in the system was removed, the temperature was raised to 180 ° C and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered through a Kiriyama funnel covered with diatomaceous earth, and the filtrate was added dropwise to 300 ml of saturated brine. The obtained precipitate was filtered, dissolved in methanol, and added dropwise to 500 ml of acetone. The obtained precipitate was filtered and dissolved in methanol with Amberlyst 15 (Hydrogen foam) (manufactured by Aldrich Co., Ltd.) was salt-exchanged into a proton type, whereby 6.4 g of the polymer A-5 was obtained.

<<Synthesis of Polymer A-6>>

3.9 g of the polymer A-6 was obtained in the same manner as in the synthesis of the polymer A-5 except that 3.42 g of hexafluorobisphenol A was changed to 1.22 g of hydroquinone.

<<Synthesis of Polymer A-7>>

To a three-necked flask equipped with a Dean-Stark tube, 4.66 g of bisphenolic acid, 8.00 g of diphenylsulfonium-4,4'-dichloro-3,3'-disulfonic acid, and 2.48 g of potassium carbonate were added. 10 g of toluene and 25 g of N-methylpyrrolidone were refluxed under a nitrogen stream for 4 hours. After the toluene in the system was removed, the temperature was raised to 180 ° C and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered using a Kiriyama funnel covered with diatomaceous earth, and then The filtrate was added to 300 ml of saturated brine. The obtained precipitate was filtered, dissolved in methanol, and added dropwise to 500 ml of acetone. The obtained precipitate was filtered and dried under reduced pressure.

The dried polymer was dissolved in 73.6 g of sulfuric acid, and 4.56 g of chlorosulfonic acid was added dropwise. After reacting for 6 hours at room temperature, the reaction liquid was added dropwise to 1.5 L of a hexane/ethyl acetate (1/1) mixture which was cooled with ice water. The supernatant was removed, and the obtained precipitate was dissolved in methanol. The obtained solution was added dropwise to 0.5 L of ethyl acetate, and the obtained precipitate was recovered by filtration. The obtained solid was dried under reduced pressure, whereby 7.5 g of polymer A-7 was obtained.

<<Synthesis of Polymer A-8>>

To a three-necked flask equipped with a Dean-Stark tube, 3.53 g of 4,4'-biphenol and 8.00 g of benzophenone-4,4'-difluoro-3,3'-disulfonic acid disodium were added. 3.14 g of potassium carbonate, 10 g of toluene, and 30 g of dimethyl hydrazine were refluxed under a nitrogen gas stream for 4 hours. After the toluene in the system was removed, the temperature was raised to 170 ° C and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered through a Kiriyama funnel covered with diatomaceous earth, and then the filtrate was added dropwise to 500 ml of saturated brine. Have done the precipitation obtained After filtration, it was dissolved in methanol and added dropwise to 800 ml of acetone. The obtained precipitate was filtered, dissolved in methanol, and then subjected to salt exchange to a proton type by Amberlyst 15 (hydrogen foam) (manufactured by Aldrich Co., Ltd.), whereby 7.2 g of polymer A-8 was obtained.

<<Synthesis of Polymer A-9>>

Sulfonation of polyetheretherketone is carried out according to the method described in J. Membr. Sci., 229, 2004, 95~, whereby polymer A-9 is obtained.

<<Synthesis of Polymer A-10>>

Sulfonation of polyphenylene oxide is carried out according to the method described in "Chinese J. Polym. Sci." 20, No. 1, 2002, 53~, thereby obtaining Polymer A-10.

<<Synthesis of Polymer A-11>>

Polymer A-11 was obtained according to the method described in Example 2 of JP-A-2008-533225.

<<Synthesis of Polymer A-12>>

The polymer A-12 is obtained by performing sulfomethylation of polyfluorene according to the method described in JP-A-2004-131662.

<<Synthesis of Polymer A-13>>

Polymer A-13 was obtained according to the method described in JP-A-2008-27890.

<<Synthesis of Polymer A-14>>

To the three-necked flask, 6.89 g of 4,4'-diaminobiphenyl-2,2'-disulfonic acid, 120 ml of m-cresol, and 4.86 g of triethylamine were added, and the mixture was stirred under a nitrogen gas stream until the solution became Evenly. To the solution, 6.20 g of 4,4'-oxydiphthalic acid and 6.84 g of benzoic acid were added, and the reaction was carried out at 80 ° C for 4 hours, followed by reaction at 180 ° C for 20 hours. After the reaction temperature was returned to room temperature, the reaction liquid was added to acetone. The obtained precipitate was filtered, dissolved in methanol, and then subjected to salt exchange to a proton type by Amberlyst 15 (hydrogen foam) (Aldrich), whereby 9.2 g of the polymer A-14 was obtained.

<<Synthesis of Polymer A-15>>

According to the method described in Journal of Membrane Science 360, 2010, and 26~, polyphosphonium phosphine is methylated to obtain a polymer A-15.

<<Synthesis of copper complex Cu-1>>

556 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 copper hydroxide. By the above manner, an aqueous solution of a copper complex (hereinafter also referred to as Engineering Plastics copper complex) Cu-1 can be obtained.

<<Synthesis of copper complex Cu-2~ copper complex Cu-15>>

The copper complex Cu was synthesized in the same manner as in the synthesis of the copper complex Cu-1 except that the mass ratio of the equivalent of the acid group contained in the polymer (A1) to the equivalent of the copper atom was changed as shown in the following Table 1. -2~ copper complex Cu-15.

<Copper complex obtained by reaction of a low molecular compound containing a coordination site and a copper component>

<<Copper complex with sulfophthalic acid as ligand (copper sulfophthalate complex)>>

A 53.1% aqueous solution of sulfophthalic acid was dissolved in 50 mL of methanol, and the solution was heated to 50 ° C, and then 1 equivalent of copper hydroxide was added to the sulfophthalic acid, and the reaction was carried out at 50 ° C for 2 hours. . After the completion of the reaction, the solvent and the produced water were distilled off by an evaporator, whereby a copper sulfophthalate complex was obtained.

<hardening compound>

Adhesive A: The following compound (Mw: 24,000)

[Chem. 46]

<Surfactant>

Surfactant A: Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.)

<Composition containing a copper compound>

Mixing the engineering plastic copper complex Cu-1 (5.07 parts by mass), copper sulfophthalate complex (15.21 parts by mass), surfactant A (0.02 parts by mass), and water 79.70 parts by mass, A composition containing a copper compound is obtained.

<Sclerosing composition>

The binder A (19.8 parts by mass) and water (80.2 parts by mass) were mixed to obtain a curable composition.

<Preparation of a film-forming composition>

The composition containing the copper compound and the curable composition were mixed in such a manner as to be described in the following Table 5 to prepare a film-forming composition. The composition containing the copper compound and the curable composition were mixed at a mass ratio of 2:3.

In addition, the composition for film formation of Experimental Example 1 is a composition obtained by mixing a composition containing a copper compound (composition 1) and a curable composition (composition 4). The film-forming composition of Experimental Example 2 is a composition obtained by mixing a composition containing a copper compound (composition 2) and a curable composition (composition 5). The film-forming composition of Experimental Example 3 is a composition obtained by mixing a composition containing a copper compound (composition 3) and a curable composition (composition 6).

<Evaluation of viscosity change>

The composition of the copper compound, the curable composition, and the film-forming composition were evaluated for the rate of change in viscosity when stored under conditions of 10° C., 25° C., and 40° C.

The viscosity of each composition was measured using a viscometer (manufactured by TOKI SANGYO, RE-85L).

The rate of change of the viscosity of the film-forming composition is the initial viscosity (V0) of the film-forming composition which is measured for 10 minutes after the preparation of the film-forming composition, and the film forming composition is measured from the reference time. The viscosity (V1) of the film-forming composition at the same temperature after 1 hour, 3 hours, 24 hours, 72 hours, 168 hours, and 720 hours, and the viscosity (V1) with respect to the initial viscosity (V0) was determined. Rate of change [((V1-V0)/V0) × 100] (%).

The change rate of the viscosity was measured in the same manner as the composition for film formation, except that the composition for the curable composition and the composition containing the copper compound was used as the reference time 10 minutes after the preparation of each composition. The results are shown in Table 5 below.

From the results shown in Table 5, it was found that the rate of change in the viscosity of the composition containing the copper compound and the curable composition with respect to the initial viscosity was small. The initial viscosity of the composition containing the copper compound is about 2 mPa. s, the initial viscosity of the hardenable composition is about 14mPa. s.

It is understood that the composition for forming a film of Experimental Example 1 to Experimental Example 3 has a larger rate of change in viscosity with respect to the initial viscosity than the composition containing the copper compound and the curable composition, that is, tends to be easily thickened.

In addition, it is understood that the composition for film formation of Experimental Example 1 to Experimental Example 3 has a viscosity change with respect to the initial viscosity within 3 days (particularly within 1 day) of the composition containing the copper compound and the curable composition. The rate is not so big.

In addition, in the period from the preparation of the film-forming composition of Experimental Example 1 to Experimental Example 3 to the application to the substrate, it was found to be stored at 25 ° C or lower, and it was found that The viscosity of the composition tends to be further suppressed.

In addition, it was found that even in the film formation compositions of Experimental Examples 1 to 3, engineering plastic copper complex Cu-2~ engineering plastic copper complex Cu-15 was used instead of the copper compound containing copper. In the film forming composition prepared in the same manner, the same results as those of the film forming compositions of Experimental Examples 1 to 3 were obtained.

<Preparation of a film containing a copper compound (near-infrared cut filter)>

The film-forming compositions of Experimental Examples 1 to 3 were applied onto a glass substrate by dropping casting (dropping method), respectively, and placed on a hot plate at 60 ° C, 10 minutes, 80 ° C, and 10 minutes. The mixture was heated stepwise at 100 ° C, 10 minutes, 120 ° C, 10 minutes, 140 ° C, and 10 minutes to prepare a near-infrared cut filter having a film thickness of 100 μm. In addition, 10 minutes after the preparation of the film-forming composition, a film for forming a film for 1 hour, 3 hours, 24 hours, 72 hours, 168 hours, and 720 hours from the reference time was used as a reference time. To obtain a near-infrared cut filter.

It is understood that the film-forming composition after 1 hour, 3 hours, 24 hours, and 72 hours from the reference time is applied to the substrate within 3 days after mixing the composition containing the copper compound and the curable composition. A film (Example) can be suitably produced. Further, it is understood that defects such as cracks in the film can be further suppressed.

On the other hand, in the near-infrared cut filter which used the composition for film formation after 168 hours and 720 hours from the reference time, it was confirmed that a crack such as a crack of the crack film occurred (comparative example).

In addition, it was found that even in the film formation compositions of Experimental Examples 1 to 3, engineering plastic copper complex Cu-2~ engineering plastic copper complex Cu-15 was used instead of the copper compound containing copper. In the near-infrared cut filter obtained in the same manner, the near-infrared ray cut-off filter obtained in the same manner as in the composition, and the near-infrared rays using the film-forming composition of Experimental Example 1 to Experimental Example 3 were also obtained. The same result as the cutoff filter.

In addition, even when the composition for forming a film is used, when a near-infrared cut filter is produced as follows, a near-infrared cut filter can be produced in the same manner. The photoresist was applied onto a glass substrate, and patterned by lithography to form a partition wall of the photoresist, thereby forming a dropping region (2 cm × 2 cm) of the film forming composition. 200 μL of each film-forming composition was dropped into the dropping region, and dried at 40° C. for 1 hour, and further 200 μL was added dropwise thereto, and dried at 40° C. for 1 hour, and then dried at 60° C. for 1 hour. Thereafter, drying was carried out by allowing to stand at room temperature for 24 hours. The film thickness of the coating film after drying was evaluated, and as a result, the film thickness was 200 μm. Further, even if a kapton tape is used as a partition wall to form a dropping region, a near-infrared cut filter can be produced in the same manner.

(Experimental Example 10)

In the composition 1 (the composition containing a copper compound) used in the above-mentioned Experimental Example 1, the low molecular copper complex A shown below was further added, and the engineering plastic copper complex Cu was determined on the basis of the solid content. The film formation composition of Experimental Example 10 was obtained in the same manner as in Experimental Example 1, except that the ratio of -1 to the low molecular weight copper complex A was changed to 7:3.

(Experimental Example 11 to Experimental Example 14)

In the film-forming composition of Experimental Example 10, the low molecular copper complex A was changed to low molecular copper complex B, low molecular copper complex C, low molecular copper complex D or low molecular copper. The film formation compositions of Experimental Examples 11 to 14 were obtained in the same manner as in Experimental Example 10 except for the above.

(Experimental Example 15 to Experimental Example 17)

In the film-forming composition of Experimental Example 10, the ratio of the engineering plastic copper complex Cu-1 to the low molecular copper complex A was 5:5, 6:4, 8:2, respectively, based on the solid content. The composition for film formation of Experimental Example 15 to Experimental Example 17 was obtained in the same manner as Experimental Example 10 except the above.

It can be confirmed that the hybrid type of the engineering plastic copper complex and the low molecular copper complex can achieve higher near-infrared shielding properties.

(low molecular copper complex)

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

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

Low Molecular Copper Complex C: Monobutyl Copper Phthalate, Tokyo Chemical Industry Co., Ltd.

Low molecular copper complex D: A copper complex of the following compound (A2-1) as a ligand. The synthesis method will be described later.

Low molecular copper complex E: copper wrong with the following compound (a-19) as a ligand Compound. The synthesis method will be described later.

<Synthesis of Low Molecular Copper Complex A>

To a three-necked flask, 4.0 g of pyrazole-3-carboxylic acid ethyl ester, 11.16 g of cesium carbonate, 5.17 g of 3-bromopentane, and 60 mL of 2,6-dimethyl-4-heptanone were placed in a nitrogen atmosphere. Heat at 150 ° C for 1 hour. After cooling to room temperature, the insoluble matter was removed by filtration, and the filtrate was concentrated, and the obtained crude product was purified by silica gel column chromatography (solvent: hexane/ethyl acetate) to obtain 1-( Ethyl 3-pentyl)pyrazole-3-carboxylate 3.3 g.

0.87 g of the product and 6 mL of ethanol were added to the flask, and 0.1 g of water and 0.46 g of potassium t-butoxide were added thereto while stirring at room temperature, followed by stirring at 70 ° C for 30 minutes. After cooling to room temperature, a solution obtained by dissolving 0.52 g of copper sulfate in 5 mL of water was added, and the mixture was stirred at room temperature for one hour. The precipitated solid was collected by filtration and dried under reduced pressure, whereby 0.7 g of a low molecular copper complex A was obtained.

<Synthesis of Low Molecular Copper Complex B>

Compound (A1-21) (886 mg, 9.84 mmol) was dissolved in 20 ml of methanol. After the temperature of the solution was raised to 50 ° C, a solution of copper hydroxide (449 mg, 4.60 mmol) in methanol (160 ml) was added dropwise, and the reaction was carried out at 50 ° C for 2 hours. After the reaction, The produced water and solvent were distilled off using an evaporator, whereby a low molecular copper complex B (1.00 g) was obtained.

<Synthesis of Low Molecular Copper Complex D>

Compound (A2-1) (0.2 g, 1.1 mmol) was dissolved in 5 ml of ethanol. After the solution was heated to 70 ° C, a solution of copper acetate (0.2 g, 1.1 mmol) in ethanol (5 ml) was added dropwise, and the reaction was carried out at 70 ° C for 2 hours. After completion of the reaction, the produced water and solvent were distilled off by an evaporator, whereby a low molecular copper complex D (0.6 g) was obtained.

<Synthesis of Low Molecular Copper Complex E>

The compound (a-19) 53.1% by mass aqueous solution (13.49 g, 29.1 mmol) was dissolved in 50 mL of methanol, and the solution was heated to 50 ° C. Then, copper hydroxide (2.84 g, 29.1 mmol) was added and the mixture was subjected to 50 ° C. 2 hours reaction. After completion of the reaction, the solvent and the produced water were distilled off by an evaporator, whereby a low molecular copper complex E (8.57 g) was obtained.

That is, in the case where the composition 1 (the composition containing a copper compound) used in Experimental Example 1 was used, and the same amount of cyclopentanone was used instead of water, the same effect was obtained. Further, even in the case of the composition 4 (curable composition) used in Experimental Example 1, when the same amount of cyclopentanone was used instead of water, the same effect was obtained.

In addition, even after the film formation composition used in Experimental Example 1 was prepared, the same effect was obtained even when it was filtered using DFA4201 NXEY (0.45 μm nylon filter) manufactured by Pall Corporation of Japan.

10‧‧‧矽 substrate

12‧‧‧ Camera Components Division

13‧‧‧Interlayer insulating film

14‧‧‧ basal layer

15B‧‧‧Blue color filter

15G‧‧‧Green color filter

15R‧‧‧Red color filter

16‧‧‧Protective layer

17‧‧‧Microlens

18‧‧‧Shade film

20‧‧‧Adhesive

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧ solder resist layer

26‧‧‧Internal electrodes

27‧‧‧ Component surface electrode

30‧‧‧ glass substrate

42‧‧‧Near-infrared cut-off filter

46‧‧‧Destivation layer

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Solid camera components

Claims (14)

A method for producing a film containing a copper compound, comprising the steps of: preparing a film-forming composition by mixing a composition containing a copper compound and a curable composition containing a curable compound, and coating the film within 3 days after preparation The step of forming the composition onto the substrate. The method for producing a copper compound-containing film according to the first aspect of the invention, wherein the film forming composition is used within one day after preparation. The method for producing a copper compound-containing film according to the first or second aspect of the invention, wherein the initial viscosity (V0) of the film-forming composition after 10 minutes from the preparation of the film-forming composition is The rate of change of the viscosity (V1) of the film-forming composition when applied at the same temperature is 140% or less, and the rate of change of the viscosity (V1) with respect to the initial viscosity (V0) is represented by the following formula. Formula: ((V1-V0)/V0) × 100. The method for producing a copper compound-containing film according to the first or second aspect of the invention, wherein the curable compound contains an oxygen heterocyclic compound. The method for producing a copper compound-containing film according to the first or second aspect of the invention, wherein the curable compound contains an epoxy compound. The method for producing a copper compound-containing film according to the first or second aspect of the invention, wherein the content of the copper compound relative to the total solid content in the film-forming composition is 10% by mass or more. A film containing a copper compound as described in claim 1 or 2 A method of producing a copper compound comprising a copper compound obtained by a reaction of a polymer comprising a coordination site with a copper component. The method for producing a copper compound-containing film according to claim 1 or 2, wherein the copper compound comprises an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain, and includes a coordination group. A copper compound obtained by a reaction between a polymer (A1) at a site and a copper component; and a copper compound obtained by a reaction of a compound having a molecular weight of 1,000 or less and a copper component in a coordination site. The method for producing a film containing a copper compound according to the first or second aspect of the invention, which comprises, after the preparation to the substrate, the film forming composition is stored at 30 ° C or lower. The method for producing a film containing a copper compound according to the first or second aspect of the invention, which is characterized in that the composition for film formation is applied to a substrate within 3 days after preparation, thereby suppressing the composition for film formation. The viscosity of the object. The method for producing a copper compound-containing film according to the first or second aspect of the invention, wherein the film containing the copper compound is a near-infrared cut filter. A solid-state image sensor comprising a copper compound-containing film obtained by the method for producing a copper compound-containing film according to any one of claims 1 to 11. A method for suppressing adhesion of a film-forming composition, which is a method for suppressing adhesion of a film-forming composition comprising a composition containing a copper compound and a curable composition containing a curable compound, comprising: The composition containing the copper compound was mixed with the curable composition within 3 days before the film forming composition was used. A kit for producing a film-forming composition comprising a composition containing a copper compound and a curable composition containing a curable compound, comprising: a composition containing a copper compound and a curable composition .