CN111095048A - Method for manufacturing near-infrared cut filter, laminate, and kit - Google Patents

Abstract

The invention provides a method for manufacturing a near infrared ray cut filter, a laminated body and a kit, wherein the method can manufacture the near infrared ray cut filter with high flatness with excellent productivity. The method for manufacturing the near infrared ray cut-off filter comprises the following steps: forming a support layer on a surface of a substrate; a step of forming a near-infrared ray absorbing composition layer by applying a near-infrared ray absorbing composition containing a near-infrared ray absorbing agent to the surface of the support layer; a step of forming a near-infrared cut filter layer by curing the near-infrared absorbing composition layer; a step of peeling off a laminate composed of a support and a near-infrared cut filter layer from a substrate; and a step of peeling the support layer from the laminate peeled from the substrate.

Description

Method for manufacturing near-infrared cut filter, laminate, and kit

Technical Field

The present invention relates to a method for manufacturing a near-infrared cut filter. The present invention also relates to a laminate and a kit used in the method for manufacturing a near-infrared cut filter.

Background

A Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), or the like, which is a solid-state imaging element for color images, is used in video cameras, digital cameras, mobile phones with camera functions, and the like. Since a silicon photodiode having sensitivity to near infrared rays is used in the light receiving portion of these solid-state imaging elements, visibility correction is required, and a near infrared ray cut filter is often used.

As the near-infrared cut filter, a film or the like obtained by coating a composition containing a near-infrared absorber on a substrate having high rigidity such as a glass substrate is used.

For example, patent document 1 describes an optical filter including a substrate and an adhesive layer disposed on the substrate, the adhesive layer including: porphyrazine-based coloring matter, diammine-based near infrared absorbing coloring matter comprising an amorphous substance of diammine salt, ultraviolet absorber, light stabilizer comprising copper complex or nickel complex, and acrylic adhesive. Paragraphs 0174 to 0177 describe the following: an adhesive film was produced by applying an adhesive composition to a release film having a silicone resin layer formed on the surface of a PET (polyethylene terephthalate) film and drying the adhesive composition to form a near infrared ray absorbing adhesive layer having a thickness of 25 μm, and the obtained adhesive film was bonded to an antireflection film, and then the release film was peeled off and bonded to a glass substrate to produce an optical filter.

Patent document 2 describes an infrared ray cut film including: a transparent substrate; a near-infrared ray absorption layer containing a near-infrared ray absorber having a maximum absorption wavelength of 750nm to 920 nm; and at least 1 near infrared ray reflecting layer for fixing the cholesteric liquid crystal phase.

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 2015-001649

Patent document 2: japanese patent laid-open No. 2014-071356

Disclosure of Invention

Technical problem to be solved by the invention

When a film is formed using a composition containing a near-infrared absorber, the composition containing the near-infrared absorber is applied to a substrate having high rigidity, such as a glass substrate, to form the film, for the purpose of suppressing unevenness in the film or the like, and the like. Conventionally, the near-infrared cut filter is used in a state in which the film is laminated on a glass substrate or the like, but in recent years, a technique has been studied in which the film itself is provided with rigidity and used as a film having self-supporting properties (self-supporting properties), and the film after the film formation is peeled from the substrate or the like.

However, according to the studies of the present inventors, when a film after film formation is peeled from a substrate or the like, cracks, fractures, or the like may be generated in the film. In particular, when the film has high rigidity, the film may not be easily peeled from the substrate, and the film may be easily cracked or broken during peeling. If a crack or a fracture occurs in the film during peeling, the yield of the product decreases, and thus the productivity decreases.

In patent documents 1 and 2, a film obtained using a composition containing a near-infrared absorbent is used by laminating it on a substrate or by laminating it by adhering it to another member, but there is no description about a film obtained by peeling only a composition containing a near-infrared absorbent from a substrate or the like.

Accordingly, an object of the present invention is to provide a method for manufacturing a near-infrared cut filter, a laminate, and a kit, by which a near-infrared cut filter having high flatness can be manufactured with excellent productivity.

Means for solving the technical problem

As a result of intensive studies, the present inventors have found that a near-infrared cut filter having high planarity can be produced with excellent productivity by the following steps, and have completed the present invention. The present invention provides the following.

< 1 > a method for manufacturing a near infrared ray cutoff filter, comprising:

forming a support layer on a surface of a substrate;

a step of forming a near-infrared ray absorbing composition layer by applying a near-infrared ray absorbing composition containing a near-infrared ray absorbing agent to the surface of the support layer;

a step of forming a near-infrared cut filter layer by curing the near-infrared absorbing composition layer;

a step of peeling the laminate composed of the support layer and the near-infrared cut filter layer from the substrate; and

and a step of peeling the support layer from the laminate peeled from the substrate.

< 2 > the method for manufacturing a near infrared ray cutoff filter according to < 1 >, wherein,

the flatness of the substrate is 14 μm or less, and the bending rigidity per 1mm width at 23 ℃ is larger than that of the support layer.

< 3 > the method for manufacturing a near infrared ray cutoff filter according to < 1 > or < 2 >, wherein,

the support layer comprises a polymer film.

< 4 > the method for manufacturing a near infrared ray cutoff filter according to < 3 >, wherein,

the softening temperature of the polymer film is higher than the maximum reaching temperature of the near infrared ray absorbing composition layer during the curing treatment.

< 5 > the method for manufacturing a near infrared ray cutoff filter according to < 3 > or < 4 >, wherein,

the elongation at break of the polymer film at 23 ℃ is more than 5% and higher than that of the near infrared ray cut filter layer,

the polymer film had a flexural rigidity per 1mm width at 23 ℃ of 4X 10^-6Pa·m⁴Bending rigidity per 1mm width of the near infrared ray cut filter layer is less than or equal to.

< 6 > the method for manufacturing a near infrared ray cutoff filter according to any one of < 1 > to < 5 >, wherein,

the support layer has a peeling force of 9N/25mm or less on the near-infrared ray cut filter layer side.

< 7 > the method for manufacturing a near infrared ray cutoff filter according to any one of < 1 > to < 6 >, wherein,

the support layer has a peel force of 15.5N/25mm or less on the substrate side.

< 8 > the method for manufacturing a near-infrared ray cutoff filter according to any one of < 1 > to < 7 >, wherein,

the support layer has a peeling force on the near-infrared ray cut filter layer side greater than that on the substrate side.

< 9 > the method for manufacturing a near infrared ray cutoff filter according to any one of < 1 > to < 7 >, wherein,

the support layer has a lower peeling force on the near-infrared ray cut filter layer side than on the substrate side.

< 10 > the method for manufacturing a near infrared ray cutoff filter according to any one of < 1 > to < 7 >, wherein,

the support layer has the same peeling force on the near-infrared cut filter layer side as that on the substrate side.

< 11 > the method for manufacturing a near-infrared ray cutoff filter according to any one of < 1 > to < 10 >, wherein,

in the step of forming the near-infrared ray absorbing composition layer, the near-infrared ray absorbing composition is applied to the surface of the support layer to form the near-infrared ray absorbing composition layer, and a blank portion where the near-infrared ray absorbing composition layer is not provided is formed in at least a part of the surface of the support layer.

< 12 > the method for manufacturing a near-infrared ray cutoff filter according to any one of < 1 > to < 11 >, wherein,

the film thickness of the support layer is 1 to 1000 μm.

< 13 > the method for manufacturing a near infrared ray cutoff filter according to any one of < 1 > to < 12 >, wherein,

the film thickness of the near infrared cut filter layer is 1 to 500 μm.

< 14 > the method for manufacturing a near infrared ray cutoff filter according to any one of < 1 > to < 13 >, wherein,

the bending rigidity of the near infrared ray cut filter layer per 1mm width at 23 ℃ is 5X 10^-6Pa·m⁴And an elongation at break at 23 ℃ of 10% or less.

< 15 > the method for manufacturing a near infrared ray cutoff filter according to any one of < 1 > to < 14 >, wherein,

the near infrared ray absorbing composition comprises a copper complex and a resin.

< 16 > the method for manufacturing a near infrared ray cutoff filter according to < 15 >, wherein,

the resin contains a resin having a crosslinkable group.

< 17 > the method for producing a near-infrared cut filter according to < 15 > or < 16 >, wherein the near-infrared absorbing composition comprises a monomer having a crosslinkable group.

< 18 > a laminate having:

a substrate, a support layer, and a near infrared ray cut filter layer containing a near infrared ray absorber,

one surface of the support layer is in contact with the substrate, the other surface of the support layer is in contact with the near infrared ray cut filter layer,

the support layer has a polymer film,

the flatness of the substrate is 14 μm or less, and the bending rigidity per 1mm width at 23 ℃ is larger than that of the support layer.

< 19 > a kit for use in the method for manufacturing a near-infrared ray cutoff filter according to any one of < 1 > to < 17 >, the kit comprising:

a support layer having a polymer film;

a substrate having a flatness of 14 μm or less and a flexural rigidity per 1mm width at 23 ℃ greater than that of the support layer; and

a near-infrared ray absorbing composition includes a near-infrared ray absorber.

Effects of the invention

According to the present invention, a method for manufacturing a near-infrared cut filter, a laminate, and a kit, which can manufacture a near-infrared cut filter having high planarity with excellent productivity, can be provided.

Drawings

Fig. 1 is a diagram illustrating a step of forming a support layer in a method of manufacturing a near-infrared cut filter.

Fig. 2 is a plan view of fig. 1, and is a plan view of the substrate 10 viewed from the lower surface side in the vertical direction.

Fig. 3 is a diagram showing a step of forming a near-infrared absorbing composition layer in the method of manufacturing a near-infrared cut filter.

Fig. 4 is a plan view of fig. 3, and is a plan view of the substrate 10 viewed from the upper surface side in the vertical direction.

Fig. 5 is a diagram illustrating a process of forming a near-infrared cut filter layer in the method of manufacturing a near-infrared cut filter.

Fig. 6 is a diagram showing a step of peeling the laminate (the 1 st peeling step) in the method of manufacturing the near-infrared cut filter.

Fig. 7 is a diagram showing a step of peeling off the near-infrared ray cut filter layer (the 2 nd peeling step) in the method of manufacturing the near-infrared ray cut filter.

Fig. 8 is a diagram showing a peeling preparation step in the method for manufacturing a near-infrared cut filter.

Detailed Description

The present invention will be described in detail below.

In the present specification, "to" is used in a meaning including the numerical values described before and after the "to" as the lower limit value and the upper limit value.

In the present specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) allyl" represents allyl and methallyl, "(meth) acrylic acid" represents acrylic acid and methacrylic acid, and "(meth) acryloyl" represents acryloyl and methacryloyl.

In the expression of the group (atomic group) in the present specification, the expression that is not described as substituted or unsubstituted includes a group (atomic group) having no substituent and also includes a group (atomic group) having a substituent.

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, the near infrared ray refers to light (electromagnetic wave) having a wavelength range of 700nm to 2500 nm.

In the present specification, the total solid content means the total mass of components after 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).

Method for manufacturing near infrared cut-off filter

A method for manufacturing a near-infrared cut filter according to the present invention will be described with reference to the drawings. Fig. 1 to 5 are views showing steps of a method for manufacturing a near-infrared cut filter according to the present invention.

The method for manufacturing a near-infrared cut filter according to the present invention includes:

a step of forming a support layer 20 on the surface of the substrate 10 (see fig. 1 and 2);

a step of applying a near-infrared absorbent composition containing a near-infrared absorbent to the surface of the support layer 20 to form a near-infrared absorbent composition layer 30 (see fig. 3 and 4);

a step of forming a near-infrared cut filter layer 31 by curing the near-infrared absorbing composition layer 30 (see fig. 5);

a step of peeling the laminate 40 including the support layer 20 and the near-infrared cut filter layer 31 from the substrate 10 (see fig. 6); and

and a step of peeling the support layer 20 from the laminate 40 peeled from the substrate (see fig. 7).

According to the method for manufacturing a near-infrared cut filter of the present invention, a near-infrared cut filter having high planarity can be manufactured with excellent productivity.

That is, since the near-infrared ray absorbing composition is applied to the substrate 10 having the support layer 20 formed on the surface thereof to form the near-infrared ray absorbing composition layer 30, the near-infrared ray absorbing composition has good coatability, and the occurrence of coating unevenness or thickness unevenness during film formation can be effectively suppressed. Therefore, a near-infrared cut filter having high planarity can be formed.

As shown in fig. 5 to 7, after the near-infrared absorbing composition layer 30 formed on the surface of the support layer 20 is cured to form the near-infrared cut filter layer 31, the laminate 40 formed of the support layer 20 and the near-infrared cut filter layer 31 is peeled from the laminate formed of the substrate 10, the support layer 20, and the near-infrared cut filter layer 31, and separated into the laminate 40 and the substrate 10, and the support layer 20 is peeled from the laminate 40 to separate the support layer 20 and the near-infrared cut filter layer 31, whereby the near-infrared cut filter layer 31 can be peeled while suppressing the curvature of the near-infrared cut filter layer 31. Therefore, the occurrence of cracking or the like of the near-infrared cut filter layer 31 at the time of peeling can be effectively suppressed. Therefore, according to the present invention, a near-infrared cut filter having high planarity can be manufactured with excellent productivity. Hereinafter, each step of the method for manufacturing a near-infrared cut filter of the present invention will be described in detail.

(Process for Forming support layer)

As shown in fig. 1 and 2, first, a support layer 20 is formed on the surface of a substrate 10. The support layer 20 can be formed on the surface of the substrate 10 by laminating the support layer 20 on the surface of the substrate 10 by pressing, rolling, or the like. In this embodiment, as shown in fig. 2, the planar area of the support body layer 20 formed on the surface of the substrate 10 is larger than the planar area of the substrate 10, and the support body layer 20 is provided with a blank portion on the outer side of the substrate 10 where the substrate 10 is not present, and the planar area of the support body layer 20 formed on the surface of the substrate 10 may be the same as the planar area of the substrate 10 or may be larger than the planar area of the substrate 10. From the viewpoint of peelability, the support layer 20 is preferably provided with a blank portion on the outer side of the substrate 10. According to this embodiment, in the step shown in fig. 6 described later, the laminated body 40 can be peeled from the substrate 10 by gripping the blank portion of the support layer 20, and the workability in peeling is good.

The material of the substrate 10 is not particularly limited, and glass, ceramic, metal, and the like can be used. The substrate 10 preferably has high flatness and high bending rigidity. By using a substrate having high bending rigidity and flatness, a near-infrared absorbing composition layer having less unevenness in coating or thickness can be formed. Therefore, a near-infrared cut filter having a higher flatness can be manufactured. Further, although the substrate having high bending rigidity is not easily bent, even when such a substrate having high bending rigidity is used, the curvature of the near infrared ray cut filter layer 31 can be reduced when the substrate 10 is peeled off according to the present invention. Therefore, the near infrared ray cut filter layer 31 can be separated from the substrate 10 without causing cracks or the like, and the effect of the present invention is more remarkable.

The flatness of the substrate 10 is preferably 14 μm or less, more preferably 10 μm or less, and further preferably 7 μm or less. The flatness of the substrate is a value measured by using a fizeau interferometer for flatness measurement and counting interference fringes in a range of 60mm in diameter.

As the measurement apparatus, "F601" (manufactured by Fujifilm Corporation) can be used.

The bending rigidity per 1mm width of the substrate 10 is preferably larger than that of the support layer. Here, the bending rigidity means a value of a degree of bending when a certain force is applied, and indicates that the larger the value of the bending rigidity, the less likely it is to bend. Even in the case of using such a substrate that is not easily bent, according to the present invention, peeling can be performed while suppressing the curvature of the near infrared ray cut filter layer when peeling the substrate 10, and the effect of the present invention is more remarkable. The bending rigidity per 1mm width of the substrate 10 is preferably 6X 10^-6Pa·m⁴Above, more preferably 2 × 10^-5Pa·m⁴Above, more preferably 9 × 10^-5Pa·m⁴The above. The flexural rigidity of the substrate is calculated based on the method according to JIS K7171 and based on the young's modulus measured at 23 ℃ and the calculated value of the moment of inertia of the cross section calculated from the shape of the substrate used.

The thickness of the substrate 10 is preferably 0.1 to 10 mm. The upper limit is preferably 8mm or less, more preferably 5mm or less. The lower limit is preferably 0.2mm or more, and more preferably 0.5mm or more. Although a thick substrate tends to be less flexible, according to the present invention, even when a thick substrate is used, the curvature of the near infrared ray cut filter layer 31 when the substrate 10 is peeled can be reduced by inserting the support layer 20, and therefore the near infrared ray cut filter layer 31 can be separated from the substrate 10 without causing a crack or the like, and the effect of the present invention is more remarkable.

The film thickness of the support layer 20 is preferably 1 to 1000 μm. The upper limit is preferably 900 μm or less, more preferably 800 μm or less. The lower limit is preferably 25 μm or more, and more preferably 40 μm or more.

The support layer 20 preferably includes a polymer film. Examples of the polymer film include films made of, or laminated films of, polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1, and polybutene-1; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; a polycarbonate resin; a polyvinyl chloride resin; polyphenylene sulfide resin; polyether sulfone resin; a polythioethylene resin; a polyphenylene ether resin; a styrene resin; (meth) acrylic resins; a polyamide resin; a polyimide resin; cellulose resins such as cellulose acetate and the like.

The softening temperature of the polymer film is preferably higher than the maximum reaching temperature of the near-infrared-absorbing composition layer 30 in the curing treatment, more preferably higher by 20 ℃ or more, and still more preferably higher by 40 ℃ or more. According to this embodiment, deformation of the support layer 20 and the like can be effectively suppressed in the curing treatment of the near-infrared-absorbing composition layer. As a result, a near-infrared cut filter layer with less thickness unevenness can be easily formed, and a near-infrared cut filter with high planarity can be more easily obtained. The softening temperature of the polymer film is preferably 100 ℃ or higher, and more preferably 150 ℃ or higher. The softening temperature of the polymer film is a value measured by the method according to JIS K7196. The maximum reaching temperature during the curing process is a temperature value at a point when the surface temperature of the near infrared ray absorbing composition layer 30 reaches a maximum point during the curing process of the near infrared ray absorbing composition layer 30.

The polymer film preferably has an elongation at break of 5% or more and more than that of the near-infrared cut filter layer 31, and has a bending rigidity per 1mm width of 4 × 10^-6Pa·m⁴Bending rigidity per 1mm width of the near infrared ray cut filter layer is less than or equal to. The elongation at break is a value at 23 ℃ measured by the method of JIS K7161. The flexural rigidity per width is a calculated value based on the Young's modulus measured at 23 ℃ in accordance with JIS K7171 and based on the second moment of area calculated from the shape of the polymer film used. By using a support layer including such a polymer film, the occurrence of cracking or the like of the near-infrared cut filter layer 31 at the time of peeling can be effectively suppressed.

The polymer thin film preferably has a thickness of 1 to 1000 μm. The upper limit is preferably 900 μm or less, more preferably 800 μm or less. The lower limit is preferably 25 μm or more, and more preferably 40 μm or more.

The support layer 20 may be composed of only a polymer film, or a release layer may be formed on the surface of a polymer film, but from the viewpoint of peelability, a release layer is preferably formed on the surface of a polymer film, and more preferably formed on both surfaces of a polymer film. Examples of the method for forming a release layer on the surface of a polymer film include a method for forming a release layer by applying and drying a release layer-forming composition containing a release agent to the surface of a polymer film, and a method for forming a release layer by attaching a release film to the surface of a polymer film. Examples of the release agent used in the composition for forming a release layer include silicone release agents and fluorine release agents. Examples of the release film include SG-1, SG-2S, TP-03, PX125H8C50, and PX125AFP2SKB50 (manufactured by PANAC Corporation).

The peeling force of the support layer 20 on the near-infrared cut filter layer 31 side is preferably 9N/25mm or less, more preferably 7N/25mm or less, and still more preferably 5N/25mm or less. The peeling force of the support layer 20 on the substrate 10 side is preferably 15.5N/25mm or less, more preferably 10N/25mm or less, further preferably 5N/25mm or less, further preferably 2N/25mm or less, further preferably 0.5N/25mm or less, further preferably 0.2N/25mm or less, particularly preferably 0.15N/25mm or less, and particularly preferably 0.1N/25mm or less. When the peeling force of the support layer 20 is in the above range, the peeling property is good, and the occurrence of cracking or the like of the near-infrared cut filter layer 31 at the time of peeling can be effectively suppressed. The peel force was measured by a method according to JIS Z0237, except that 31B tape (manufactured by NITTO DENKO CORPORATION) was used for the bonded object, the peel speed was 300mm/min, and the peel angle was 180 degrees.

The peeling force of the support layer 20 on the near-infrared cut filter layer 31 side may be the same as the peeling force of the support layer 20 on the substrate 10 side, may be smaller than the peeling force of the support layer 20 on the substrate 10 side, or may be larger than the peeling force of the support layer 20 on the substrate 10 side. When the peeling force of the support layer 20 on the near-infrared-ray-cut filter layer 31 side is larger than the peeling force of the support layer 20 on the substrate 10 side, the near-infrared-ray-cut filter layer 31 is less likely to peel off from the support layer 20 and an unexpected bending stress can be less likely to be applied to the near-infrared-ray-cut filter layer when the laminate 40 is peeled off in the peeling step 1 described later, and therefore, the near-infrared-ray-cut filter layer can be made less likely to be broken or the like. The peeling force of the support layer 20 can be adjusted by appropriately changing the raw materials, production conditions, and the like constituting the support layer 20. For example, when the support layer 20 is formed only of a polymer film, the adjustment can be performed by appropriately changing the material, production conditions, and the like of the polymer film. When the surface of the polymer film has a release layer, the material for forming the release layer can be appropriately selected and adjusted.

(Process for Forming near Infrared ray absorbing composition layer, Process for Forming near Infrared ray cut Filter layer)

Next, a near-infrared absorbing composition containing a near-infrared absorber is applied to the surface of the support layer to form a near-infrared absorbing composition layer (see fig. 3 and 4). Next, the near infrared ray absorption composition layer is heat-cured to form a near infrared ray cut filter layer (refer to fig. 5). The near-infrared absorbing composition will be described later. In this embodiment, as shown in fig. 4, the plane area of the near infrared ray absorbing composition layer 30 formed on the surface of the support layer 20 is smaller than the plane area of the support layer 20, and a part of the support layer 20 is a blank portion where the near infrared ray absorbing composition layer 30 is not provided, but the plane area of the near infrared ray absorbing composition layer 30 may be the same as the plane area of the support layer 20. The blank portion is preferably provided from the viewpoint of peelability. The blank portion is preferably provided at least in a part of the end portion of the support layer 20. According to this embodiment, in the step shown in fig. 7 described later, the support layer 20 in the blank portion can be gripped and the support layer 20 can be peeled from the near-infrared cut filter layer 31, and the workability in peeling can be improved. That is, in the present invention, in the step of forming the near infrared ray absorbing composition layer, it is preferable that the near infrared ray absorbing composition layer 30 is formed by applying the near infrared ray absorbing composition to the surface of the support body layer 20, and a margin where the near infrared ray absorbing composition layer 30 is not provided is formed in at least a part of the surface of the support body layer 20, and the margin is preferably formed in a range of 1 to 5mm from the end of the support body layer 20.

In the step of forming the near-infrared ray absorbing composition layer, a known method can be used as a method for applying the near-infrared ray absorbing composition. For example, a dropping method (droplet application); slit coating method; spraying; a roll coating method; spin coating (spin coating); tape casting coating method; slit and spin methods; a prewet method (for example, the method described in Japanese patent laid-open No. 2009-145395); various printing methods such as ink jet (for example, on-demand method, piezoelectric method, thermal method), jet-based printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; nano-imprinting; knife coating; a bar coating method; applicator coating methods, and the like. The method to be applied by the inkjet is not particularly limited as long as it is a method capable of ejecting the composition, and for example, methods described in patent publications (especially, 115 to 133 pages) shown in "unlimited possibility in scalable inkjet-patent publication", published in 2.2005, Sumibe Techno Research ", and methods described in japanese patent laid-open publication nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-16925etc. can be used.

After the near infrared ray absorbing composition layer is formed and before the curing treatment is performed, a drying treatment may be performed. The drying conditions may vary depending on the type, content, and the like of each component contained in the near-infrared-absorbing composition. For example, the drying temperature is preferably 40 to 160 ℃. The lower limit is preferably 60 ℃ or higher, and more preferably 80 ℃ or higher. The upper limit is preferably 140 ℃ or lower, more preferably 120 ℃ or lower. The heating time is preferably 1 to 600 minutes. The lower limit is preferably 10 minutes or more, and more preferably 30 minutes or more. The upper limit is preferably 300 minutes or less, more preferably 180 minutes or less. Further, a method of raising the temperature from room temperature (e.g., 25 ℃) to a predetermined drying temperature at a constant rate of temperature rise and drying the product while maintaining the temperature may be mentioned. The temperature rise is preferably 0.5 to 10 ℃/min, more preferably 1.0 to 5 ℃/min.

The curing method of the near infrared ray absorbing composition layer is not particularly limited, and can be appropriately selected according to the purpose. For example, exposure treatment, heating treatment, and the like are mentioned, and the heating treatment is preferably performed because a near-infrared cut filter layer having excellent mechanical properties is easily obtained. Here, in the present invention, the term "exposure" is used to include not only irradiation with light of various wavelengths but also irradiation with radiation such as electron beams and X-rays.

When a composition containing a resin having a crosslinkable group or a monomer having a crosslinkable group is used as the near-infrared ray-absorbing composition, the curing treatment of the near-infrared ray-absorbing composition layer is preferably performed under conditions such that the crosslinking rate of the near-infrared ray-absorbing composition layer is 50 to 90%. Here, the crosslinking ratio is the number of crosslinkable groups to be crosslinked/total number of crosslinkable groups, and can be measured by a method such as NMR (nuclear magnetic resonance).

The exposure treatment is preferably performed by irradiating the near-infrared ray absorbing composition layer with radiation. The radiation is preferably ultraviolet rays such as electron beam, KrF, ArF, g-ray, h-ray, i-ray, and the like. Examples of the exposure method include step exposure and exposure using a high-pressure mercury lamp. The exposure is preferably 5 to 3000mJ/cm². The upper limit is preferably 2000mJ/cm²Hereinafter, more preferably 1000mJ/cm²The following. The lower limit is preferably 10mJ/cm²Above, more preferably 50mJ/cm²The above. The exposure apparatus is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include an ultraviolet exposure apparatus such as an ultrahigh-pressure mercury lamp.

The heating temperature in the heating treatment is preferably 100 to 180 ℃. The lower limit is preferably 120 ℃ or higher, more preferably 140 ℃ or higher. The upper limit is preferably 170 ℃ or lower, more preferably 160 ℃ or lower. The heating time is preferably 0.5 to 48 hours. The lower limit is preferably 1 hour or more, and more preferably 1.5 hours or more. The upper limit is preferably 24 hours or less, more preferably 6 hours or less. The heating device is not particularly limited, and may be appropriately selected from known devices according to 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 cured near infrared ray absorption composition layer (near infrared ray cut filter layer) may be aged (Aging). In the aging, the near infrared ray absorbing composition layer (near infrared ray cut filter layer) is preferably subjected to a high temperature and high humidity treatment. The aging temperature is preferably 60 to 150 ℃. The lower limit is preferably 70 ℃ or higher, more preferably 80 ℃ or higher. The upper limit is preferably 140 ℃ or lower, more preferably 130 ℃ or lower. The humidity is preferably 30 to 100%. The lower limit is preferably 40% or more, and more preferably 50% or more. The upper limit is preferably 95% or less, more preferably 90% or less. The aging time is preferably 0.5 to 100 hours. The lower limit is preferably 1 hour or more, more preferably 2 hours or more. The upper limit is preferably 50 hours or less, more preferably 25 hours or less. The aging apparatus is not particularly limited, and may be appropriately selected from known apparatuses according to the purpose, and examples thereof include a high-temperature high-humidity furnace.

Further, the aging may be performed in a state where the curing step is not performed on the near infrared ray absorbing composition layer formed by applying the near infrared ray absorbing composition to the surface of the support layer. In this embodiment, the aging step is combined with the curing step.

The thickness of the near-infrared cut filter layer 31 is preferably 1 to 500 μm. The upper limit is preferably 450 μm or less, more preferably 400 μm or less. The lower limit is more preferably 5 μm or more, more preferably 10 μm or more, still more preferably 25 μm or more, still more preferably 50 μm or more, and particularly preferably 60 μm or more. Conventionally, the near infrared ray cut filter layer 31 tends to be easily broken at the time of peeling as the film thickness of the near infrared ray cut filter layer 31 increases, but according to the present invention, even if the film thickness of the near infrared ray cut filter layer 31 is increased, the occurrence of breakage or the like at the time of peeling can be effectively suppressed.

The near-infrared cut filter layer 31 of the present invention is particularly effective when the bending rigidity and the elongation at break are small. The near-infrared cut filter layer having low bending rigidity and elongation at break is weak against bending stress, and therefore is not easily peeled by a conventional method, but according to the present invention, even the near-infrared cut filter layer 31 having such mechanical properties can be peeled without causing cracking or the like.

The near infrared ray cut filter layer 31 used in the present invention has a bending rigidity of 5 × 10 per 1mm width^{- 6}Pa·m⁴The following is particularly effective when the elongation at break is 10% or less. In thatThe bending strength of the near infrared ray cut filter layer 31 was 3 × 10^-6Pa·m⁴The following is more effective, and 9 × 10^-7Pa·m⁴The following is more effective. Further, the near-infrared cut filter layer 31 is more effective when the breaking elongation is 8% or less, and is more effective when the breaking elongation is 6% or less. The bending rigidity of the near-infrared cut filter layer 31 is a calculated value of the second moment of area calculated from the young's modulus measured at 23 ℃ according to JIS K7171 and the shape of the near-infrared cut filter layer, and the elongation at break is a value at 23 ℃ measured according to the method of JIS K7171. The near-infrared cut filter layer having such mechanical properties tends to have a weak bending stress, but according to the present invention, even the near-infrared cut filter layer 31 having such mechanical properties can be peeled off without causing a crack or the like, and therefore the effect of the present invention is more remarkable. The near-infrared cut filter layer 31 having the mechanical properties also has characteristics as a self-supporting film. Here, the self-supporting film is a film which has self-supporting properties and can maintain the shape of the film even in the absence of a substrate or the like. More specifically, it means a film capable of holding its shape by its strength against a vertical downward force generated by its own weight.

The mechanical properties of the near-infrared cut filter layer 31 can be achieved in any manner, but can be achieved by appropriately adjusting the type and content of components such as resin of the near-infrared absorbing composition, film forming conditions (for example, adjustment of drying conditions, curing conditions, and crosslinking ratio), and the like in the process of producing the near-infrared cut filter layer 31. For example, a method of forming the near-infrared cut filter layer 31 using a resin having a crosslinkable group and/or a near-infrared absorbing composition containing a monomer having a crosslinkable group is given as an example. It is preferable to use a resin having a crosslinkable group and a monomer having a crosslinkable group in combination. In this case, the near-infrared ray absorption composition preferably contains the monomer having a crosslinkable group in an amount of 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and still more preferably 5 to 15 parts by mass, based on 100 parts by mass of the resin having a crosslinkable group. Further, the crosslinking rate of the resin film can be adjusted to 50 to 90% by appropriately adjusting the drying temperature, curing conditions, and the like of the near-infrared absorbing composition. Here, the crosslinking ratio is the number of crosslinkable groups that have been crosslinked/total number of crosslinkable groups, and can be measured by a method such as NMR (nuclear magnetic resonance).

In the method of manufacturing the near-infrared cut filter of the present invention, after the near-infrared cut filter layer 31 is formed, various functional layers may be further formed on the surface of the near-infrared cut filter layer 31. Examples of the functional layer include an inorganic film such as an electrolyte multilayer film, and an ultraviolet absorbing layer. These functional layers may be formed after the step of fig. 5 and before the step of fig. 6, after the step of fig. 6 and before the step of fig. 7, or after the step of fig. 7. When the step of fig. 8 is performed, the step may be performed after the step of fig. 8 and before the step of fig. 7.

(step of peeling laminate (1 st peeling step))

Next, as shown in fig. 6, the laminate including the support layer 20 and the near-infrared cut filter layer 31 is peeled off from the substrate 10. The method for peeling the laminate 40 is not particularly limited. The peeling is preferably performed so that a bending stress is not applied to the near infrared ray cut filter layer 31. For example, there may be mentioned: a method of holding the support and pulling the support at an angle close to horizontal so as not to apply bending stress to the near-infrared-ray-cut filter layer 31, a method of sequentially vacuum-sucking the vicinity of the peeling point with an appropriate force and peeling the support.

(Process for peeling off near Infrared ray cut Filter layer (No. 2 peeling off Process))

Next, as shown in fig. 7, the support layer 20 is peeled off from the laminate 40 peeled off from the substrate 10, and separated into the support layer 20 and the near-infrared cut filter layer 31. In this way, when the near infrared ray cut filter is formed of a single film of the near infrared ray cut filter layer 31 or when the surface of the near infrared ray cut filter layer 31 further includes a functional layer, the near infrared ray cut filter is formed of a laminated film of the near infrared ray cut filter layer 31 and other functional layers.

The method for peeling the support layer 20 is not particularly limited. The peeling is preferably performed so that a bending stress is not applied to the near infrared ray cut filter layer 31. For example, there may be mentioned: a method of bending the support layer 20 side greatly and peeling it off so that bending stress is not applied to the near-infrared ray cut filter 31 side, and a method of peeling the support layer 20 side by fixing the entire surface of the near-infrared ray cut filter 31 by vacuum suction or the like.

As shown in fig. 8, it is also preferable that after the notch 32 is formed near the end of the near-infrared cut filter layer 31, the near-infrared cut filter layer 31 is peeled from the support layer 20. According to this embodiment, the near-infrared cut filter layer 31 has good peelability from the support layer 20, and the occurrence of cracking or the like of the near-infrared cut filter layer 31 can be more effectively suppressed. Further, the thickness of the near infrared ray cut filter layer 31 formed by coating may be reduced at the end portion, but in this case, it is more effective to add a notch. When the notch 32 is formed near the end of the near-infrared cut filter layer 31, the notch 32 is preferably formed within a range of 1 to 5mm from the end of the support body layer 20.

The near-infrared cut filter obtained according to the present invention can be used in various devices such as solid-state imaging elements such as CCDs (charge coupled devices) and CMOSs (complementary metal oxide semiconductors), infrared sensors, and image display devices.

< composition absorbing near infrared ray >

Next, the near-infrared absorbing composition used in the method for manufacturing a near-infrared cut filter of the present invention will be described.

The near-infrared ray absorbing composition contains a near-infrared ray absorber. Examples of the near infrared ray absorber include compounds having a maximum absorption wavelength in a wavelength range of 700 to 1500 nm. The near-infrared absorber is more preferably a compound having a maximum absorption wavelength in a wavelength range of 700 to 1300nm, and still more preferably a compound having a maximum absorption wavelength in a wavelength range of 700 to 1200 nm. Examples of the near-infrared absorber include copper complexes, pyrrolopyrrole compounds, cyanine compounds, squaric acid compounds, phthalocyanine compounds, naphthalocyanine compounds, quartene compounds, merocyanine compounds, oxonium compounds, oxonol compounds, dihydride compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, methine azo compounds, anthraquinone compounds, and dibenzofuranone compounds. Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of Japanese patent application laid-open No. 2009-263614, compounds described in paragraphs 0037 to 0052 of Japanese patent application laid-open No. 2011-068731, and compounds described in paragraphs 0010 to 0033 of International publication WO2015/166873, and these contents are incorporated herein. Examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of Japanese patent application laid-open No. 2009-108267, compounds described in paragraphs 0026 to 0030 of Japanese patent application laid-open No. 2002-194040, compounds described in Japanese patent application laid-open No. 2015-172004, compounds described in Japanese patent application laid-open No. 2015-172102, compounds described in Japanese patent application laid-open No. 2008-88426, and compounds described in Japanese patent application laid-open No. 2017-031394, and the contents of these compounds are incorporated in the present specification. As the squaric acid compound, there may be mentioned a compound described in paragraphs 0044 to 0049 of Japanese patent laid-open No. 2011-208101, a compound described in paragraphs 0060 to 0061 of Japanese patent laid-open No. 6065169, a compound described in paragraph 0040 of International publication No. WO2016/181987, a compound described in International publication No. WO2013/133099, a compound described in International publication No. WO2014/088063, a compound described in Japanese patent laid-open No. 2014-126642, a compound described in Japanese patent laid-open No. 2016-146619, a compound described in Japanese patent laid-open No. 2015-open No. 046, a compound described in Japanese patent laid-open No. 2017-open 25311, a compound described in International publication No. WO2016/154782, a compound described in Japanese patent laid-open No. 176 5884953, a compound described in patent laid-open No. 6036689, a compound described in patent laid-open No. 5810604, a compound described in Japanese patent laid-open No. 0049, Compounds described in Japanese patent laid-open publication No. 2017-068120, etc., which are incorporated herein by reference. Examples of the phthalocyanine compound include compounds described in paragraph 0093 of Japanese patent laid-open No. 2012 and 077153, oxytitanium phthalocyanine described in Japanese patent laid-open No. 2006 and 343631, compounds described in paragraphs 0013 to 0029 of Japanese patent laid-open No. 2013 and 195480, and vanadium phthalocyanine described in Japanese patent laid-open No. 6081771, and these contents are incorporated herein. Examples of the naphthalocyanine compound include compounds described in paragraph 0093 of Japanese patent laid-open No. 2012-077153, which is incorporated herein. Examples of the bicorchorine compound include compounds described in japanese unexamined patent publication No. 2008-528706, which are incorporated herein by reference.

The near-infrared ray absorber used in the near-infrared ray absorbing composition is preferably a copper complex. The copper complex is preferably a complex of copper and a compound (ligand) having a coordination site for copper. Examples of the coordinating site for copper include a coordinating site coordinating with an anion, and a coordinating atom coordinating with an unshared electron pair. The copper complex may have more than 2 ligands. When 2 or more ligands are present, the ligands may be the same or different. The copper complex shows 4 coordination, 5 coordination, and 6 coordination, more preferably 4 coordination and 5 coordination, and still more preferably 5 coordination. The copper complex preferably has a 5-membered ring and/or a 6-membered ring formed by copper and a ligand. The copper complex is stable in shape and excellent in stability.

The copper complex is preferably a copper complex other than a copper phthalocyanine complex. Here, the phthalocyanine copper complex refers to a copper complex in which a compound having a phthalocyanine skeleton is used as a ligand. The compound having a phthalocyanine skeleton expands a pi-electron conjugated system in the whole molecule and adopts a planar structure. The copper phthalocyanine complex absorbs light by pi-pi transition. In order to absorb light in the near infrared region by pi-pi transition, a compound forming a ligand needs to take a long conjugated structure. However, when the conjugated structure of the ligand is lengthened, the transparency tends to be lowered. Therefore, the phthalocyanine copper complex may have insufficient transparency.

The copper complex is preferably a copper complex having as a ligand a compound having no maximum absorption wavelength in a wavelength region of 400 to 600 nm. Since a copper complex having a ligand of a compound having a maximum absorption wavelength in a wavelength region of 400 to 600nm absorbs in a visible region (for example, in a wavelength region of 400 to 600 nm), the visible transparency may be insufficient. The compound having a maximum absorption wavelength in a wavelength region of 400 to 600nm has a long conjugated structure, and is a compound having a large absorption of light in a pi-pi transition. Specifically, compounds having a phthalocyanine skeleton are exemplified.

The copper complex can be obtained by, for example, mixing, reacting, or the like a compound (ligand) having a coordination site to copper with respect to a copper component (copper or a compound containing copper). The compound (ligand) having a coordinating site for copper may be a low molecular weight compound or a polymer. Both can be used in combination.

The copper component is preferably a compound containing copper in valence 2. The copper component may be used in only 1 kind, or may be used in 2 or more kinds. As the copper component, for example, copper oxide or copper salt can be used. The copper salt is preferably, for example, a copper carboxylate (e.g., copper acetate, copper ethylacetoacetate, copper formate, copper benzoate, copper stearate, copper naphthenate, copper citrate, copper 2-ethylhexanoate, etc.), copper sulfonate (e.g., copper methanesulfonate, etc.), copper phosphate, copper phosphonate, copper phosphinate, copper amide, copper sulfonamide, copper imide, copper acylsulfonimide, copper bissulfonylimide, copper methide, copper alkoxide, copper phenoxide, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper perchlorate, copper fluoride, copper chloride, copper bromide, more preferably a copper carboxylate, copper sulfonate, copper imide, copper acylsulfonimide, copper bissulfonylimide, copper alkoxide, copper phenoxide, copper hydroxide, copper carbonate, copper fluoride, copper chloride, copper sulfate, copper nitrate, and still more preferably a copper carboxylate, Copper acylsulfonimide, copper phenoxy, copper chloride, copper sulfate, and copper nitrate, and particularly copper carboxylate, copper acylsulfonimide, copper chloride, and copper sulfate are preferable.

(Low molecular type copper Complex)

As the low-molecular-weight type 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 coordinates copper of a central metal, and copper is usually 2-valent copper. The copper complex can be obtained, for example, by reacting a copper component with a compound or a salt thereof that serves as a ligand L.

Cu(L)_n1·(X)_n2Formula (Cu-1)

In the above formula, L represents a ligand coordinating 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 counter ion. Besides neutral complexes having no electric charge, copper complexes may be cationic complexes or anionic complexes. In this case, a counter ion is present as necessary to neutralize the charge of the copper complex.

When the counter ion is a negatively charged counter ion (counter anion), it may be, for example, an inorganic anion or an organic anion. For example, as the counter ion, a hydroxide ion, a halogen anion, a substituted or unsubstituted alkylcarboxylate ion, a substituted or unsubstituted arylcarboxylate ion, a substituted or unsubstituted alkylsulfonate ion, a substituted or unsubstituted arylsulfonate ion, an aryldisulfonate ion, an alkylsulfate ion, a sulfate ion, a thiocyanate ion, a nitrate ion, a perchlorate ion, a borate ion, a sulfonate ion, an imide ion, a phosphate ion, a hexafluorophosphate ion, a picrate ion, an amide ion (including an amide substituted with an acyl group or a sulfonyl group), a methyl ion (including a methyl group substituted with an acyl group or a sulfonyl group) may be cited. For details of the counter anion, reference can be made to the description in paragraph 0024 of japanese patent application laid-open No. 2017-067824, which can be incorporated into the present specification.

When the counter ion is a counter ion (counter cation) having a positive charge, for example, an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion such as a tetrabutylammonium ion, a triethylbenzylammonium ion, a pyridinium ion, or the like), a phosphonium ion (for example, a tetraalkylphosphonium ion such as a tetrabutylphosphonium ion, an alkyltriphenylphosphonium ion, a triethylphenylphosphonium ion, or the like), an alkali metal ion, or a proton can be cited.

The counter ion may be a metal complex ion (e.g., a copper complex ion).

The ligand L is a compound having a coordination site for copper, and examples thereof include 1 or more compounds having a coordination site selected from a coordination site for coordinating copper with an anion and a coordination atom for coordinating copper with an unshared electron pair. The coordination site coordinated by the anion may be dissociated or undissociated. The ligand L is preferably a compound having 2 or more coordinating sites for copper (polydentate ligand). In order to improve the visible transparency, it is preferable that a plurality of ligands L are not continuously bonded to a pi conjugated system such as an aromatic system. The ligand can also be a compound having 1 coordination site for copper (monodentate ligand) and a compound having 2 or more coordination sites for copper (polydentate ligand) in combination. Examples of monodentate ligands include a monodentate ligand having an anion, which is a compound having 1 coordination site coordinating copper with an anion, and a monodentate ligand having an unshared electron pair, which is a compound having 1 coordinating atom coordinating copper with an unshared electron pair. As a specific example of monodentate ligands, reference can be made to the description in paragraph 0025 of Japanese patent application laid-open No. 2017-067824, which is incorporated herein by reference.

The anion having the ligand L is preferably an oxygen anion, a nitrogen anion or a sulfur anion as long as it can coordinate to a copper atom. The anionic coordination site is preferably at least 1 kind selected from the following group of functional groups having a valence of 1 (AN-1) or 2 (AN-2). The wave line in the following structural formula is a bonding position with an atomic group constituting a ligand.

Group (AN-1)

[ chemical formula 1]

Group (AN-2)

[ chemical formula 2]

In the 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. For the details of the above formula, reference can be made to the description in paragraph 0029 of japanese patent application laid-open No. 2017-067824, which is incorporated in the present specification.

The coordinating atom that the ligand L has to coordinate with unshared electron pairs is preferably an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom, more preferably an oxygen atom, a nitrogen atom, or a sulfur atom, even more preferably an oxygen atom or a nitrogen atom, and particularly preferably a nitrogen atom. When the coordinating atom coordinating the unshared electron pair is a nitrogen atom, the atom adjacent to the nitrogen atom is preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom.

The coordinating atom coordinated with the unshared electron pair is preferably contained in the ring or in at least 1 part structure selected from the following group consisting of a 1-valent functional group (UE-1), a 2-valent functional group (UE-2), and a 3-valent functional group (UE-3). The wave line in the following structural formula is a bonding position with an atomic group constituting a ligand.

Group (UE-1)

[ chemical formula 3]

Group (UE-2)

[ chemical formula 4]

Group (UE-3)

[ chemical formula 5]

In groups (UE-1) to (UE-3), R¹Represents a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl or heteroaryl group, R²Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, an amino group or an acyl group. For the details of the above formula, reference can be made to the description in paragraph 0037 of jp 2017-a 067824, which can be incorporated into the present specification.

Coordinating atoms that coordinate with unshared pairs of electrons may be included in the ring. When the coordinating atom coordinating with an unshared electron pair is contained in the ring, the ring containing the coordinating atom coordinating with an unshared electron pair may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The ring containing a coordinating atom coordinating to an unshared electron pair is preferably a 5-to 12-membered ring, more preferably a 5-to 7-membered ring.

The ligand L is preferably a compound having at least 2 coordination sites (also referred to as a polydentate ligand). The ligand L preferably has at least 3 coordinating sites, more preferably 3 to 5, and particularly preferably 4 to 5. The polydentate ligand acts as a chelating ligand for the copper component. That is, at least 2 coordinating sites of the polydentate ligand are chelate-coordinated with copper, so that the structure of the copper complex is deformed, excellent visible transparency is obtained, the light absorption capability of infrared rays can be improved, and the color value can be improved. The polydentate ligand is preferably a compound containing a coordinating atom that coordinates with an unshared electron pair, more preferably a compound containing a nitrogen atom as a coordinating atom that coordinates with an unshared electron pair, and even more preferably a compound containing a nitrogen atom as a coordinating atom that coordinates with an unshared electron pair, the nitrogen atom being substituted with an alkyl group (preferably a methyl group). For details of the polydentate ligand, reference may be made to the descriptions in paragraphs 0042 to 0043 of jp 2017-067824 a, which are incorporated herein by reference.

Specific examples of the compound serving as a ligand include the compounds described in paragraphs 0022 to 0042 of Japanese patent application laid-open No. 2014-041318, paragraphs 0021 to 0039 of Japanese patent application laid-open No. 2015-043063, paragraphs 0049 of Japanese patent application laid-open No. 2016-006476, and paragraphs 0045 and 0052 of Japanese patent application laid-open No. 2017-067824, and these contents can be incorporated in the present specification.

Examples of the copper complex include the following embodiments (1) to (5), more preferably (2) to (5), still more preferably (3) to (5), and still more preferably (4) or (5). For details of these, reference can be made to the descriptions in paragraphs 0047 to 0051 of japanese patent application laid-open No. 2017 and 067824, and the contents can be incorporated into the present specification.

(1) A copper complex having 1 or 2 compounds having 2 coordinating sites as ligands.

(2) A copper complex having a compound having 3 coordinating sites as a ligand.

(3) The copper complex includes a compound having 3 coordination sites and a compound having 2 coordination sites as ligands.

(4) A copper complex having a compound having 4 coordinating sites as a ligand.

(5) A copper complex having a compound having 5 coordinating sites as a ligand.

(Polymer type copper complex)

Examples of the polymer type copper complex include a copper-containing polymer having a copper complex site in a side chain thereof. Examples of the copper complex site include a copper complex site having copper and a site (coordination site) coordinating to copper. The site coordinating copper may be an anion or a site coordinating an unshared electron pair. The copper complex site preferably has a site having 4-dentate or 5-dentate coordination with respect to copper. The details of the coordinating site include those described for the low-molecular-weight copper compound, and the preferable ranges are the same.

Examples of the copper-containing polymer include a polymer obtained by reacting a polymer containing a coordination site (also referred to as a polymer (B1)) with a copper component, and a polymer obtained by reacting a polymer having a reactive site in a polymer side chain (hereinafter also referred to as a polymer (B2)) with a copper complex having a functional group capable of reacting with the reactive site of the polymer (B2). The weight average molecular weight of the copper-containing polymer is preferably 2000 or more, more preferably 2000 to 200 ten thousand, and further preferably 6000 to 200,000.

The copper-containing polymer may contain a repeating unit having a copper complex site, and may contain other repeating units. Examples of the other repeating unit include a repeating unit having a crosslinkable group.

The content of the near-infrared absorbent is preferably 5 to 90% by mass based on the total solid content of the near-infrared absorbent composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and further 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 complex can be used alone in 1 kind, and can also be used in combination with 2 or more kinds. In the case of using 2 or more copper complexes in combination, the total amount is preferably within the above range. The near infrared ray absorbing agent can be used alone in 1 kind, can also be combined with more than 2 kinds. When 2 or more kinds of near-infrared ray absorbers are used in combination, the total amount of these is preferably within the above range.

The near-infrared absorber preferably contains 50% by mass or more of the copper complex, more preferably 60% by mass or more, and still more preferably 70% by mass or more.

The content of the copper complex is preferably 5 to 90% by mass based on the total solid content of the near-infrared-absorbing composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and further 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 complex can be used alone in 1 kind, and can also be used in combination with 2 or more kinds. In the case of using 2 or more copper complexes in combination, the total amount of these is preferably within the above range.

The near-infrared absorbing composition preferably 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 polyolefins, chlorinated polyolefins, and cycloolefin polymers; a polystyrene resin; (meth) acrylic resins; a vinyl acetate resin; a halogenated vinyl resin; a polyvinyl alcohol resin; a polyamide resin; a polyurethane resin; polyester resins such as polyethylene terephthalate (PET) and Polyarylate (PAR); a polycarbonate resin; an epoxy resin; a polymaleimide resin; a polyurea resin; polyvinyl acetal resins such as polyvinyl butyral resins. Among them, (meth) acrylic resins, polyurethane resins, polyester resins, polymaleimide resins, and polyurea resins are preferable, and (meth) acrylic resins, polyurethane resins, and polyester resins are more preferable. Further, as the resin, a sol-gel cured product of a compound having an alkoxysilyl group is also preferably used. Examples of the compound having an alkoxysilyl group include those described as crosslinkable compounds described later. The weight average molecular weight of the resin is preferably 1000 to 300,000. The lower limit is more preferably 2000 or more, still more preferably 3000 or more, and particularly preferably 5000 or more. The upper limit is more preferably 100,000 or less, and still more preferably 50,000 or less. The number average molecular weight of the resin is preferably 500 to 150,000. The lower limit is more preferably 1000 or more, and still more preferably 2,000 or more. The upper limit is preferably 100,000 or less.

The resin is also preferably a resin having at least 1 kind of repeating unit represented by the following formulae (A1-1) to (A1-7).

[ chemical formula 6]

In the formula, R¹Represents a hydrogen atom or an alkyl group, L¹～L⁴Each independently represents a single bond or a 2-valent linking group, R¹⁰～R¹³Each independently represents an alkyl group or an aryl group. R¹⁴And R¹⁵Each independently represents a hydrogen atom or a substituent.

R¹The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R¹Preferably a hydrogen atom or a methyl group.

As L¹～L⁴As the 2-valent linking group, there may be mentioned alkylene, arylene, -O-, -S-, -SO-, -CO-, -COO-, -OCO-, -SO₂-、-NR^a-(R^aRepresenting a hydrogen atom or an alkyl group) or a group comprising a combination of these. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 10. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be any of linear, branched, and cyclic. The cyclic alkylene group may be a monocyclic or polycyclic one. The number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, and further preferably 6 to 10.

R¹⁰～R¹³The alkyl group represented may be any of linear, branched, or cyclic. The alkyl group may have a substituent or may be unsubstituted. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. R¹⁰～R¹³The number of carbon atoms of the aryl group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6.

R¹⁰Preferably a linear or branched alkyl or aryl group, more preferably a linear or branched alkyl group.

R¹¹And R¹²Preferably each independently a linear or branched alkyl group, more preferably a linear alkyl group.

R¹³Preferably a linear or branched alkyl or aryl group.

R¹⁴And R¹⁵The substituents include halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, -NR^a1R^a2、-COR^a3、-COOR^a4、-OCOR^a5、-NHCOR^a6、-CONR^a7R^a8、-NHCONR^a9R^a10、-NHCOOR^a11、-SO₂R^a12、-SO₂OR^a13、-NHSO₂R^a14or-SO₂NR^a15R^a16。R^a1～R^a16Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. Wherein R is¹⁴And R¹⁵At least one of them preferably represents cyano or-COOR^a4。R^a4Preferably represents a hydrogen atom, an alkyl group or an aryl group.

Examples of commercially available resins having a repeating unit represented by formula (a1-7) include ARTONF4520 (manufactured by jsrccorporation). Further, as for details of the resin having the repeating unit represented by the formula (A1-7), reference can be made to the descriptions in paragraphs 0053 to 0075 and 0127 to 0130 of Japanese patent application laid-open No. 2011-100084, which can be incorporated herein.

The resin is preferably a resin having a repeating unit represented by the formula (A1-4), more preferably a resin having a repeating unit represented by the formula (A1-1) and a repeating unit represented by the formula (A1-4). According to this embodiment, a near-infrared cut filter having excellent thermal shock resistance can be manufactured. Further, the compatibility of the copper complex with the resin is improved, and a near-infrared cut filter containing less precipitates and the like can be easily obtained.

The resin also preferably 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 alkoxysilyl group, more preferably a group having an ethylenically unsaturated bond, a cyclic ether group or an alkoxysilyl group, still more preferably a cyclic ether group or an alkoxysilyl group, and particularly preferably an alkoxysilyl group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, (meth) allyl group, and (meth) acryloyl group. Examples of the cyclic ether group include an epoxy group (oxirane group), an oxetane group, and an alicyclic epoxy group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group.

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

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

The resin having a crosslinkable group is preferably a resin containing a repeating unit having a crosslinkable group, and is preferably a resin containing a repeating unit represented by formula (A1-1) and/or formula (A1-4) and a repeating unit having a crosslinkable group.

The repeating unit having a crosslinkable group includes repeating units represented by the following formulae (A2-1) to (A2-4), and the like, and preferably repeating units represented by the formulae (A2-1) to (A2-3).

[ chemical formula 7]

R²Represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R²Preferably a hydrogen atom or a methyl group.

L⁵¹Represents a single bond or a 2-valent linking group. As the linking group having a valence of 2, there may be mentioned L of the above-mentioned formulae (A1-1) to (A1-7)¹～L⁴The linking group having a valence of 2 as specified in (1). L is⁵¹Preferably alkylene or alkylene and-O-A group formed by combining. Form L⁵¹The number of atoms of the bond (c) is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. The upper limit can be set to 200 or less, for example.

P¹Represents a crosslinkable group. Examples of the crosslinkable group include a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group, and an alkoxysilyl group, and the group having an ethylenically unsaturated bond, a cyclic ether group, and an alkoxysilyl group are preferable, and a cyclic ether group and an alkoxysilyl group are more preferable, and an alkoxysilyl group is even more preferable. The details of the group having an ethylenically unsaturated bond, the cyclic ether group, and the alkoxysilyl group are as described above. The number of carbon atoms of the alkoxy group in the alkoxysilyl 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 the repeating unit having a crosslinkable group in all the repeating units of the resin. The lower limit is preferably 6 mol% or more, more preferably 8 mol% or more, and further preferably 10 mol% or more. The upper limit is preferably 95 mol% or less, more preferably 80 mol% or less, and still more preferably 60 mol% or less. According to this embodiment, a resin layer having excellent mechanical properties can be easily formed.

The resin may contain other repeating units in addition to the above repeating units. Regarding the components constituting the other repeating units, reference can be made to the descriptions in paragraphs 0068 to 0075 of japanese patent application laid-open No. 2010-106268 (paragraphs 0112 to 0118 of the corresponding U.S. patent application publication No. 2011/0124824), and these contents can be incorporated in the present specification.

Specific examples of the resin include resins having the following structures.

[ chemical formula 8]

When the near-infrared ray absorbing composition contains a resin, the content of the resin is preferably 10 to 90% by mass based on the total solid content of the near-infrared ray absorbing composition. The lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, further 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 content of the resin having a crosslinkable group in the total amount of the resin is preferably 5 to 100% by mass, more preferably 8 to 100% by mass, and still more preferably 10 to 100% by mass. The number of the resin may be 1 or 2 or more. In the case of 2 or more species, the total amount is preferably within the above range.

The near-infrared absorbing composition preferably contains a monomer having a crosslinkable group (hereinafter, also referred to as a crosslinking agent). Examples of the crosslinkable group include a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group, and an alkoxysilyl group, and the group having an ethylenically unsaturated bond, a cyclic ether group, and an alkoxysilyl group are preferable, and a cyclic ether group and an alkoxysilyl group are more preferable, and an alkoxysilyl group is even more preferable. The details of the group having an ethylenically unsaturated bond, the cyclic ether group and the alkoxysilyl group include those explained for the resin having a crosslinkable group.

The molecular weight of the cross-linking agent is preferably 100-3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more.

The crosslinking agent preferably has a crosslinkable group value of 3 to 20 mmol/g. The lower limit is preferably 3.5mmol/g or more, more preferably 4mmol/g or more, and still more preferably 5mmol/g or more. The upper limit is preferably 19mmol/g or less, more preferably 17mmol/g or less, and still more preferably 15mmol/g or less. The crosslinkable group value of the crosslinking agent means the equivalent of the crosslinkable group contained in 1g of the crosslinking agent. The value of the crosslinkable group 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 1 molecule. The upper limit of the number of crosslinkable groups 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 1 molecule. The upper limit of the number of Si atoms is preferably 4 or less, and more preferably 3 or less. The number of Si atoms in the crosslinking agent is preferably 2. The crosslinking agent is preferably a compound containing 2 to 5 alkoxysilyl groups in 1 molecule. The upper limit of the number of alkoxysilanes is preferably 4 or less, and more preferably 3 or less. The number of alkoxysilyl groups is preferably 2. The alkoxysilyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group, and more preferably a trialkoxysilyl group. The 2 alkoxysilyl groups of the crosslinking agent are preferably bonded through 2 to 10 atoms, more preferably through 3 to 9 atoms, and still more preferably through 4 to 8 atoms. The 2 alkoxysilyl groups are preferably bonded via an alkylene group having 2 to 10 carbon atoms, more preferably bonded via an alkylene group having 3 to 9 carbon atoms, and still more preferably bonded via an alkylene group having 4 to 8 carbon atoms.

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

As the compound having an alkoxysilyl group, the compounds described in paragraph 0167 of Japanese patent laid-open publication No. 2017-067824 can be used, and the contents thereof can be incorporated into the present specification. As the compound having a group having an ethylenically unsaturated bond, the compounds described in paragraphs 0150 to 0152 of Japanese patent application laid-open No. 2017-067824 can be used, and the contents thereof are incorporated in the present specification. As the compound having a cyclic ether group, compounds described in paragraphs 0034 to 0036 of Japanese patent application laid-open No. 2013-011869, paragraphs 0147 to 0156 of Japanese patent application laid-open No. 2014-043556, and paragraphs 0085 to 0092 of Japanese patent application laid-open No. 2014-089408 can be used, and these contents can be incorporated in the present specification.

When the near-infrared ray absorbing composition contains the crosslinking agent, the near-infrared ray absorbing composition preferably contains the crosslinking agent in an amount of 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 7 to 15 parts by mass, based on 100 parts by mass of the resin. The near-infrared ray absorbing composition preferably contains 3 to 30 parts by mass of a crosslinking agent, more preferably 5 to 20 parts by mass, and further 7 to 15 parts by mass, based on 100 parts by mass of the resin having a crosslinkable group. The crosslinking agent may be only 1 kind, or may be 2 or more kinds. In the case of 2 or more species, the total amount of these species is preferably within the above range.

The near-infrared absorbing composition can contain a polymerization initiator. The polymerization initiator is not particularly limited as long as it has an ability to initiate crosslinking of the resin having a crosslinkable group or the crosslinking agent by either light or heat or both. In the case of crosslinking by light, a polymerization initiator having photosensitivity to light from an ultraviolet region to a visible region is preferable. When crosslinking is carried out by heat, a polymerization initiator which decomposes at 150 to 250 ℃ is preferable.

Examples of the polymerization initiator include acylphosphine compounds, acetophenone compounds, α -hydroxyketone compounds, α -aminoketone compounds, benzophenone compounds, benzoin ether compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, metallocene compounds and other onium salt compounds, organic boron salt compounds, disulfone compounds, thiol compounds, and the like, oxime compounds, α -hydroxyketone compounds, α -aminoketone compounds, and acylphosphine compounds are preferable, and oxime compounds such as oxime compounds listed in the radical scavenger described below can be used.

When the near-infrared ray absorbing composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30% by mass based on the total solid content of the near-infrared ray absorbing composition. The lower limit is preferably 0.1 mass% or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. The number of polymerization initiators may be 1 or 2 or more. In the case of 2 or more species, the total amount of these is preferably within the above range.

The near infrared ray absorbing composition can contain a solvent. As the solvent, an organic solvent can be cited. The type of the solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the composition. Examples of the organic solvent include ester-based, ether-based, ketone-based, and aromatic hydrocarbon-based solvents. For details of these, reference can be made to paragraph 0223 of International publication WO2015/166779, which can be incorporated into the present specification. Further, ester solvents in which a cyclic alkyl group is substituted and ketone solvents in which a cyclic alkyl group is substituted can also be preferably used. Specific examples of the organic solvent include methylene chloride, methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. From the viewpoint of improving solubility, 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide are also preferable. In the present invention, 1 kind of organic solvent may be used alone, or 2 or more kinds may be used in combination. Among them, it is sometimes preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent (for example, 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less may be set with respect to the total amount of organic solvents) from the viewpoint of environmental aspects and the like.

The content of the solvent is preferably an amount such that the concentration of the solid content (total solid content) of the near-infrared-absorbing composition is 5 to 80 mass%. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less. By increasing the solid content concentration (total solid content) of the near infrared ray absorbing composition, a near infrared ray absorbing composition layer having a thickness can be formed by 1 coating. For example, by setting the total solid content of the near infrared ray absorbing composition to 50 mass% or more, a near infrared ray absorbing composition layer having a thickness of 5 to 40 μm can be formed by 1 coating. Further, as long as the total solid content of the near infrared ray absorbing composition is 80 mass% or less, the solubility of the components in the near infrared ray absorbing composition is good. The total amount of the solvent may be only 1 kind, or 2 or more kinds, and in the case of 2 or more kinds, the total amount is preferably in the above range.

The near infrared absorbing composition may include a catalyst. For example, when a resin having a crosslinkable group such as an alkoxysilyl group is used or when a crosslinking agent is used, the near-infrared ray absorbing composition contains a catalyst to promote the crosslinking reaction of the crosslinkable group, and thus a near-infrared ray cut filter having excellent mechanical properties, solvent resistance, heat resistance, and the like can be easily obtained. The catalyst includes an organometallic catalyst, an acid catalyst, an amine catalyst, and the like, and preferably an organometallic catalyst. The organometallic catalyst is preferably at least 1 selected from the group consisting of oxides, sulfides, halides, carbonates, carboxylates, sulfonates, phosphates, nitrates, sulfates, alkoxides, hydroxides, and acetoacetone complexes which may have substituents, containing at least 1 metal selected from the group consisting of Na, K, Ca, Mg, Ti, Zr, Al, Zn, Sn, and Bi. Among them, at least 1 selected from the group consisting of halides, carboxylates, nitrates, sulfates, hydroxides, and optionally substituted acetoacetone complexes of the above metals is preferable, and the acetoacetone complex is more preferable. Specific examples of the organometallic catalyst include tris (2, 4-pentanedionato) aluminum and the like. When the near-infrared ray absorbing 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 near-infrared ray absorbing 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 near-infrared absorbing composition can contain a radical scavenger. Examples of the radical scavenger include oxime compounds. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF Corporation, supra), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 (manufactured by ADEKACORPORATION), ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in Japanese patent application laid-open publication No. 2012 and 014052). Further, as the oxime compound, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24 and 36 to 40 described in Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in Japanese patent application laid-open No. 2013-164471. This matter can be incorporated into the present specification. As the oxime compound, an oxime compound having a nitro group can be used. Oxime compounds having a nitro group are also preferred as dimers. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, those described in paragraphs 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, those described in paragraphs 0007 to 0025 of patent application laid-open No. 4223071, and those described in paragraphs ADEKAARKLS NCI to 831 (manufactured by ADEKA CORPORATION). Further, as the oxime compound, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compounds described in Japanese patent laid-open publication No. 2014-137466. This matter can be incorporated into the present specification. As the oxime compound, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include compounds OE-01 to OE-75 disclosed in International publication WO 2015/036910.

When the near-infrared ray absorbing composition contains a radical scavenger, the content of the radical scavenger is preferably 0.01 to 30% by mass based on the total solid content of the near-infrared ray absorbing composition. The lower limit is preferably 0.1 mass% or more. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less.

The near-infrared absorbing composition can further contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used, and a fluorine-based surfactant and a silicone-based surfactant are preferable, and a fluorine-based surfactant is more preferable. The fluorine content in the fluorine-based surfactant is preferably 3 to 40 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. If the fluorine content in the fluorine-based surfactant is within the above range, the fluorine-based surfactant is effective in uniformity of thickness of the coating film and in liquid saving. Examples of the fluorine-based surfactant include compounds having the following structures.

[ chemical formula 9]

The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% representing the proportion of the repeating unit is mol%.

As the surfactant, reference can be made to the descriptions in paragraphs 0187 to 0189 of Japanese patent application laid-open No. 2017 and 067824, the contents of which are incorporated herein by reference.

When the near-infrared ray absorbing composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 5% by mass based on the total solid content of the near-infrared ray absorbing composition. The lower limit is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. The upper limit is preferably 2% by mass or less, and more preferably 1% by mass or less.

The surfactant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The near-infrared ray absorbing composition may further contain an ultraviolet absorber, an antioxidant, a dispersant, a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion accelerator, and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a perfume, a surface tension adjusting agent, a chain transfer agent, and the like). The components can be described in paragraphs 0191 to 0196 of Japanese patent application laid-open No. 2017-067824, paragraphs 0052 to 0072 of Japanese patent application laid-open No. 2012-208374, paragraphs 0317 to 0334 of Japanese patent application laid-open No. 2013-68814, and paragraphs 0101 to 0104 and 0107 to 0109 of Japanese patent application laid-open No. 2008-250074, and these contents can be incorporated into the present specification.

The near-infrared absorbing composition can be prepared by mixing the above components. In the preparation of the near-infrared ray absorbing composition, the respective components constituting the near-infrared ray absorbing composition may be prepared at one time, or may be prepared successively after dissolving and/or dispersing the respective components in a solvent. The order of charging and the working conditions in the preparation are not particularly limited.

The viscosity of the near-infrared absorbing composition is preferably 1 to 3000 mPas. The lower limit is preferably 10 mPas or more, and more preferably 100 mPas or more. The upper limit is preferably 2000 mPas or less, more preferably 1500 mPas or less.

< laminate >

Next, the laminate of the present invention will be explained.

The laminate of the present invention is characterized by comprising:

a substrate, a support layer, and a near infrared ray cut filter layer containing a near infrared ray absorber,

one surface of the support layer is in contact with the substrate, the other surface of the support layer is in contact with the near infrared ray cut filter layer,

the support layer has a polymer film,

the flatness of the substrate is 14 μm or less, and the bending rigidity per 1mm width at 23 ℃ is larger than that of the support layer.

Preferred ranges of the substrate, the support layer, and the near-infrared cut filter layer used in the laminate are the same as those described above, and preferred ranges are also the same.

< external member >

Next, the kit of the present invention will be explained.

The kit of the present invention is used in the method for manufacturing a near-infrared cut filter of the present invention, and includes:

a support layer having a polymer film;

a substrate having a flatness of 14 μm or less and a bending rigidity per 1mm width at 23 ℃ greater than that of the support; and

a near-infrared ray absorbing composition includes a near-infrared ray absorber.

The preferable ranges of the substrate, the support layer and the near-infrared absorbing composition are the same as those described above, and the preferable ranges are also the same.

Examples

The present invention will be described more specifically with reference to examples. The materials, the amounts used, the ratios, the contents of the treatments, the procedures of the treatments and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

< weight average molecular weight (Mw) >)

The weight average molecular weight (Mw) was measured by Gel Permeation Chromatography (GPC) in the following method.

The device comprises the following steps: HLC-8220GPC (manufactured by TOSOH CORPORATION)

A detector: RI (reactive index) detector

Pipe column: connected with a protective column HZ-L, a TSK gel Super HZM-M, a TSK gel Super HZ4000, a TSKgel Super HZ3000 and a TSK gel Super HZ2000 (manufactured by TOSOH CORPORATION)

Eluent: tetrahydrofuran (containing stabilizer)

Temperature of the pipe column: 40 deg.C

Injection amount: 10 μ L

Analysis time: and (8) the time is 26min.

Flow rate: flow rate 0.35mL/min (sample pump) 0.20mL/min (reference pump)

Calibration curve base resin: polystyrene

< measurement of flexural rigidity >

The bending rigidity of the glass substrate, the support layer, and the near-infrared cut filter layer was calculated based on the method according to JIS K7171, and based on the young's modulus measured at 23 ℃.

Flexural rigidity (E × I)

E: young's modulus [ Pa]And I: moment of inertia of cross section [ m ]⁴]

The shapes of the glass substrate, the support layer, and the near-infrared cut filter layer to be calculated were regarded as rectangles, and the sectional moments of inertia thereof were calculated by the following equations.

Moment of inertia in cross section I ═ b × h³/12

b: width [ m ], h is thickness/2 [ m ]

< determination of elongation at Break >

The elongation at break was measured by a method according to JIS K7161. The value of elongation at break is a value at 23 ℃.

< preparation of near Infrared ray-absorbing composition >

A near-infrared ray absorbing composition having a solid content concentration of 62 mass% was prepared by mixing the following raw materials.

… … 40 parts by mass of a near-infrared absorber (copper complex having the following structure)

[ chemical formula 10]

… … 49 parts by mass of a resin (resin having the following structure, Mw 15000, and the numerical value indicated on the side chain as a molar ratio) … …

[ chemical formula 11]

Cross-linking agent (KBM-3066, manufactured by Shin-Etsu Chemical Co., Ltd., 1, 6-bis (trimethoxysilyl) hexane) … … 6 parts by mass

… … 5 parts by mass of a radical scavenger (compound having the following structure)

[ chemical formula 12]

Catalyst (tris (2, 4-pentanedionato) aluminum) (III)) … … 0.03.03 parts by mass

… … 0.01.01 parts by mass of a surfactant (the following compound, Mw: 14,000, and% of the ratio of the repeating units being mol%)

[ chemical formula 13]

Cyclopentanone … … remainder

< production of support body layer >

(support body layers 1 to 5)

An optical adhesive film (product name PD-S1, manufactured by PANAC Corporation) having a thickness of 25 μm was used, and the release layers of the films described in the following tables were rolled toward the outside using a roller to form a support layer. The peeling force of the surface of the support layer is also shown in the following table. The values of the peeling force described in the table are values measured by a method according to JIS Z0237, except that 31B tape (manufactured by NITTO DENKO CORPORATION) was used for the bonded object, the peeling speed was set to 300mm/min, and the peeling angle was set to 180 degrees. The peeling force of the support layers 6 and 7 is also the same.

[ Table 1]

(support layer 6)

A single-sided release paper was obtained from an optical adhesive film (product name PD-S1, manufactured by PANAC Corporation) having a thickness of 25 μm, and used as a support layer. The peeling force of the surface of the support layer (the surface from which the release paper was peeled) was 15.5N/25 mm.

(support layer 7)

SG-2S was used as a support layer. The peeling force of the surface of the support layer was 4N/25 mm.

< manufacture of near Infrared ray cut-off Filter >

(examples 1 to 5)

The support layers described in the following tables were laminated on the surface of a glass substrate (flatness 7 μm) having a thickness of 1 mm. Next, the near-infrared absorbing composition was spin-coated on the surface of the support layer to form a near-infrared absorbing composition layer. Then, the near infrared ray absorption composition layer was dried at 100 ℃ for 1 hour using a hot plate, and then heated at 150 ℃ for 1.5 hours using a hot plate to form a near infrared ray cut filter layer having a thickness of 200 μm.

Next, the laminate including the support layer and the near-infrared cut filter layer was peeled from the glass substrate, and then the support layer was peeled from the laminate peeled from the substrate, thereby obtaining a near-infrared cut filter (near-infrared cut filter layer).

The glass substrate has a bending rigidity per 1mm width at 23 ℃ higher than that of the support layers 1 to 6. The bending rigidity of the obtained near-infrared cut filter (near-infrared cut filter layer) per 1mm width at 23 ℃ was 5 × 10^-6Pa·m⁴And an elongation at break at 23 ℃ of 10% or less. The support layer used in the examples had an elongation at break at 23 ℃ of 5% or more and greater than that of the near-infrared cut filter layer. And the support layer is 1 at 23 ℃Bending rigidity of 4X 10mm width^-6Pa·m⁴Bending rigidity per 1mm width of the near infrared ray cut filter layer is less than or equal to.

Comparative example 1

A near-infrared cut filter (near-infrared cut filter layer) was obtained through the same steps as in examples 1 to 5, except that the support layer was not used.

Comparative examples 2 and 3

A near-infrared cut filter (near-infrared cut filter layer) was obtained through the same steps as in examples 1 to 5, except that no substrate was used.

< evaluation of planarity >

The obtained film thickness distribution of the near infrared ray cut filter was divided into 9 equal parts by a range of 10mm excluding the outer side of the near infrared ray cut filter layer forming range, and the center point of each region was measured by a contact film thickness meter, and the planarity was evaluated in accordance with the following criteria.

A: the film thickness distribution is in the range of 95 to 105% of the average film thickness.

B: there are cases where the distribution of film thickness is less than 95% or more than 105% of the average film thickness.

< evaluation of peeling quality >

The surface of the near-infrared cut filter (near-infrared cut filter layer) was visually observed for cracking when the substrate was peeled and when the support layer was peeled, and the peeling quality was evaluated in accordance with the following criteria.

A: there was no cracking.

B: in a part where there is a fracture, but there is a part where it can be used

C: the near infrared ray cut filter layer is not usable or peeled from the lower layer due to the crack on the entire surface

[ Table 2]

As shown in the above table, in the examples, the near infrared ray cut filter having good planarity and no crack or the like was obtained. Therefore, in the embodiment, the near-infrared cut filter having high planarity can be manufactured with excellent productivity.

Description of the symbols

10-substrate, 20-support layer, 30-near infrared ray absorption composition layer, 31-near infrared ray cut filter layer, 32-notch, 40-laminate.

Claims (19)

1. A method of manufacturing a near-infrared cut filter, comprising:

forming a support layer on a surface of a substrate;

a step of forming a near-infrared absorbing composition layer by applying a near-infrared absorbing composition containing a near-infrared absorber on the surface of the support layer;

a step of forming a near-infrared cut filter layer by curing the near-infrared absorbing composition layer;

a step of peeling the laminated body of the support layer and the near-infrared cut filter layer from the substrate; and

and a step of peeling the support layer from the laminate peeled from the substrate.

2. The method for manufacturing a near-infrared cut filter according to claim 1,

the substrate has a flatness of 14 μm or less, and has a bending rigidity per 1mm width at 23 ℃ greater than that of the support layer.

3. The method for manufacturing a near-infrared cut filter according to claim 1 or 2,

the support layer comprises a polymer film.

4. The method for manufacturing a near-infrared cut filter according to claim 3,

the softening temperature of the polymer film is higher than the maximum reaching temperature of the near infrared ray absorption composition layer during the curing treatment.

5. The method for manufacturing a near-infrared cut filter according to claim 3 or 4,

the breaking elongation of the polymer film at 23 ℃ is more than 5 percent and is higher than that of the near infrared ray cut filter layer,

the polymer film has a bending rigidity per 1mm width at 23 ℃ of 4X 10^-6Pa·m⁴Bending rigidity per 1mm width of the near infrared ray cut filter layer is less than or equal to.

6. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 5,

the support layer has a peeling force of 9N/25mm or less on the near-infrared ray cut filter layer side.

7. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 6,

the support layer has a peeling force of 15.5N/25mm or less on the substrate side.

8. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 7,

the support layer has a peeling force on the near-infrared cut filter layer side greater than a peeling force on the substrate side.

9. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 7,

the support layer has a peeling force on the near-infrared cut filter layer side smaller than a peeling force on the substrate side.

10. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 7,

the support layer has the same peeling force on the near-infrared cut filter layer side as that on the substrate side.

11. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 10,

in the step of forming the near-infrared absorbent composition layer, the near-infrared absorbent composition is applied to the surface of the support layer to form the near-infrared absorbent composition layer, and a blank portion where the near-infrared absorbent composition layer is not provided is formed in at least a part of the surface of the support layer.

12. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 11,

the film thickness of the support layer is 1 to 1000 μm.

13. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 12,

the film thickness of the near infrared ray cut filter layer is 1-500 mu m.

14. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 13,

the bending rigidity of the near infrared ray cut filter layer per 1mm width at 23 ℃ is 5X 10^-6Pa·m⁴And an elongation at break at 23 ℃ of 10% or less.

15. The method for manufacturing a near-infrared cut filter according to any one of claims 1 to 14,

the near infrared ray absorbing composition comprises a copper complex and a resin.

16. The method for manufacturing a near-infrared cut filter according to claim 15,

the resin includes a resin having a crosslinkable group.

17. The method for manufacturing a near-infrared cut filter according to claim 15 or 16,

the near-infrared ray absorbing composition contains a monomer having a crosslinkable group.

18. A laminate, comprising:

a substrate, a support layer, and a near infrared ray cut filter layer containing a near infrared ray absorber,

one surface of the support layer is in contact with the substrate, and the other surface of the support layer is in contact with the near-infrared cut filter layer,

the support layer has a polymer film,

the substrate has a flatness of 14 μm or less, and has a bending rigidity per 1mm width at 23 ℃ greater than that of the support layer.

19. A kit used for the method of manufacturing the near-infrared ray cutoff filter according to any one of claims 1 to 17, the kit having:

a support layer having a polymer film;

a substrate having a flatness of 14 μm or less and a bending rigidity per 1mm width at 23 ℃ that is greater than that of the support layer; and

a near-infrared ray absorbing composition includes a near-infrared ray absorber.

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