JP2024024600A - Light-selective cut optical member, resin composition, and phthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-selective cut optical member capable of suppressing ripples on a transmission spectrum in a transmissive region.

SOLUTION: A light-selective cut optical member is provided, comprising a base material, an absorption layer, and a dielectric film, the absorption layer being formed of a resin composition containing a water-soluble resin and a water-soluble dye.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a light-selective cut optical member, a resin composition for forming an absorption layer of the light-selective cut optical member, and a phthalocyanine that can be suitably used as a dye contained in the absorption layer of the light-selective cut optical member. It is related to system compounds.

2. Description of the Related Art Imaging devices, such as mobile phone cameras, digital cameras, in-vehicle cameras, video cameras, and display elements (LEDs, etc.), typically use imaging elements that convert light from a subject into electrical signals and output the electrical signals. Such an image sensor is equipped with a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor), and a lens. It may be equipped with a near-infrared cut filter to remove noise (for example, ghosts and flares). Such near-infrared cut filters are usually provided with a dielectric film composed of a layer of a high refractive index material such as titanium oxide and a layer of a low refractive index material such as silicon oxide. By adjusting the thickness and number of layers of the refractive index material layer, light in a predetermined wavelength range of the incident light can be reflected and cut.

When a dielectric film cuts incident light in a predetermined wavelength range, the cut wavelength range or transmission wavelength range of the dielectric film changes depending on the incident angle. For example, when the incident angle changes from the vertical direction to the oblique direction, the cut wavelength range or the transmission wavelength range shifts to the shorter wavelength side. Therefore, with respect to obliquely incident light, the dielectric film may not be able to sufficiently cut out light in an intended wavelength range, or may also cut out light in an unintended wavelength range. In order to reduce such incidence angle dependence, an absorption layer containing a dye has been provided. By providing an absorption layer containing a dye in addition to the dielectric film, the dye contained in the absorption layer absorbs light in the wavelength range near the boundary between the cut wavelength range and the transmission wavelength range of the dielectric film, improving optical properties. The dependence of the angle of incidence on the angle of incidence can be reduced. For example, Patent Documents 1 and 2 disclose near-infrared cut filters (light selective cut optical members) that include a glass substrate, an absorption layer containing a near-infrared absorbing dye, and a dielectric film. On the other hand, water-soluble dyes are known as dyes, and such water-soluble dyes are disclosed in Patent Documents 3 and 4, for example. Application is not disclosed.

Japanese Patent Application Publication No. 2014-126642 Japanese Patent Application Publication No. 2012-008532 Japanese Patent Application Publication No. 2005-220060 Patent No. 5066417

In a near-infrared cut filter, light in the near-infrared region of the incident light is selectively cut by a dielectric film and an absorption layer, and light in the visible light region passes through the near-infrared cut filter as transmitted light. In this case, it is desirable that the light in the transmission region exhibits a transmission spectrum close to the transmission spectrum specific to the dye, which facilitates the optical design of the near-infrared cut filter. However, in conventional light-selective cutting optical members such as near-infrared cut filters, ripples occur in the transmission spectrum in the transmission region, causing the transmission spectrum to waver, resulting in deviation from the transmission spectrum specific to the dye.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a light selective cutting optical member that can suppress the occurrence of ripples in the transmission spectrum in the transmission region. The present invention also provides an imaging device equipped with the light selectively cutting optical member of the present invention, a resin composition for forming an absorption layer of the light selectively cutting optical member, and a resin composition included in the absorbing layer of the light selectively cutting optical member. A phthalocyanine compound that can be suitably used as a dye is also provided.

［式（１）中、
Ｍは、金属原子、金属酸化物または金属ハロゲン化物を表し、
Ｒ^１～Ｒ^１６はそれぞれ独立して、水素原子、ハロゲン原子、－ＯＲ^１７または－ＳＲ^１８を表し、
Ｒ^１７とＲ^１８はそれぞれ独立して、置換基を有していてもよいアリール基、置換基を有していてもよいアラルキル基、置換基を有していてもよいヘテロアリール基、または置換基を有していてもよいアルキル基を表し、
Ｒ^１～Ｒ^１６のうち５つ以上が－ＯＲ^１７または－ＳＲ^１８であり、当該Ｒ^１７およびＲ^１８は、カルボキシ基またはその塩を有するアリール基、またはカルボキシ基またはその塩を有するアラルキル基である。］ The present invention includes the following light selective cutting optical member, image sensor, resin composition, and phthalocyanine compound.
[1] A light selective cutting optical member having a base material, an absorbing layer, and a dielectric film, wherein the absorbing layer is formed from a resin composition containing a water-soluble resin and a water-soluble dye. Optical member for selectively cutting light.
[2] The light selective cutting optical member according to [1], wherein the water-soluble dye is at least one selected from near-infrared absorbing dyes and ultraviolet absorbing dyes.
[3] The water-soluble dye is selected from phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, croconium compounds, cyanine compounds, dipyrromenthene compounds, diimonium compounds, metal dithiol complex compounds, and metal diamine complex compounds. The light selective cutting optical member according to [1] or [2], which is at least one near-infrared absorbing dye.
[4] The water-soluble dye includes a triazine compound, a benzotriazole compound, an acrylate compound, a benzoxazinone compound, an azomethine compound, an azoxy compound, a cyanobiphenyl compound, a cyanophenyl ester compound, and a benzoic acid ester. at least one type of ultraviolet absorbing dye selected from a cyclohexanecarboxylic acid phenyl ester compound, a cyanophenylcyclohexane compound, a phenylpyrimidine compound, a phenyldioxane compound, a cinnamate compound, and a tolan compound [1] The light selective cutting optical member according to any one of ~[3].
[5] The light selective cutting optical member according to any one of [1] to [4], wherein the water-soluble resin has an amino group, a carbonyl group, an ether group, or a sulfonyl group.
[6] The light selective cutting optical member according to any one of [1] to [5], wherein the base material is a glass substrate, and the absorption layer is formed on the glass substrate.
[7] The light selective cutting optical member according to any one of [1] to [6], wherein the difference in refractive index between the water-soluble resin and the base material is 0.30 or less.
[8] An imaging device comprising the light selective cutting optical member according to any one of [1] to [7].
[9] A resin composition for forming an absorption layer of the light selective cutting optical member according to any one of [1] to [7], characterized by containing a water-soluble resin and a water-soluble dye. resin composition.
[10] A phthalocyanine compound represented by the following formula (1).

[In formula (1),
M represents a metal atom, metal oxide or metal halide,
R ¹ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom, -OR ¹⁷ or -SR ¹⁸ ,
R ¹⁷ and R ¹⁸ are each independently an aryl group that may have a substituent, an aralkyl group that may have a substituent, a heteroaryl group that may have a substituent, or a substituted represents an alkyl group that may have a group,
Five or more of R ¹ to R ¹⁶ are -OR ¹⁷ or -SR ¹⁸ , and R ¹⁷ and R ¹⁸ are an aryl group having a carboxy group or a salt thereof, or an aralkyl group having a carboxy group or a salt thereof. be. ]

According to the light selective cut optical member of the present invention, ripples in the transmission spectrum of light transmitted through the light selective cut optical member, that is, the transmission spectrum of the transmission region can be suppressed. Therefore, the optical design of the light selective cutting optical member becomes easy.

2 shows the transmission spectra of the optical member produced in Example 1 before and after curing. 3 shows the transmission spectrum of the optical member produced in Example 1 after the dielectric film was deposited. 3 shows an enlarged view of the transmission spectrum in the transmission region of the optical member produced in Example 1. FIG. 3 shows an enlarged view of the transmission spectrum in the transmission region of the optical member manufactured in Comparative Example 1. FIG. 3 shows an enlarged view of the transmission spectrum in the transmission region of the optical member manufactured in Comparative Example 2. FIG. FIG. 4 shows an enlarged view of the transmission spectrum in the transmission region of the optical member manufactured in Comparative Example 3.

The light-selective cut optical member of the present invention has a base material, an absorption layer, and a dielectric film, and the absorption layer is formed from a resin composition containing a water-soluble resin and a water-soluble dye (light-selective absorption dye). It is something that Light selective cutting optical members can selectively cut light in a certain wavelength range of incident light using a dielectric film and an absorption layer, but some of the incident light is not reflected by the dielectric film and is absorbed. The light that is not absorbed by the layer also passes through the light selective cutting optical member as transmitted light. For example, when the light selective cutting optical member cuts light in the near-infrared region and/or ultraviolet region, light in the visible light region becomes transmitted light. In this case, it is desirable that the light in the transmission region exhibits a transmission spectrum close to the transmission spectrum specific to the photoselective absorption dye, which facilitates the optical design of the light selective cutting optical member. However, when an absorption layer is formed on a base material using a water-insoluble resin or a water-insoluble dye, ripples occur in the transmission spectrum in the transmission region, resulting in deviations from the transmission spectrum specific to the dye. . Specifically, the transmission spectrum in the transmission region is waved, and the transmittance of light at some wavelengths becomes higher than the transmittance spectrum unique to the dye, or conversely, the transmittance of light at some other wavelengths becomes higher than the transmittance spectrum unique to the dye. The transmission spectrum was lower than that of . On the other hand, in the light-selective cut optical member of the present invention, the absorption layer is formed from a resin composition containing a water-soluble resin and a water-soluble dye, and thereby the light transmitted through the light-selective cut optical member is transmitted. Spectral ripple can be suppressed. Therefore, the optical design of the light selective cutting optical member becomes easy. In addition, by using a resin composition containing a water-soluble resin and a water-soluble dye, it is possible to use aqueous solvents such as water and alcohol instead of organic solvents, which improves the environment when manufacturing light-selective cutting optical members. The load can be reduced.

In the present invention, the light cut by the light selective cutting optical member may be light in at least a part of the wavelength range in the near-infrared region, or light in at least a part of the wavelength range in the ultraviolet region. It may be light in at least a part of the wavelength range of the visible light region, or a combination thereof. The light selective cutting optical member preferably transmits at least part of the wavelength range from the ultraviolet region to the near-infrared region of the incident light, and transmits light in the visible light region. It is more preferable. Thereby, the light selective cutting optical member can be suitably applied to an image sensor such as a camera.

Examples of the light selective cutting optical member include filters and lenses that can selectively cut light in a predetermined wavelength range. Examples of the filter include near-infrared cut filters, ultraviolet cut filters, color filters, and the like. The lens can be formed by forming a predetermined pattern on the surface of the light selective cutting optical member or by forming the light selective cutting optical member into a predetermined shape. The lens also has light selective cutting performance. Hereinafter, the light selective cutting optical member of the present invention will be explained in detail.

In a light-selective cut optical member, a base material is used as a support for an absorption layer or a dielectric film. The base material may be uncolored or colored as long as it is transparent and has light transmittance. The base material can be made of glass, resin, or the like.

The shape of the base material is not particularly limited, and can be appropriately set depending on the use and installation location of the light selective cutting optical member. Examples of the shape of the base material include plate-like, sheet-like, spherical, ellipsoidal, lenticular, cubic, columnar, rod-like, conical, lumpy, and granular shapes.

The base material is preferably made of glass from the viewpoint of improving the heat resistance and durability of the light selective cutting optical member. If a glass base material is used, it becomes possible to mount a light selective cut optical member on an electronic component by, for example, solder reflow, and it is possible to downsize the electronic component. Furthermore, the glass substrate is less likely to crack or warp even when exposed to high temperatures, making it easier to ensure adhesion with the absorbent layer. As the glass substrate, it is preferable to use plate-shaped glass, that is, a glass substrate.

The glass substrate can be made of known glasses such as silicate glass, borosilicate glass, boric acid glass, and phosphate glass. In these glasses, silicon atoms, boron atoms, or phosphorus atoms form a network structure with oxygen atoms to form the main skeleton of the glass, and in addition to these atoms, sodium, potassium, calcium, Atoms or ions such as magnesium, barium, aluminum, iron, silver, copper, cobalt, nickel, lead, zinc, fluorine, etc. may be present.

The thickness of the base material is, for example, preferably 0.05 mm or more, more preferably 0.1 mm or more in terms of ensuring strength, and preferably 0.4 mm or less, more preferably 0.3 mm or less in terms of thinning. preferable.

A dielectric film is usually constructed as a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are laminated alternately, but it may be constructed from only one of the high refractive index material layer and the low refractive index material layer. may be done. As the material constituting the high refractive index material layer, a material with a refractive index of 1.7 or more can be used, and a material with a refractive index in the range of 1.7 or more and 2.5 or less is preferably selected. The range of the refractive index is more preferably 1.8 or more, and even more preferably 2.0 or more. Examples of materials constituting the high refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; silicon nitride nitrides such as; mixtures of the oxides and nitrides, and those doped with metals such as aluminum and copper, and carbon (for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. Can be mentioned. As the material constituting the low refractive index material layer, a material with a refractive index of less than 1.7 can be used, and a material with a refractive index of 1.2 to 1.6 is preferably selected. More preferably, a material with a diameter of .3 to 1.5 is selected. Examples of the material constituting the low refractive index material layer include silicon oxide (silica, SiOx (x=1 to 2)), alumina, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride, and the like. Among these, the high refractive index material layer is preferably composed of titanium oxide, and the low refractive index material layer is preferably composed of silicon oxide.

The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably adjusted to a range of 0.1 λ to 0.5 λ, and 0.2 λ to 0.5 λ of the wavelength λ (nm) of the light to be blocked. It is more preferable to adjust to a range of 3λ. By forming a dielectric film in this way, it is possible to selectively reflect light in a desired wavelength range. film) etc. can be formed. The ultraviolet reflection film and the near-infrared reflection film may be one having an ultraviolet reflection function and a near-infrared reflection function.

The number of layers of the dielectric film is not particularly limited as long as it is one or more layers, but from the viewpoint of exhibiting the desired optical performance as an ultraviolet reflective film, a near-infrared reflective film, an antireflection film, etc., the number of layers is, for example, 2 to 80 layers. It is preferable that there be. The number of layers of the dielectric film may be 5 or more, 10 or more, or 20 or more, or 70 or less or 60 or less. The thickness of the dielectric film is not particularly limited, and may be, for example, in the range of 0.01 μm to 10 μm, but from the viewpoint of sufficiently blocking the incidence of light in a desired wavelength range, it is preferably 0.02 μm or more, and 0.02 μm or more. The thickness is more preferably 0.03 μm or more, and from the viewpoint of thinning, the thickness is preferably 5 μm or less, and even more preferably 3 μm or less.

The dielectric film can be formed as a deposited film. The dielectric film may be deposited by a known method. For example, as a heating means for the evaporation source, known heating means such as resistance heating, electron beam heating, high frequency induction heating, laser beam heating, etc. can be used. Note that it is preferable to use ion-assisted vapor deposition for vapor deposition, which makes it easier to form a dense and highly smooth dielectric film, and makes it easier to impart desired optical performance. As the ion assist, an ion gun, ion plating, plasma gun, etc. can be used.

The dielectric film may be provided so as to constitute any layer of the light selective cutting optical member, and may be provided adjacent to the base material, adjacent to the absorption layer, and may be provided adjacent to the base material. It may be provided neither adjacent to the material nor to the absorbent layer. The light selective cut optical member may have, for example, an absorbing layer provided on one side of a base material and a dielectric film provided on the other side, or an absorbing layer provided on one side of the base material, and a base material of the absorbing layer. A dielectric film may be provided on the opposite side of the material. Note that the dielectric film is preferably provided closer to the light incident side than the absorption layer.

The absorption layer is formed from a resin composition containing a water-soluble resin and a water-soluble dye. In the light selective cutting optical member of the present invention, ripples in the transmission spectrum in the transmission region can be suppressed by forming the absorption layer in this manner. As a result, the transmission spectrum of the light transmitted through the light selective cutting optical member becomes close to the transmission spectrum specific to the dye, and the optical design of the light selective cutting optical member becomes easy. A possible reason why the occurrence of ripples is suppressed in this way is that, for example, the use of a water-soluble resin increases the affinity between the absorbing layer and the base material, thereby suppressing internal reflection. Note that the transmission region of the transmission spectrum means a wavelength range in which the transmittance is relatively high in the wavelength range of 300 nm to 1000 nm, and for example, the transmission region can be a range in which the transmittance is 70% or more.

The absorbent layer is preferably provided on the substrate, ie adjacent to the substrate. The absorbent layer may be provided on only one main surface of the base material, or may be provided on both surfaces.

The water-soluble resin is not particularly limited as long as it is a resin that dissolves in water, and any known water-soluble resin can be used. Examples of water-soluble resins include polyacrylic acid and its salts, polyvinyl acetal, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethyleneimine, polyacrylamide, styrene-maleic anhydride copolymer, polyvinylamine, polyallylamine, polysulfonamide. and salts thereof, hydroxyethyl cellulose, carboxymethyl cellulose, oxazoline group-containing water-soluble resins, water-soluble urethane resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble melamine resins, water-soluble urea resins, alkyd resins, and the like. The absorbent layer may contain only one type of water-soluble resin, or may contain two or more types of water-soluble resin.

The water-soluble resin preferably has an amino group, a carbonyl group, an ether group, or a sulfonyl group. If such a water-soluble resin is used, it becomes easy to improve the heat resistance of the absorbent layer while ensuring solubility in water. Examples of water-soluble resins having an amino group include polyvinylpyrrolidone, polyethyleneimine, polyacrylamide, polyvinylamine, polyallylamine, polysulfonamide and its salts, water-soluble urethane resin, water-soluble melamine resin, and water-soluble urea resin. . Examples of water-soluble resins having a carbonyl group include polyacrylic acid and its salts, polyvinylpyrrolidone, polyacrylamide, styrene-maleic anhydride copolymer, carboxymethyl cellulose, water-soluble urethane resin, water-soluble urea resin, and alkyd. Examples include resin. Examples of water-soluble resins having ether groups include polyacrylic acid and its salts, polyvinyl acetal, polyethylene glycol, styrene-maleic anhydride copolymer, hydroxyethyl cellulose, carboxymethyl cellulose, oxazoline group-containing water-soluble resins, and water-soluble urethane. Examples include resins, water-soluble epoxy resins, and alkyd resins. Examples of the water-soluble resin having a sulfonyl group include polysulfonamide and salts thereof. The water-soluble resin may have two or more groups selected from amino groups, carbonyl groups, ether groups, and sulfonyl groups, such as amide groups, carboxy groups, urethane groups, and sulfonamide groups. There may be. Such water-soluble resins include polyacrylic acid and its salts, polyvinylpyrrolidone, polyacrylamide, styrene-maleic anhydride copolymer, polysulfonamide and its salts, carboxymethylcellulose, water-soluble urethane resin, water-soluble urea resin, Examples include alkyd resins. The water-soluble resin may have a phenolic hydroxyl group such as a water-soluble phenol resin. On the other hand, the water-soluble resin may not have alcoholic hydroxyl groups.

The water-soluble resin preferably has a solubility in water of 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and even more preferably 5% by mass or more. The water-soluble resin may have even higher solubility in water, and may be 10% by mass or more, 20% by mass or more, or 30% by mass or more. On the other hand, the upper limit of the water solubility of the water-soluble resin is not particularly limited, and may be 80% by mass or less, 60% by mass or less, or 50% by mass or less. Whether or not the water-soluble resin has been dissolved in water can be determined by adding the water-soluble resin to water while stirring at 25° C. and visually checking for the presence of insoluble matter. For example, if a resin is added to water at a predetermined concentration (for example, a concentration of 0.1% by mass) and insoluble matter is observed, it can be determined that the solubility is less than the predetermined concentration.

The water-soluble dye is not particularly limited as long as it is a dye that dissolves in water. The water-soluble dye is not particularly limited, and may be an organic dye, an inorganic dye, or an organic-inorganic composite dye (for example, an organic compound to which a metal atom or ion is coordinated). The absorption layer may contain only one type of dye, or may contain two or more types of dye.

The water-soluble dye preferably has a solubility in water of 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and even more preferably 5% by mass or more. The water-soluble dye may have even higher solubility in water, and may be 10% by mass or more, 20% by mass or more, or 30% by mass or more. On the other hand, the upper limit of the water solubility of the water-soluble dye is not particularly limited, and may be 80% by mass or less, 60% by mass or less, or 50% by mass or less. Whether or not the water-soluble dye has dissolved in water can be determined by adding it to water while stirring at 25° C. and visually checking for the presence of insoluble matter. For example, if a dye is added to water at a predetermined concentration (for example, a concentration of 0.1% by mass) and insoluble matter is observed, it can be determined that the solubility is less than the predetermined concentration.

The water-soluble pigment may be a pigment that absorbs visible light, a pigment that absorbs near-infrared rays with a longer wavelength than visible light, or a pigment that absorbs ultraviolet rays with a shorter wavelength than visible light. It may be. The water-soluble dye preferably has an absorption maximum in the wavelength range of 200 nm to 1100 nm, considering its use as a light selective cutting optical member.

When the water-soluble dye is a visible light-absorbing dye, the water-soluble dye may have maximum absorption in the visible light region (for example, a wavelength range of more than 420 nm and less than 680 nm), such as a wavelength of 500 nm, which has high visibility. It is preferable that the material has maximum absorption in a range of 680 nm or more. If the water-soluble dye is a visible light absorbing dye, the light selective cutting optical member can be applied to colored filters, blue light reduction filters, and the like.

When the water-soluble dye is a near-infrared absorbing dye, the water-soluble dye preferably has an absorption maximum in a wavelength range of 680 nm or more and 1100 nm or less, for example. If the water-soluble dye is a near-infrared absorbing dye, the light selective cutting optical member can be applied to a near-infrared cutting optical member that cuts light in the red to near-infrared region.

The near-infrared absorbing dye has an absorption spectrum in the wavelength range of 200 nm or more and 1100 nm or less, and has an absorption maximum in the wavelength range of 680 nm or more and 1100 nm or less, and the absorption maximum of the absorption peak is in the wavelength range of 200 nm or more and 1100 nm or less. It is preferable to take the maximum value. The maximum absorption wavelength is more preferably 685 nm or more, even more preferably 690 nm or more, more preferably 1000 nm or less, even more preferably 900 nm or less, and even more preferably 800 nm or less.

When the water-soluble dye is an ultraviolet absorbing dye, the water-soluble dye preferably has an absorption maximum in the range of, for example, from 200 nm to 420 nm. If the water-soluble dye is an ultraviolet absorbing dye, the light selective cutting optical member can be applied to an ultraviolet cutting optical member that cuts light in the ultraviolet region. Furthermore, even if the resin composition is exposed to ultraviolet light during storage or during the manufacturing and processing of optical components (e.g., vapor deposition and mounting), the ultraviolet light may damage the resin components and other components contained in the resin composition. It is possible to protect components and suppress deterioration of these components.

The ultraviolet absorbing dye has an absorption spectrum in the wavelength range of 200 nm or more and 1100 nm or less, and has an absorption maximum in the wavelength range of 200 nm or more and 420 nm or less, and the absorption maximum of the absorption peak is in the wavelength range of 200 nm or more and 1100 nm or less. It is preferable to take the maximum value. The absorption maximum wavelength is more preferably 250 nm or more, further preferably 300 nm or more, and even more preferably 400 nm or less.

The water-soluble dye is preferably at least one selected from near-infrared absorbing dyes and ultraviolet absorbing dyes. As a result, the light-selective cut optical member suppresses the transmission of light in the near-infrared region and/or ultraviolet region, and preferentially transmits light in the visible light region, making it suitable for near-infrared cut optical members and ultraviolet cut optical members. It can be suitably applied. The absorption layer preferably contains a near-infrared absorbing dye and an ultraviolet absorbing dye as water-soluble dyes, and more preferably allows light in the visible region to pass therethrough. Thereby, the light selective cutting optical member can be suitably applied to an image sensor such as a camera.

When the water-soluble dye is a near-infrared absorbing dye, examples of the water-soluble dye include phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, croconium compounds, cyanine compounds, dipyrromentene compounds, diimonium compounds, and metal dithiol complexes. It is preferable to use at least one selected from compounds and metal diamine complex compounds. These compounds can suitably absorb light in the near-infrared region, and can easily increase the transmittance of light in the visible region.

As the water-soluble dye having an absorption region in the near-infrared region, for example, phthalocyanine compounds can be suitably used. The water-soluble phthalocyanine-based compound has a phthalocyanine skeleton, that is, a cyclic structure in which four phthalic acid imides are bridged with nitrogen atoms, and can be used without particular limitations as long as it is water-soluble. If a phthalocyanine compound is used as a water-soluble dye, it is possible to selectively absorb transmitted light in the near-infrared region. Furthermore, since the phthalocyanine compound has a high decomposition temperature, it becomes easy to obtain a light selective cutting optical member with excellent heat resistance.

As the phthalocyanine compound, it is preferable to use a compound represented by the following formula (1). In formula (1), M represents a metal atom, a metal oxide or a metal halide, R ¹ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom, -OR ¹⁷ or -SR ¹⁸ , and R ¹⁷ and R ¹⁸ are each independently an aryl group that may have a substituent, an aralkyl group that may have a substituent, a heteroaryl group that may have a substituent, or a substituent Represents an alkyl group that may have. The metal element constituting M may be bonded or coordinated with other elements such as oxygen and halogen.

In formula (1), examples of the metal element constituting M include copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, and lead. Among these metal elements, copper, vanadium, and zinc are preferred, and copper and zinc are more preferred, from the viewpoint of visible light transmittance and light resistance. Copper phthalocyanine (copper complex of phthalocyanine) is less degraded by light and has excellent light resistance. Zinc phthalocyanine (zinc complex of phthalocyanine) has excellent visible light transparency.

In formula (1), examples of the halogen atom for R ¹ to R ¹⁶ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom and a chlorine atom being preferred.

When R ¹ to R ¹⁶ represent -OR ¹⁷ or -SR ¹⁸ , examples of the aryl group of R ¹⁷ and R ¹⁸ include phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl group, etc. Can be mentioned. The aryl group may have a substituent, and examples of the substituent that the aryl group has include an alkyl group, an alkoxy group, a heteroaryl group, an aryloxy group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a carboxy group, or a salt thereof. , sulfo group (sulfonic acid group) or its salt, cyano group, nitro group, amino group, thiocyanate group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group , an arylsulfonyl group, a sulfamoyl group, and the like. The number of carbon atoms in the aryl group (number of carbon atoms excluding substituents) is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6 to 10.

When R ¹ to R ¹⁶ represent -OR ¹⁷ or -SR ¹⁸ , examples of the aralkyl group of R ¹⁷ and R ¹⁸ include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, naphthylmethyl group, etc. can be mentioned. The aralkyl group may have a substituent, and examples of the substituent that the aralkyl group has include an alkyl group, an alkoxy group, an aryloxy group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a carboxy group or a salt thereof, a sulfo group, or Salts thereof, cyano groups, nitro groups, thiocyanate groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, sulfamoyl groups, and the like. The number of carbon atoms in the aralkyl group (number of carbon atoms excluding substituents) is preferably 7 to 25, more preferably 7 to 15, and even more preferably 7 to 11.

When R ¹ to R ¹⁶ represent -OR ¹⁷ or -SR ¹⁸ , examples of the heteroaryl group of R ¹⁷ and R ¹⁸ include a thienyl group, thiopyranyl group, isothiochromenyl group, pyrrolyl group, imidazolyl group, and pyrazolyl group. , pyridyl group, pyraridinyl group, pyrimidinyl group, pyridazinyl group, thiazolyl group, isothiazolyl group, furanyl group, pyranyl group, and the like. The heteroaryl group may have a substituent, and examples of the substituent that the heteroaryl group has include an alkyl group, an alkoxy group, an aryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a carboxy group or a salt thereof, and a sulfo group. or salt thereof, cyano group, amino group, nitro group, thiocyanate group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, etc. can be mentioned. The number of carbon atoms in the heteroaryl group (number of carbon atoms excluding substituents) is preferably 2 to 15, more preferably 3 to 10, and even more preferably 4 to 8.

When R ¹ to R ¹⁶ represent -OR ¹⁷ or -SR ¹⁸ , the alkyl groups of R ¹⁷ and R ¹⁸ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t- Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group Straight chain or branched alkyl groups such as; cyclic (alicyclic) alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. can be mentioned. The alkyl group may have a substituent, and such substituents include an aryl group, an aryloxy group, a heteroaryl group, an alkoxy group, a halogeno group, a hydroxyl group, a carboxy group or a salt thereof, a sulfonic acid group, or Examples include salts thereof, cyano groups, nitro groups, amino groups, and the like. Examples of the alkyl group having a halogeno group include a monohalogenoalkyl group, a dihalogenoalkyl group, an alkyl group having a trihalogenomethyl unit, and a perhalogenoalkyl group. As the halogeno group, a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a fluorine atom is particularly preferable. The number of carbon atoms in the alkyl group (number of carbon atoms excluding substituents) is preferably 1 to 20, and specifically, in the case of a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 20. The number of carbon atoms is preferably 10, more preferably 1 to 5, and if it is a cyclic alkyl group, the number of carbon atoms is preferably 4 to 10, more preferably 5 to 8.

In the phthalocyanine compound represented by formula (1), at least one of R ¹ to R ¹⁶ is -OR ¹⁷ or -SR ¹⁸ , and R ¹⁷ and R ¹⁸ are , an aryl group having a carboxyl group or a salt thereof, an aryl group having a sulfo group or a salt thereof, an aralkyl group having a carboxyl group or a salt thereof, or a heteroaryl group. These aryl groups, aralkyl groups, and heteroaryl groups may have a substituent, and the substituent is preferably an alkyl group having 1 to 3 carbon atoms, a halogeno group, a hydroxyl group, an amino group, or a nitro group. More preferred is a halogeno group. Hereinafter, the -OR ¹⁷ or -SR ¹⁸ will be referred to as a specific -OR ¹⁷ or -SR ¹⁸ . In the phthalocyanine compound represented by formula (1), it is more preferable that four or more of R ¹ to R ¹⁶ are a specific -OR ¹⁷ or -SR ¹⁸ , and five or more are a specific -OR ¹⁷ or -SR 18. -SR ¹⁸ is more preferred, and it is even more preferred that six or more are the specific -OR ¹⁷ or -SR ¹⁸ . Also, one or more of R ¹ to R ⁴ , one or more of R ⁵ to R ⁸ , one or more of R ⁹ to R ¹² , and one or more of R ¹³ to R ¹⁶ is preferably the specific -OR ¹⁷ or -SR ¹⁸ . Further, R ¹⁷ and R ¹⁸ are preferably an aryl group having a carboxyl group or a salt thereof, an aralkyl group having a carboxyl group or a salt thereof, or a heteroaryl group, and an aryl group having a carboxyl group or a salt thereof, or More preferably, it is a heteroaryl group.

In the phthalocyanine compound represented by formula (1), it is also preferable that at least one of R ¹ to R ¹⁶ is a halogen atom. This shifts the absorption wavelength of the phthalocyanine compound to the longer wavelength side, making it easier to cut off the transmission of light in the near-infrared region. In the phthalocyanine compound, it is more preferable that four or more of R ¹ to R ¹⁶ are halogen atoms, and it is even more preferable that six or more are halogen atoms. Also, one or more of R ¹ to R ⁴ , one or more of R ⁵ to R ⁸ , one or more of R ⁹ to R ¹² , and one or more of R ¹³ to R ¹⁶ is preferably a halogen atom.

The phthalocyanine compound represented by formula (1) particularly preferably contains one or more of R ¹ to R ⁴ , one or more of R ⁵ to R ⁸ , and one or more of R ⁹ to R ¹² . and one or more of R ¹³ to R ¹⁶ are the specific -OR ¹⁷ or -SR ¹⁸ described above, and one or more of R ¹ to R ⁴ , R ⁵ to One or more of R ⁸ , one or more of R ⁹ to R ¹² , and one or more of R ¹³ to R ¹⁶ are halogen atoms. Further, R ¹⁷ and R ¹⁸ are preferably aryl groups or heteroaryl groups having a carboxy group or a salt thereof, and these aryl groups and heteroaryl groups may have a halogeno group as a substituent. Examples of such phthalocyanine compounds include compounds represented by the following formulas (1A) and (1B).

The phthalocyanine compound may be synthesized using a known method, and can generally be obtained by heating a phthalonitrile derivative without a solvent or in the presence of a solvent. For the synthesis of water-soluble phthalocyanine compounds, reference may be made to, for example, JP-A No. 2005-220060, Japanese Patent No. 5066417, and the like.

Examples of water-soluble cyanine dyes having an absorption region in the near-infrared region include S0524, S0316, S2146, S0121, S0456, S2433, S2163, S0837, S0306, S2161, S2180, S2493, manufactured by FEW Chemicals, Tokyo, Japan. Indocyanine green (ICG), ICG carboxylic acid, IR754 carboxylic acid, etc. manufactured by Kasei Kogyo Co., Ltd. can be used.

When the water-soluble dye is an ultraviolet absorbing dye, examples of the water-soluble dye include triazine compounds, benzotriazole compounds, acrylate compounds, benzoxazinone compounds, azomethine compounds, azoxy compounds, cyanobiphenyl compounds, and cyanobiphenyl compounds. At least one selected from phenyl ester compounds, benzoic acid ester compounds, cyclohexanecarboxylic acid phenyl ester compounds, cyanophenylcyclohexane compounds, phenylpyrimidine compounds, phenyldioxane compounds, cinnamate compounds, and tolan compounds. It is preferable to use These compounds can suitably absorb light in the ultraviolet region, and can easily increase the transmittance of light in the visible region.

As a water-soluble dye having an absorption region in the ultraviolet region, it is preferable to use a compound having a cinnamate structure represented by the following formula (2) as a cinnamate-based compound. If the compound represented by formula (2) is used, it is possible to selectively absorb the transmission of light in the ultraviolet region. For example, an absorption wavelength range is formed in the wavelength range of 350 nm to 395 nm, and the absorption wavelength range is On the long wavelength side, it is possible to form a sharp boundary between the absorption wavelength range and the transmission wavelength range. Further, since the compound represented by formula (2) has a high decomposition temperature, it becomes easy to obtain a light selective cutting optical member having excellent heat resistance.

In the above formula (2), R ²¹ represents a hydrogen atom, an organic group, or a metal cation or onium ion forming a carboxylate, and R ²² represents a hydrogen atom, a hydrogen atom, a cyano group, an acyl group, a sulfonyl group, or a carboxylic acid salt. group, carboxylic acid ester group, amide group, hydrocarbon group, or heteroaryl group, ^R23 represents a hydrogen atom or an alkyl group, ^R24 represents a hydrogen atom, an organic group, or a polar functional group; ²⁴ may be the same or different from each other, X represents a sulfur atom, oxygen atom, or imino group, L represents a divalent or more linking group, a represents an integer of 2 or more, The groups may be the same or different from each other. Note that at least one of R ²¹ included in the plurality of groups bonded to L is a metal cation or an onium ion that forms a carboxylate. In formula (2), -COOR ²¹ (or R ²² ) may be in the cis position or in the trans position with respect to R ²³ .

Examples of the organic group for R ²¹ include an alkyl group, an aryl group, and a heteroaryl group. For specific examples of these alkyl groups, aryl groups, and heteroaryl groups, refer to the explanations regarding the alkyl groups, aryl groups, and heteroaryl groups of R ¹⁷ and R ¹⁸ above, respectively.

Examples of the metal element that provides the metal cation that forms the carboxylate of R ²¹ include alkali metal elements, alkaline earth metal elements, transition metal elements, and metal elements of Groups 12 to 14. Examples of the alkali metal elements include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal elements include calcium, magnesium, strontium, barium, and the like. The transition metal elements include metal elements of Groups 3 to 11, such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zirconium, molybdenum, and tungsten. Examples of the metal elements of Groups 12 to 14 include aluminum, zinc, gallium, cadmium, tin, and lead. In addition, when the metal cation of R ²¹ is a divalent or higher valence metal cation, two or more R ^21s in the same molecule may represent one metal cation, and two or more R ^21s belonging to different molecules may represent one metal cation. It may also represent a metal cation. Among these, as the metal element that provides the metal cation of ^R21 , elements in the second to fifth periods are preferable, and elements in the second to fourth periods are more preferable. Further, alkali metal elements, alkaline earth metal elements, and metal elements of Groups 12 to 14 are preferable, and lithium, sodium, potassium, calcium, and zinc are more preferable. When R ²¹ is a metal cation, the solubility of the cinnamate-based compound in water can be further increased.

Examples of the onium ion forming the carboxylate of ^R21 include ammonium ion, organic ammonium ion (eg, tetrabutylammonium ion), phosphonium ion, organic phosphonium ion, boron cation, and the like. When R ²¹ is an onium ion, it becomes easy to ensure solubility in organic solvents in addition to solubility in water.

In the compound represented by formula (2), at least one R ²¹ of R ²¹ contained in the compound may be a metal cation or an onium ion, and half or more of R ²¹ are metal cations or onium ions. is preferred, and more preferably all R ²¹ are metal cations or onium ions. Thereby, the solubility of the cinnamate-based compound of formula (2) in water can be increased. In addition, such cinnamate-based compounds exhibit a maximum absorption peak in the UVA region on the relatively short wavelength side of the ultraviolet region (for example, about 320 nm to 360 nm), and are unable to cut relatively high-energy UVA. can.

Examples of the acyl group (alkanoyl group) for ^R22 include methanoyl group, ethanoyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group, dodecanoyl group, and tridecanoyl group. , tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, eicosanoyl group, and the like. In the acyl group, some of the hydrogen atoms may be substituted with an aryl group, an alkoxy group, a halogeno group, a hydroxyl group, or the like. The alkyl group in the acyl group may be linear or branched. The number of carbon atoms in the acyl group (the number of carbon atoms excluding substituents) is preferably 2 to 21, more preferably 2 to 11, and still more preferably 2 to 6.

Examples of the carboxylic acid ester group for R ²² include those represented by the formula: -C(=O)-O-R ^a1 , where R ^a1 is an alkyl group, an aryl group, or an aralkyl group. For specific examples of alkyl groups, aryl groups, and aralkyl groups, refer to the explanations of these groups for R ¹⁷ and R ¹⁸ above.

The amide group of R ²² is represented by the formula: -C(=O)-NR ^a2 R ^a3 , where R ^a2 is a hydrogen atom or an alkyl group, and R ^a3 is an alkyl group, an acyl group, an aryl group, or an aralkyl group. Examples include those that are. For specific examples of the alkyl group, aryl group, and aralkyl group of R ^a2 and R ^a3 , refer to the explanation of these groups for R ¹⁷ and R ¹⁸ above, and for specific examples of the acyl group of R ^a3 , refer to the above R ²² Reference is made to the explanation of the acyl group in .

Examples of the hydrocarbon group for ^R22 include an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group). The aliphatic hydrocarbon group may be either saturated or unsaturated, and may be linear, branched, or cyclic. For specific examples of the aliphatic saturated hydrocarbon group, refer to the explanation of the alkyl groups of R ¹⁷ and R ¹⁸ above, and for specific examples of the aliphatic unsaturated hydrocarbon group, refer to the alkyl groups of R ¹⁷ and R ¹⁸ explained above. Examples include groups in which some of the carbon-carbon single bonds are replaced with double bonds or triple bonds. For specific examples of the aromatic hydrocarbon group (aryl group), refer to the explanation of the aryl group of R ¹⁷ and R ¹⁸ above.

For specific examples of the heteroaryl group of R ²² , refer to the above description of the heteroaryl groups of R ¹⁷ and R ¹⁸ . In the heteroaryl group, it is preferable that the carbon atom is bonded to the carbon atom of the ethylene double bond in formula (2), and the carbon atom adjacent to the heteroatom is bonded to the carbon atom of the ethylene double bond in formula (2). It is more preferable that the compound is bonded to , which facilitates the synthesis of the cinnamate-based compound.

R ²³ in formula (2) represents a hydrogen atom or an alkyl group, and for specific examples of the alkyl group, refer to the explanation regarding the alkyl groups of R ¹⁷ and R ¹⁸ above. The alkyl group for R ²³ preferably has 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. A hydrogen atom is particularly preferred as R ²³ .

Examples of the organic group for ^R24 in formula (2) include an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, and an aryl group. Examples include an oxycarbonyl group, an arylsulfonyl group, an arylsulfinyl group, a heteroaryl group, an amino group, an amide group, a sulfonamide group, a carboxy group (carboxylic acid group), and a cyano group. Examples of the polar functional group for R ²⁴ in formula (2) include a halogeno group, a hydroxyl group, a nitro group, and a sulfo group (sulfonic acid group).

For specific examples of the alkyl group of R ²⁴ and the alkyl group contained in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group, and alkylsulfinyl group, refer to the explanation of the alkyl group of R ¹⁷ and R ¹⁸ above. . For specific examples of the aryl group of R ²⁴ and the aryl group contained in the aryloxy group, arylthio group, aryloxycarbonyl group, arylsulfonyl group, and arylsulfinyl group, refer to the explanation of the aryl group of R ¹⁷ and R ¹⁸ above. be done. For specific examples of the aralkyl group and heteroaryl group of R ²⁴ , refer to the above description of the aralkyl group and heteroaryl group of R ¹⁷ and R ¹⁸ , respectively. For specific examples of the amide group of R ²⁴ , refer to the above explanation of the amide group of R ²² .

The amino group for R ²⁴ is represented by the formula: -NR ^a4 R ^a5 , where R ^a4 and R ^a5 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heteroaryl group. Examples include those that are bases. For specific examples of alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups, refer to the explanations of these groups above.As alkenyl groups and alkynyl groups, one of the carbon-carbon single bonds of the alkyl groups listed above Examples include groups in which the moiety is replaced with a double bond or triple bond. R ^a4 and R ^a5 may be linked to each other to form a ring.

Examples of the sulfonamide group for R ²⁴ include those represented by the formula: -NH-SO ₂ -R ^a6 , where R ^a6 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. For specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group, refer to the above explanations of these groups.

Examples of the halogeno group for R ²⁴ include a fluoro group, a chloro group, a bromo group, and an iodo group.

^R24 is preferably one or more selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group, and an arylthio group, and is preferably a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 to 3. Among the four ^R24s bonded to the benzene ring in formula (2), two or more are preferably hydrogen atoms, more preferably three or more are hydrogen atoms, and all four are hydrogen atoms. It is particularly preferable that there be.

In formula (2), X represents a sulfur atom, an oxygen atom or an imino group. The imino group is represented by the formula: -NR ²⁵ -, where R ²⁵ represents a hydrogen atom or an organic group. Preferred examples of the organic group for R ²⁵ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and a heteroaryl group. Specific examples of these groups include R ^a4 and the amino group of R ²⁴ above. Reference is made to the description of R ^a5 . X may be bonded to the ethylene structure including COOR ²¹ , R ²² and R ²³ at the ortho position, meta position, or para position. In addition, from the viewpoint of ease of manufacturing the compound, it is preferable that X is bonded to the para position with respect to the ethylene structure. X is preferably a sulfur atom or an imino group, more preferably a sulfur atom.

In formula (2), L represents a divalent or higher-valent linking group. The linking group L is a single divalent, trivalent, tetravalent, pentavalent, or hexavalent organic group for a linking group, or a divalent, trivalent, tetravalent, pentavalent, or hexavalent organic group for a linking group. It may be an n-valent group formed by bonding groups.

Examples of organic groups for divalent linking groups include alkylene groups, cycloalkylene groups, arylene groups, heteroarylene groups, -O-, -CO-, -S-, -SO-, SO ₂ -, -NH-, etc. included. The alkylene group, cycloalkylene group, arylene group, and heteroarylene group may have a hydroxyl group and/or a thiol group.

The alkylene group includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, and a pentadecylene group. Examples include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms, such as hexadecylene group, heptadecylene group, and octadecylene group.

Examples of the cycloalkylene group include carbon-based groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, and cyclohexane-1,4-diyl group. Examples include cycloalkylene groups having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.

The arylene group includes 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group, 1, 5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,3-naphthylene group, 2,4-naphthylene group, 2,5-naphthylene group, 2,6 Examples include arylene groups having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms, such as -naphthylene group and 2,7-naphthylene group.

The heteroarylene group has 3 to 20 carbon atoms, such as a furan-2,3-diyl group, a furan-2,4-diyl group, a furan-2,5-diyl group, and a furan-3,4-diyl group. , preferably a heteroarylene group having 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms.

As the organic group for the divalent linking group, the above-mentioned alkylene group, the above-mentioned cycloalkylene group, the above-mentioned arylene group, etc. are preferable.

When the divalent linking group L is a divalent group formed by bonding an organic group for a linking group, for example, a group bonded in this order of an alkylene group, -O-, and an alkylene group; an alkylene group , -S-, an alkylene group bonded in this order; an alkylene group, -CO-, -O-, an alkylene group bonded in this order; an alkylene group, -CO-, -NH-, an alkylene group bonded in that order Examples include groups in which an alkylene group, -O-, an alkylene group, -O-, and an alkylene group are bonded in this order; an arylene group, an alkylene group, and a group in which an arylene group is bonded in this order.

The organic group for the trivalent linking group includes a methine group (-C<), -N<, a trivalent benzene ring that may have an alkyl group, and a trivalent benzene ring that may have an alkyl group. Contains naphthalene rings. For the alkyl group that the benzene ring or naphthalene ring may have, refer to the above explanation regarding the alkyl groups of R ¹¹ to R ¹⁸ . Examples of the trivalent benzene ring include benzene-1,2,3-triyl group and benzene-1,3,5-triyl group. Examples of the trivalent naphthalene ring include a naphthalene-1,2,3-tolyl group and a naphthalene-1,3,6-tolyl group. As the trivalent organic group for the linking group, a trivalent benzene ring is preferred.

A trivalent group constituted by a trivalent linking group L bonding an organic group for a linking group is, for example, a methylene group, a methine group, a group bonded in this order to a methylene group (n-propane-1,2 , 3-triyl group), ethylene group, methine group, and a group bonded in the order of ethylene group (n-hexane-1,3,6-triyl group); C _3-20 alkanetriyl group; three methine groups A cycloC _3-10 alkantriyl group such as a trivalent group formed by cyclically bonding with one or more methylene groups as necessary; >C< having an alkyl group and the divalent linkage A group to which three of the organic groups are bonded, for example, >C< having a C _1-4 alkyl group, and three of the C _2-4 alkanoic acid C _1-4 alkyl ester residues (divalent group) A group to which is bonded; and the like.

Examples of the tetravalent organic group for a linking group include >C<, a tetravalent benzene ring which may have an alkyl group, a tetravalent naphthalene ring which may have an alkyl group, and the like. For the alkyl group that the benzene ring or naphthalene ring may have, refer to the above explanation regarding the alkyl groups of R ¹¹ to R ¹⁸ . Examples of the tetravalent benzene ring include benzene-1,2,3,4-tetrayl group and benzene-1,2,4,5-tetrayl group. Examples of the tetravalent naphthalene ring include naphthalene-1,2,3,4-tetrayl group, naphthalene-2,3,6,7-tetrayl group, naphthalene-1,4,5,6-tetrayl group, etc. .

When the tetravalent linking group L is a tetravalent group formed by bonding an organic group for a linking group, for example, a group (n -butane-1,2,3,4-tetryl group), ethylene group, methine group, methine group, group bonded in order of ethylene group (n-hexane-1,3,4,6-tetryl group), etc. C _4-20 alkantetrayl group; a group in which >C< having an alkyl group and four of the divalent linking group organic groups are bonded, for example, >C< having a C _1-4 alkyl group and the C A group in which _{four 2-4} alkanoic acid C _1-4 alkyl ester residues (divalent group) are bonded; and the like.

The pentavalent organic group for connecting group includes a pentavalent benzene ring which may have an alkyl group, a pentavalent naphthalene ring which may have an alkyl group, and the like. For the alkyl group that the benzene ring or naphthalene ring may have, refer to the above explanation regarding the alkyl groups of R ¹¹ to R ¹⁸ . Examples of the pentavalent benzene ring include benzene-1,2,3,4,5-pentyl group. As the pentavalent naphthalene ring, naphthalene-1,2,3,4,5-pentyl group, naphthalene-1,2,3,5,6-pentyl group, naphthalene-1,2,3,6,7- Examples include pentyl groups.

The hexavalent organic group for a linking group includes a hexavalent benzene ring, a hexavalent naphthalene ring, and the like. Examples of the hexavalent naphthalene ring include naphthalene-1,2,3,4,5,6-hexyl group and naphthalene-1,2,3,5,6,7-hexyl group.

When the hexavalent linking group L is a hexavalent group formed by bonding an organic group for a linking group, for example, the C _2-4 alkanoic acid C1-4 alkyl ester residue (a divalent group ) are bonded to >C<, methylene group, -O-, methylene group, and >C< to which three of the above C _2-4 alkanoic acid C _1-4 alkyl ester residues (divalent group) are bonded. Three of the divalent organic groups for connecting group such as groups bonded in order>C<, alkylene group, -O-, alkylene group, three of the organic groups for divalent connecting group bonded> Examples include groups bonded in the order of C<.

The divalent, trivalent, tetravalent, pentavalent, or hexavalent organic group for the linking group may have a substituent such as a halogeno group, a cyano group, an amino group, or a nitro group, if necessary. good. As the organic group for the connecting group having a substituent, a trivalent to hexavalent benzene ring having a cyano group, a trivalent to hexavalent naphthalene ring having a cyano group, etc. are preferable, and a trivalent to hexavalent benzene ring having a cyano group is more preferred, and a tetravalent benzene ring having a cyano group is more preferred. Examples of the tetravalent benzene ring having a cyano group include 5,6-dicyanobenzene-1,2,3,4-tetrayl group, 3,6-dicyanobenzene-1,2,4,5-tetrayl group, etc. can be mentioned.

From the viewpoint of increasing the heat resistance of the compound of formula (2), the linking group L is an alkylene group in which some of the hydrogen atoms may be replaced with a hydroxyl group and/or a thiol group, or an alkylene group in which some of the hydrogen atoms are replaced with a hydroxyl group and/or a thiol group. / or a cycloalkylene group which may be substituted with a thiol group, an arylene group where some of the hydrogen atoms may be replaced with a hydroxyl group and/or a thiol group, -O-, -S-, and these groups. Combination linking groups are preferred (provided that the ether and thioether bonds are not consecutive). The number of consecutive carbon atoms in the alkylene group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The number of carbon atoms in the cycloalkylene group is preferably 4 or more, more preferably 5 or more, and preferably 10 or less, and more preferably 8 or less. The number of carbon atoms in the arylene group is preferably 5 or more, more preferably 6 or more, and preferably 10 or less, and more preferably 8 or less.

As the cinnamate-based compound, a compound represented by the following formula (3) is particularly preferred. For example, such cinnamate-based compounds have a peak with an absorption maximum in the wavelength range of 300 nm to 420 nm, can effectively absorb light in the ultraviolet (UVA) to violet region, and have excellent stability, making it difficult to manufacture. becomes easier. In the following formula (3), for the explanation of R ^21a and R ^21b , refer to the above explanation of R ²¹ , for the explanation of R ^22a and R ^22b , refer to the above explanation of R ^{22, and for the explanation of R 23a and} R ^23b , refer to the above explanation of R 22. The above description of R ²³ is referred to, and the description of X ^a and X ^b is referred to the above description of X.

The compound represented by formula (2) or formula (3) can be synthesized with reference to International Publication No. 2019/009093.

The content of the water-soluble dye in the absorption layer may be adjusted as appropriate depending on the desired optical performance of the light selective cutting optical member, but for example, the content of the dye is 0.5% by mass in 100% by mass of the absorption layer. It is preferably at least 1% by mass, more preferably at least 2% by mass, further preferably at most 25% by mass, more preferably at most 20% by mass, even more preferably at most 15% by mass. By adjusting the dye content in the absorption layer in this manner, it becomes easier to have a sufficiently wide absorption wavelength band in a desired wavelength region, and it becomes easier to increase light transmittance in other wavelength regions. In addition, the content of the dye in the absorption layer explained here is the content of the dye in the solid content of the resin composition (i.e., the resin composition excluding the solvent) in the resin composition used when forming the absorption layer. It can be applied to the content. The content of other components in the absorbent layer, which will be described later, can be similarly applied to the content in the solid content of the resin composition.

When the water-soluble dyes contained in the absorption layer are two or more types selected from visible light absorbing dyes, near-infrared absorbing dyes, and ultraviolet absorbing dyes, the content ratio of each dye is determined according to the desired light selection of the light selective cutting optical member. It may be adjusted as appropriate depending on the cutting characteristics. For example, out of 100% by mass of all the pigments contained in the absorption layer, the content of each pigment may be adjusted as appropriate within the range of 5% by mass to 90% by mass (preferably 10% by mass to 80% by mass). As an example, when a light selective cut optical member is one that cuts light in the near-infrared region and ultraviolet region, the content ratio of the near-infrared absorbing dye and the ultraviolet absorbing dye contained in the absorption layer is determined by the mass ratio (near-infrared absorbing The ratio (dye content/ultraviolet absorbing dye content) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2.

The refractive index of the water-soluble resin contained in the absorption layer is not particularly limited, but the refractive index difference between the water-soluble resin and the base material is preferably 0.30 or less, more preferably 0.25 or less, and even more preferably 0.20 or less. It is preferably 0.15 or less, and even more preferably 0.15 or less. This makes it easier to suppress ripples in the transmission spectrum. Note that the refractive index difference described here represents an absolute value. The lower limit of the refractive index difference between the water-soluble resin and the base material is not particularly limited and may be 0 or more, but may be 0.01 or more.

The resin composition forming the absorbent layer may contain at least one selected from a silane coupling agent, a hydrolyzate of a silane coupling agent, and a hydrolyzed condensate of a silane coupling agent. Thereby, the adhesion of the absorbent layer to the base material can be improved. More preferably, the resin composition contains a hydrolyzed condensate of a silane coupling agent.

The silane coupling agent preferably has an epoxy group-containing group, an amino group-containing group, a mercapto group-containing group, or a polymerizable double bond-containing group, and it is preferable to use a compound having such a functional group and an alkoxysilyl group. preferable. The silane coupling agent may contain only one or more of the above functional groups, and may contain only one or more alkoxysilyl groups. Good too.

When the silane coupling agent contains a plurality of alkoxysilyl groups, a polymer type polyfunctional silane coupling agent can be used as the silane coupling agent. A polymer-type polyfunctional silane coupling agent has a structure in which a group and an alkoxysilyl group-containing group are bonded to an organic polymer chain, and contains multiple alkoxysilyl groups in one molecule, as well as epoxy groups, amino groups, and mercapto groups. It can also contain a plurality of functional groups such as groups and polymerizable double bond groups. Note that the organic chain of the polymer type polyfunctional silane coupling agent does not contain polysiloxane. By configuring the polymer type polyfunctional silane coupling agent in this way, many reaction points with the resin and the base material are formed, and the adhesion of the absorbent layer to the base material can be improved.

A hydrolyzate of a silane coupling agent can be obtained by converting an alkoxysilyl group contained in the silane coupling agent into a silanol group by hydrolysis. Further, the hydrolyzed condensate of the silane coupling agent can be obtained by dehydrating and condensing silanol groups contained in the hydrolyzate of the silane coupling agent to form a siloxane bond (-Si-O-Si-). I can do it. Normally, when a silane coupling agent is hydrolyzed, a hydrolyzate of the silane coupling agent is obtained, and a dehydration condensation reaction of the silanol groups contained in the hydrolyzate also occurs, resulting in hydrolysis and condensation of the silane coupling agent. Things can be obtained easily. The hydrolyzed condensate of a silane coupling agent may be a dehydrated condensate of a hydrolyzate of the same type of silane coupling agent, or a dehydrated condensate of a hydrolyzate of a different type of silane coupling agent. .

The content of the silane coupling agent, the hydrolyzate of the silane coupling agent, and the hydrolyzed condensate of the silane coupling agent in the absorbent layer may be 0% by mass or more based on 100% by mass of the absorbent layer, It may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

The absorbent layer may contain a surface conditioner. By including the surface conditioner in the absorbent layer, it is possible to suppress appearance defects such as striations and dents from occurring in the absorbent layer when the absorbent layer is formed by curing the resin composition. The surface conditioner may be contained in an amount of, for example, 0.01 to 1% by mass based on 100% by mass of the absorbent layer.

The type of surface conditioning agent is not particularly limited, and siloxane surfactants, acetylene glycol surfactants, fluorine surfactants, acrylic leveling agents, and the like can be used. Among these, it is preferable to use a siloxane-based surfactant or an acrylic-based leveling agent, and it is more preferable to use a siloxane-based surfactant as the surface conditioner.

The siloxane surfactant is not particularly limited as long as it has a siloxane bond, such as polyether-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polydimethylsiloxane, etc. can be mentioned. Among these, polyether-modified polydimethylsiloxane is preferred from the viewpoint of dispersibility of dyes (especially squarylium compounds and croconium compounds) in the absorption layer. The polyether-modified polydimethylsiloxane is particularly preferably a nonionic surfactant whose hydrophilic group is polyalkylene oxide (more preferably ethylene oxide or propylene oxide) and whose hydrophobic group is dimethylsiloxane.

In addition to the above additives, the absorbent layer may contain plasticizers, dispersants, viscosity modifiers, antifoaming agents, preservatives, resistivity modifiers, pH modifiers, stability improvers, and adhesion agents as necessary. Various additives such as improvers may be included.

The absorption layer can be formed from a resin composition containing a water-soluble resin and a water-soluble dye, but the resin composition may be a thermoplastic resin composition that can be used for molding such as injection molding. Often, the resin composition may be made into a paint so that it can be coated onto a substrate. In the present invention, since the resin composition forming the absorption layer contains a water-soluble resin and a water-soluble dye, it is preferable that the resin composition is made into a paint using an aqueous solvent. The resin component contained in the resin composition is not only a polymerized resin but also a resin raw material (including a resin precursor, a raw material for the precursor, a monomer constituting the resin, etc.), and the resin composition It is also possible to use materials that are incorporated into resins through polymerization or crosslinking reactions when molding objects. As the resin component, each of the water-soluble resins described above can be used.

Examples of resin compositions made into paints include resin compositions containing a solvent. The solvent may function to dissolve each component contained in the resin composition, or may function as a dispersion medium. As the solvent, it is preferable to use an aqueous solvent such as water or alcohol. Examples of alcohol include methanol, ethanol, isopropyl alcohol, etc. having 5 or less carbon atoms (preferably 4 or less carbon atoms, more preferably 3 or less carbon atoms). ) is preferably used. This makes it possible to reduce the environmental burden during manufacturing of the light selective cutting optical member. It is particularly preferable to use water as the solvent.

The content of the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less based on 100% by mass of the resin composition formed into a coating. It is preferably 80% by mass or less, and more preferably 80% by mass or less.

The resin composition made into a paint can be applied by spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, slit coating, screen printing, flexographic printing, inkjet printing, etc. Can be constructed. In this case, by coating a liquid resin composition on a base material (for example, a resin plate, a film, a glass plate, etc.), a film-like material with a thickness of 200 μm or less or a film with a thickness of more than 200 μm can be formed on the base material. A sheet-like absorbent layer can be formed.

The thickness of the absorption layer is not particularly limited, but from the viewpoint of ensuring desired light selective cutting performance, it is preferably 0.5 μm or more, and more preferably 1 μm or more, for example. The upper limit of the thickness of the absorbing layer may be, for example, 1 mm or less, 500 μm or less, 200 μm or less, or 50 μm or less. From the viewpoint of forming a thinner light selective cutting optical member, the thickness of the absorption layer is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 2 μm or less.

The light selective cutting optical member may have other layers (films) in addition to the base material, absorption layer, and dielectric film. Examples of other layers (films) include a layer having anti-glare properties, a layer having anti-scratch properties, and a metal film.

It is preferable that the thickness of the light selective cutting optical member is, for example, 1 mm or less. Thereby, for example, the demand for miniaturization of image sensors can be fully met. The thickness of the light selective cutting optical member is more preferably 500 μm or less, still more preferably 300 μm or less, even more preferably 150 μm or less, and preferably 30 μm or more, and even more preferably 50 μm or more.

The light selective cutting optical member of the present invention can be suitably applied as a sensor, that is, it can be used as a light selective cutting optical member for a sensor. Examples of the sensor include an image sensor, an illuminance sensor, and a proximity sensor. An image sensor is used as an electronic component that converts light from a subject into an electrical signal or the like and outputs it, and examples thereof include a CCD (Charge Coupled Device) and a CMOS (Complementary Metal-Oxide Semiconductor). Image sensors can be used in mobile phone cameras, digital cameras, in-vehicle cameras, surveillance cameras, display elements (LEDs, etc.), and the like.

The present invention also provides a phthalocyanine compound that can be suitably used as a dye contained in the absorption layer of the light selective cutting optical member of the present invention. The phthalocyanine compound of the present invention is represented by the following formula (1), and in the following formula (1), M and R ¹ to R ¹⁶ are as explained above. However, five or more (preferably six or more) of R ¹ to R ¹⁶ are -OR ¹⁷ or -SR ¹⁸ , and R ¹⁷ and R ¹⁸ are aryl groups having a carboxy group or a salt thereof, or carboxy An aralkyl group having a group or a salt thereof, preferably an aryl group having a carboxy group or a salt thereof. These aryl groups and aralkyl groups may have a substituent other than a carboxy group, and the substituent is preferably an alkyl group having 1 to 3 carbon atoms, a halogeno group, a hydroxyl group, an amino group, or a nitro group. , a halogeno group is more preferred. The phthalocyanine compound of the present invention has excellent solubility in water.

In the above formula (1), the phthalocyanine compound of the present invention includes one or more of R ¹ to R ⁴ , one or more of R ⁵ to R ⁸ , and one or more of R ⁹ to R ¹² . , and one or more of R ¹³ to R ¹⁶ is preferably -OR ¹⁷ or -SR ¹⁸ described above. Further, at least one of R ¹ to R ¹⁶ is preferably a halogen atom, more preferably four or more are halogen atoms, even more preferably six or more are halogen atoms, and R ¹ ~ One or more of R ⁴ , one or more of R ⁵ to R ⁸ , one or more of R ⁹ to R ¹² , and one or more of R ¹³ to R ¹⁶ are halogen atoms It is preferable that

EXAMPLES The present invention will be explained in more detail by showing Examples below, but the scope of the present invention is not limited thereto.

(1) Synthesis of dye (1-1) Synthesis example 1: Synthesis of near-infrared absorbing dye A In a 2000 mL four-necked separable flask, 108 g (0.54 mol) of tetrafluorophthalonitrile and 69.0 g of potassium fluoride ( 1.18 mol) and 252 g of acetone were charged. A dropping funnel containing 254 g (1.1 mol) of 3-chloro-4-hydroxybenzoic acid methoxyethyl ester and 432 g of acetone was attached to this flask, and while stirring under ice cooling, 3-chloro-4- The hydroxybenzoic acid methoxyethyl ester solution was added dropwise over about 2 hours, and stirring was continued for an additional 2 hours. Thereafter, the temperature of the reaction solution in the flask was slowly raised to room temperature and stirred overnight. The reaction solution was filtered, acetone was distilled off from the filtrate using a rotary evaporator, and methanol was added to perform recrystallization. The obtained crystals were filtered and vacuum dried to obtain 217.4 g (yield 64.8%) of intermediate (1).

In a 500 mL flat bottom flask, put 150.0 g (0.2414 mol) of the intermediate (1) obtained above, 19.26 g (0.0603 mol) of zinc (II) iodide, and 225.0 g of benzonitrile, The temperature of the reaction solution in the flask was raised to 160° C. under nitrogen flow (10 ml/min) and stirring at 200 rpm using a flat stirring blade, and the phthalocyanination reaction was carried out at the same temperature. After the reaction was completed, 470 g of methyl cellosolve was added to the reaction solution, which was dropped into a mixed solution of 3.8 kg of methanol and 0.6 kg of water to precipitate crystals, and after suction filtration, a wet cake was obtained. The obtained cake was again stirred and washed with a mixed solution of 1.9 kg of methanol and 0.3 kg of water, and filtered under suction. The resulting cake was dried at 90° C. for 24 hours using a vacuum dryer to obtain 137.0 g (yield: 89.1%) of phthalocyanine compound intermediate (2).

In a 300 mL round bottom flask, add 12.76 g (0.005 mol) of the intermediate (2) obtained above, 1.60 g (0.04 mol) of sodium hydroxide, and 76.09 g (1 mol) of 2-methoxyethanol. The temperature of the reaction solution in the flask was raised to 100° C. under nitrogen flow (50 ml/min) and stirring with a rotor, and the saponification reaction was carried out at the same temperature. After the reaction was completed, the reaction solution was concentrated using an evaporator and vacuum dried at 80° C. overnight to obtain water-soluble near-infrared absorbing dye A shown in Table 1 (yield 98.2%).

(1-2) Synthesis Example 2: Synthesis of Near Infrared Absorbing Dye B Water-soluble near infrared absorbing dye B shown in Table 1 was synthesized according to the method described in Example 1 of Japanese Patent No. 5066417.

(1-3) Synthesis Example 3: Synthesis of near-infrared absorbing dye D According to the method described in Example 1-18 of JP-A-2016-74649, water-insoluble near-infrared absorbing dye D shown in Table 1 was synthesized. did.

(1-4) Synthesis Example 4: Synthesis of Near-Infrared Absorbing Dye E According to Synthesis Example 2 of JP-A-2020-132699, water-insoluble near-infrared absorbing dye E shown in Table 1 was synthesized.

(1-5) Synthesis Example 5: Synthesis of UV absorbing dye B In a 200 mL four-necked flask, 4.98 g (0.039 mol) of 4-fluorobenzaldehyde and 2.72 g (2.72 g) of ethylene glycol bis(2-mercaptoethyl) ether ( 0.020 mol), 10.86 g (0.079 mol) of potassium carbonate, and 74 g of acetonitrile were charged, and reacted at 60° C. for 12 hours while stirring using a stirring blade under nitrogen flow (10 mL/min). After the reaction was completed, insoluble matter was removed by vacuum filtration, and then the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200 mL four-necked flask, and 5.19 g (0.079 mol) of isobutyl cyanoacetate, 3.32 g (0.039 mol) of piperidine, and 68 g of methanol were added thereto, and under reflux temperature conditions, The reaction was allowed to proceed for 4 hours. After the reaction, the solvent was distilled off using an evaporator, and the resulting concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 4.6 g of water-insoluble ultraviolet absorbing dye B shown in Table 2. (yield 79.6%).

(1-6) Synthesis Example 6: Synthesis of Ultraviolet Absorbing Dye A In a 500 mL four-necked flask, 5.24 g (0.0082 mol) of the ultraviolet absorbing dye B obtained in Synthesis Example 6 and 0.0 g of sodium hydroxide were added. 66 g (0.0164 mol) and 80 g of methanol were added, and while stirring using a magnetic stirrer under nitrogen flow (10 mL/min), the mixture was heated to 60° C. using a water bath and stirred for about 5 hours. Thereafter, the reaction solution was cooled to room temperature, and 200 g of acetone was further added and stirred for about 30 minutes. After stirring, the precipitated crystals were filtered under reduced pressure. The filtered crystals were dried at 60° C. for 12 hours using a vacuum drier to obtain 4.2 g (yield: 87.5%) of water-soluble ultraviolet absorbing dye A shown in Table 2.

(2) Synthesis of resin (2-1) Synthesis of polyarylate resin In a 2 L reaction vessel equipped with a stirring blade, 10.01 g (0.044 mol) of 2,2'-bis(4-hydroxyphenyl)propane, After preparing and dissolving 3.59 g (0.090 mol) of sodium hydroxide and 300 g of ion exchange water, 0.89 g (0.009 mol) of triethylamine was added and dissolved therein. A solution of 3.57 g (0.021 mol) of terephthalic acid dichloride and 3.57 g (0.021 mol) of isophthalic acid dichloride dissolved in 500 g of methylene chloride was placed in a dropping funnel, which was attached to the reaction vessel. The solution in the reaction vessel was stirred while being maintained at 20°C, and a methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Furthermore, a solution of 0.71 g (0.005 mol) of benzoyl chloride dissolved in 10 g of methylene chloride was added thereto, and the mixture was stirred for 60 minutes. The resulting reaction solution was neutralized by adding an acetic acid aqueous solution to adjust the pH of the aqueous phase to 7, and then the oil phase and the aqueous phase were separated using a separating funnel. The obtained oil phase was added dropwise to methanol with stirring to reprecipitate the polymer, and the precipitate was collected by filtration and dried in an oven at 80° C. to obtain a white solid polyarylate resin. Yield was 11.5g. The weight average molecular weight (Mw) of the obtained polyarylate resin was 33,780, and the number average molecular weight (Mn) was 8,130. The weight average molecular weight and number average molecular weight of the polyarylate resin are polystyrene equivalent values determined by gel permeation chromatography measurement.

(2-2) Synthesis of fluorinated aromatic resin A reactor equipped with a thermometer, cooling tube, gas introduction tube, and stirring blade was equipped with 4,4'-bis(2,3,4,5,6-pentafluorocarbon). 16.74 g of benzoyl) diphenyl ether, 10.5 g of 9,9-bis(4-hydroxyphenyl)fluorene, 4.34 g of potassium carbonate, and 90 g of dimethylacetamide were charged. The solution in the reaction vessel was heated to 80° C. while stirring, and reacted for 8 hours. After the reaction was completed, the reaction solution was poured into a 1% aqueous acetic acid solution while being vigorously stirred with a blender. The precipitated reaction product was filtered, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated aromatic resin. The glass transition temperature (Tg) of the fluorinated aromatic resin was 242°C, and the number average molecular weight (Mn) was 70,770. The number average molecular weight of the fluorinated aromatic resin is a polystyrene equivalent value determined by gel permeation chromatography measurement.

(3) Preparation of hydrolyzed solution of silane coupling agent 24.7 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Dow Toray Industries, OFS-6040), 32.1 g of 2-propanol, and 3.4 g of distilled water. were blended and mixed uniformly at 25°C. 1.54 g of formic acid was added thereto and mixed for 90 minutes to advance the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane, thereby preparing a hydrolyzate of 3-glycidoxypropyltrimethoxysilane. .

(4) Preparation of resin composition (4-1) Preparation example 1
1,800 parts by mass of ion-exchanged water was added to 100 parts by mass of polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., K-90), 5 parts by mass of near-infrared absorbing dye A was added thereto, and the mixture was uniformly mixed at room temperature. This was filtered through a filter with a pore size of 0.45 μm (manufactured by GL Sciences, water system 13A) to remove foreign substances, and resin composition 1 was obtained.

(4-2) Preparation example 2
Add 2,000 parts by mass of ion-exchanged water to 100 parts by mass of polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., K-90), add 5 parts by mass of near-infrared absorbing dye A and 11 parts by mass of ultraviolet absorbing dye A, and mix at room temperature. The mixture was mixed uniformly to obtain a resin composition 2.

(4-3) Preparation example 3
60 parts by mass of polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., K-90), 40 parts by mass of water-soluble melamine resin (manufactured by Sanwa Chemical Co., Ltd., Nikalac (registered trademark) MX035), and 1800 parts by mass of ion-exchanged water were blended. 5 parts by mass of near-infrared absorbing dye A was added and mixed uniformly at room temperature to obtain resin composition 3.

(4-4) Preparation example 4
Resin composition 4 was obtained in the same manner as in Preparation Example 1 except that near-infrared absorbing dye A in Preparation Example 1 was changed to near-infrared absorbing dye B.

(4-5) Preparation example 5
Resin composition 5 was obtained in the same manner as in Preparation Example 1, except that the near-infrared absorbing dye A in Preparation Example 1 was changed to near-infrared absorbing dye C (manufactured by FEW Chemicals, S2493) shown in Table 1.

(4-6) Preparation example 6
Add 100 parts by mass of polyarylate resin to a mixed solvent of 350 parts by mass of toluene and 530 parts by mass of o-xylene, and further add 6.3 parts by mass of near-infrared absorbing dye D and 2.6 parts by mass of near-infrared absorbing dye E. , 11.2 parts by mass of ultraviolet absorbing dye B, 0.3 parts by mass of BYK-310 (polyether-modified polydimethylsiloxane) manufactured by BYK Chemie as a surface conditioner, and 3.0 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate). 10 parts by mass of a hydrolyzed solution of a silane coupling agent were added and mixed uniformly. This was filtered through a filter with a pore size of 0.1 μm (manufactured by GL Science Co., Ltd., non-aqueous 13N) to remove foreign substances, and resin composition 6 was obtained.

(4-7) Preparation example 7
Add 1,800 parts by mass of toluene to 100 parts by mass of polystyrene resin (manufactured by PS Japan, HF77), add thereto 2.6 parts by mass of near-infrared absorbing dye E, and 11.2 parts by mass of ultraviolet absorbing dye B, and mix uniformly. did. This was filtered through a filter with a pore size of 0.1 μm (manufactured by GL Sciences, non-aqueous 13N) to remove foreign substances, and resin composition 7 was obtained.

(4-8) Preparation example 8
Resin composition 8 was obtained in the same manner as in Preparation Example 7, except that the polystyrene resin in Preparation Example 7 was changed to a fluorinated aromatic resin.

(5) Preparation of light selective cutting optical member After dropping 2 cc of resin compositions 1 to 8 on a glass substrate (manufactured by Schott, D263Teco), using a spin coater (manufactured by Mikasa, 1H-D7), The resin composition was formed into a film on a glass substrate by increasing the rotation speed to 1900 rotations for 20 seconds, holding the rotation speed at that rotation speed for 20 seconds, and then reducing the rotation speed to 0 rotation for 0.2 seconds. The glass substrate on which the resin composition was formed was initially dried at 100° C. for 3 minutes using a precision thermostat (DH611, manufactured by Yamato Scientific Co., Ltd.) (before curing). Thereafter, nitrogen substitution was performed at 50° C. for 30 minutes using an inert oven (manufactured by Yamato Scientific Co., Ltd., DN610I). When resin compositions 1 to 6 were used, an absorption layer (resin layer) was formed on the glass substrate by raising the temperature to 180°C in about 15 minutes and drying in a nitrogen atmosphere for 30 minutes (after curing). ). When resin compositions 7 and 8 were used, an absorption layer (resin layer) was formed on the glass substrate by raising the temperature to 190°C in about 15 minutes and drying it in a nitrogen atmosphere for 1 hour (after curing). ). The thickness of the absorption layer formed on the glass substrate was about 2 μm.

On the absorption layer of the absorption layer laminated substrate obtained above, a silicon oxide layer of 500 nm was formed by ion-assisted electron beam evaporation using a high-speed IAD vacuum thin film forming apparatus (BIS-1300D, manufactured by Synchron). A dielectric film was formed by vapor deposition to a thickness of (after vapor deposition), and a light selective cut optical member was obtained. The evaporation source used for the evaporation of silicon oxide was Patinal Evaporation Materials Item No. manufactured by MERCK. 1080441000 was used. The vacuum pressure during film formation was 2×10 ⁻² Pa (absolute pressure), the assist power acceleration voltage was 1000 V, and the acceleration current was 1200 mA. Oxygen gas was introduced into the IAD (ion gun) at a flow rate of 60 sccm, and the substrate heater temperature was set at 90°C. Examples prepared using resin compositions 1 to 5 were designated as Examples 1 to 5, respectively, and examples prepared using resin compositions 6 to 8 were designated as comparative examples 1 to 3, respectively.

(6) Evaluation (6-1) Transmission spectrum measurement The transmission spectrum was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-1800) at a measurement pitch of 1 nm, and the transmittance of light in the wavelength range of 300 nm to 1000 nm was determined. . Transmission spectra were measured for each optical member before curing, after curing, and after vapor deposition. As a specific example, the transmission spectra of the optical member before curing, after curing, and after vapor deposition of Example 1 are shown in FIGS. 1 and 2, respectively. Further, Table 3 shows the results of transmittance changes at a wavelength of 500 nm before and after curing.

(6-2) Evaluation of ripples After curing, the transmission spectrum of the optical member in a transmission region (for example, a wavelength range of 450 nm to 550 nm or 450 nm to 600 nm) was observed to confirm the presence or absence of ripples. As a specific example, enlarged views of the transmission spectra of the transmission regions of the optical members of Example 1 and Comparative Examples 1 to 3 after curing are shown in FIGS. 3 to 6. Table 3 shows the results of determining the difference between the maximum transmittance and the minimum transmittance in the wavelength range of 500 nm to 520 nm as an index of the degree of ripple occurrence.

(6-3) Heat resistance evaluation For the optical members before and after curing, the difference between the transmittance before and after curing at a wavelength of 500 nm was determined, and the results are shown in Table 3. Based on this result, the heat resistance of the absorbent layer was evaluated.

(6-4) Adhesion evaluation (6-4-1) Initial peeling resistance test Make incisions in the optical member after vapor deposition using a cutter (manufactured by NT Corporation, A-300), and make 10 incisions in vertical and horizontal rows at 2 mm intervals. A sample substrate for evaluation was prepared by creating 81 squares of 4 mm ² by providing cross-cut lines of the book. A tape (Scotch (registered trademark) Transparent Adhesive Tape Transparent Bicolor (registered trademark), manufactured by 3M Co., Ltd.) was attached to this sample substrate to prevent air from entering, and the sample substrate was left for 5 seconds. Thereafter, the tape was peeled from the sample substrate in a 60° direction within 1 second, and evaluated according to the following criteria. Note that the tape was peeled off so that the peeling force was constant in all squares.
A: Out of the 81 squares created, not one square was peeled off. B: Out of the 81 squares created, peeling occurred in 1 to 9 squares. C: Out of the 81 squares created, peeling occurred in 1 to 9 squares. , peeling occurred in squares 10 to 81.

(6-4-2) Peeling resistance test after boiling in water Cut the optical member after vapor deposition with a cutter (manufactured by NT Corporation, A-300), and make 10 cross-cut lines at 2 mm intervals in each column and row. By providing 81 squares of 4 mm ² , a sample substrate for evaluation was prepared. Next, this sample substrate was placed in ultrapure water heated to a boiling state and boiled for 2 hours. Subsequently, a tape (Scotch (registered trademark) Transparent Adhesive Tape Transparent Bicolor (registered trademark), manufactured by 3M) was attached at room temperature to prevent air from entering, and left for 5 seconds. Thereafter, the tape was peeled from the sample substrate in a 60° direction within 1 second, and evaluated according to the following criteria. Note that the tape was peeled off so that the peeling force was constant in all squares.
A: Out of the 81 squares created, not one square was peeled off. B: Out of the 81 squares created, peeling occurred in 1 to 9 squares. C: Out of the 81 squares created, peeling occurred in 1 to 9 squares. , peeling occurred in squares 10 to 81.

(7) Results In Examples 1 to 5, the absorption layer contains a water-soluble resin and a water-soluble dye, and the optical member in which the absorption layer is formed on a glass substrate has ripples in the transmission spectrum in the transmission region. was not recognized. Furthermore, the difference between the maximum transmittance and the minimum transmittance in the wavelength range of 500 nm to 520 nm was also small. On the other hand, in Comparative Examples 1 to 3, the absorption layer contains a water-insoluble resin and a water-insoluble dye, and in the optical member in which the absorption layer is formed on a glass substrate, ripples occur in the transmission spectrum in the transmission region. was confirmed. Furthermore, the difference between the maximum transmittance and the minimum transmittance in the wavelength range of 500 nm to 520 nm was larger than in the example. Regarding heat resistance, both Examples 1 to 5 and Comparative Examples 1 to 3 had sufficient heat resistance, with small changes in transmittance before and after curing at a wavelength of 500 nm. Examples 1 to 5 were also excellent in both initial adhesion and adhesion after boiling in water.

The light selective cutting optical member of the present invention can be used in various fields such as optical devices such as display elements and image pickup elements. For example, it can be used for electronic components such as mobile phone cameras, digital cameras, in-vehicle cameras, surveillance cameras, and display elements (LEDs, etc.).

Claims (10)

A light selective cutting optical member having a base material, an absorption layer, and a dielectric film,
The light selective cutting optical member is characterized in that the absorption layer is formed from a resin composition containing a water-soluble resin and a water-soluble dye. The light selective cutting optical member according to claim 1, wherein the water-soluble dye is at least one selected from near-infrared absorbing dyes and ultraviolet absorbing dyes. The water-soluble dye is at least one selected from phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, croconium compounds, cyanine compounds, dipyrromenthene compounds, diimonium compounds, metal dithiol complex compounds, and metal diamine complex compounds. The light selective cutting optical member according to claim 1, which is a kind of near-infrared absorbing dye. The water-soluble dyes include triazine compounds, benzotriazole compounds, acrylate compounds, benzoxazinone compounds, azomethine compounds, azoxy compounds, cyanobiphenyl compounds, cyanophenyl ester compounds, benzoate ester compounds, 2. The ultraviolet absorbing dye according to claim 1, which is at least one type of ultraviolet absorbing dye selected from cyclohexanecarboxylic acid phenyl ester compounds, cyanophenylcyclohexane compounds, phenylpyrimidine compounds, phenyldioxane compounds, cinnamate compounds, and tolan compounds. Optical material for selectively cutting light. The light selective cutting optical member according to claim 1, wherein the water-soluble resin has an amino group, a carbonyl group, an ether group, or a sulfonyl group. The light selective cutting optical member according to claim 1, wherein the base material is a glass substrate, and the absorption layer is formed on the glass substrate. The light selective cutting optical member according to claim 1, wherein the difference in refractive index between the water-soluble resin and the base material is 0.30 or less. An imaging device comprising the light selective cutting optical member according to any one of claims 1 to 7. A resin composition for forming an absorption layer of the light selective cutting optical member according to any one of claims 1 to 7, comprising:
A resin composition characterized by containing a water-soluble resin and a water-soluble dye. A phthalocyanine compound represented by the following formula (1).

[In formula (1),
M represents a metal atom, metal oxide or metal halide,
R ¹ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom, -OR ¹⁷ or -SR ¹⁸ ,
R ¹⁷ and R ¹⁸ are each independently an aryl group that may have a substituent, an aralkyl group that may have a substituent, a heteroaryl group that may have a substituent, or a substituted represents an alkyl group that may have a group,
Five or more of R ¹ to R ¹⁶ are -OR ¹⁷ or -SR ¹⁸ , and R ¹⁷ and R ¹⁸ are an aryl group having a carboxy group or a salt thereof, or an aralkyl group having a carboxy group or a salt thereof. be. ]

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