TW201838168A - Near infrared blocking filter, solid-state imaging element, camera module and image display device - Google Patents

Abstract

Provided is a near infrared blocking filter which is able to be reduced in thickness, while having excellent transparency in the visible region, excellent near infrared shielding properties and excellent dicing resistance. Also provided are a solid-state imaging element, a camera module and an image display device, each of which is provided with this near infrared blocking filter. This near infrared blocking filter comprises a glass containing copper, a resin layer containing a copper compound, and a layer containing an infrared absorbing dye.

Description

Near-infrared cut filter, solid-state imaging element, camera module, and image display device

The present invention relates to a near-infrared cut filter, a solid-state imaging element, a camera module, and an image display device.

A charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS) as a solid-state image sensor of a color image is used in a video camera, a digital camera, a mobile phone with an imaging function, and the like. Since these solid-state imaging elements use a germanium photodiode having sensitivity to near-infrared light in the light receiving portion, it is necessary to perform luminance sensitivity correction, and a near-infrared cut filter is generally used.

As a near-infrared cut filter, it has been studied to use a resin layer containing a copper compound (see Patent Documents 1 and 2). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. WO2016/158818 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2015-28621

In the near-infrared cut filter, it is required to have excellent transparency and near-infrared shielding properties. By increasing the thickness of the near-infrared cut filter itself, it is possible to improve the near-infrared shielding property of the near-infrared cut filter, and in recent years, it is desirable to thin the near-infrared cut filter.

Further, in recent years, a near-infrared cut filter has been used by dicing by dicing.

An object of the present invention is to provide a near-infrared cut filter which has excellent visible transparency and near-infrared shielding properties, can be thinned, and is excellent in cut resistance. Moreover, an object of the present invention is to provide a solid-state imaging device including a near-infrared cut filter, a camera module, and an image display device.

As a result of active research, the present inventors have found that the above object can be achieved by the following constitution, and the present invention has been completed. The present invention provides the following. <1> A near-infrared cut filter comprising: a glass containing copper, a resin layer containing a copper compound, and a layer containing an infrared absorbing dye. <2> The near-infrared cut filter according to <1>, wherein the glass containing copper has a film thickness of 10 to 10,000 μm, and the resin layer containing a copper compound has a film thickness of 1 to 500 μm and contains an infrared absorbing pigment. The film thickness of the layer is 0.01 to 10 μm. <3> The near-infrared cut filter according to <2>, wherein a ratio of a film thickness of the glass containing copper to a film thickness of the resin layer containing a copper compound is a film thickness of the glass containing copper: containing a copper compound The film thickness of the resin layer = [1:30] to [5,000:1]. <4> The near-infrared cut filter according to <2> or <3>, wherein a ratio of a film thickness of the glass containing copper to a film thickness of a layer containing the infrared absorbing dye is a film thickness of the glass containing copper : film thickness of the layer containing the infrared absorbing dye = [2:1] to [500,000:1]. The near-infrared cut filter according to any one of the above aspects, wherein the ratio of the film thickness of the resin layer containing the copper compound to the film thickness of the layer containing the infrared absorbing dye is Film thickness of the resin layer of the copper compound: film thickness of the layer containing the infrared absorbing dye = [1:5] to [30,000:1]. The near-infrared cut filter according to any one of <1> to <5> wherein the layer containing the infrared absorbing dye has a maximum absorption wavelength in a wavelength range of 600 to 1100 nm. The near-infrared cut filter according to any one of <1> to <6> wherein the maximum absorption wavelength of the layer containing the infrared absorbing dye is shorter than the maximum absorption wavelength of the resin layer containing the copper compound. wavelength. The near-infrared cut-off filter according to any one of <1> to <7> wherein the glass containing copper is in contact with one of the surfaces of the resin layer containing the copper compound, and the layer containing the infrared absorbing pigment It is in contact with the other side of the resin layer containing the copper compound. The near-infrared cut filter according to any one of the aspects of the present invention, wherein the copper compound is a compound represented by the following formula (1); Cu (L) _n1 (X) _{In the} formula, L is a ligand having a coordination site for a copper atom, and represents a compound having at least one selected from the group consisting of the following groups, the group comprising a group having a coordination site at which an anion coordinates a copper atom, and a group containing a coordinating atom that coordinates a copper atom with an unshared electron pair, X represents a counterion, and n1 represents a 1-4 An integer, n2 represents an integer from 0 to 4. The near-infrared cut filter according to any one of <1> to <9>, further comprising at least one selected from the group consisting of a dielectric multilayer film and an ultraviolet absorbing layer. <11> A solid-state imaging device having the near-infrared cut filter according to any one of <1> to <10>. <12> A camera module having the near-infrared cut filter according to any one of <1> to <10>. <13> An image display device having the near-infrared cut filter according to any one of <1> to <10>. [Effect of the invention]

According to the present invention, it is possible to provide a near-infrared cut filter which has excellent visible transparency and near-infrared shielding properties, can be thinned, and is excellent in cut resistance. Further, it is possible to provide a solid-state imaging device including a near-infrared cut filter, a camera module, and an image display device.

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)allyl" means allyl and methallyl, "(meth)acrylic ( "meth)acryl)" means acryl and metha cryl, and "(meth)acryloyl" means propylene fluorenyl and methacryl fluorenyl. In the label of the group (atomic group) in the present specification, a substituted or unsubstituted label, a group having no substituent (atomic group), and a group having a substituent (atomic group) are also not included. In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group. In the present specification, near-infrared light refers to light (electromagnetic wave) having a wavelength region of 700 to 2500 nm. In the present specification, the total solid content means the total mass of the components obtained by removing the solvent from all the components of the composition. In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).

<Near-infrared cut filter> The near-infrared cut filter according to the present invention includes a glass containing copper, a resin layer containing a copper compound, and a layer containing an infrared absorbing dye.

The near-infrared cut filter of the present invention is excellent in visible transparency and near-infrared ray shielding properties even if it is a film, including a glass containing copper, a resin layer containing a copper compound, and a layer containing an infrared absorbing dye. A near-infrared cut filter excellent in cut resistance. That is, the resin layer containing a copper compound has excellent visible transparency and near-infrared shielding properties. Further, the glass containing copper has moderate near-infrared shielding properties. The near-infrared cut filter of the present invention comprises a glass containing copper and a resin layer containing a copper compound, thereby obtaining excellent visible transparency and near-infrared shielding properties. Further, even if the thickness of the copper-containing glass and/or the copper compound-containing resin layer is reduced, excellent visible transparency and near-infrared shielding properties can be maintained, so that excellent visible transparency and near-infrared shielding properties can be obtained. Achieve thin film. Further, the layer containing the infrared absorbing dye alone tends to have a narrow wavelength range of the light to be shielded. However, by using a combination of a glass containing copper and a resin layer containing a copper compound, the following shielding properties can be improved, that is, only The shielding property of light having a wavelength which is not sufficiently shielded by a copper-containing glass or a resin layer containing a copper compound, or a shielding property of light having a wavelength which is intended to further improve shielding properties. For example, a glass containing copper or a resin layer containing a copper compound is insufficient in shielding property of light in the vicinity of about 700 to 800 nm, but a layer containing an infrared absorbing dye contains absorption in the vicinity of 700 to 800 nm. The layer of the infrared absorbing dye can be a near-infrared cut filter excellent in light shielding properties in a wide range of near-infrared regions. In addition, since the glass containing copper has moderate flexibility, the near-infrared cut filter of the present invention can absorb the impact of the near-infrared cut filter during cutting by the glass containing copper, and can absorb the impact of the near-infrared cut filter. The generation of cracks or the like is suppressed, and the cut resistance of the near-infrared cut filter can be improved. Further, since the difference in hardness from the resin layer is reduced, when the copper-containing glass is directly contacted with the resin layer, damage occurring at the interface between the resin layer and the glass containing copper can be expected to be reduced. The effect of suppressing peeling of the resin layer is suppressed. Further, in the near-infrared cut filter of the present invention, by using a glass containing copper and a resin layer containing a copper compound, even if the thickness of the resin layer containing a copper compound is thin, excellent visible transparency and near-infrared shielding properties can be obtained. Therefore, it is also possible to suppress the occurrence of warpage or the like.

In the near-infrared cut filter of the present invention, the thickness of the glass containing copper is preferably 10 to 10,000 μm. The lower limit of the film thickness is preferably 50 μm or more, more preferably 100 μm or more, and still more preferably 150 μm or more. The upper limit of the film thickness is preferably 2000 μm or less, more preferably 1000 μm or less, still more preferably 500 μm or less, and particularly preferably 300 μm or less.

In the near-infrared cut filter of the present invention, the thickness of the resin layer containing the copper compound is preferably from 1 to 500 μm. The lower limit of the film thickness is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more, and particularly preferably 30 μm or more. The upper limit of the film thickness is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 75 μm or less, and particularly preferably 50 μm or less.

In the near-infrared cut filter of the present invention, the film thickness of the layer containing the infrared absorbing dye is preferably 0.01 to 10 μm. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.3 μm or more, further preferably 0.5 μm or more, and particularly preferably 0.7 μm or more. The upper limit of the film thickness is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less.

In the near-infrared cut filter of the present invention, the ratio of the film thickness of the glass containing copper to the film thickness of the resin layer containing the copper compound is the film thickness of the glass containing copper: the film thickness of the resin layer containing the copper compound = [ 1:50]~[10,000:1] is preferable, [1:30] to [5,000:1] is more preferable, [1:1] to [100:1] is further preferable, [2:1] Further, it is more preferable that [3:1] to [20:1], and [4:1] to [10:1] are particularly preferable. When the film thickness ratio of both is within the above range, the near-infrared cut filter of the near-infrared cut filter is excellent.

In the near-infrared cut filter of the present invention, the ratio of the film thickness of the glass containing copper to the film thickness of the layer containing the infrared absorbing dye is the film thickness of the glass containing copper: the film thickness of the layer containing the infrared absorbing dye = [ 1:1]~[1,000,000:1] is preferred, [2:1]~[500,000:1] is better, [10:1]~[1000:1] is further preferred, [30:1] ～[700:1] is further preferred, and [50:1] to [700:1] is further more preferable, and [100:1] to [300:1] are particularly preferable. When the film thickness ratio of both is within the above range, the near-infrared cut filter has good visibility and near-infrared shielding properties.

In the near-infrared cut filter of the present invention, the ratio of the film thickness of the resin layer containing the copper compound to the film thickness of the layer containing the infrared absorbing dye is a film thickness of the resin layer containing the copper compound: a layer containing the infrared absorbing dye layer. The film thickness = [1:10] to [50,000:1] is preferable, [1:5] to [30,000:1] is more preferable, and [1:1] to [300:1] is further preferable, [ 3:1] to [200:1] are further preferable, [5:1] to [100:1] are further more preferable, and [10:1] to [50:1] are particularly preferable. When the film thickness ratio of both is within the above range, the near-infrared cut filter has good visibility and near-infrared shielding properties.

In a preferred embodiment of the near-infrared cut filter of the present invention, the film containing copper has a thickness of 100 to 500 μm, and the resin layer containing a copper compound has a thickness of 10 to 100 μm, and a film containing a layer of an infrared absorbing dye. The thickness is 0.5 to 2.0 μm, and the wavelength of the maximum absorption wavelength of the layer containing the infrared absorbing dye is preferably shorter than the wavelength of the maximum absorption wavelength of the resin layer containing the copper compound. According to this aspect, it is possible to provide a near-infrared cut filter which is excellent in visible transparency and excellent in light shielding properties in a wide range of near-infrared regions. Moreover, the cut resistance is also excellent.

In the near-infrared cut filter of the present invention, in the range of the wavelength of 700 nm or more and less than 800 nm, the average value of the transmittance of the light irradiated from the vertical direction with respect to the film surface of the near-infrared cut filter is 20% or less. 15% or less is more preferable, 10% or less is further preferable, and 5% or less is particularly preferable. Further, in the near-infrared cut filter of the present invention, in the total range of the wavelength of 800 to 1000 nm, the transmittance of the light irradiated from the vertical direction with respect to the film surface of the near-infrared cut filter is preferably 20% or less, 15 % or less is more preferable, 10% or less is further preferable, and 5% or less is particularly preferable. Further, in the near-infrared cut filter of the present invention, in the range of 800 to 1100 nm, the average value of the transmittance of the light irradiated from the vertical direction with respect to the film surface of the near-infrared cut filter is preferably 20% or less. 15% or less is more preferable, 10% or less is further preferable, and 5% or less is particularly preferable. Further, in the near-infrared cut filter of the present invention, in the total range of the wavelength of 800 to 1100 nm, the transmittance of the light irradiated from the vertical direction with respect to the film surface of the near-infrared cut filter is preferably 20% or less. % or less is more preferable, 10% or less is further preferable, and 5% or less is particularly preferable.

In the near-infrared cut filter of the present invention, the average value of the reflectance in the range of 700 to 1100 nm is preferably 20% or less, more preferably 10% or less, and still more preferably 5% or less. Further, in the near-infrared cut filter of the present invention, the reflectance is preferably 20% or less in a total range of wavelengths of 700 to 1100 nm, more preferably 10% or less, still more preferably 5% or less. According to this aspect, it is possible to provide a near-infrared cut filter having a wide viewing angle and excellent infrared shielding properties. The reflectance was measured by using U-4100 (manufactured by Hitachi High-Technologies Corporation), the surface normal direction of the near-infrared cut filter was set to 0°, and the incident angle was set to 5°.

In the near-infrared cut filter of the present invention, it is preferable that the transmittance of the light irradiated from the vertical direction with respect to the film surface of the near-infrared cut filter satisfies at least one of the following conditions (1) to (13), and the following is satisfied. All of the conditions (1) to (4) are more preferable, and all the conditions satisfying (1) to (13) are further preferable. (1) The light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, further preferably 92% or more, and particularly preferably 95% or more. (2) The light transmittance at a wavelength of 450 nm is preferably 80% or more, more preferably 90% or more, further preferably 92% or more, and particularly preferably 95% or more. (3) The light transmittance at a wavelength of 500 nm is preferably 80% or more, more preferably 90% or more, further preferably 92% or more, and particularly preferably 95% or more. (4) The light transmittance at a wavelength of 550 nm is preferably 80% or more, more preferably 90% or more, further preferably 92% or more, and particularly preferably 95% or more. (5) The light transmittance at a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, 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, further preferably 10% or less, and particularly preferably 5% or less. (7) The light transmittance at a wavelength of 800 nm is preferably 20% or less, more preferably 15% or less, 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, further 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. (10) The light transmittance at a wavelength of 950 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less. (11) The light transmittance at a wavelength of 1000 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less. (12) The light transmittance at a wavelength of 1050 nm is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 5% or less. (13) The light transmittance at a wavelength of 1100 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

In the near-infrared cut filter of the present invention, the transmittance in all ranges of 400 to 550 nm is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more. The higher the transmittance of the visible region, the better.

Hereinafter, the near-infrared cut filter of the present invention will be described in detail.

<<Glass Containing Copper>> The near-infrared cut filter of the present invention comprises a glass containing copper. Examples of the copper glass include phosphate glass containing copper and fluorophosphate glass containing copper. The content of copper in the glass containing copper is preferably 0.1 to 20% by mass, more preferably 0.3 to 17% by mass, still more preferably 0.5 to 15% by mass.

In the present invention, it is preferred that the glass containing copper has a maximum absorption wavelength in the range of 700 to 1100 nm. The lower limit is preferably 800 nm or more, more preferably 900 nm or more. The upper limit is preferably 1050 nm or less, more preferably 1000 nm or less.

Specific examples of the glass containing copper include the following. (1) In terms of mass%, including P ₂ O ₅ 46 to 70%, AlF ₃ 0.2 to 20%, ΣRF (R = Li, Na, K) 0 to 25%, ΣR'F ₂ (R' = Mg, Ca, Sr, Ba, and Pb) are from 1 to 50%, and the appearance of the base glass is 0.5 to 7 parts by mass based on 100 parts by mass of the base glass containing 0.5 to 32% of F and 26 to 54% of O. (2) In terms of mass%, including P ₂ O ₅ 25 to 60%, Al ₂ O ₃ 1 to 13%, MgO 1 to 10%, CaO 1 to 16%, BaO 1 to 26%, and SrO 0 to 16%. ZnO 0 to 16%, Li ₂ O 0 to 13%, Na ₂ O 0 to 10%, K ₂ O 0 to 11%, CuO 1 to 7%, ΣRO (R = Mg, Ca, Sr, Ba) 15 ～40%, ΣR′ ₂ O (R′=Li, Na, K) 3 to 18% (where 39% of the O ² ions before the mole is replaced by F) glass. (3) In terms of mass%, it contains 5 to 45% of P ₂ O ₅ , 1 to 35% of AlF ₃ , 0 to 40% of ΣRF (R=Li, Na, K), and ΣR'F ₂ (R'=Mg, Ca, Sr, Ba, Pb, Zn) 10 to 75%, R"F _m (R" = La, Y, Cd, Si, B, Zr, Ta, m is the number of valences equivalent to R") ～15% (in which 70% of the total amount of fluoride can be replaced by an oxide) and 0.20 to 15% of CuO. (4) P ⁵⁺ 11 to 43%, Al, in terms of cationic % ³⁺ 1～29%, ΣR cation (R=Mg, Ca, Sr, Ba, Pb, Zn) 14～50%, ΣR′ cation (R′=Li, Na, K) 0～43%, ΣR” cation (R" = La, Y, Gd, Si, B, Zr, Ta) 0 to 8% and Cu ²⁺ 0.5 to 13%, and contain ^- 17 to 80% of glass in terms of anion %. In terms of cationic percentage, it contains P ⁵⁺ 23 to 41%, Al ³⁺ 4 to 16%, Li ⁺ 11 to 40%, Na ⁺ 3 to 13%, and ΣR cation (R = Mg, Ca, Sr, Ba, Zn). 12 to 53% and Cu ²⁺ 2.6 to 4.7%, and contain F ^- 25 to 48% and O ^{2 to} 52 to 75% of glass in terms of anion %. (6) In terms of mass%, relative to P ₂ O _{5 70 ~ 85%, Al 2} O 3 8 ~ 17%, B 2 O 3 1 ~ 10%, Li 2 O 0 _{3%, Na 2 O 0 ~} 5%, K 2 O 0 ~ 5% ( where _{ΣR 2 O (R = Li,} Na, K) 0.1 ~ 5%, SiO 2 0 ~ 3%) of the base glass 100 parts by mass The outer percentage is a glass containing 0.1 to 5 parts by mass of CuO.

A commercially available product can also be used for the glass containing copper. As a commercial item of the glass containing copper, NF-50 (made by AGC TECHNO GLASS CO., LTD.) etc. are mentioned.

<<Resin layer containing a copper compound>> The near-infrared cut filter of the present invention contains a resin layer containing a copper compound (hereinafter also referred to as a resin layer).

In the present invention, it is preferred that the resin layer has a maximum absorption wavelength in the range of 700 to 1100 nm. The lower limit is preferably 800 nm or more, more preferably 900 nm or more. The upper limit is preferably 1050 nm or less, more preferably 1000 nm or less. Further, the difference between the maximum absorption wavelength of the resin layer and the maximum absorption wavelength of the copper-containing glass is preferably 300 nm or less, more preferably 200 nm or less, and still more preferably 150 nm or less. The lower limit is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, and further preferably 50 m or more. Further, the maximum absorption wavelength of the resin layer is preferably on the longer wavelength side than the maximum absorption wavelength of the glass containing copper.

The content of the copper compound in the resin layer is preferably from 5 to 90% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less. The details of the copper compound will be described later.

The content of the resin in the resin layer is preferably from 10 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.

The resin layer can be formed using a resin composition containing a copper compound and a resin. In the following, a resin composition (resin composition for resin layer formation) which can be preferably used for forming a resin layer in the near-infrared cut filter of the present invention will be described.

The resin composition contains a copper compound. As the copper compound, a copper complex is preferred. As the copper complex, a complex of copper and a compound (coordination) having a coordination site for copper is preferred. Examples of the coordination site for copper include a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair. The copper complex may also have two or more ligands. When there are two or more ligands, each of the ligands may be the same or different. The copper complex can be exemplified by 4 coordination, 5 coordination and 6 coordination, 4 coordination and 5 coordination are more preferred, and 5 coordination is further preferred. Further, it is preferred that the copper complex is formed of a 5-membered ring and/or a 6-membered ring by copper and a ligand. The copper complex is stable in shape and excellent in stability.

In the present invention, the copper complex is preferably a copper complex other than the beryllium bronze complex. Here, the indigo bronze complex refers to a copper complex which has a compound having a indigo skeleton as a ligand. The compound having a indigo skeleton diffuses a π-electron conjugated system in the entire molecule, and adopts a planar structure. The beryllium bronze complex absorbs light by a π-π* transition. When the light in the infrared region is absorbed by the π-π* transition, the compound forming the ligand needs to adopt a longer conjugated structure. However, when the conjugated structure of the ligand is made longer, it is seen that the transparency tends to decrease. Therefore, the visible transparency of the beryllium bronze complex is sometimes insufficient. Further, the copper complex is preferably a copper complex which has a compound having a maximum absorption wavelength in a wavelength region of 400 to 600 nm as a ligand. In a copper complex which has a compound having a maximum absorption wavelength in a wavelength region of 400 to 600 nm as a ligand, since it has absorption in a visible region (for example, a wavelength region of 400 to 600 nm), transparency may not be observed. full. Examples of the compound having a maximum absorption wavelength in a wavelength region of 400 to 600 nm include a compound having a long conjugated structure and a large absorption of light of a π-π* transition. Specifically, a compound having an indigo skeleton can be mentioned.

The copper complex can be obtained, for example, by mixing, reacting, or the like with a compound (coordinator) having a coordination site for copper and a copper component (copper or a compound containing copper). The compound (coordination) having a coordination site for copper may be a low molecular compound or a polymer. It is also possible to use both.

The copper component is preferably a compound containing divalent copper. The copper component may be used alone or in combination of two or more. As the copper component, for example, copper oxide or a copper salt can be used. The copper salt is, for example, copper carboxylate (for example, copper acetate, copper ethyl acetate, copper formate, copper benzoate, copper stearate, copper naphthenate, copper citrate, copper 2-ethylhexanoate, etc.) Copper sulfonate (for example, copper methanesulfonate, etc.), copper phosphate, copper phosphate, copper phosphonate, copper phosphonate, copper phosphinate, copper amide, copper sulfonamide, copper bismuth amide, bismuth Copper sulfonimide, copper bissulfonimide, copper methylate, copper alkoxide, copper phenoxide, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper perchlorate, copper fluoride Copper chloride, copper bromide is preferred, copper carboxylate, copper sulfonate, copper sulfonamide, copper guanidinium, copper sulfonium sulfoximine, copper bissulfonimide, copper alkoxide, More preferably, copper phenoxide, copper hydroxide, copper carbonate, copper fluoride, copper chloride, copper sulfate or copper nitrate, copper carboxylate, copper sulfonium sulfoxide, copper phenoxide, copper chloride, Further, copper sulfate or copper nitrate is further preferred, and copper carboxylate, copper sulfonium sulfoximine, copper chloride, and copper sulfate are particularly preferred.

The copper compound is preferably a compound having a maximum absorption wavelength in the range of 700 to 1200 nm. The maximum absorption wavelength of the copper compound is more preferably in the range of 720 to 1200 nm, and further preferably in the range of 800 to 1100 nm. The maximum absorption wavelength of the copper compound can be measured, for example, using Cary 5000 UV-Vis-NIR (spectrophotometer Agilent Technologies, Inc.). The Mohr absorbance coefficient 120 (L/mol·cm) or more at the maximum absorption wavelength in the wavelength region of the copper compound is preferably 150 (L/mol·cm) or more, and 200 (L/mol·· More preferably, the above is more preferably 300 (L/mol·cm) or more, and more preferably 400 (L/mol·cm) or more. The upper limit is not particularly limited, and for example, it can be set to 30,000 (L/mol·cm) or less. When the molar absorption coefficient of the copper compound is 100 (L/mol·cm) or more, a near-infrared cut filter excellent in infrared shielding properties can be used even in the case of a film. The gram absorption coefficient at a wavelength of 800 nm of the copper compound is preferably 0.11 (L/g·cm) or more, more preferably 0.15 (L/g·cm) or more, and further preferably 0.24 (L/g·cm) or more. . Further, in the present invention, the molar absorption coefficient and the gram extinction coefficient of the copper compound can be prepared by dissolving a copper compound in a measurement solvent to prepare a solution having a concentration of 1 g/L, and measuring the absorption spectrum of the solution in which the copper compound is dissolved. Out. As the measuring device, UV-1800 (wavelength region 200 to 1100 nm) manufactured by SHIMADZU CORPORATION, Cary 5000 (wavelength region 200 to 1300 nm) manufactured by Agilent, or the like can be used. Examples of the measurement solvent include water, N,N-dimethylformamide, propylene glycol monomethyl ether, 1,2,4-trichlorobenzene, and acetone. In the present invention, a copper compound capable of dissolving the measurement target is selected from the above-mentioned measurement solvents. When it is a copper compound dissolved in propylene glycol monomethyl ether, it is preferable to use propylene glycol monomethyl ether as a measurement solvent. Further, the dissolution system indicates a state in which the solubility of the copper compound with respect to the solvent at 25 ° C exceeds 0.01 g / 100 g of the solvent (Solvent). In the present invention, the molar absorption coefficient and the gram extinction coefficient of the copper compound are preferably measured by using any one of the above-mentioned measurement solvents, and the value obtained by measurement using propylene glycol monomethyl ether is more preferable.

[Low-Molecular Copper Complex] As the copper complex, for example, a copper complex represented by the formula (Cu-1) can be used. The copper complex is a copper complex in which a ligand L is coordinated to the copper of the central metal, and the copper is usually divalent copper. The copper complex can be obtained, for example, by reacting a compound which is a ligand L or a salt thereof with a copper component. Cu(L) _n1・(X) _n2 Formula (Cu-1) In the above formula, L represents a ligand coordinated to copper, and X represents a counter ion. N1 represents an integer of 1 to 4. N2 represents an integer of 0 to 4.

X represents a relative ion. The copper complex compound may be a cation complex or an anion complex in addition to a charge-neutral complex. In this case, relative ions are present as needed to neutralize the charge of the copper complex. When the counter ion is a counter ion with a negative charge (relative anion), it may be, for example, an inorganic anion or an organic anion. For example, examples of the counter ion include a hydroxide ion, a halogen anion (for example, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, etc.), a substituted or unsubstituted alkylcarboxylic acid ion ( Acetate ion, trifluoroacetate ion, etc., substituted or unsubstituted aryl carboxylic acid ion (benzoic acid ion, etc.), substituted or unsubstituted alkyl sulfonate ion (methanesulfonate ion, trifluoromethyl Sulfonic acid ion, etc., substituted or unsubstituted arylsulfonate ion (eg, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), aryldisulfonate ion (eg, 1,3-benzenedisulfonate) Acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalene disulfonic acid ion, etc.), alkyl sulfate ion (such as methyl sulfate ion, etc.), sulfate ion, thiocyanate ion, nitrate ion, over Chloride ion, boric acid ion (for example, tetrafluoroboric acid ion, tetraarylboronic acid ion, tetrakis(pentafluorophenyl)borate ion (B ^- (C ₆ F ₅ ) ₄ ), etc.), sulfonate ion (for example, P-toluenesulfonate ion, etc., quinone imine ion (eg, sulfonimide) , N,N-bis(fluorosulfonate) quinone imine ion, bis(trifluoromethanesulfonate) quinone imine ion, bis(nonafluorobutanesulfonate) quinone imine ion, N,N-hexafluoro- 1,3-disulfonyl quinone imine ion, etc.), phosphate ion, hexafluorophosphate ion, picric acid ion, guanamine ion (containing decyl or sulfonyl substituted guanamine), methylation Ionic (containing a methyl group substituted by a sulfhydryl group or a sulfonyl group), a halogen anion, a substituted or unsubstituted alkylcarboxylic acid ion, a sulfate ion, a nitrate ion, a tetrafluoroborate ion, a tetraarylboronic acid ion, A hexafluorophosphate ion, a guanamine ion (containing a guanamine substituted with a sulfhydryl group or a sulfonyl group), a methylated ion (a methyl group substituted with a thiol group or a sulfonyl group) is preferred. Further, it is preferred that the relative anion is a low nucleophilic anion. A low nucleophilic anion refers to an anion formed by dissociating a proton by an acid having a low pKa, generally referred to as a super acid. The definition of super acid varies from literature to literature, but is a general term for acids with lower pKa than methanesulfonic acid. It is known in J. Org. Chem. 2011, 76, 391-395, the equilibrium acidity of superacids ( The structure of Equilibrium Acidities of Super acids). The pKa of the low nucleophilic anion is preferably, for example, -11 or less, and preferably -11 to -18. The pKa can be measured, for example, by the method described in J. Org. Chem. 2011, 76, 391-395. The pKa value in the present specification is a pKa in 1,2-dichloroethane unless otherwise specified. When the relative anion is a low nucleophilic anion, the decomposition reaction of the copper complex or the resin hardly occurs, and the heat resistance is good. a low nucleophilic anionic tetrafluoroboric acid ion, a tetraarylboronic acid ion (containing an aryl group substituted by a halogen atom or a fluoroalkyl group), a hexafluorophosphate ion, a quinone imine ion (including a sulfhydryl group or a sulfonyl group) Substituted decylamine), methylated ion (containing a methyl group substituted with a mercapto group or a sulfonyl group), more preferably a tetraarylboronic acid ion (containing an aryl group substituted by a halogen atom or a fluoroalkyl group), hydrazine Imidium ions (including decylamine substituted by a sulfonyl group) and methylated ions (including a methyl compound substituted with a sulfonyl group) are particularly preferred. Further, in the present invention, an anionic halogen anion, a carboxylic acid ion, a sulfonate ion, a boric acid ion, a sulfonate ion, or a quinone imide ion is also preferable. Specific examples include chloride ions, bromide ions, iodide ions, acetate ions, trifluoroacetate ions, formate ions, phosphate ions, hexafluorophosphate ions, p-toluenesulfonate ions, and tetra Fluoroborate ion, tetrakis(pentafluorophenyl)borate ion, N,N-bis(fluorosulfonyl)phosphonium ion, bis(trifluoromethanesulfonate) quinone imine ion, bis(nonafluorobutanesulfonate)醯imino ion, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonyl quinone imine ion, N,N-hexafluoro-1,3-disulfonyl quinone imine ion, etc. Trifluoroacetic acid ion, hexafluorophosphate ion, tetrafluoroboric acid ion, tetrakis(pentafluorophenyl)borate ion, N,N-bis(fluorosulfonyl)phosphonium ion, bis(trifluoromethanesulfonate) Imine ion, bis(nonafluorobutanesulfonate) quinone imine ion, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonyl quinone imine ion, N,N-hexafluoro-1, 3-disulfonyl quinone imine ion is preferred, trifluoroacetate ion, tetrakis(pentafluorophenyl)borate ion, N,N-bis(fluorosulfonyl)indolide ion, bis(trifluoromethanesulfonate)醯) 醯 imine ion, double (non-fluorine Butanesulfonate) quinone imine ion, nonafluoro-N-[(trifluoromethane)sulfonyl]butasulfonyl quinone imine ion, N,N-hexafluoro-1,3-disulfonyl fluorene Amine ions are preferred. When the counter ion is a counter ion having a positive charge (relative cation), for example, an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion such as a tetrabutylammonium ion or a triethylbenzylammonium ion) may be mentioned. , pyridinium ion, etc.), cesium ions (for example, tetraalkylphosphonium ions such as tetrabutylphosphonium ions, alkyltriphenylphosphonium ions, triethylphenylphosphonium ions, etc.), alkali metal ions or protons. Further, the counter ion may be a metal complex ion (for example, a copper complex ion or the like).

The ligand L is a compound having a coordination site for copper, and one of a coordination atom selected from a coordination site in which an anion is coordinated to copper and a coordination atom in which an unshared electron pair is coordinated with copper is exemplified. More than one compound. The coordination site coordinated by the anion may or may not be dissociated. The ligand L is preferably a compound having two or more coordination sites for copper (polydentate ligand). Further, in the ligand L, in order to improve the visible transparency, it is preferred that the π-conjugated system such as an aromatic group is not continuously bonded in plural. The ligand L can also be used in combination with a compound having one coordination site for copper (monodentate ligand) and a compound having two or more coordination sites for copper (polydentate ligand). As the monodentate ligand, a monodentate ligand which is coordinated by an anion or an unshared electron pair can be mentioned. Examples of the ligand coordinated by an anion include a halogen anion, a hydroxide anion, an alkoxide anion, a phenoxide anion, and an amide anion. An anthracene substituted by a sulfhydryl group or a sulfonyl group, an anthracene anion (a quinone imine substituted with a sulfhydryl group or a sulfonyl group), an anionic anion (an aniline substituted with a thiol group or a sulfonyl group), sulfur Alkoxide anion, hydrogencarbonate anion, carboxylate anion, thiocarboxylate anion, dithiocarboxylate anion, hydrogen sulfate anion, sulfonate anion, dihydrogen phosphate anion, phosphodiester anion, phosphonate monoester anion, phosphine Acid hydride anion, phosphinic acid anion, nitrogen-containing heterocyclic anion, nitrate anion, hypochlorous acid anion, cyanide anion, cyanate anion, isocyanate anion, sulfur A thiocyanate anion, an isothiocyanate anion, an azide anion, or the like. Examples of the monodentate ligand coordinated by an unshared electron pair include water, alcohol, phenol, ether, amine, aniline, decylamine, quinone imine, imine, nitrile, isonitrile, thiol, sulfur. An ether, a carbonyl compound, a thiocarbonyl compound, an anthracene, a heterocyclic ring, or a carbonic acid, a carboxylic acid, a sulfuric acid, a sulfonic acid, a phosphoric acid, a phosphonic acid, a phosphinic acid, nitric acid or an ester thereof.

The anion of the ligand L may be coordinated to a copper atom, and an oxyanion, a nitrogen anion or a sulfur anion is preferred. The coordination site coordinated by the anion is preferably at least one selected from the group consisting of the following monovalent functional group (AN-1) or divalent functional group (AN-2). Further, the wave line in the following structural formula is a bonding position with the atomic group constituting the ligand.

Group (AN-1) [Chemical Formula 1]

Group (AN-2) [Chemical Formula 2]

In the above formula, 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 a linear form is preferred. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. An example of the alkyl group is a methyl group. The alkyl group may also have a substituent. Examples of the substituent include a halogen atom, a carboxyl group, and a heterocyclic group. The heterocyclic group as a substituent may be a single ring or a polycyclic ring, or may be aromatic or non-aromatic. The number of the hetero atoms constituting the hetero ring is preferably from 1 to 3, and preferably 1 or 2. A nitrogen atom constituting a hetero atom of a hetero ring is preferred. When the alkyl group has a substituent, it may further have a substituent. The alkenyl group represented by R may be linear, branched or cyclic, but a linear form is preferred. The alkenyl group has preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms. The alkenyl group may be unsubstituted or may have a substituent. Examples of the substituent include the above. The alkynyl group represented by R may be linear, branched or cyclic, but a linear form is preferred. The alkynyl group has preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms. The alkynyl group may be unsubstituted or may have a substituent. Examples of the substituent include the above. The aryl group represented by R may be a single ring or a polycyclic ring, and a single ring is preferred. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and further preferably 6 is further preferred. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the above. The heteroaryl group represented by R may be a single ring or a polycyclic ring. The number of the hetero atoms constituting the heteroaryl group is preferably from 1 to 3. The hetero atom of the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom. The carbon number of the heteroaryl group is preferably from 6 to 18, more preferably from 6 to 12. The heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the above.

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 mentioned. 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 carboxyl group, a quinone acid group, and the like, and a sulfonic acid group or a carboxyl group. It is better.

A coordinating atomic oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom coordinated with an unshared electron pair is preferred, and an oxygen atom, a nitrogen atom or a sulfur atom is more preferred, and an oxygen atom or a nitrogen atom is further preferred. The nitrogen atom is particularly good. When the coordinating atom coordinated by the unshared electron pair is a nitrogen atom, an atomic carbon atom or a nitrogen atom adjacent to the nitrogen atom is preferred, and a carbon atom is more preferable.

The coordinating atom coordinated with the unshared electron pair is contained in the ring or is selected from the group consisting of the following monovalent functional group (UE-1), the divalent functional group (UE-2), and the trivalent functional group. It is preferable that at least one partial structure of (UE-3) is used. Further, the wave line in the following structural formula is a bonding position with the atomic group constituting the ligand. Group (UE-1) [Chemical Formula 3]

Group (UE-2) [Chemical Formula 4]

Group (UE-3) [Chemical Formula 5]

In the group (UE-1) to (UE-3), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. , aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkylthio, arylthio, heteroarylthio, amine or fluorenyl.

Coordination atoms coordinated with unshared electron pairs may also be included in the ring. When a coordinating atom coordinated by an unshared electron pair is contained in a ring, the ring containing a coordinating atom coordinated by an unshared electron pair may be a single ring, a polycyclic ring, or a fragrance. A family can also be non-aromatic. It is preferred to have a ring system 5 to 12 member ring containing a coordinating atom coordinated by an unshared electron pair, and a 5 to 7 member ring is more preferable. The ring containing a coordinating atom coordinated by an unshared electron pair may have a substituent, and examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; An aryl group of ～12, a halogen atom or a ruthenium atom; an alkoxy group having 1 to 12 carbon atoms; a fluorenyl group having 2 to 12 carbon atoms; an alkylthio group having 1 to 12 carbon atoms; a carboxyl group; When the ring having a coordinating atom coordinated by an unshared electron pair has a substituent, the substituent may further have a group including a ring containing a coordinating atom coordinated by an unshared electron pair; a group containing at least one partial structure selected from the group consisting of the above groups (UE-1) to (UE-3); an alkyl group having 1 to 12 carbon atoms; a fluorenyl group having 2 to 12 carbon atoms; and a hydroxyl group.

When a coordinating atom coordinated by an unshared electron pair is included in a partial structure represented by a group (UE-1) to (UE-3), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, Aryl or heteroaryl, R ² represents a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkylthio, arylthio, Heteroarylthio, amine or sulfhydryl. The definitions of the alkyl group, the alkenyl group, the alkynyl group, the aryl group and the heteroaryl group are the same as those of the alkyl group, the alkenyl group, the alkynyl group, the aryl group and the heteroaryl group described in the coordination site coordinated by the above anion. The scope is also the same. The alkoxy group has preferably 1 to 12 carbon atoms, more preferably 3 to 9 carbon atoms. The aryloxy group has preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. The heteroaryloxy group may be a single ring or a polycyclic ring. The definition of the heteroaryl group constituting the heteroaryloxy group is the same as the heteroaryl group described in the coordination site coordinated by the above anion, and the preferred range is also the same. The alkylthio group has preferably 1 to 12 carbon atoms, more preferably 1 to 9 carbon atoms. The arylthio group has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. The heteroarylthio group may be a single ring or a polycyclic ring. The definition of the heteroaryl group constituting the heteroarylthio group is the same as the heteroaryl group described in the coordination site coordinated by the above anion, and the preferred range is also the same. The carbon number of the fluorenyl group is preferably from 2 to 12, more preferably from 2 to 9. R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and a hydrogen atom or an alkyl group is more preferable, and an alkyl group is particularly preferable. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. By setting a substituent on the N atom, that is, R ¹ as an alkyl group, the ligand contribution rate to the molecular orbital of the copper complex is increased, the molar absorption coefficient at the maximum absorption wavelength is increased, and the near infrared ray is obtained. The tendency to increase the shielding and visible transparency. In particular, an alkyl group is preferred from the viewpoint of balance between heat resistance, near-infrared shielding properties, and visible transparency.

When a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair are contained in one molecule of the ligand, a coordination site coordinated by an anion and an unshared electron are bonded The number of atoms of the coordination atom to be coordinated is preferably 1 to 6, and more preferably 1 to 3. By adopting such a configuration, the structure of the copper complex is more easily deformed, so that the color value can be further improved, the visible transparency can be improved, and the molar absorption coefficient can be easily increased. The type of the atomic site to which the anion is coordinated and the atom of the coordinating atom which is not shared by the electron pair may be one or two or more. A carbon atom or a nitrogen atom is preferred.

When there are two or more coordinating atoms coordinated by an unshared electron pair in one molecule of the ligand, the number of coordinating atoms coordinated by the unshared electron pair may be three or more, and has 2 to 2 Five are preferred, and four are preferred. It is preferable that the number of atoms of the coordination atoms to be coordinated by the unshared electron pair is 1 to 6, and more preferably 1 to 3, further preferably 2 to 3, and particularly preferably 3. With such a configuration, the structure of the copper complex is more easily deformed, so that the color value can be further improved. The atom of each of the coordinating atoms which are coordinated by the unshared electron pair may be one or two or more. It is preferred to link the atomic carbon atoms of the coordinating atoms coordinated by the unshared electron pair.

In the present invention, a compound having at least two coordination sites (also referred to as a polydentate ligand) is preferred. The ligand system is preferably at least 3 coordination sites, more preferably 3 to 5, and particularly preferably 4 to 5. The multidentate ligand acts as a chelate ligand relative to the copper component. That is, it is considered that by at least two coordination sites of the multidentate ligand, chelate coordination with copper, the structure of the copper complex is deformed and excellent visible transparency is obtained, thereby improving the light absorption capability of infrared rays. And the color value is also improved. Thereby, even if the near-infrared cut filter is used for a long period of time, the characteristics are not impaired, and the camera module can be stably manufactured. Further, the polydentate ligand is preferably a compound containing a coordinating atom coordinated by an unshared electron pair, and a compound having a nitrogen atom as a coordinating atom coordinated by an unshared electron pair is more preferable. As the coordinating atom coordinated by the unshared electron pair, a compound containing a nitrogen atom and an alkyl group (preferably a methyl group) is substituted with the nitrogen atom is more preferable.

The polydentate ligand includes a compound having one or more coordination sites coordinated by an anion, one or more compounds having a coordination atom coordinated by an unshared electron pair, and two or more unshared electron pairs. A compound in which a coordinating coordinating atom is carried out, a compound containing two coordination sites coordinated by an anion, and the like. These compounds can be used alone or in combination of two or more. Further, a compound having only one coordination site can also be used as the compound to be a ligand.

The polydentate ligand is preferably a compound represented by the following formulas (IV-1) to (IV-14). For example, when the ligand is a compound having four coordination sites, a compound represented by the following formulas (IV-3), (IV-6), (IV-7), (IV-12) is preferred. The compound represented by (IV-12) is more preferable from the viewpoint of easily forming a stable 5-coordinate complex which is more strongly coordinated in the metal center and has high heat resistance. Further, for example, when the ligand is a compound having five coordination sites, the following formulae (IV-4), (IV-8) to (IV-11), (IV-13), (IV-14) The compound represented by the above is preferable, and it is considered to be (IV-9) to (IV-10) from the reason that it is easy to form a stable 5-coordinate complex which is more strongly coordinated in the center of the metal and has high heat resistance. The compound represented by (IV-13) or (IV-14) is more preferable, and the compound represented by (IV-13) is particularly preferable. [Chemical Formula 6]

In the formulae (IV-1) to (IV-14), X ¹ to X ⁵⁹ each independently represent a coordination site, and L ¹ to L ²⁵ each independently represent a single bond or a divalent linking group, and L ²⁶ to L ³² respectively The trivalent linking group is independently represented, and L ³³ to L ³⁴ each independently represent a tetravalent linking group. X ¹ to X ⁴² each independently represent a group including a ring containing a coordinating atom coordinated by an unshared electron pair, and at least one selected from the group (AN-1) or the group (UE-1). It is better. X ⁴³ to X ⁵⁶ each independently represent a group including a ring containing a coordinating atom coordinated by an unshared electron pair, and at least one selected from the group (AN-2) or the group (UE-2). It is better. It is preferable that X ⁵⁷ to X ⁵⁹ independently represent at least one selected from the above group (UE-3). L ¹ to L ²⁵ each independently represent a single bond or a divalent linking group. As the divalent linking group, an alkyl group having 1 to 12 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -SO-, -O-, -SO ₂ - or a group including a combination thereof is preferred. More preferably, the alkyl group having 1 to 3 carbon atoms, phenylene group, -SO ₂ - or a combination comprising the same is preferred. L ²⁶ to L ³² each independently represent a trivalent linking group. The trivalent linking group may be a group obtained by removing one hydrogen atom from the above divalent linking group. L ³³ to L ³⁴ each independently represent a tetravalent linking group. The tetravalent linking group may be a group obtained by removing two hydrogen atoms from the above divalent linking group. Here, the group (AN-1) ~ in the (AN-2) and the R group (UE-1) ~ (UE -3) R 1, R also can be between one another, each other R ¹ Alternatively, R and R ¹ are linked to form a ring. For example, as a specific example of the formula (IV-2), the following compound (IV-2A) can be mentioned. ^{Further, X 3, X 4, X} 43 is a group of the following, L ^2, L ³ is methylene, R ¹ is methyl, R ¹ 'can also be performed by connecting each other to form a ring, thus becoming (IV-2B) and (IV-2C). [Chemical Formula 7]

Specific examples of the compound forming the ligand include a compound which is a preferred specific example of the polydentate ligand described later and a salt of the compound. Examples of the atom constituting the salt include a metal atom and tetrabutylammonium. As the metal atom, an alkali metal atom or an alkaline earth metal atom is more preferable. Examples of the alkali metal atom include sodium and potassium. Examples of the alkaline earth metal atom include calcium and magnesium. In addition, the compounds described in paragraphs 0021 to 0043 of JP-A-2014-41318, paragraphs 0021 to 0039 of JP-A-2015-43063, and paragraph 0049 of JP-A-2016-006476, These contents are incorporated in this specification.

Examples of the copper complex compound include the following (1) to (5), and (2) to (5) are more preferable, and (3) to (5) are further preferred. (4) Or (5) is further preferred. (1) A copper complex compound having one or two compounds having two coordination sites as a ligand. (2) A copper complex compound having a compound having three coordination sites as a ligand. (3) A copper complex compound having a compound having three coordination sites and a compound having two coordination sites as a ligand. (4) A copper complex compound having a compound having four coordination sites as a ligand. (5) A copper complex compound having a compound having five coordination sites as a ligand.

In the aspect of the above (1), the compound having two coordination sites is a compound having two coordination atoms coordinated by an unshared electron pair or a coordination site having an anion coordination Compounds which do not share an electron pair to coordinate a coordinating atom are preferred. Further, when two compounds having two coordination sites are provided as a ligand, the compounds of the ligand may be the same or different. Further, in the aspect of (1), the copper complex can further have a single-dentate ligand. The number of single-dentate ligands can be set to 0, and can be set to 1 to 3. As the type of the monodentate ligand, any one of the single-dentate ligands coordinated by the anion and the single-dentate ligand coordinated by the unshared electron pair is also preferable. When a compound having two coordination sites is a compound having two coordinating atoms coordinated by an unshared electron pair, a single-dentate ligand coordinated by an anion is considered from the viewpoint of strong coordination force. For better. When a compound having two coordination sites is a compound having a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair, the reason why the copper complex does not have a charge as a whole is considered. It is better to use a single tooth ligand that is not shared by the pair of electrons.

In the aspect of the above (2), the compound having three coordination sites is preferably a compound having a coordinating atom coordinated by an unshared electron pair, and three are coordinated by an unshared electron pair. The compound of the coordinating atom is further preferred. Further, in the aspect of (2), the copper complex can further have a single tooth ligand. The number of single tooth ligands can be set to zero. Further, it may be one or more, preferably 1 to 3 or more, more preferably 1 to 2, and still more preferably 2 or more. As the type of the single-dentate ligand, any one of the single-dentate ligand coordinated by an anion and the single-dentate ligand coordinated by an unshared electron pair is also preferable, for the above reasons, It is more preferred that the anion is coordinated with a single tooth ligand.

In the aspect of the above (3), the compound having three coordination sites is preferably a compound having a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair. Further, it is further preferred that two coordination sites coordinated by an anion and one complex atom coordinated by an unshared electron pair are further preferred. Further, it is particularly preferable that the two coordination sites coordinated by anions are different. Further, a compound having two coordination sites is preferably a compound having a coordinating atom coordinated by an unshared electron pair, and a compound having two coordinating atoms coordinated by an unshared electron pair is further Preferably. Wherein the compound having three coordination sites is a compound having two coordination sites coordinated by an anion and one coordination atom coordinated by an unshared electron pair, and a compound having two coordination sites It is particularly preferred to be a combination of two compounds having a coordinating atom coordinated by an unshared electron pair. Further, in the aspect of (3), the copper complex can further have a single-dentate ligand. The number of single-dentate ligands can be set to 0, and it can be set to one or more. 0 is better.

In the aspect of the above (4), the compound having four coordination sites is preferably a compound having a coordinating atom coordinated by an unshared electron pair, and two or more of the compounds are coordinated by an unshared electron pair. A compound having a coordinating atom at a position is more preferable, and a compound having four coordinating atoms coordinated by an unshared electron pair is further preferable. Further, in the aspect of (4), the copper complex can further have a single-dentate ligand. The number of the single-dentate ligands can be set to 0, and can be one or more, or two or more. One is preferred. As the type of the monodentate ligand, any one of the single-dentate ligands coordinated by the anion and the single-dentate ligand coordinated by the unshared electron pair is also preferable.

In the aspect of the above (5), the compound having five coordination sites is preferably a compound having a coordinating atom coordinated by an unshared electron pair, and two or more of the compounds are coordinated by an unshared electron pair. A compound having a coordinating atom at a position is more preferable, and a compound having five coordinating atoms coordinated by an unshared electron pair is further preferable. Further, in the aspect of (5), the copper complex can further have a single-dentate ligand. The number of single-dentate ligands can be set to 0, and it can be set to one or more. It is preferred that the number of single tooth ligands is zero.

The polydentate ligand may be a compound having two or more coordination sites or a compound shown below, among the compounds described in the specific examples of the above ligand. [Chemical Formula 8] [Chemical Formula 9]

[Phosphate Copper Complex] In the present invention, a copper phosphate complex compound can also be used as the copper compound. The copper phosphate complex is a compound in which copper is used as a central metal and a phosphate compound is used as a ligand. The phosphate compound which forms the ligand of the copper phosphate complex is preferably a compound represented by the following formula (L-100) or a salt thereof. (HO) _n -P(=O)-(OR ¹ ) _3-n (L-100) wherein R ¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a carbon number An aralkyl group of 7 to 18 or an alkenyl group having 2 to 18 carbon atoms, or -OR ¹ represents a polyoxyalkyl group having 4 to 100 carbon atoms or a (meth) acryloxyalkyl group having 4 to 100 carbon atoms or A (meth) propylene fluorene polyoxyalkyl group having 4 to 100 carbon atoms, and n represents 1 or 2. When n is 1, R ² may be the same or different. Specific examples of the phosphate compound include the above ligand. Further, the descriptions of paragraphs 0022 to 0044 of JP-A-2014-41318 can be referred to, and the contents are incorporated in the present specification.

[Copper Sulfate Complex] In the present invention, a copper sulfonate complex can also be used as the copper complex. The copper sulfonate complex is a group in which copper is used as a central metal and a sulfonic acid compound is used as a ligand. The sulfonic acid compound which forms the ligand of the copper sulfonate complex is preferably a compound represented by the following formula (L-200) or a salt thereof. R ² -SO ₂ -OH formula (L-200)

In the formula, R ² represents a monovalent organic group. The monovalent organic group may, for example, be an alkyl group, an aryl group or a heteroaryl group. The alkyl group, the aryl group, and the heteroaryl group may be unsubstituted or may have a substituent. Specific examples of the sulfonic acid compound include the above ligands. Further, the descriptions of paragraphs 0021 to 0039 of JP-A-2015-43063 can be referred to, and the contents are incorporated in the present specification.

In the present invention, as the copper compound, a copper-containing polymer having a copper complex portion in a polymer side chain can be used.

Examples of the copper complex portion include copper and a site (coordination site) coordinated to copper. The site to be coordinated with copper may be a site that is coordinated by an anion or an unshared electron pair. Further, the copper complex portion is preferably a portion having a 4-dental coordination or a 5-dental coordination with respect to copper. The details of the coordination site are described by the above-described low molecular type copper compound, and the preferred range is also the same.

The copper-containing polymer may, for example, be a polymer containing a coordination site (also referred to as a polymer (B1)), a polymer obtained by reacting with a copper component, or a polymerization having a reactive site in a polymer side chain. The polymer (hereinafter, also referred to as polymer (B2)), a polymer obtained by reacting a reactive portion of the polymer (B2) with a copper complex having a reactive functional group. The weight average molecular weight of the copper-containing polymer is preferably 2,000 or more, more preferably from 2,000 to 2,000,000, still more preferably from 6,000 to 200,000.

The copper-containing polymer may contain other repeating units in addition to the repeating unit having a copper complex moiety. Examples of the other repeating unit include a repeating unit having a crosslinkable group.

The content of the copper compound is preferably from 5 to 90% by mass based on the total solid content of the resin composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less. The copper compound can be used alone or in combination of two or more. It is preferred to use two or more kinds of copper complexes. When two or more kinds of copper compounds are used in combination, the total amount is preferably in the above range.

The resin composition contains a resin. The type of the resin is not particularly limited as long as it can be used for an optical material. The resin is preferably a resin having high transparency. Specific examples thereof include polyolefin resins such as polyethylene, polypropylene, carboxylated polyolefin, chlorinated polyolefin, and cycloolefin polymer; polystyrene resin; (meth) acrylate resin; and (meth) propylene. (meth)acrylic resin such as guanamine resin; vinyl acetate resin; vinyl halide resin; polyvinyl alcohol resin; polyamide resin; polyurethane resin; polyethylene terephthalate (PET) or polyarylate (PAR) Polyester resin; polycarbonate resin; epoxy resin; poly-m-butenylene imide resin; polyurea resin; polyvinyl acetal resin such as polyvinyl butyral resin. Among them, a (meth)acrylic resin, a polyurethane resin, a polyester resin, a polysuccinimide resin, a polyurea resin are preferred, and a (meth)acrylic resin, a polyurethane resin, and a polyester resin are further preferred. . Further, a sol-gel cured product of a compound having an alkoxyfluorenyl group as a resin is also preferred. The compound having an alkoxyfluorenyl group is exemplified as a crosslinkable compound which will be described later. The weight average molecular weight of the resin is preferably from 1,000 to 300,000. The lower limit is preferably 2,000 or more, more preferably 3,000 or more, and most preferably 5,000 or more. The upper limit is preferably 100,000 or less, and more preferably 50,000 or less. The number average molecular weight of the resin is preferably from 500 to 150,000. The lower limit is preferably 1000 or more, and more preferably 2,000 or more. The upper limit is preferably 200,000 or less, and more preferably 100,000 or less.

The resin is preferably at least one type of resin having a repeating unit represented by the following formulas (A1-1) to (A1-7). [Chemical Formula 10] In the formula, R ¹ represents a hydrogen atom or an alkyl group, and L ¹ to L ⁴ each independently represent a single bond or a divalent linking group, and R ¹⁰ to R ¹³ each independently represent an alkyl group or an aryl group. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a substituent.

The alkyl group represented by R ¹ has a carbon number of from 1 to 5, more preferably from 1 to 3, and particularly preferably 1 is preferred. R ¹ is a hydrogen atom or a methyl group is preferred.

Examples of the divalent linking group represented by L ¹ to L ⁴ include an alkyl group, an aryl group, -O-, -S-, -SO-, -CO-, -COO-, -OCO-, - SO ₂ -, -NR ^a - (R ^a represents a hydrogen atom or an alkyl group) or a group including a combination thereof. The carbon number of the alkylene group is preferably from 1 to 30, more preferably from 1 to 15, and further preferably from 1 to 10. The alkylene group may have a substituent, but unsubstituted is preferred. The alkylene group may be any of a straight chain, a branch, and a ring. Further, the cyclic alkyl group may be either a single ring or a polycyclic ring. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 14, and further preferably from 6 to 10.

The alkyl group represented by R ¹⁰ to R ¹³ may be any of a straight chain, a branch or a ring. The alkyl group may have a substituent or may be unsubstituted. The alkyl group has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aryl group represented by R ¹⁰ to R ¹³ preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 carbon atoms. The R ¹⁰ is a linear or branched alkyl or aryl group, and a linear or branched alkyl group is more preferred. R ¹¹ and R ¹² are each independently a linear or branched alkyl group, and a linear alkyl group is more preferred. A linear or branched alkyl or aryl group of R ¹³ is preferred.

The substituent represented by R ¹⁴ and R ¹⁵ may, for example, be a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group or an aryloxy group. Heteroaryloxy, alkylthio, arylthio, heteroarylthio, -NR ^a1 R ^a2 , -COR ^a3 , -COOR ^a4 , -OCOR ^a5 , -NHCOR ^a6 , -CONR ^a7 R ^a8 , -NHCONR ^a9 R ^A10 , -NHCOOR ^a11 , -SO ₂ R ^a12 , -SO ₂ OR ^a13 , -NHSO ₂ R ^a14 or -SO ₂ NR ^a15 R ^a16 . R ^a1 to R ^a16 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. Among them, at least one of R ¹⁴ and R ¹⁵ represents a cyano group or -COOR ^a4 is preferred. R ^a4 represents a hydrogen atom, an alkyl group or an aryl group.

As a commercial item of the resin which has the repeating unit represented by Formula (A1-7), ARTON F4520 (made by JSR Corporation) etc. are mentioned. In addition, the details of the resin having the repeating unit represented by the formula (A1-7) can be referred to in paragraphs 0053 to 0,075 and 0127 to 0130 of JP-A-2011-100084, and the contents are incorporated herein. In the manual.

As the resin, a resin having a repeating unit represented by the formula (A1-4) is preferred, and a repeating unit represented by the formula (A1-1) and a repeating unit represented by the formula (A1-4) are used. For better. According to this aspect, the thermal shock resistance of the resin film tends to be improved. Further, the compatibility of the copper complex with the resin is improved, and a resin film having a small amount of precipitates or the like is easily obtained.

It is also preferred that the resin has a crosslinkable group. The crosslinkable group is preferably a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group or an alkoxyfluorenyl group, a group having an ethylenically unsaturated bond, a cyclic ether group, and an alkoxy group. The fluorenyl group is more preferably a cyclic ether group or an alkoxy fluorenyl group, and an alkoxy fluorenyl group is particularly preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. Examples of the cyclic ether group include an epoxy group (oxiranyl group), an oxetanyl group, and an alicyclic epoxy group. The alkoxyfluorenyl group may, for example, be a monoalkoxyfluorenyl group, a dialkoxyfluorenyl group or a trialkoxyfluorenyl group.

In the resin having a crosslinkable group, the crosslinking base of the resin is preferably from 0.5 to 4 mmol/g. The lower limit is preferably 0.6 mmol/g or more, more preferably 0.8 mmol/g or more, and still more preferably 1 mmol/g or more. The upper limit is preferably 3.5 mmol/g or less, more preferably 3 mmol/g or less, and still more preferably 2 mmol/g or less. Further, the crosslinking basic value of the resin is the equivalent of the crosslinking group contained in 1 g of the resin. The crosslinking base value of the resin can be measured by a method such as titration.

When the crosslinkable group of the resin is an alkoxyfluorenyl group, the Si value of the resin is preferably 0.5 to 4 mmol/g. The lower limit is preferably 0.6 mmol/g or more, more preferably 0.8 mmol/g or more, and still more preferably 1 mmol/g or more. The upper limit is preferably 3.5 mmol/g or less, more preferably 3 mmol/g or less, and still more preferably 2 mmol/g or less. Further, the Si value of the resin is the equivalent of the alkoxyfluorenyl group contained in 1 g of the resin. The Si value of the resin can be measured by a method such as titration.

As the resin having a crosslinkable group, a resin containing a repeating unit having a crosslinkable group is preferable, and a repeating unit represented by the formula (A1-1) and/or the formula (A1-4) and having a cross-linking are contained. The resin of the repeating unit of the group is preferred.

Examples of the repeating unit having a crosslinkable group include a repeating unit represented by the following formulas (A2-1) to (A2-4), and are represented by the formulas (A2-1) to (A2-3). A repeating unit is preferred. [Chemical Formula 11]

R ² represents a hydrogen atom or an alkyl group. The alkyl group has preferably 1 to 5 carbon atoms, more preferably 1 to 3, and 1 is particularly preferred. R ² is a hydrogen atom or a methyl group is preferred.

L ⁵¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent linking group described in L ¹ to L ⁴ of the above formulae (A1-1) to (A1-7). It is preferred that L ⁵¹ is an alkyl group or a group in which an alkyl group is bonded to -O-. The number of atoms constituting the chain of L ⁵¹ is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. The upper limit can be set to 200 or less, for example.

P ¹ represents a crosslinkable group. Examples of the crosslinkable group include a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group, an alkoxyfluorenyl group, a group having an ethylenically unsaturated bond, a cyclic ether group, and the like. The alkoxy fluorenyl group is preferred, the cyclic ether group and the alkoxy fluorenyl group are more preferred, and the alkoxy fluorenyl group is further preferred. The details of the group having an ethylenically unsaturated bond, a cyclic ether group, and an alkoxyfluorenyl group are as described above. The alkoxy group in the alkoxyfluorenyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

When the resin is a resin containing a repeating unit having a crosslinkable group, the resin preferably contains 5 to 100 mol% of a repeating unit having a crosslinkable group in all repeating units of the resin. The lower limit is preferably 6 mol% or more, more preferably 8 mol% or more, and still more preferably 10 mol% or more. The upper limit is preferably 95% by mole or less, more preferably 80% by mole or less, and still more preferably 60% by mole or less. According to this aspect, it is easy to form a resin layer excellent in mechanical properties.

The resin contains other repeating units in addition to the above repeating unit. For the components constituting the other repeating units, the descriptions of paragraphs 0068 to 0075 of the Japanese Patent Application Laid-Open No. 2010-106268 (paragraphs 0112 to 0118 of the specification of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to. The content is incorporated in this specification.

Specific examples of the resin include resins having the structures shown below. [Chemical Formula 12]

The content of the resin is preferably from 10 to 90% by mass based on the total solid content of the resin composition. The lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. Further, the content of the resin having a crosslinkable group in the total amount of the resin is preferably from 5 to 100% by mass, more preferably from 8 to 100% by mass, even more preferably from 10 to 100% by mass. The resin may be used alone or in combination of two or more. When it is two or more types, it is preferable that the total amount is in the above range.

The resin composition preferably contains a compound having a crosslinkable group (hereinafter also referred to as a crosslinking agent). Examples of the type of the crosslinkable group include a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group, an alkoxyfluorenyl group, a group having an ethylenically unsaturated bond, and a cyclic ether. The alkoxy group is preferably a cyclic ether group or an alkoxy group, and an alkoxy group is further preferred. The details of the group having an ethylenically unsaturated bond, a cyclic ether group, and an alkoxyfluorenyl group include the groups described in the resin having a crosslinkable group. As the alkoxyfluorenyl group, a dialkoxyfluorenyl group and a trialkoxyfluorenyl group are preferred. Further, the alkoxy group in the alkoxyfluorenyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

The molecular weight of the crosslinking agent is preferably from 100 to 3,000. The upper limit is preferably 2,000 or less, and more preferably 1,500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. A crosslinking agent-based monomer is preferred.

The crosslinking base of the crosslinking agent is preferably from 3 to 20 mmol/g. The lower limit is preferably 3.5 mmol/g or more, more preferably 4 mmol/g or more, and still more preferably 5 mmol/g or more. The upper limit is preferably 19 mmol/g or less, more preferably 17 mmol/g or less, and still more preferably 15 mmol/g or less. Further, the crosslinking base of the crosslinking agent is the equivalent of the crosslinking group contained in the crosslinking agent 1g. The crosslinking base value of the crosslinking agent can be measured by a method such as titration.

The crosslinking agent is preferably a compound having 2 to 5 crosslinkable groups in one molecule. The upper limit of the crosslinkable group is preferably 4 or less, and more preferably 3 or less.

The crosslinking agent is preferably a compound containing 2 to 5 or more Si atoms in one molecule. The upper limit of the Si atom is preferably 4 or less, and more preferably 3 or less. The number of Si atoms in the crosslinking agent is preferably two. Further, it is preferable that two Si atoms in the crosslinking agent are bonded via 2 to 10 atoms, and it is preferably bonded via 3 to 9 atoms, and bonded to each other via 4 to 8 atoms. Further preferred. Here, in the case where two Si atoms are bonded via 2 to 10 atoms, the number of atoms constituting a bond connecting Si atoms to each other is 2 to 10. For example, in the case of the following compounds, two Si atoms are bonded via six atoms. [Chemical Formula 13]

Further, two Si atoms are preferably bonded via an alkylene group having 2 to 10 carbon atoms, and are preferably bonded via an alkyl group having 3 to 9 carbon atoms, and are bonded via an alkyl group having 4 to 8 carbon atoms. The bonding is further preferred.

Further, the crosslinking agent is preferably a compound containing 2 to 5 or more alkoxyfluorenyl groups per molecule. The upper limit of the alkoxythio group is preferably 4 or less, more preferably 3 or less. The number of alkoxythio groups is preferably two. The alkoxyindenyldialkyloxyindenyl or trialkoxyindenyl group is preferred, and the trialkoxyindenyl group is more preferred. Further, the two alkoxyfluorenyl groups of the crosslinking agent are preferably bonded via 2 to 10 atoms, and are preferably bonded via 3 to 9 atoms, and are 4 to 8 atoms apart. The bonding is further preferred. Further, the two alkoxyfluorenyl groups are preferably bonded via an alkylene group having 2 to 10 carbon atoms, and more preferably bonded via an alkyl group having 3 to 9 carbon atoms, and a carbon number of 4 to 8 is bonded. It is further preferred to form an alkyl group and bond.

Further, when the crosslinking agent is a compound having an alkoxyfluorenyl group, the Si value of the crosslinking agent is preferably from 3 to 20 mmol/g. The lower limit of the Si value is preferably 3.5 mmol/g or more, more preferably 4 mmol/g or more, and still more preferably 5 mmol/g or more. The upper limit of the Si value is preferably 19 mmol/g or less, more preferably 17 mmol/g or less, and still more preferably 15 mmol/g or less. Further, the Si value of the crosslinking agent is the equivalent of the crosslinking group contained in the crosslinking agent 1g. The Si value of the crosslinking agent can be measured by a method such as titration.

Specific examples of the compound having an alkoxyfluorenyl group include tetraethoxydecane, methyltrimethoxydecane, dimethyldimethoxydecane, phenyltrimethoxydecane, and methyltriethoxygen. Base decane, dimethyl diethoxy decane, phenyl triethoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, hexyl trimethoxy decane, hexyl triethoxy decane, Octyltriethoxydecane, decyltrimethoxydecane, 1,6-bis(trimethoxydecyl)hexane, trifluoropropyltrimethoxydecane, hexamethyl disilazane , vinyl trimethoxy decane, vinyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, 3-glycidoxy propyl methyl dimethoxy decane , 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, p-styrenetrimethoxy Decane, 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3- Acryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-2-(amine Ethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-amine Propyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N- Hydrochloride of (vinylbenzyl)-2-amineethyl-3-aminopropyltrimethoxydecane, tris-(trimethoxymercaptopropyl)isocyanurate, 3-ureidopropyl Ethoxy decane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxymethylpropyl)tetrasulfide, 3-isocyanatepropyltriethyl Oxydecane, etc. Further, the following compounds can also be used. [Chemical Formula 14]

As a commercial item, KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033 manufactured by Shin-Etsu Chemical Co., Ltd. , KBM-3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM -303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603 , KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053 , X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S , KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213 , X-40-2308, X-40-9238, etc.

In the present invention, as the crosslinking agent, a compound containing a group having an ethylenically unsaturated bond can be used. As the compound containing a group having an ethylenically unsaturated bond, a (meth) acrylate compound is preferable, and a 3- to 15-functional (meth) acrylate compound is more preferable, and a 3- to 6-functional (meth) group is preferable. An acrylate compound is further preferred. An example of a compound containing a group having an ethylenically unsaturated bond can be referred to in paragraphs 0033 to 0034 of JP-A-2013-253224, which is incorporated herein by reference. As a specific example, a vinyloxy modified neopentyltetraol tetraacrylate (commercially available as NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (available from the city) The product sold is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), two new Pentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA) ; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (meth)acrylonyl groups via ethylene glycol residues or propylene glycol residue bonds The structure of the junction is preferred. Also, their oligomer types can be used. In addition, the paragraph number 0477 of the specification of the Japanese Patent Application Laid-Open No. 2012-208494 (paragraph 0585 of the specification of the corresponding US Patent Application Publication No. 2012/0235099) The contents of this document are incorporated in this specification. Further, as a specific example of the compound containing a group having an ethylenically unsaturated bond, it is also possible to use a diglycerin EO (ethylene oxide) modified (meth) acrylate (commercial product is M-460; by TOAGOSEI (manufactured by CO., LTD.), neopentyl alcohol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd. Manufacturing, KAYARAD HDDA). Also, their oligomer types can be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) or the like can be given.

The compound containing a group having an ethylenically unsaturated bond may further have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. As a commercial item, the ARONIX series (for example, M-305, M-510, M-520) manufactured by TOAGOSEI CO., LTD., etc. are mentioned, for example.

For compounds containing a group having an ethylenically unsaturated bond, a compound having a caprolactone structure is also preferred. As a compound having a caprolactone structure, the description of paragraphs 0044 to 0045 of JP-A-2013-253224 can be referred to, and the content is incorporated in the present specification. As a commercially available product, for example, SR-494 having four ethylene-functional chains of four ethyleneoxy chains manufactured by Sartomer Company, Inc., and Nippon Kayaku Co., Ltd., having six pentene oxides, may be mentioned. DPCA-60 of a hexylene acrylate having a pentyleneoxy chain, TPA-330 having a trifunctional acrylate of three isobutyleneoxy chains, and the like.

In the present invention, a compound having a cyclic ether group can also be used as the crosslinking agent. The cyclic ether group is preferably an epoxy group or an oxetanyl group, and an epoxy group is preferred. Examples of the commercially available product of the compound having a cyclic ether group include EHPE 3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), and the like. In addition, as a compound having a cyclic ether group, paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and JP-A-2014-089408 can be used. The compound described in Paragraph No. 0085 to 0092 of the Gazette. These contents are incorporated in this specification.

When the resin composition contains a crosslinking agent, the resin composition preferably contains 3 to 30 parts by mass of the crosslinking agent per 100 parts by mass of the resin, more preferably 5 to 20 parts by mass, even more preferably 7 to 15 parts by mass. Further preferred. Further, the resin composition is preferably contained in an amount of 3 to 30 parts by mass based on 100 parts by mass of the resin having a crosslinkable group, more preferably 5 to 20 parts by mass, even more preferably 7 to 15 parts by mass. good. The crosslinking agent may be used alone or in combination of two or more. When it is two or more types, it is preferable that the total amount is in the above range.

The resin composition can contain a polymerization initiator. The polymerization initiator is not particularly limited as long as it has the ability to initiate crosslinking of a resin having a crosslinkable group or a crosslinking agent by either or both of light and heat. When crosslinking is carried out by light, a polymerization initiator which is photosensitive to light from the ultraviolet region to the visible region is preferable. Further, when crosslinking is carried out by heat, a polymerization initiator which is decomposed at 150 to 250 ° C is preferred.

As the polymerization initiator, a compound having an aromatic group is preferred. For example, a mercaptophosphine compound, an acetophenone compound, an α-hydroxyketone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound, and a 9-oxosulfanyl Yamaguchi can be mentioned. Thioxanthone compound, hydrazine compound, hexaarylbiimidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazo compound, hydrazine compound, hydrazine compound, azinium compound, metallocene An onium salt compound such as a compound, an organic boron salt compound, a diterpene compound, a thiol compound, or the like. The polymerization initiator can be referred to the description of paragraphs 0217 to 0228 of JP-A-2013-253224, which is incorporated herein by reference.

The polymerization initiator is preferably an anthracene compound, an α-hydroxyketone compound, an α-aminoketone compound, and a mercaptophosphine compound. As the ruthenium compound, a ruthenium compound or the like exemplified as a radical scavenger described later can also be used.

The content of the polymerization initiator is preferably 0.01 to 30% by mass based on the total solid content of the resin composition. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. The polymerization initiator may be used alone or in combination of two or more. When it is two or more types, it is preferable that the total amount is in the above range.

It is preferred that the resin composition contains a solvent. The solvent is not particularly limited as long as it can dissolve or disperse each component uniformly, and can be appropriately selected depending on the purpose. For example, water or an organic solvent can be used. Examples of the organic solvent include alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, and dimethylformamide, dimethylacetamide, dimethylammonium, and a ring. Ding Wei and so on. These may be used alone or in combination of two or more. Specific examples of the alcohols, the aromatic hydrocarbons, and the halogenated hydrocarbons include the solvents described in paragraph 0136 of JP-A-2012-194534, and the contents thereof are incorporated herein by reference. Specific examples of the esters, the ketones, and the ethers include the solvents described in paragraph 0497 of the Japanese Patent Application Laid-Open No. 2012-208494 (paragraph No. 0609 of the specification of the corresponding US Patent Application Publication No. 2012/0235099). . Further, as the solvent, an ester solvent substituted with a cyclic alkyl group or a ketone solvent substituted with a cyclic alkyl group can also be used. Specific examples of the solvent include acetic acid-n-amyl ester, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, and ethylene. Alcohol monobutyl ether acetate, 1-methoxy-2-propanol, cyclohexyl acetate, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone , butyl acetate, ethyl lactate, propylene glycol monomethyl ether, 3-methoxybutyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin , 3-methoxybutanol, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, cyclohexanol acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol Methyl-n-propyl ether, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, and the like. These may be used alone or in combination of two or more.

Further, as the solvent, a solvent having a boiling point of 150 ° C or less (preferably, a boiling point of 30 to 145 ° C, more preferably 50 to 140 ° C) (hereinafter also referred to as a low boiling point solvent) may be used alone or as a single solvent. A solvent having a boiling point of 150 ° C or higher (preferably, a boiling point of 155 to 300 ° C, more preferably 160 to 250 ° C) (hereinafter also referred to as a high boiling point solvent) may be used in combination with a low boiling point solvent and a high boiling point solvent. By using a high boiling point solvent, the evaporation rate of the solvent in the resin composition becomes slow, and it is easy to stabilize the drying and suppress the precipitation of the residue. In particular, when the solid content concentration of the resin composition is low (for example, when the solid content concentration is 35% by mass or less), a high boiling point solvent and a low boiling point solvent are used together from the viewpoint of drying stabilization and precipitation precipitation. It is preferred as a solvent. Further, when a high boiling point solvent and a low boiling point solvent are used in combination, the difference between the boiling point of the high boiling point solvent and the boiling point of the low boiling point solvent is preferably from 20 to 250 ° C, more preferably from 50 to 150 ° C. Further, the mass ratio of the high-boiling solvent to the low-boiling solvent is not particularly limited, and the high-boiling solvent: low-boiling solvent = [99:1] to [55:45] is preferable, and [95:5] to [70:30]. ] is better. Examples of the high boiling point solvent include 3-methoxybutyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, and 3-methoxy Butanol, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, cyclohexanol acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol methyl-positive Alkyl ether, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, and the like. Examples of the low boiling point solvent include cyclopentanone, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether.

In the present invention, a solvent having a small metal content is preferably used, and the metal content of the solvent is, for example, 10 mass ppb (parts per billion) or less. A solvent having a mass ppt (parts per trillion) level, which is supplied, for example, by TOYO Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015), may also be used as needed.

Examples of the method for removing impurities such as metals from the solvent include distillation (such as molecular distillation or thin film distillation) or filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may also contain isomers (compounds of the same number of atoms and different structures). Further, the isomer may be contained alone or in combination of plural kinds.

The content of the solvent is preferably from 5 to 80% by mass based on the total solid content of the resin composition. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and even more preferably 55% by mass or more, and 60% by mass. The above is especially good. The upper limit is preferably 75 mass% or less, more preferably 70 mass% or less. By increasing the solid content concentration (total solid content) of the resin composition, a thick resin layer can be formed by one application. For example, by setting the total solid content of the resin composition to 50% by mass or more, a resin layer having a thickness of 5 to 40 μm can be formed by one application. In addition, when the total solid content of the resin composition is 80% by mass or less, the solubility of the components in the resin composition is good. The solvent may be used alone or in combination of two or more. When the amount is two or more, the total amount is preferably in the above range.

The resin composition may also contain a catalyst. For example, when a resin having a crosslinkable group such as an alkoxyfluorenyl group or a crosslinking agent is used, it is easy to obtain a crosslink of a crosslinkable group by containing a catalyst in a resin composition. A resin film excellent in mechanical properties, solvent resistance, heat resistance, and the like.

Examples of the catalyst include an organometallic catalyst, an acid catalyst, and an amine catalyst, and an organic metal catalyst is preferred. The organometallic-based catalyst contains at least one metal selected from the group consisting of Na, K, Ca, Mg, Ti, Zr, Al, Zn, Sn, and Bi, and is selected from the group consisting of oxides, sulfides, and halides. At least one of the group consisting of a carbonate, a carboxylate, a sulfonate, a phosphate, a nitrate, a sulfate, an alkoxide, a hydroxide, and a acetamidine complex which may have a substituent is preferred. Wherein at least one selected from the group consisting of a halide, a carboxylate, a nitrate, a sulfate, a hydroxide, and a acetamidine complex which may have a substituent is preferred; An acetone complex is further preferred. In particular, an acetamidineacetate complex of Al is preferred. Specific examples of the organometallic catalyst include tris(2,4-pentanedione)aluminum and the like.

When the resin composition contains a catalyst, the content of the catalyst is preferably 0.01 to 5% by mass based on the total solid content of the resin composition. The upper limit is preferably 3% by mass or less, and more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more.

The resin composition can also contain a radical scavenger. As the radical scavenger, an anthracene compound is mentioned. As a commercial product of a ruthenium compound, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF Corporation), TR-PBG-304 (manufactured by Changzhou Power Electronic New Material Co., Ltd.), ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION), ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in JP-A-2012-14052) Wait.

Further, as the ruthenium compound, a ruthenium compound having a fluorine atom can also be used. Specific examples of the ruthenium compound having a fluorine atom include the compound described in JP-A-2010-262028, and the compound 24 and compounds 36 to 40 described in JP-A-2014-500852, JP-A-2013 Compound (C-3) or the like described in JP-164471. This content is incorporated in this specification.

Further, as the ruthenium compound, a ruthenium compound having a nitro group can be used. It is also preferred that the ruthenium compound having a nitro group be a dimer. Specific examples of the ruthenium compound having a nitro group include those described in paragraphs 0031 to 0047 of JP-A-2013-114249 and paragraphs 0008 to 0102 and 0070 to 0079 of JP-A-2014-137466. The compound, ADEKA ARKLSNCI-831 (manufactured by ADEKA CORPORATION), and the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4,223,071.

Further, as the ruthenium compound, a ruthenium compound having an anthracene ring can also be used. Specific examples of the ruthenium compound having an anthracene ring include the compounds described in JP-A-2014-137466. This content is incorporated in this specification.

Further, as the ruthenium compound, a ruthenium compound having a benzofuran skeleton can also be used. Specific examples include the compounds OE-01 to OE-75 described in WO 2015/036910.

The content of the radical scavenger is preferably 0.01 to 30% by mass based on the total solid content of the resin composition. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less.

The resin composition can also contain a surfactant. The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.0001 to 5% by mass based on the total solid content of the near-infrared absorbing composition. The lower limit is preferably 0.005 mass% or more, more preferably 0.01 mass% or more. The upper limit is preferably 2% by mass or less, more preferably 1% by mass or less. When the resin composition contains a surfactant, for example, when the resin composition is repeatedly applied to form a resin layer, the wettability of the resin composition can be improved.

As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a polyoxyn surfactant can be used, and a fluorine-based surfactant can be used. A polyoxo-based surfactant is preferred, and a fluorine-based surfactant is more preferred. The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. When the fluorine content in the fluorine-based surfactant is within the above range, it is effective in terms of uniformity of coating film thickness and liquid-saving property.

The surfactants described in, for example, paragraphs 0060 to 0064 of the Japanese Patent Publication No. 2014-41318 (corresponding to paragraphs 0060 to 0064 of International Publication No. 2014/17669, etc.), etc. The surfactants described in paragraphs 0117 to 0132 of JP-A-2011-132503, the contents of which are incorporated herein by reference. Examples of commercially available products of the fluorine-based surfactant include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (above, Manufactured by DIC Corporation, Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381 , SC-383, S393, KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA Solutions Inc.) and the like.

In addition, as the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group having a fluorine atom can be suitably used, and when heated, the functional group of the fluorine atom is partially cut off. The fluorine atom is volatilized. Examples of such a fluorine-based surfactant include the MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016 and Nikkei Industry News, February 23, 2016), such as MEGAFACE DS-21. And can use these.

As the fluorine-based surfactant, a block polymer can also be used. For example, the compound described in JP-A-2011-89090 can be mentioned. As the fluorine-based surfactant, a fluorine-containing polymer compound containing: a repeating unit derived from a (meth) acrylate compound having a fluorine atom; and The above (preferably 5 or more) repeating units of a (meth) acrylate compound of an alkoxy group (preferably a vinyloxy group, a propyleneoxy group). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention. [Chemical Formula 15] The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. Among the above compounds, the % indicating the ratio of the repeating unit is % by mass.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation. , RS-72-K, etc. As the fluorine-based surfactant, the compound described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

The nonionic surfactant activity described in JP-A No. 2012-208494, paragraph 0553 (paragraph 0679 of the specification of the corresponding US Patent Application Publication No. 2012/0235099) This content is incorporated in this specification. The cation-based surfactant described in JP-A No. 2012-208494, paragraph No. 0554 (paragraph 0680 of the specification of the corresponding US Patent Application Publication No. 2012/0235099), This content is incorporated in this specification. Examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.). For example, KF6001 (Shin-Etsu Chemical Co., Ltd.), and JP-A-2012-208494, Paragraph No. 0556 (corresponding U.S. Patent Application Publication No. 2012/) The polyfluorene-based surfactant described in Paragraph No. 0682) of the specification No. 0235099 is incorporated herein by reference.

The resin composition can contain a UV absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyl triazine compound, or the like can be used. Among them, the benzotriazole compound and the hydroxyphenyl triterpene compound are considered from the viewpoints of good compatibility with the copper compound, and further suitable copper compound and absorption wavelength, thereby maintaining excellent visible transparency and improving the shielding property of ultraviolet rays. It is better. For the details of the above, the descriptions of paragraphs 0033 to 0723 of JP-A-2012-208374, and paragraphs 0317 to 0334 of JP-A-2013-68814 are incorporated herein by reference. Commercial products of the benzotriazole compound include TINUVIN PS, TINUVIN 99-2, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, and TINUVIN 1130 (above, manufactured by BASF Corporation). Further, as the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by MIYOSHI OIL & FAT CO., LTD. can also be used. The content of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the resin composition.

The resin composition may further contain a dispersant, a sensitizer, a hardening accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, a adhesion promoter, and other auxiliary agents (for example, conductive particles, a filler, Defoamer, flame retardant, leveling agent, peeling accelerator, antioxidant, perfume, surface tension adjuster, chain transfer agent, etc.). For the above-mentioned components, the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of JP-A-2008-250074 can be referred to, and the contents are incorporated in the present specification. Further, examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. A phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. These may also be used in combination of 2 or more types. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. Particularly, a compound having a substituent at a site adjacent to the phenolic hydroxyl group (ortho) is preferred. As the above substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, and the like. Isoamyl, tertiary pentyl, hexyl, octyl, isooctyl, 2-ethylhexyl are more preferred. Further, a compound having an phenol group and a phosphite group (antioxidant) in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be suitably used. As the phosphorus-based antioxidant, it is exemplified to include three [2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3 , 2] dioxaphosphepine-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo) [d,f][1,3,2]dioxaphosphole-2-enyloxy]ethyl]amine and ethyl bisphosphite (2,4-di-tertiary butyl- At least one compound of the group of 6-methylphenyl). These can be easily obtained as commercially available products, and include ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO-80, ADKSTAB AO-330 (ADEKA CORPORATION), etc. The content of the antioxidant is preferably from 0.01 to 20% by mass, more preferably from 0.3 to 15% by mass, based on the total solid content of the resin composition. The antioxidant may be used alone or in combination of two or more. When it is two or more types, it is preferable that the total amount is in the above range.

When the resin film is formed by coating, the viscosity of the resin composition is preferably from 1 to 3,000 mPa·s. The lower limit is preferably 10 mPa·s or more, and more preferably 100 mPa·s or more. The upper limit is preferably 2000 mPa·s or less, and more preferably 1500 mPa·s or less.

The above resin composition can be prepared by mixing the components. In the preparation of the resin composition, the components constituting the resin composition may be uniformly blended, or the components may be dissolved and/or dispersed in a solvent and then blended one by one. Further, the order of input and the operating conditions at the time of blending are not particularly limited.

The storage container of the resin composition is not particularly limited, and a known storage container can be used. Further, as a storage container, it is preferable to use a multi-layer bottle or a resin having six layers of six kinds of resin to form a seven-layered bottle, in order to prevent impurities from being mixed into a material or a composition. As such a container, for example, a container described in JP-A-2015-123351 can be cited.

The resin layer containing a copper compound can be formed by applying the resin composition to a support such as a glass containing copper or an infrared absorbing pigment layer to form a resin composition layer, and drying the resin composition layer. . The film thickness can be appropriately selected within the above range depending on the purpose.

As a method of applying the resin composition, a known method can be used. For example, a dropping method (drop casting), a slit coating method, a spray coating method, a roll coating method, a spin coating method (spin coating method), a casting coating method, a slit spin coating method, and a pre-wetting method ( For example, the method described in JP-A-2009-145395); inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle discharge, and the like, discharge printing, flexographic printing, offset printing, and gravure printing. Various printing methods such as reverse lithography and metal mask printing; transfer methods using a mold or the like; nanoimprint method; blade coating method; bar coating method; applicator coating method Wait. The method of applying the inkjet is not particularly limited as long as it can eject the composition. For example, the "expandable, injectable inkjet-infinite possibilities seen in the patent" can be used, and is issued in February 2005. The method described in the patent publication shown in Sumibe Techno Research Co., Ltd. (especially pages 115 to 133), or JP-A-2003-262716, JP-A-2003-185831, and JP-A The method described in Japanese Laid-Open Patent Publication No. JP-A-2006-169325, and the like.

The drying conditions of the resin composition layer can be appropriately adjusted depending on the type and content of each component contained in the resin composition. For example, as the drying temperature, 40 to 160 ° C is preferred. The lower limit is preferably 60 ° C or higher, and more preferably 80 ° C or higher. The upper limit is preferably 140 ° C or less, more preferably 120 ° C or less. As the heating time, 1 to 600 minutes is preferred. The lower limit is preferably 10 minutes or more, more preferably 30 minutes or more. The upper limit is preferably 300 minutes or less, and more preferably 180 minutes or less. Further, a method may be employed in which the temperature is raised from a room temperature (for example, 25 ° C) to a predetermined drying temperature at a constant temperature increase rate, and then the temperature is maintained and dried. The temperature increase rate is preferably 0.5 to 10 ° C / min, more preferably 1.0 to 5 ° C / min.

In the method of forming the resin layer, other steps may also be included. The other steps are not particularly limited and can be appropriately selected depending on the purpose. For example, a hardening treatment step or the like can be given.

In the hardening treatment step, the method of curing the resin composition layer is not particularly limited, and can be appropriately selected depending on the purpose. For example, exposure treatment, heat treatment, and the like are mentioned, and from the viewpoint of easily obtaining a resin layer having excellent mechanical properties, heat treatment is preferred. Here, in the present invention, the "exposure" is used to include not only light of various wavelengths but also radiation such as electron beams and X-rays.

As the exposure treatment, it is preferred to irradiate the resin composition layer with radiation. As the radiation, ultraviolet rays such as an electron beam, KrF, ArF, g-ray, h-ray, or i-ray are preferable. Examples of the exposure method include step exposure, exposure using a high pressure mercury lamp, and the like. The exposure amount is preferably from 5 to 3,000 mJ/cm ² . The upper limit is preferably 2000 mJ/cm ² or less, more preferably 1000 mJ/cm ² or less. The lower limit is preferably 10 mJ/cm ² or more, and more preferably 50 mJ/cm ² or more. The exposure apparatus is not particularly limited, and can be appropriately selected depending on the purpose, and examples thereof include an ultraviolet exposure machine such as an ultrahigh pressure mercury lamp.

The heating temperature in the heat treatment is preferably 100 to 180 °C. The lower limit is preferably 120 ° C or more, more preferably 140 ° C or more. The upper limit is preferably 170 ° C or less, more preferably 160 ° C or less. As the heating time, 0.5 to 48 hours is preferred. The lower limit is preferably 1 hour or longer, more preferably 1.5 hours or longer. The upper limit is preferably 24 hours or less, more preferably 6 hours or less. The heating device is not particularly limited, and can be appropriately selected from known devices depending on the purpose, and examples thereof include a hot air dryer, a drying oven, a hot plate, an infrared heater, and a wavelength control dryer.

Further, the resin composition layer (resin layer) after the hardening treatment may be aged. In the aging, it is preferred to subject the resin composition layer (resin layer) to high temperature and high humidity treatment. As the aging temperature, 60 to 150 ° C is preferred. The lower limit is preferably 70 ° C or higher, and more preferably 80 ° C or higher. The upper limit is preferably 140 ° C or lower, and more preferably 130 ° C or lower. As the humidity, 30 to 100% is preferable. The lower limit is preferably 40% or more, more preferably 50% or more. The upper limit is preferably 95% or less, and more preferably 90% or less. As the aging time, 0.5 to 100 hours is preferred. The lower limit is preferably 1 hour or longer, more preferably 2 hours or longer. The upper limit is preferably 50 hours or less, more preferably 25 hours or less. The aging apparatus is not particularly limited, and can be appropriately selected from known apparatuses depending on the purpose, and examples thereof include a high-temperature high-humidity furnace.

Further, the resin composition layer formed by applying the resin composition to the support may be subjected to the above-described deterioration without passing through the above-described curing treatment step. That is, the resin composition layer may be aged without passing through a hardening step to form a resin layer. In this aspect, the aging has both a hardening treatment step. Moreover, as an aging condition (temperature, humidity, time), the said conditions are mentioned.

<<Layer Containing Infrared Absorbing Pigment>> The near-infrared cut filter of the present invention includes a layer containing an infrared absorbing dye (hereinafter also referred to as an infrared absorbing pigment layer or an IR dye composition layer).

The infrared absorbing pigment layer preferably has a maximum absorption wavelength in a wavelength range of 600 to 1100 nm. The lower limit is preferably 620 nm or more, more preferably 650 nm or more, and still more preferably 680 nm or more. The upper limit is preferably 900 nm or less, more preferably 850 nm or less, and still more preferably 800 nm or less. Further, the maximum absorption wavelength λ1 of the infrared absorbing pigment layer is preferably shorter than the maximum absorption wavelength λ2 of the resin layer containing the copper compound. According to this aspect, it is possible to provide a near-infrared cut filter excellent in shielding properties against light in a wide range of near-infrared regions. The difference between the maximum absorption wavelength λ2 of the resin layer containing the copper compound and the maximum absorption wavelength λ1 of the infrared absorbing pigment layer (λ2-λ1) is preferably 20 to 350 nm, more preferably 50 to 300 nm, and further preferably 100 to 250 nm. .

The content of the infrared absorbing dye in the infrared absorbing pigment layer is preferably from 10 to 90% by mass. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 45% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 65% by mass or less.

It is preferred that the infrared absorbing pigment layer contains a resin. The content of the resin in the infrared absorbing pigment layer is preferably from 5 to 90% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less.

The infrared absorbing pigment layer can be formed using a composition containing an infrared absorbing pigment. In the following, a composition (infrared absorbing pigment layer forming composition) which can be preferably used in forming the infrared absorbing pigment layer in the near-infrared cut filter of the present invention will be described.

The composition for forming an infrared absorbing pigment layer contains an infrared absorbing dye. The infrared absorbing dye is preferably a compound having a maximum absorption wavelength in the range of 600 to 1100 nm. The lower limit is preferably 620 nm or more, more preferably 650 nm or more, and still more preferably 680 nm or more. The upper limit is preferably 900 nm or less, more preferably 850 nm or less, and still more preferably 800 nm or less.

The infrared absorbing dye is selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, an indigo compound, a naphthoquinone compound, a quaterrylene compound, a merocyanine compound, and a ketone. Croconium compound, oxonium compound, diimmonium compound, dithiol compound, triarylmethane compound, pyrrolemethylene compound, azomethine compound, hydrazine compound and dibenzofuranone compound At least one of them is preferably selected from at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaraine compound, an indigo compound, a naphthoquinone compound, and a tetralin compound. Further, at least one of the pyrrolopyrrole compound, the cyanine compound and the squaraine compound is further preferably a pyrrolopyrrole compound. The diimmonium compound is, for example, a compound described in JP-A-2008-528706, which is incorporated herein by reference. For example, the compound described in paragraph 0093 of JP-A-2012-77153, and the oxytitanium phthalocyanine described in JP-A-2006-343631, JP-A-2013-195480 The compounds described in paragraphs 0013 to 0029 are incorporated in the present specification. The naphthoquinone compound is, for example, a compound described in paragraph 0093 of JP-A-2012-77153, which is incorporated herein by reference. Further, as the cyanine compound, the indigo compound, the naphthoquinone compound, the diimonium compound, and the squaraine compound, the compound described in paragraphs 0010 to 0081 of JP-A-2010-111750 may be used, and the content is incorporated. In this manual. In addition, the cyanine compound can be referred to, for example, "functional coloring matter, Okawa Shinshin / Matsuoka Kenji / Kitajima Jiro / Hiratsuka Hiroshi, Kodansha Scientific Ltd.", which is incorporated herein by reference. Further, as the infrared absorbing dye, a compound described in JP-A-2016-146619 can be used, and the content is incorporated in the present specification.

As the pyrrolopyrrole compound, a compound represented by the formula (PP) is preferred. [Chemical Formula 16] In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ may be bonded to each other to form a ring. And R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B or a metal atom, and R ⁴ may also be bonded to at least one selected from the group consisting of R ^1a , R ^1b and R ³ . A valence bond or a coordination bond, and R ^4A and R ^4B each independently represent a substituent. For the details of the formula (PP), reference is made to paragraphs 0017 to 0047 of JP-A-2009-263614, paragraphs 0011 to 0036 of JP-A-2011-68731, and paragraphs of WO01/166873. The contents of the numbers 0010 to 0024 are incorporated in the present specification.

R ^1a and R ^1b each independently represent an aryl group or a heteroaryl group, and an aryl group is more preferable. Further, the alkyl group, the aryl group and the heteroaryl group represented by R ^1a and R ^1b may have a substituent or may be unsubstituted. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, -OCOR ¹¹ , -SOR ¹² , -SO ₂ R ¹³ and the like. R ¹¹ to R ¹³ each independently represent a hydrocarbon group or a heterocyclic group. Further, examples of the substituent include the substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. Among them, as the substituent, an alkoxy group, a hydroxyl group, a cyano group, a nitro group, -OCOR ¹¹ , -SOR ¹² or -SO ₂ R ¹³ are preferable. The group represented by R ^1a or R ^1b is an aryl group having an alkoxy group having a branched alkyl group as a substituent, an aryl group having a hydroxyl group as a substituent or a group represented by -OCOR ¹¹ as a substituent. The aryl group is preferred. The branched alkyl group has preferably 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.

It is preferred that at least one of R ² and R ³ is an electron withdrawing group, R ² represents an electron withdrawing group (preferably a cyano group), and R ³ represents a heteroaryl group. A heteroaryl 5-membered or 6-membered ring is preferred. Further, a heteroaryl monocyclic ring or a condensed ring is preferred, and a monocyclic ring or a condensed ring having a condensation number of 2 to 8 is preferred, and a monocyclic ring or a condensed ring having a condensation number of 2 to 4 is more preferable. The number of hetero atoms constituting the heteroaryl group is preferably from 1 to 3, more preferably from 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. It is preferred that the heteroaryl group has one or more nitrogen atoms. The two R ² in the formula (PP) may be the same as or different from each other. Further, two R ³ in the formula (PP) may be the same as or different from each other.

R ⁴ is a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by -BR ^4A R ^4B , and a hydrogen atom, an alkyl group, an aryl group or a group represented by -BR ^4A R ^4B The group is more preferably, and the group represented by -BR ^4A R ^4B is further preferred. As the substituent represented by R ^4A and R ^4B , a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group is preferred, and an alkyl group, an aryl group or a heteroaryl group is more preferable, and an aryl group is a special one. good. These groups may further have a substituent. The two R ⁴ in the formula (PP) may be the same as or different from each other.

Specific examples of the compound represented by the formula (PP) include compounds having the following structures. In the following structural formula, Me represents a methyl group, and Ph represents a phenyl group. In addition, examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0054 of JP-A-2009-263614, and the compounds described in paragraphs 0037 to 0052 of JP-A-2011-68731. The compound described in Paragraph No. 0010 to 0033 of WO2015/166873 is disclosed, and the contents are incorporated in the present specification. [Chemical Formula 17]

As the squaraine compound, a compound represented by the following formula (SQ) is preferred. [Chemical Formula 18] In the formula (SQ), A ¹ and A ² each independently represent an aryl group, a heteroaryl group or a group represented by the formula (A-1); [Chemical Formula 19] In the formula (A-1), Z ¹ represents a non-metal atomic group forming a nitrogen-containing hetero ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a linking bond. For the details of the formula (SQ), the descriptions of paragraphs 0020 to 0049 of JP-A-2011-208101 can be referred to, and the contents are incorporated in the present specification.

Further, in the formula (SQ), as described below, the cation is present non-localized. [Chemical Formula 20]

Specific examples of the squaraine compound include the compounds shown below. In the following structural formula, EH represents an ethylhexyl group. Further, examples of the squaraine compound include the compounds described in paragraphs 0044 to 0049 of JP-A-2011-208101, the contents of which are incorporated herein by reference. [Chemical Formula 21]

The cyanine compound is preferably a compound represented by the formula (C). Formula (C) [Chemical Formula 22] Wherein Z ¹ and Z ² are each independently a non-metal atomic group forming a nitrogen-containing heterocyclic ring capable of performing a condensed ring of 5 or 6 members, and R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group or an alkynyl group. , aralkyl or aryl, L ¹ represents a methine chain having an odd number of methine groups, a and b are each independently 0 or 1, and when a is 0, a carbon atom and a nitrogen atom are bonded by a double bond. When b is 0, a carbon atom and a nitrogen atom are bonded by a single bond. When a moiety represented by Cy is a cation moiety, X ¹ represents an anion, and c represents a quantity required to maintain a charge balance, and Cy is used in the formula. When the site indicated is an anion moiety, X ¹ represents a cation, and c represents the amount required to maintain the balance of charge. When the charge of the moiety represented by Cy in the formula is neutralized in the molecule, c is 0.

The compound described in paragraphs 0044 to 0045 of JP-A-2009-108267, and the compound described in paragraphs 0026 to 0030 of JP-A-2002-194040, JP-A-2015 The compound described in the Japanese Patent Publication No. 2015-172102, the compound described in JP-A-2008-88426, and the like are incorporated herein by reference.

In the present invention, a commercially available product can also be used as the infrared absorbing dye. For example, SDO-C33 (manufactured by ARIMOTO CHEMICAL Co., Ltd.), EXCOLOR IR-14, EXCOLOR IR-10A, EXCOLOR TX-EX-801B, and EXCOLOR TX-EX-805K (manufactured by NIPPON SHOKUBAI CO., LTD.) ), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839 (manufactured by HAKKO CHEMICAL), Epolite V-63, Epolight 3801, Epolight 3036 (manufactured by EPOLIN), PRO-JET825LDI (manufactured by FUJIFILM Corporation), NK-3027, NK-5060 (manufactured by HAYASHIBARA CO., LTD.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.), and the like.

In the infrared absorbing pigment layer-forming composition, the content of the infrared absorbing dye is preferably from 10 to 90% by mass based on the total solid content of the infrared absorbing pigment layer-forming composition. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 45% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 65% by mass or less.

The composition for forming an infrared absorbing pigment layer can contain a resin. The resin described in the above resin composition is exemplified as the resin. Further, as the resin used in the composition for forming an infrared absorbing pigment layer, a resin having an acid group can also be used. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. These acid groups may be used alone or in combination of two or more. A resin having an acid group can be preferably used as the alkali-soluble resin. The composition for forming an infrared absorbing pigment layer contains an alkali-soluble resin, and a desired pattern can be formed by alkali development.

For the resin having an acid group, the descriptions of paragraphs 0558 to 0571 of the Japanese Patent Application Laid-Open No. 2012-208494 (paragraphs 0685 to 0700 of the specification of the corresponding US Patent Application Publication No. 2012/0235099) The contents of paragraphs 0063 to 00009 of the Japanese Patent Publication No. 2012-198408 are incorporated herein by reference.

The acid value of the acid group-containing resin is preferably from 30 to 200 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The upper limit is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less.

The composition for forming an infrared absorbing pigment layer can contain a dispersant as a resin. In particular, when a pigment is used as the infrared absorbing dye, a resin as a dispersing agent is preferably used. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (basic resin). The dispersant preferably contains at least an acidic dispersant, and more preferably an acidic dispersant. Since the dispersant contains at least an acidic dispersant, the dispersibility of the pigment is improved, and excellent developability can be obtained. Therefore, the pattern can be appropriately formed by the photolithography method. In addition, the dispersing agent is only an acidic dispersing agent. For example, the content of the acidic dispersing agent in the total mass of the dispersing agent is preferably 99% by mass or more, and may be 99.9% by mass or more.

Here, the acidic dispersant (acidic resin) means a resin having a larger amount of acid groups than the amount of the basic group. When the total amount of the acid group and the amount of the basic group is 100 mol%, the acid dispersant (acid resin) is preferably a resin having an acid group content of 70 mol% or more. A resin including only an acid group is more preferable. The acid group-based carboxyl group which the acidic dispersing agent (acid resin) has is preferable. The acid value of the acidic dispersant (acid resin) is preferably 40 to 105 mgKOH/g, more preferably 50 to 105 mgKOH/g, and still more preferably 60 to 105 mgKOH/g. Further, the alkaline dispersant (basic resin) is a resin having a larger amount of a basic group than the acid group. The alkaline dispersing agent (basic resin) is preferably a resin having an amount of the basic group of more than 50 mol% when the total amount of the acid group and the amount of the basic group is 100 mol%. The basic base amine group which the alkaline dispersant has is preferable.

A resin-based graft copolymer used as a dispersant is also preferred. Since the graft copolymer has affinity with a solvent by a graft chain, it is excellent in the dispersibility of a pigment, and the dispersion stability after the elapsed time. The details of the graft copolymer can be referred to in paragraphs 0025 to 0094 of JP-A-2012-255128, which is incorporated herein by reference.

Further, in the present invention, the resin (dispersant) is preferably an oligoimide-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine-based dispersant is preferably a resin having a structural unit and a side chain, and having at least one of a main chain and a side chain having a basic nitrogen atom, and the structural unit contains a functional group having a pKa of 14 or less. Part of the structure X, the side chain containing a side chain Y having an atomic number of 40 to 10,000. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. For the oligo-imine-based dispersant, the descriptions of paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents are incorporated in the present specification. Specific examples of the oligomeric imide-based dispersant include the following examples. The following resin is also a resin having an acid group (alkali-soluble resin). Further, as the oligomeric imide-based dispersant, the resin described in paragraphs 0168 to 0174 of JP-A-2012-255128 can also be used. [Chemical Formula 23]

The dispersant can also be obtained as a commercial product, and as such a specific example, Disperbyk-111 (manufactured by BYK Chemie Co., Ltd.) or the like can be mentioned. Further, the pigment dispersant described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the content is incorporated in the present specification.

The content of the resin is preferably from 5 to 90% by mass based on the total solid content of the infrared absorbing pigment layer-forming composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less.

The composition for forming an infrared absorbing pigment layer can contain a crosslinking agent. A compound (crosslinking agent) having a crosslinkable group can be contained. The crosslinking agent is exemplified by the resin composition described above. The content of the crosslinking agent is preferably from 5 to 90% by mass based on the total solid content of the infrared absorbing pigment layer-forming composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less.

<<Pigment Derivative>> The composition for forming an infrared absorbing pigment layer can further contain a pigment derivative. The pigment derivative may be a compound having a structure in which a part of the pigment is substituted with an acid group, a basic group, a salt-containing group or a phthalimidomethyl group. As the pigment derivative, a compound represented by the formula (B1) is preferred.

[Chemical Formula 24] In the formula (B1), P represents a dye structure, L represents a single bond or a linking group, and X represents an acid group, a basic group, a group having a salt structure or a phthalimidomethyl group, and m represents 1 or more. An integer, n represents an integer of 1 or more, and when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of Xs may be different from each other.

In the formula (B1), P represents a dye structure, and is selected from the group consisting of pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone dye structure, anthraquinone pigment structure, diterpene pigment structure, benzopyrene Pigment structure, thiazolidine structure, azo pigment structure, quinoline yellow pigment structure, indigo pigment structure, naphthoquinone pigment structure, diterpene pigment structure, anthraquinone pigment structure, purple ring ketone pigment structure, benzimidazole At least one of a ketone dye structure, a benzothiazole dye structure, a benzimidazole dye structure, and a benzoxazole dye structure is preferred, and is selected from the group consisting of a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, and a quinacridone. At least one of the dye structure and the benzimidazolone dye structure is further preferred, and the pyrrolopyrrole dye structure is particularly preferable.

In the formula (B1), L represents a single bond or a linking group. As the linking group, a group comprising 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms is preferred, and Unsubstituted, it may further have a substituent.

In the formula (B1), X represents an acid group, a basic group, a group having a salt structure or a phthalimidomethyl group, and an acid group or a basic group is preferred. Examples of the acid group include a carboxyl group and a sulfo group. The basic group may, for example, be an amine group.

For example, JP-A-56-118462, JP-A-63-264674, JP-A-1-217077, JP-A-3-9961, and JP-A JP-A Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compounds described in paragraphs 0063 to 0094 and the like are incorporated in the present specification.

When the infrared absorbing pigment layer-forming composition contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 50 parts by mass based on 100 parts by mass of the infrared absorbing dye. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. When the content of the pigment derivative is within the above range, the dispersibility of the infrared absorbing dye can be improved, and aggregation of the infrared absorbing dye can be effectively suppressed. The pigment derivative may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably in the above range.

The composition for forming an infrared absorbing pigment layer can further contain a polymerization initiator, a solvent, a surfactant, an ultraviolet absorber, an antioxidant, and the like. The details of these are mentioned by the resin composition mentioned above. Further, as the polymerization initiator, V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) or the like can also be used. The composition for forming an infrared absorbing pigment layer can further contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, tert-butyl catechol, benzoquinone, and 4,4'-thiobis. (3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-tertiarybutylphenol), N-nitrosophenylhydroxylamine salt ( Ammonium salts, trivalent cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.001 to 5% by mass based on the total solid content of the infrared absorbing pigment layer-forming composition.

The infrared absorbing pigment layer forming composition can be prepared by mixing the components. When the composition for forming an infrared absorbing pigment layer is prepared, the components constituting the composition for forming an infrared absorbing pigment layer may be uniformly blended, or may be blended one by one after being dissolved and/or dispersed in a solvent. Further, the order of input and the operating conditions at the time of blending are not particularly limited. The storage container which is a composition for forming an infrared absorbing pigment layer is not particularly limited, and those described above using the resin composition can be used.

The infrared ray absorbing pigment layer can be formed by applying the composition for forming an infrared ray absorbing pigment layer to a copper-containing glass or a resin layer containing a copper compound to form a composition layer, and drying the composition layer. .

As a method of applying the composition for forming an infrared absorbing pigment layer, a method described as a method of applying the resin composition can be mentioned. The drying conditions of the composition layer can be appropriately adjusted depending on the type and content of each component contained in the infrared absorbing pigment layer-forming composition. For example, as the drying temperature, 40 to 160 ° C is preferred. The lower limit is preferably 60 ° C or higher, and more preferably 80 ° C or higher. The upper limit is preferably 140 ° C or less, more preferably 120 ° C or less. As the drying time, 1 to 600 minutes is preferred. The lower limit is preferably 10 minutes or more, more preferably 30 minutes or more. The upper limit is preferably 300 minutes or less, and more preferably 180 minutes or less.

The method of forming the composition for forming an infrared absorbing pigment layer may also include other steps. The other steps are not particularly limited and can be appropriately selected depending on the purpose. For example, a hardening treatment step or the like can be given.

The hardening treatment method of the composition layer is not particularly limited, and can be appropriately selected depending on the purpose. For example, an exposure process, a heat process, etc. are mentioned. The exposure treatment is preferably carried out by irradiating the composition layer with radiation. As the radiation, ultraviolet rays such as an electron beam, KrF, ArF, g-ray, h-ray, or i-ray are preferable. Examples of the exposure method include step exposure, exposure using a high pressure mercury lamp, and the like. The exposure amount is preferably from 5 to 3,000 mJ/cm ² . The upper limit is preferably 2000 mJ/cm ² or less, more preferably 1000 mJ/cm ² or less. The lower limit is preferably 10 mJ/cm ² or more, and more preferably 50 mJ/cm ² or more. The exposure apparatus is not particularly limited, and can be appropriately selected depending on the purpose, and examples thereof include an ultraviolet exposure machine such as an ultrahigh pressure mercury lamp.

The heating temperature in the heat treatment is preferably 120 to 250 °C. The heating time is preferably from 3 minutes to 180 minutes, more preferably from 5 minutes to 120 minutes. The heating device is not particularly limited, and can be appropriately selected from known devices depending on the purpose, and examples thereof include a hot air dryer, a drying oven, a hot plate, an infrared heater, and a wavelength control dryer.

<<Dielectric Multilayer Film, Ultraviolet Absorbing Layer>> The near-infrared cut filter of the present invention preferably contains at least one selected from the group consisting of a dielectric multilayer film and an ultraviolet absorbing layer. Further, the near-infrared cut filter further includes a dielectric multilayer film, and it is easy to obtain a near-infrared cut filter having a wide viewing angle and excellent near-infrared shielding properties. In addition, the near-infrared cut filter further includes an ultraviolet absorbing layer, and the ultraviolet shielding property of the near-infrared cut filter can be improved. When the near-infrared cut filter is combined with a solid-state imaging device or the like, the purple fringe can be suppressed. Images, etc.

Further, in the present invention, the dielectric multilayer film is a film that shields infrared rays or the like by the interference effect of light. Specifically, a dielectric layer (a high refractive index material layer and a low refractive index material layer) having different refractive indices is alternately laminated to form a film of two or more layers.

As a material of the dielectric multilayer film, for example, ceramic can be used. In order to form an infrared cut filter that utilizes the interference effect of light, it is preferable to use two or more kinds of ceramics having different refractive indices. Specifically, as the dielectric multilayer film, a configuration in which a high refractive index material layer and a low refractive index material layer are alternately laminated can be suitably used.

As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a range of the refractive index is usually selected from a material of 1.7 to 2.5. Examples of the material include titanium oxide, zirconium oxide, antimony pentoxide, antimony pentoxide, antimony oxide, antimony oxide, zinc oxide, zinc sulfide, or indium oxide, and a small amount of titanium oxide and tin oxide. And / or yttrium oxide and the like.

As the material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a range of the refractive index is usually selected from 1.2 to 1.6. Examples of the material include cerium oxide, aluminum oxide, cerium fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The method for forming the dielectric multilayer film is not particularly limited, and examples thereof include forming a high refractive index material layer by a CVD (chemical vapor deposition) method, a sputtering method, a vacuum deposition method, or the like. a dielectric multilayer film in which a plurality of refractive index material layers are alternately laminated, and a method in which the dielectric multilayer film is bonded to a transparent layer containing copper and/or an infrared absorbing layer by an adhesive; and a transparent layer containing copper And a method of forming a dielectric multilayer film by alternately laminating a high refractive index material layer and a low refractive index material layer by a CVD method, a sputtering method, a vacuum deposition method or the like on the surface of the infrared absorbing layer.

The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1 to 0.5 λ with respect to the infrared wavelength λ (nm) to be interrupted. By setting the thickness to the above range, it is easy to control the shielding and transmission of light of a specific wavelength. Further, the number of layers in the dielectric multilayer film is preferably 2 to 100 layers, more preferably 2 to 60 layers, and still more preferably 2 to 40 layers.

The ultraviolet absorbing layer is preferably a layer containing a UV absorber. Examples of the ultraviolet absorber include an ultraviolet absorber described above using the resin composition. Further, the ultraviolet absorbing layer can be referred to in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO2015/099060, and the contents are incorporated in the present specification.

In the present invention, the dielectric multilayer film and the ultraviolet absorbing layer may be disposed on one surface side of the glass containing copper or may be disposed on both surfaces. Further, it is preferable that the dielectric multilayer film is disposed on the outermost layer of the near-infrared cut filter. By disposing the dielectric multilayer film on the outermost layer of the near-infrared cut filter, the manufacturing steps are simplified. Further, the ultraviolet absorbing layer may be disposed on the outermost layer of the near-infrared cut filter, or may be disposed between the glass containing copper and the resin layer containing the copper compound, between the glass containing copper and the infrared absorbing pigment layer, and containing a copper compound. Either between the resin layer and the infrared absorbing pigment layer.

<Layer configuration of the near-infrared cut filter> The near-infrared cut filter of the present invention may have a structure in which a glass containing copper, a resin layer containing a copper compound, and an infrared absorbing pigment layer are provided in an arbitrary arrangement. Among them, the glass containing copper is in contact with one surface of the resin layer containing the copper compound, and the layer containing the infrared absorbing dye is preferably in contact with the other surface of the resin layer containing the copper compound. In other words, a resin layer containing a copper compound is disposed between the glass containing copper and the infrared absorbing pigment layer, and the resin layer containing the copper compound is preferably laminated in contact with the glass containing copper and the infrared absorbing pigment layer. According to this aspect, it is possible to provide a near-infrared cut filter excellent in adhesion between the layers.

An example of the layer configuration of the infrared cut filter of the present invention is shown below. (1) Copper-containing glass/copper-containing resin layer/infrared absorbing pigment layer (2) Copper-containing glass/infrared absorbing pigment layer/copper-containing resin layer (3) Copper-containing resin layer/copper-containing Glass/infrared absorbing pigment layer

When the dielectric multilayer film is further included in the aspect of (1), it is preferable to arrange a dielectric multilayer film on the surface of the glass containing copper and/or the infrared absorbing pigment layer. When the dielectric multilayer film is further included in the aspect of (2), it is preferable to arrange a dielectric multilayer film on the surface of the glass containing copper and/or the resin layer containing a copper compound. When the dielectric multilayer film is further included in the aspect of (3), it is preferable to arrange a dielectric multilayer film on the surface of the resin layer containing the copper compound and/or the infrared absorbing pigment layer.

When the ultraviolet absorbing layer is further included in the aspect of (1), an ultraviolet absorbing layer may be disposed on the surface of the glass containing copper and/or the infrared absorbing pigment layer, or an ultraviolet absorbing layer may be disposed between the layers. When the ultraviolet absorbing layer is further included in the aspect of (2), the ultraviolet absorbing layer may be disposed on the surface of the copper-containing glass and/or the resin layer containing the copper compound, or the ultraviolet absorbing layer may be disposed between the layers. When the ultraviolet absorbing layer is further provided in the aspect of (3), the ultraviolet absorbing layer may be disposed on the surface of the resin layer containing the copper compound and/or the infrared absorbing pigment layer, or the ultraviolet absorbing layer may be disposed between the layers.

Further, when the dielectric multilayer film and the ultraviolet absorbing layer are further included in the aspect of (1) to (3), it is preferable that the dielectric multilayer film be the outermost layer. At this time, the dielectric multilayer film may be disposed on only one of the surface sides with respect to the glass containing copper, or may be disposed on the other surface side.

The near-infrared cut filter of the present invention can be used in various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), or an infrared sensor or an image display device.

<Solid-State Imaging Device and Camera Module> The solid-state imaging device of the present invention includes the near-infrared cut filter of the present invention. Further, the camera module of the present invention includes the near-infrared cut filter of the present invention.

Fig. 1 is a schematic cross-sectional view showing the configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention. The camera module 10 shown in FIG. 1 includes a solid-state imaging device 11 and a planarization layer 12 provided on a main surface side (light receiving side) of the solid-state imaging device; a near-infrared cut filter 13; and a lens holder 15 disposed in the lens holder 15 The imaging lens 14 is provided above the near-infrared cut filter and in the internal space. In the camera module 10, incident light from the outside is sequentially transmitted through the imaging lens 14, the near-infrared cut filter 13, and the planarization layer 12, and then reaches the imaging element portion of the solid-state imaging device 11. As the near-infrared cut filter 13, only the above-described physical resin film can be used, and a laminate of a resin film and a support can be used. Examples of the material of the support include tempered glass such as sapphire glass and Gorilla glass, transparent ceramics, and plastics. As the material of the imaging lens 14, in addition to general glass, tempered glass such as sapphire glass or Gorilla glass, transparent ceramics, plastic, or the like can be given.

The solid-state imaging device 11 is provided with, for example, a photodiode, an interlayer insulating film (not shown), a base layer (not shown), a color filter 17, and an overcoat layer (not shown) on the main surface of the substrate 16. And microlens 18. The color filter 17 (red color filter, green color filter, blue color filter) and the microlens 18 are disposed to correspond to the solid-state imaging element 11, respectively. In addition, a form of the near-infrared cut filter 13 may be provided between the surface of the microlens 18, the base layer and the color filter 17, or between the color filter 17 and the overcoat layer, instead of the planarization layer 12. The near-infrared cut filter 13 is provided on the surface. For example, the near-infrared cut filter 13 may be disposed at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens. When the near-infrared cut filter 13 is provided at this position, the step of forming the near-infrared cut filter can be simplified. Further, it is possible to sufficiently cut off unnecessary near-infrared rays incident on the microlens, and it is possible to further improve infrared shielding properties. Further, in Fig. 1, the number of the imaging lenses 14 is one, but the number of the imaging lenses 14 may be two or more.

Since the near-infrared cut filter of the present invention is excellent in heat resistance, it can be used in a solder reflow step. By manufacturing the camera module by the solder reflow step, 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 the productivity as compared with the case where the solder reflow step is not used. Moreover, since it can be automatically performed, it is also possible to achieve cost reduction. When used in the solder reflow step, it is exposed to a temperature of about 250 to 270 ° C. Therefore, the near-infrared cut filter has heat resistance that can withstand the solder reflow step (hereinafter also referred to as "resistance to solder reflow"). good. In the present specification, "having solder reflow resistance" means maintaining the characteristics as a near-infrared cut filter after heating at 180 ° C for 1 minute. More preferably, the properties are maintained after heating at 230 ° C for 10 minutes. It is further preferred to maintain the properties after heating at 250 ° C for 3 minutes. When heating is not performed under the above conditions when the solder reflow resistance is not obtained, the infrared shielding property of the near-infrared cut filter may be lowered or the function as a film may be insufficient. The camera module of the present invention can further have an ultraviolet absorbing layer. According to this aspect, the ultraviolet shielding property can be improved. The ultraviolet absorbing layer can be referred to, for example, in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO2015/099060, and the contents are incorporated in the present specification.

2 to 4 are schematic cross-sectional views showing an example of a peripheral portion of a near-infrared cut filter in the camera module.

As shown in FIG. 2, the camera module may have a solid-state imaging element 11, a planarization layer 12, an ultraviolet/infrared light reflection film 19, a transparent substrate 20, a near-infrared cut filter 21, and an anti-reflection layer 22 in this order. For the ultraviolet/infrared light reflecting film 19, for example, paragraphs 0033 to 0039 of JP-A-2013-68688 and paragraphs 0110 to 0114 of International Publication WO2015/099060 can be referred to, and the contents are incorporated in the present specification. The transparent substrate 20 is such that the light of the wavelength of the visible region is transmitted. For example, the paragraphs 0026 to 0032 of JP-A-2013-68688 can be referred to in the present specification. The antireflection layer 22 has a function of improving the transmittance by preventing reflection of light incident on the near-infrared cut filter 21, and has a function of effectively utilizing incident light. For example, the paragraph number of JP-A-2013-68688 can be referred to. The contents of 0040 are incorporated in this specification.

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

As shown in FIG. 4, the camera module may also have a solid-state imaging element 11, a near-infrared cut-off filter 21, an ultraviolet/infrared light reflecting film 19, a planarization layer 12, an anti-reflection layer 22, a transparent substrate 20, and an anti-reflection layer. Reflective layer 22.

Another embodiment of the camera module of the present invention is shown in FIG. In the camera module shown in FIG. 1, the near-infrared cut filter 13 is disposed outside the lens holder 15, and the camera module is different from the camera module shown in FIG. That is, in the camera module shown in FIG. 5, the near-infrared cut filter 13 is disposed on the incident light side from the outside of the imaging lens 14. In the camera module, incident light from the outside is sequentially transmitted through the near-infrared cut filter 13, the imaging lens 14, and the planarization layer 12, and then reaches the imaging element portion of the solid-state imaging device 11. When the near-infrared cut filter 13 is disposed on the incident light side from the outside of the imaging lens 14, by opening the distance between the near-infrared cut filter 13 and the light receiving portion, even if there is a defect in the near-infrared cut filter It is also possible to blur these defects to reduce the influence of the defects on the image. Further, in FIG. 5, the near-infrared cut filter 13 is disposed outside the lens holder 15, but may be disposed in the lens holder 15. In addition, in FIG. 5, the near-infrared cut filter 13 is disposed from the surface of the imaging lens 14 at a predetermined interval, but the near-infrared cut filter 13 may be directly formed on the surface of the imaging lens 14. Further, in FIG. 5, the number of the imaging lenses 14 is one, but the number of the imaging lenses 14 may be two or more. Further, when two or more imaging lenses 14 are provided, the near-infrared cut filter 13 may be disposed on the outer side (incident light side) of the imaging lens 14 disposed on the outermost side (incident light side), or A near-infrared cut filter 13 is disposed between the imaging lenses. For example, when there are two or more imaging lenses 14, the near-infrared cut filter, the imaging lens, and the imaging lens may be sequentially arranged from the incident light side, or may be an imaging lens, a near-infrared cut filter, or an imaging lens. The order is configured separately.

<Image Display Device> The image display device of the present invention has the near-infrared cut filter of the present invention. The near-infrared cut filter of the present invention can also be used in an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device. The definition of the display device or the details of each display device is described, for example, in "Electronic display devices (Kosuke Chosuke, Kogyo Chosakai Publishing Co., Ltd., 1990)", "Display devices (Ibuki Shun, Sangyo Tosho) Co., Ltd. issued in the first year of Heisei) and so on. Further, the liquid crystal display device is described, for example, in "Next Generation Liquid Crystal Display Technology (Koryo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The image display device may also be a white organic EL element. As the white organic EL element, a series structure is preferable. The series structure of the organic EL device is described in "The Frontline of Organic EL Technology Development - High Brightness, High Accuracy, Long Life, and Technology Set -" (Technical Information) Association, pp. 326-328, 2008). The spectrum of the white light emitted from the organic EL element is preferably a blue region (430 nm to 485 nm), a green region (530 nm to 580 nm), and a yellow region (580 nm to 620 nm) having a strong maximum luminescence peak. In addition to these luminescence peaks, it is more preferable to have a large luminescence peak in the red region (650 nm to 700 nm). [Examples]

Hereinafter, the present invention will be further specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing steps, 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 invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality benchmarks unless otherwise stated.

<Weight average molecular weight (Mw)> The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) by the following method. Device: HLC-8220 GPC (manufactured by TOSOH CORPORATION) Detector: RI (Refractive Index) detector column: connected with protective column HZ-L, TSK gel Super HZM-M, TSK gel Super HZ4000, TSK Gel Super HZ3000, TSK gel Super HZ2000 (manufactured by TOSOH CORPORATION) column eluant: tetrahydrofuran (with stabilizer) Column temperature: 40 ° C Injection amount: 10 μL Analysis time: 26 min. Flow rate: flow rate 0.35 mL / Min.(sample pump) 0.20mL/min. (reference pump) calibration curve base resin: polystyrene

<Preparation of Resin Composition> (Resin Compositions 1 to 7) The materials shown in the following table were mixed with the blending amount (parts by mass) shown in the following table to prepare solid components described in the following tables. The concentration of the resin composition. Further, the adjustment of the solid content concentration in the resin composition is carried out by adjusting the blending amount of the solvent.

[Table 1]

(Resin Composition 8) 28.9 parts by mass of tetraethoxysilane, 28.9 parts by mass of phenyltriethoxysilane, and 30.6 parts by mass of 10% hydrochloric acid were mixed at room temperature for 4 hours to obtain a sol. To the sol, a solution obtained by dissolving 26.0 parts by mass of copper complex A-5 in 85.5 parts by mass of cyclopentanone at room temperature for 20 minutes, and then using a nylon filter having a pore size of 0.45 μm (NIHON PALL LTD) Production) The resin composition 8 was prepared by filtration.

(Resin Composition 9) A resin composition 9 was prepared in the same manner as in the resin composition 8, except that the copper complex A-6 was used instead of the copper complex A-5 in the resin composition 8.

The materials used in the resin compositions 1 to 9 are as follows. In the resin shown below, the value attached to the main chain is the molar ratio.

(Copper complex) A-1 to A-4: copper complex of the following structure [Chemical Formula 25] A-5: Copper complex having the following compound as a ligand [Chemical Formula 26] A-6: copper complex having the following compound as a ligand [Chemical Formula 27] (Resin) B-1: Resin of the following structure (Mw = 15,000) B-2: Resin of the following structure (Mw = 13,000) B-3: Resin of the following structure (Mw = 20,000) [Chemical Formula 28]

(crosslinking agent) M-1: KBM-3066 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(radical scavenger) D-1: a compound of the following structure [Chemical Formula 29]

(catalyst) E-1: tris(2,4-pentanedione)aluminum (III) (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Interacting Agent) W-1: The following compound (weight average molecular weight = 14,000. The % of the ratio of the repeating unit is % by mass.) [Chemical Formula 30]

(solvent) CP: cyclopentanone

<Preparation of Infrared Absorbing Pigment Layer-Forming Composition (IR Pigment Composition)> (IR Pigment Composition 1 and IR Pigment Composition 2) The following raw materials were mixed to prepare an IR Pigment Composition 1 and an IR Pigment Composition 2. Dispersion A or dispersion B ... 42 parts by mass of the resin described in the following table: 7.1 parts by mass of the crosslinking agent described in the following table... 4.5 parts by mass of the surfactant described in the following table... 0.04 Parts by mass of the solvent described in the following table...46.36 parts by mass

(IR Pigment Compositions 3 to 9) The following pigment materials were mixed to prepare IR Pigment Compositions 3 to 9. Infrared absorbing dyes described in the following table: 1.7 parts by mass of the resin described in the following table: 15.9 parts by mass of the polymerization initiator described in the following table: 1.5 parts by mass of the crosslinking agent described in the following table 2.7 parts by mass of the surfactant described in the following table: 9.6 parts by mass of a polymerization inhibitor (p-methoxyphenol) 0.001 parts by mass of a solvent described in the following table: 68.4 parts by mass

(IR Pigment Compositions 10 to 12) The following raw materials were mixed to prepare IR Pigment Compositions 10 to 12 having a solid concentration of 20% by mass. The solid content concentration of the IR dye composition is adjusted by adjusting the blending amount of the solvent. Resin B-12 ... 100 parts by mass The infrared absorbing dye described in the following table ... 0.03 parts by mass The solvent described in the following table ... The remainder

[Table 2]

The materials used in the IR dye compositions 1 to 12 are as follows.

(Dispersion A) 10 parts by mass of the infrared absorbing dye (A-101), 1 part by mass of the pigment derivative (F-1) having the following structure, 7 parts by mass of the dispersing agent (B-101), and propylene glycol monomethyl ether B 150 parts by mass of the acid ester (PGMEA) and 230 parts by mass of zirconia beads having a diameter of 0.3 mm were mixed, and dispersion treatment was carried out for 5 hours using a paint shaker, and the beads were separated by filtration to produce a dispersion A.

(Dispersion B) 10 parts by mass of the infrared absorbing dye (A-102), 1 part by mass of the pigment derivative (F-1) having the following structure, 7 parts by mass of the dispersing agent (B-101), and propylene glycol monomethyl ether B 150 parts by mass of the acid ester (PGMEA) and 230 parts by mass of zirconia beads having a diameter of 0.3 mm were mixed, and dispersion treatment was carried out for 5 hours using a paint shaker, and the beads were separated by filtration to produce a dispersion B.

(Infrared absorbing dye) Infrared absorbing dyes A-101 to A-109: Compounds A-101 to A-109 having the following structures were used. In the following structural formula, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group. [Chemical Formula 31] Infrared absorbing dye A-110: Compound (a-1) described in paragraph No. 0173 of JP-A-2016-146619. Infrared absorbing dye A-111: Paragraph No. 0173 of JP-A-2016-146619 Compound (a-2) Infrared Absorbing Pigment A-112: Compound (a-3) described in Paragraph No. 0173 of JP-A-2016-146619

(Pigment Derivative) F-1: a compound of the following structure [Chemical Formula 32]

(Dispersant) B-101: Resin having the following structure (acid value = 32.3 mgKOH/g, amine value = 45.0 mgKOH/g, weight average molecular weight = 22,900, and the value attached to the main chain indicates the number of moles of the repeating unit, The value attached to the side chain indicates the number of repeating units.) [Chemical Formula 33] (Resin) B-11: Resin of the following structure (Mw=40000, the value attached to the main chain is the number of moles) [Chemical Formula 34] B-12: Resin A synthesized by the method described in paragraphs 0169 to 0171 of JP-A-2016-146619

(Polymerization initiator) C-11: V-601 (manufactured by Wako Pure Chemical Industries, Ltd.)

(crosslinking agent) M-11: EPICLON N-695 (manufactured by DIC Corporation) M-12: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(Interacting Agent) W-1: The following compound (weight average molecular weight = 14,000. The % of the ratio of the repeating unit is mol%. [Chemical Formula 35] W-2: MEGAFACE RS-72-K (manufactured by DIC Corporation)

(solvent) PGMEA: propylene glycol monomethyl ether acetate CP: cyclopentanone DCM: dichloromethane

<A composition for forming an ultraviolet absorbing layer (UV absorbing composition)> (UV absorbing composition 1) 11.01 parts by mass of a resin B-11, 2.38 parts by mass of a UV absorber (TINUVIN 928, manufactured by BASF Corporation), and a crosslinking agent ( KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 1.72 parts by mass, a polymerization initiator (IRGACURE OXE-01, manufactured by BASF Corporation), 1.89 parts by mass, propylene glycol monomethyl ether acetate (PGMEA) as a solvent, 83.0 parts by mass After mixing and stirring, the mixture was filtered using a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.5 μm to prepare a UV absorbing composition 1.

<Manufacturing Method of Near-Infrared Cut Filter> (Production Example 1) The resin composition described in the following table was spin-coated on the glass described in the following table to form a resin composition layer. Next, the resin composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then the resin composition layer was heated at 150 ° C for 10 minutes using a hot plate to form a resin having the thickness described in the following table. Floor. Then, the IR dye composition described in the following table was spin-coated on the resin layer to form an IR dye composition layer. The IR pigment composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then subjected to full exposure at 1000 mJ/cm ² using an i-ray stepper. Subsequently, the film was heated at 150 ° C for 60 minutes to be subjected to a curing treatment to form an infrared absorbing pigment layer (IR layer) having the thickness described in the following table.

(Production Example 2) The IR dye composition described in the following table was spin-coated on the glass described in the following table to form an IR dye composition layer. The IR pigment composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then subjected to full exposure at 1000 mJ/cm ² using an i-ray stepper. Subsequently, the film was heated at 150 ° C for 60 minutes to be subjected to a curing treatment to form an IR layer having the thickness described in the following table. Then, the resin composition described in the following table was spin-coated on the IR layer to form a resin composition layer. Next, the resin composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then the resin composition layer was heated at 150 ° C for 10 minutes using a hot plate to form a resin having the thickness described in the following table. Floor.

(Production Example 3) The resin composition described in the following table was spin-coated on the glass described in the following table to form a resin composition layer. Next, the resin composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then the resin composition layer was heated at 150 ° C for 10 minutes using a hot plate to form a resin having the thickness described in the following table. Floor. Then, the IR dye composition described in the following table was spin-coated on the resin layer to form an IR dye composition layer. The IR pigment composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then subjected to full exposure at 1000 mJ/cm ² using an i-ray stepper. Subsequently, the film was heated at 150 ° C for 60 minutes to be subjected to a curing treatment to form an IR layer having the thickness described in the following table. Then, the UV absorbing composition 1 was spin-coated on the IR layer to form a UV absorbing composition layer, which was dried at 100 ° C for 120 seconds, and then comprehensively performed at 1000 mJ/cm ² using an i-ray stepper. exposure. Subsequently, post-heating (post-baking) at 220 ° C for 300 seconds was performed to form an ultraviolet absorbing layer having a film thickness of 1.0 μm.

(Production Example 4) The IR dye composition described in the following table was spin-coated on the glass described in the following table to form an IR dye composition layer. The IR pigment composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then subjected to full exposure at 1000 mJ/cm ² using an i-ray stepper. Next, the hardening treatment was carried out by heating at 150 ° C for 60 minutes to form an IR layer having the thickness described in the following table.

(Production Example 5) The resin composition described in the following table was spin-coated on the glass described in the following table to form a resin composition layer. Next, the resin composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then the resin composition layer was heated at 150 ° C for 10 minutes using a hot plate to form a resin having the thickness described in the following table. Floor.

(Production Example 6) The resin composition described in the following table was spin-coated on a glass substrate to which a Kapton film (thickness: 100 μm, manufactured by DU PONT-TORAY CO., LTD.) was adhered to form a resin. Composition layer. Next, the resin composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then heated at 150 ° C for 10 minutes to form a resin layer having the thickness described in the following table. Then, the IR dye composition described in the following table was spin-coated on the resin layer to form an IR dye composition layer. The IR pigment composition layer was dried at 100 ° C for 120 seconds using a hot plate, and then subjected to full exposure at 1000 mJ/cm ² using an i-ray stepper. Subsequently, the film was heated at 150 ° C for 60 minutes to be subjected to a curing treatment to form an IR layer having the thickness described in the following table. Finally, the laminate of the resin composition layer/IR layer was manually peeled off from the glass substrate to prepare a near-infrared cut filter.

<Evaluation of Spectroscopic Characteristics> The transmittance of the near-infrared cut filter was measured using U-4100 (manufactured by Hitachi High-Technologies Corporation). The measurement wavelength range was 400 to 1300 nm, and the transmittance per 5 nm was measured. The average value of the transmittance was calculated by dividing the sum of the transmittances per 5 nm by the wavelength range. The visible transparency, the near-infrared shielding property 1, and the near-infrared shielding property 2 were evaluated by the following criteria. (Visible transparency) A: The average transmittance at a wavelength of 450 to 550 nm is 90% or more. B: The average transmittance of the wavelength of 450 to 550 nm is 85% or more and less than 90%. C: The average transmittance of the wavelength of 450 to 550 nm is 80% or more and less than 85%. D: The average transmittance of the wavelength of 450 to 550 nm is less than 80%. (Near Infrared Shielding Property 1) A: The average transmittance of a wavelength of 700 nm or more and less than 800 nm is 5% or less. B: The average transmittance of a wavelength of 700 nm or more and less than 800 nm exceeds 5% and is 10% or less. C: The average transmittance of a wavelength of 700 nm or more and less than 800 nm exceeds 10% and is 20% or less. D: The average transmittance of a wavelength of 700 nm or more and less than 800 nm exceeds 20%. (Near Infrared Shielding Property 2) A: The average transmittance of a wavelength of 800 nm or more and less than 1100 nm is 5% or less. B: The average transmittance of a wavelength of 800 nm or more and less than 1100 nm exceeds 5% and is 10% or less. C: The average transmittance of a wavelength of 800 nm or more and less than 1100 nm exceeds 10% and is 20% or less. D: The average transmittance of a wavelength of 800 nm or more and less than 1100 nm exceeds 20%.

(Cutting resistance) Using DAD3350 (manufactured by DISCO Corporation) as a cutting device, B1A862SD1200L50MT38 (53×0.1×40) was used as a blade, and the near-infrared cut filter was cut into 22×28 mm at a feed rate of 2 mm/sec and a rotation speed of 20,000 rpm. the size of. The cut resistance was evaluated by the following criteria. A: The chipping of the glass and the resin layer is 0.1 mm or less. B: Fragmentation of the glass and the resin layer exceeds 0.1 mm and is 0.5 mm or less. C: Fragmentation of the glass and the resin layer exceeds 0.5 mm and is 1.0 mm or less. D: The glass and resin layers were broken more than 1.0 mm.

(warpage) The magnitude of the warpage of the near-infrared cut filter was evaluated using an interferometer. A: The maximum value of the floating width of the end portion when the near-infrared cut filter is horizontally placed to protrude downward is 100 μm or less. B: The maximum value of the floating width of the end portion when the near-infrared cut filter is horizontally placed to protrude downward is more than 100 μm and is 500 μm or less. C: The maximum value of the floating width of the end portion when the near-infrared cut filter is horizontally placed to protrude downward is more than 500 μm and is 1000 μm or less. D: The maximum value of the floating width of the end portion when the near-infrared cut filter is horizontally placed to protrude downward is more than 1000 μm.

(Adhesiveness) After the near-infrared cut filter was added to boiling water for 1 hour, a tape peeling test was performed and the adhesion was evaluated. Specifically, a slit is formed on the glass film of each near-infrared cut filter by using a cutter to form 100 squares of 10 mm × 10 mm, and after the tape manufactured by Nichiban Co., Ltd. is attached to the square, The operation of peeling off the tape was repeated 5 times. The number of peeling of the opponent grid was counted, and the adhesiveness of the Example and the comparative examples 1-3 was evaluated. A: The number of peeling of the square is 0. B: The number of peeling of the square is 1 to 50. C: The number of peeling of the square is 51 or more.

[table 3] [Table 4] [table 5] [Table 6] [Table 7] [Table 8] [Table 9]

In the above table, the glass 1 is a glass containing copper (product name NF-50, manufactured by AGC TECHNO GLASS CO., LTD.), and the glass 2 is a glass containing no copper (product name B270i, manufactured by Schott).

As shown in the above table, in the examples, transparency, near-infrared ray shielding property 1 and near-infrared ray shielding property 2 were excellent, and the cut resistance was also excellent.

10‧‧‧ camera module

11‧‧‧ Solid-state imaging components

12‧‧ ‧ flattening layer

13‧‧‧Near-infrared cut-off filter

14‧‧‧ imaging lens

15‧‧‧ lens holder

16‧‧‧矽 substrate

17‧‧‧ color filter

18‧‧‧Microlens

19‧‧‧UV/Infrared Reflective Film

20‧‧‧Transparent substrate

21‧‧‧Near-infrared cut-off filter

22‧‧‧Anti-reflection layer

Fig. 1 is a schematic cross-sectional view showing the configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention. 2 is a schematic cross-sectional view showing an example of a peripheral portion of a near-infrared cut filter in a camera module. 3 is a schematic cross-sectional view showing an example of a peripheral portion of a near-infrared cut filter in a camera module. 4 is a schematic cross-sectional view showing an example of a peripheral portion of a near-infrared cut filter in a camera module. Fig. 5 is a schematic cross-sectional view showing the configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention.

Claims (13)

A near-infrared cut filter comprising: a glass containing copper, a resin layer containing a copper compound, and a layer containing an infrared absorbing dye. The near-infrared cut filter according to claim 1, wherein the copper-containing glass has a film thickness of 10 to 10,000 μm, and the copper compound-containing resin layer has a film thickness of 1 to 500 μm, and the infrared absorption is contained. The film thickness of the pigment layer is 0.01 to 10 μm. The near-infrared cut filter according to claim 2, wherein a ratio of a film thickness of the copper-containing glass to a film thickness of the copper compound-containing resin layer is a film thickness of the glass containing copper: containing copper The film thickness of the resin layer of the compound = [1:30] to [5,000:1]. The near-infrared cut filter according to the second or third aspect of the invention, wherein the ratio of the film thickness of the copper-containing glass to the film thickness of the layer containing the infrared absorbing dye is a film containing copper glass. Thickness: The film thickness of the layer containing the infrared absorbing pigment = [2:1] to [500,000:1]. The near-infrared cut filter according to the second or third aspect of the invention, wherein a ratio of a film thickness of the resin layer containing the copper compound to a film thickness of the layer containing the infrared absorbing dye is a copper compound. Film thickness of the resin layer: film thickness of the layer containing the infrared absorbing dye = [1:5] to [30,000:1]. The near-infrared cut filter according to any one of claims 1 to 3, wherein the layer containing the infrared absorbing dye has a maximum absorption wavelength in a wavelength range of 600 to 1100 nm. The near-infrared cut filter according to any one of claims 1 to 3, wherein a maximum absorption wavelength of the layer containing the infrared absorbing dye is shorter than a maximum absorption wavelength of the resin layer containing the copper compound. The wavelength. The near-infrared cut filter according to any one of claims 1 to 3, wherein the copper-containing glass is in contact with one of the surfaces of the resin layer containing the copper compound, and the infrared absorbing dye is contained The layer is in contact with the other surface of the resin layer containing the copper compound. The near-infrared cut filter according to any one of the items 1 to 3, wherein the copper compound is a compound represented by the following formula (1); Cu (L) _n1 (X) _{In the} formula, L is a ligand having a coordination site for a copper atom, and represents a compound having at least one selected from the group consisting of the following groups, the group comprising a group of a coordination site at which an anion coordinates a copper atom, and a group containing a coordinating atom that coordinates a copper atom with an unshared electron pair, X represents a relative ion, and n1 represents an integer of 1 to 4, n2 Indicates an integer from 0 to 4. The near-infrared cut filter according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of a dielectric multilayer film and an ultraviolet absorbing layer. A solid-state imaging device having a near-infrared cut filter as described in any one of claims 1 to 10. A camera module having a near-infrared cut filter as described in any one of claims 1 to 10. An image display device having a near-infrared cut filter as described in any one of claims 1 to 10.