TW202237749A - Base material, optical filters and uses thereof wherein the optical filter is excellent in both optical properties and heat resistance, can achieve further thinning, and is less prone to warpage or cracking - Google Patents

Abstract

The present invention provides a base material suitable for the following optical filters, an optical filter comprising the base material, and a camera module and a solid-state imaging device comprising the optical filter. The optical filter is excellent in both optical properties such as near-infrared shielding and heat resistance, can achieve further thinning, and is less prone to warpage or cracking. A base material has a layer containing nanofibers, and the maximum absorption wavelength is in the wavelength range of 600 nm to 1200 nm.

Description

Substrates, optical filters and their uses

The present invention relates to a substrate suitable for optical filters, an optical filter comprising the substrate and uses thereof.

In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, a charge coupled device (CCD) or a complementary metal oxide semiconductor (complementary metal oxide semiconductor) is used as a solid-state imaging element for color images. semiconductor, CMOS) image sensor. In these solid-state imaging devices, a silicon photodiode sensitive to near-infrared rays that cannot be sensed by the human eye is used for the light-receiving part. In addition, even in optical sensor devices, silicon photodiodes and the like are used. For example, in solid-state imaging devices, it is necessary to perform visibility correction to produce natural colors seen by the human eye, and optical filters (such as near-infrared cut filters) that selectively pass or cut light in specific wavelength regions are often used .

As such a near-infrared cut filter, filters manufactured by various methods have been used heretofore. For example, there are known near-infrared cut filters that use a resin as a base material and contain a near-infrared-absorbing pigment in the resin (see, for example, Patent Document 1) or absorbing glass optical filters in which copper oxide is dispersed in phosphoric acid glass (for example, Refer to Patent Document 2).

However, the near-infrared cut filter described in Patent Document 1 may not necessarily have sufficient near-infrared absorption characteristics.

In addition, in recent years, solid-state imaging devices have been required to be thinner, and optical filters used have also been required to be thinner. However, there is a problem that if the thickness of the optical filter is reduced, warpage or cracks are likely to occur. Furthermore, along with the above-mentioned reduction in thickness, it is also required to improve the heat resistance of the optical filter.

[Prior art literature] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 6-200113 [Patent Document 2] International Publication No. 2011/071157

[Problem to be Solved by the Invention] In view of the problems of the prior art, an object of the present invention is to provide a base material suitable for the following optical filters, an optical filter including the base material, and a solid-state imaging device and a camera module including the optical filter. The optical filter has excellent optical properties such as near-infrared shielding properties and heat resistance, can achieve further thinning, and is less prone to warping or cracking.

[Technical means to solve the problem] As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention found that the above-mentioned problems can be solved as in the following structural examples, and completed the present invention. Structural examples of the present invention are shown below.

[1] A substrate having a layer containing nanofibers and having an absorption maximum wavelength within a wavelength range of 600 nm to 1200 nm. [2] The substrate according to item [1], wherein the nanofibers have an average fiber diameter of 3 nm to 200 nm, and an average fiber length of 0.2 μm to 10 μm.

[3] The base material according to item [1] or item [2], wherein the nanofibers have a specific surface area of 70 m ² /g to 300 m ² /g. [4] The substrate according to any one of items [1] to [3], wherein the crystallinity of the nanofibers is 43% or more.

[5] The substrate according to any one of items [1] to [4], wherein the nanofibers are hydrophobic cellulose nanofibers that can be dispersed in an organic solvent. [6] The base material according to any one of items [1] to [5], including a resin substrate containing the nanofiber and an absorption maximum wavelength at a wavelength of 600 nm to 1200 nm range of compounds (A).

[7] The base material according to item [6], wherein when the total of the content of the resin constituting the resin substrate and the content of the nanofiber is 100 parts by mass, the content of the nanofiber is 5 to 50 parts by mass.

[8] The substrate according to any one of items [1] to [5], including: a substrate made of a resin selected from a compound (A) containing a compound (A) whose maximum absorption wavelength is in the wavelength range of 600 nm to 1200 nm; a substrate and a near-infrared-absorbing glass substrate; and a resin layer formed on both sides of the substrate and containing the nanofibers.

[9] The substrate according to any one of items [1] to [5], comprising: a support made of resin or glass; and a resin layer formed on both sides of the support and containing the A nanofiber and a compound (A) having a maximum absorption wavelength in a wavelength range of 600 nm to 1200 nm. [10] The base material according to item [8] or item [9], wherein when the total content of the resin constituting the resin layer and the content of the nanofiber is 100 parts by mass, the nanofiber The content of the rice fiber is 5 to 70 parts by mass.

[11] The substrate according to any one of items [6] to [8], wherein the resin constituting the resin substrate is selected from the group consisting of cyclic polyolefin-based resins, aromatic polyether-based resins, Polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polyether resin, polyether resin , polyparaphenylene resin, polyamide imide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, Sesquite Silicone-based UV-curable resin, maleimide-based resin, alicyclic epoxy thermosetting resin, polyetheretherketone-based resin, polyarylate-based resin, allyl ester-based curable resin, acrylic-based UV-curable resin At least one resin selected from the group consisting of curable resins, vinyl-based ultraviolet curable resins, and resins formed by a sol-gel method and containing silica as a main component.

[12] The base material according to item [9] or item [10], wherein the resin constituting the resin layer is selected from the group consisting of cyclic polyolefin-based resins, aromatic polyether-based resins, and polyimide-based resins. Resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polyether resin, polyether resin, polyparaphenylene Resin, polyamide imide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane UV Hardening resins, maleimide resins, alicyclic epoxy thermosetting resins, polyether ether ketone resins, polyarylate resins, allyl ester curable resins, acrylic UV curable resins, vinyl At least one resin selected from the group consisting of a base-based ultraviolet curable resin and a resin formed by a sol-gel method and containing silica as a main component.

[13] An optical filter comprising the base material according to any one of item [1] to item [12], and a dielectric multilayer film. [14] The optical filter according to item [13], which has a thickness of 150 μm or less.

[15] An imaging device comprising the optical filter described in item [13] or item [14]. [16] A camera module, characterized in that it includes the optical filter described in item [13] or item [14].

[Effect of the invention] According to the present invention, there can be provided an optical filter, a substrate suitable for the optical filter, a solid-state imaging device and a camera module including the optical filter, and the near-infrared shielding properties of the optical filter, etc. It has excellent properties, achieves further thinning, and is excellent in low warpage and heat resistance.

Hereinafter, embodiments of the substrate and the optical filter of the present invention will be described with reference to the drawings and the like. However, the present invention can be implemented in a plurality of different forms, and should not be limitedly interpreted by the description of the following exemplary embodiments. Regarding the drawings, in order to explain more clearly, the width, thickness, shape, etc. of each part may be schematically shown compared with the actual form, but it is an example and does not limit the interpretation of the present invention. In addition, in the specification and each figure, it is sometimes appropriate to indicate the same symbols or similar symbols (only symbols such as "'" after the numbers) for the same elements as those described above. Detailed description is omitted.

In addition, in the present invention, descriptions such as "A to B" indicating a numerical range have the same meaning as "more than A and less than B", and A and B are included in the numerical range. In addition, in the present invention, the wavelengths A nm to B nm mean the characteristics at the wavelength resolution of 1 nm in the wavelength range from the wavelength A nm to the wavelength B nm.

＜Substrate＞ The base material of the present invention has a layer containing nanofibers described later, and has an absorption maximum wavelength in a wavelength range of 600 nm to 1200 nm. The base material of the present invention is not particularly limited in material, shape, etc. as long as the effect of the present invention is not impaired, but a transparent plate-like body is preferred. As a material of such a base material, various glass and resin are mentioned, for example.

The base material can be a single layer or a multi-layer, and can include one material selected from the above materials, or multiple materials, and can also be a material mixed appropriately.

As a preferred form of the base material, there are listed Form (i), including a resin substrate containing the nanofiber and a compound (A) whose maximum absorption wavelength is in the range of 600 nm to 1200 nm; Form (ii), comprising: a substrate selected from a resin substrate containing the compound (A) and a near-infrared-absorbing glass substrate; and a resin layer formed on both sides of the substrate and containing the nanofiber; The aspect (iii) includes: a support made of resin or glass; and a resin layer formed on both surfaces of the support and containing the nanofiber and the compound (A). In addition, the nanofibers and the compound (A) may be included in the same layer, or may be included in different layers.

In the aspect (i), if necessary, at least one surface layer of the resin substrate may include a resin layer such as an overcoat layer of curable resin or the like. In Fig. 1(a), as an example of the base material of form (i), it is shown that the resin substrate 1a containing the nanofibers and the compound (A) has an overcoat (resin layer) on both sides. ) Example of the form of 2a. In (b) of FIG. 1 , as an example of the base material of the form (ii), an example of a form having the resin layer 2 b containing the nanofibers on both surfaces of the substrate 1 b is shown. In (c) of FIG. 1 , as an example of the substrate of the form (iii), a form in which a resin layer 2c containing the nanofibers and the compound (A) is provided on both sides of the support 1c is shown. example.

Hereinafter, a layer containing at least one compound (A) and a resin is also referred to as a "transparent resin layer".

In the base material, the minimum value (T ₁ ) of the transmittance in a wavelength range of 600 nm to 1200 nm is preferably 3% or less, more preferably 2% or less, further preferably 1% or less. When T ₁ is in the above-mentioned range, the transmittance cutoff of the absorption band can be sufficiently cut off, and ghosts around the light source can be suppressed in the camera image, which is preferable.

In the base material, the optimum range of the shortest wavelength (Xc) in which the transmittance exceeds 50% and becomes 50% or less in the wavelength range of 550 nm or longer depends on the type of application. As an example, in imaging applications, Xc is preferably from 630 nm to 655 nm, more preferably from 632 nm to 652 nm, and still more preferably from 634 nm to 650 nm. If Xc is less than 628 nm, the transmittance in the wavelength region corresponding to red tends to decrease, and the color reproducibility tends to decrease. If Xc exceeds 658 nm, sufficient intensity of absorption cannot be ensured, and it may appear in the camera image. The tendency of color shades.

The haze value of the base material is preferably 0.5% or less, more preferably 0.4% or less, particularly preferably 0.35% or less. When the haze value is within the above-mentioned range, it is possible to suppress the flare around the light source in the camera image, which is preferable.

The linear expansion coefficient (coefficient of thermal expansion (CTE)) of the substrate in the range of 40°C to 100°C is preferably 60 ppm/°C or less, more preferably 50 ppm/°C or less, most preferably 40 ppm/°C. below ppm/°C. When the CTE of the base material is within the above range, thermal deformation of the optical filter at the time of forming the dielectric multilayer film can be suppressed, and heat resistance is improved, which is preferable.

The tensile modulus of the base material is preferably at least 3.0 GPa, more preferably at least 3.5 GPa, and most preferably at least 4.0 GPa. When the tensile modulus of the base material is within the above-mentioned range, the warpage of the optical filter at the time of forming the dielectric multilayer film can be reduced, which is preferable.

The Martens hardness (Martens hardness) of the substrate in the form (ii) and the resin layer (coating film) formed on the support in the form (iii) is preferably 200 N/mm ² or more, and more preferably The best is 210 N/mm ² or more, and the most preferred is 215 N/mm ² or more. When the Martens hardness of a coating film exists in the said range, when an object comes into contact with the surface of a coating film, since scratches are hard to generate|occur|produce in a coating film, it is preferable.

When the substrate is in the form (i), the following effects are exhibited. 1. By including nanofibers, it is possible to increase the strength of the substrate and lower the CTE, and to reduce the warpage of the optical filter. Due to the improvement of such mechanical properties, it is possible to reduce the thickness of the base material. 2. By including nanofibers, even in an environment above the glass transition temperature of the resin constituting the resin substrate, softening of the base material can be suppressed, and the heat resistance as an optical filter can be improved. 3. The inclusion of nanofibers suppresses the propagation of cracks when the optical filter is punched, and improves the durability of the punched end of the optical filter.

When the substrate is in the form (ii), the following effects are exhibited. 1. When forming a coating film containing nanofibers, it is possible to suppress dent defects that cause poor appearance. 2. By including nanofibers, the scratch resistance of the surface of the coating film is improved, and the adhesion of scratches that cause poor appearance can be suppressed. 3. By including nanofibers, it is possible to increase the strength of the base material and lower the CTE, and to reduce the warpage of the optical filter. Due to the improvement of such mechanical properties, it is possible to reduce the thickness of the base material. 4. When a resin substrate is used, by including nanofibers, even in an environment above the glass transition temperature of the resin constituting the resin substrate, the softening of the substrate can be suppressed, and the heat resistance as an optical filter can be improved.

When the base material is in the form (iii), the following effects are exhibited. 1. When forming a coating film containing the compound (A), by including nanofibers in the coating solution, the dispersibility of the pigment is improved, and the haze of the coating film can be reduced. 2. When forming a coating film containing nanofibers, it is possible to suppress dent defects that cause poor appearance. 3. By including nanofibers, the scratch resistance of the surface of the coating film is improved, and the adhesion of scratches that cause poor appearance can be suppressed. 4. By including nanofibers, it is possible to increase the strength of the base material and lower the CTE, and to reduce the warpage of the optical filter. Due to the improvement of such mechanical properties, it is possible to reduce the thickness of the base material itself. 5. When using a resin support, by including nanofibers, even in an environment above the glass transition temperature of the resin constituting the support, softening of the base material can be suppressed, and the heat resistance as an optical filter can be improved.

The thickness of the substrate can be appropriately selected according to the desired application, and there is no special limitation. In the case of a resin-based substrate, it is preferably 20 μm to 120 μm, further preferably 30 μm to 110 μm, and most preferably 40 μm It is preferably 70 μm to 250 μm, more preferably 90 μm to 200 μm, and most preferably 100 μm to 180 μm in the case of a glass-based substrate.

If the thickness of the base material is within the above range, the present filter using the base material can be reduced in thickness and weight, and can be suitably used in various applications such as solid-state imaging devices. In particular, when the single-layer base material is used for a lens unit of a camera module or the like, it is preferable because the profile and weight of the lens unit can be reduced.

＜Optical Filter＞ The optical filter of the present invention (hereinafter also referred to as "this filter") is characterized by comprising the above-mentioned substrate of the present invention.

This filter may have a structure including only the base material, and may have a dielectric multilayer film or other functional film formed on at least one side of the base material if necessary.

The average value of the transmittance of the filter when measured from a direction perpendicular to the surface of the filter in the wavelength range of 430 nm to 580 nm is preferably 65% or more, more preferably 70% or more, and still more preferably It is more than 75%, and the best is more than 80%. When the average value of the transmittance in the wavelength region is within the above range, excellent imaging sensitivity can be achieved when the present filter is used for a solid-state imaging device.

In addition, the average value of the transmittance of the filter when measured from a direction perpendicular to the surface of the filter in the wavelength range of 900 nm to 1050 nm is preferably 10% or less, more preferably 7% or less, and further Preferably it is 6% or less, especially preferably 5% or less. When the average value of the transmittance in the wavelength region is within the above range, when the present filter is used for a solid-state imaging device, light that is invisible to the human eye and unnecessary for sensing can be blocked.

The value (Xa) of the shortest wavelength at which the transmittance of this filter becomes 50% when measured from the vertical direction of this filter in the wavelength range of 600 nm to 800 nm is 30 from the vertical direction relative to this filter. The transmittance when measured at an angle of ° becomes the absolute value of the difference of the wavelength value (Xb) of 50% |Xa-Xb|, preferably less than 20 nm, more preferably 15 nm or less, further preferably 10 nm or less . When |Xa-Xb| is in the above-mentioned range, color shading can be suppressed when this filter is used for a solid-state imaging device.

The thickness of the present filter may be appropriately selected according to the desired application, and it is preferable that the thickness of the present filter is also thin due to trends such as thinning and weight reduction of solid-state imaging devices in recent years. Since the present filter includes the base material, it can be thinned.

When the base material is a resin base material, the thickness of the filter is preferably 150 μm or less, more preferably 100 μm or less, further preferably 70 μm or less, particularly preferably 40 μm or less, and the lower limit is not specified. As a limitation, thinner thickness is preferable for thinning the solid-state imaging device. In addition, when the substrate is a glass-based substrate, the thickness of the filter is preferably not more than 270 μm, more preferably not more than 230 μm, further preferably not more than 170 μm, particularly preferably not more than 140 μm.

＜Nanofiber＞ The nanofibers are not particularly limited, and examples thereof include fibrous substances having a diameter (average fiber diameter) of 1 nm to 100 nm and a length (average fiber length) of 100 times or more the diameter. Such fibrous substances include, for example, polymer nanofibers made of polypropylene or polyethylene terephthalate, cellulose nanofibers, deoxyribonucleic acid (Deoxyribonucleic Acid, DNA) nanofibers, carbon nanofibers, etc. Nanofibers, metal nanofibers, etc. Among these, cellulose nanofibers are preferred, chemically modified cellulose nanofibers are more preferred, and hydrophobic cellulose nanofibers capable of dispersing in organic solvents are particularly preferred. .

Here, "cellulose nanofibers" refer to nanofibers containing cellulose (cellulose nanofibers) or nanofibers containing lignocellulose (lignocellulose nanofibers), and both are collectively referred to as It is "CNF (cellular nanofiber)". In addition, the so-called "chemically modified cellulose nanofibers" refer to chemically modified cellulose nanofibers or chemically modified lignocellulose nanofibers, and are also collectively referred to as "chemically modified CNF". In addition, the so-called "dispersible in organic solvents" means that nanofibers do not aggregate or precipitate during mixing with organic solvents.

The cellulose nanofibers can be obtained by defibrating raw cellulose fibers. Examples of raw cellulose fibers include fibers isolated from plant fibers such as pulp from plants, wood, cotton, hemp, bamboo, cotton, kenaf, hemp, jute, bananas, coconuts, and seaweeds; Fibers separated from animal fibers produced by sea squirts, or bacterial cellulose produced by acetic acid bacteria. Of these, fibers separated from plant fibers, more preferably fibers obtained from plant fibers of pulp, cotton, and the like can be preferably used.

In the chemically modified CNF, by introducing an alkyl group such as an acetyl group to replace a hydrogen atom of a hydroxyl group of a sugar chain constituting cellulose (that is, the hydroxyl group is chemically modified), the hydroxyl group of the cellulose molecule is blocked, and the cellulose In addition to suppressing the hydrogen bonding force of molecules, the crystalline structure originally possessed by cellulose fibers is maintained at a specific ratio.

Modification methods can be performed according to known methods. For example, after adding and dispersing the defibrated cellulose fibers in water or an appropriate solvent, a chemical modifier is added thereto and reacted under appropriate reaction conditions. Regarding the method of performing chemical modification, in that case, in addition to the chemical modifier, a reaction catalyst may be added if necessary, for example, pyridine, N,N-dimethylaminopyridine, triethylamine, sodium methoxide, Basic catalysts such as sodium ethoxide and sodium hydroxide, or acid catalysts such as acetic acid, sulfuric acid, and perchloric acid, are preferably basic catalysts such as pyridine in order to prevent a decrease in the reaction rate or degree of polymerization. The reaction temperature is preferably about 40° C. to 100° C. from the viewpoint of suppressing deterioration such as yellowing of cellulose fibers and a decrease in the degree of polymerization, and ensuring a reaction rate. The reaction time may be appropriately selected such as the modifying agent used or the treatment conditions.

As chemically modified CNF, for example, hydrophobized CNF in which hydroxyl groups existing on the surface of nanofibers are hydrophobized by modification with an acyl group or an alkyl group, etc.; Modified CNF modified by the modification of alkyl ammonium halide or its halohydrin type compound, etc. to modify the hydroxyl cation existing on the surface of the nanofiber; Monoesterification with an acid anhydride, modification with a silane coupling agent having a carboxyl group, etc., modified CNF that modifies hydroxyl anions existing on the surface of nanofibers, etc.

Among these, in terms of ease of production, CNF in which the hydroxyl group of the sugar chain constituting CNF is modified with an alkylyl group is preferable (alkanyl group-modified CNF), and CNF in which a lower alkylyl group is modified (lower alkyl group) is more preferable. Acyl-modified CNF), and further preferably acetyl-modified CNF (also referred to as Ac-CNF) in terms of ease of manufacture and manufacturing cost.

The degree of acylation (degree of substitution, DS (degree of substitution)) in the sugar chain hydroxyl group of the chemically modified CNF obtained by the acylation reaction is preferably about 0.05 to 2.5, more preferably about 0.1 to 1.7, and still more preferably 0.15 ~ 1.5 or so. The maximum value of the degree of substitution (DS) depends on the amount of sugar chain hydroxyl groups in CNF, and is about 2.7. By setting the degree of substitution (DS) at about 0.05-2.5, chemically modified CNF with moderate crystallinity and solubility parameter (Solubility Parameter, SP) values can be obtained. For example, in acetylated CNF, the preferable DS is 0.29 to 2.52, and the crystallinity can be maintained at about 42.7% or more in the DS in this range. In addition, the degree of substitution (DS) can be determined by elemental analysis, neutralization titration, Fourier Transform-Infrared Spectroscopy (FT-IR), two-dimensional nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) (1H and 13C- NMR) and other analytical methods.

The average fiber diameter of the nanofibers is preferably from 3 nm to 200 nm, more preferably from 3 nm to 150 nm, and still more preferably from 3 nm to 100 nm. If the average fiber diameter is within the above range, the light scattering caused by nanofibers can be reduced, and when applied to optical filters, it can bring about an increase in transmittance and a reduction in haze (Haze), and it is possible to make the base material high Intensification and low CTE.

The average fiber length of the nanofibers is preferably from 0.2 μm to 10 μm, more preferably from 0.3 μm to 5 μm, and still more preferably from 0.4 μm to 3 μm. If the average fiber diameter is within the above range, the light scattering caused by nanofibers can be reduced, and when applied to optical filters, it can bring about an increase in transmittance and a reduction in haze (Haze), and it is possible to make the base material high Intensification and low CTE.

In the present invention, in the measurement of "average fiber diameter" and "average fiber length", a transmission electron microscope or a scanning electron microscope can be used to observe nanofibers at a magnification of 10,000 times, and then for the obtained image, 100 fibers were randomly selected, and the fiber diameter and fiber length of each fiber were analyzed using image processing software, and calculated as their simple numerical average.

The specific surface area of the nanofiber is preferably 70 m ² /g-300 m ² /g, more preferably 70 m ² /g-250 m ² /g, and more preferably 100 m ² /g-200 m 2 /g ² /g. When the specific surface area is within the above range, the mechanical strength of the base material increases, and the occurrence of warpage or cracking can be suppressed.

The crystallinity of the nanofibers is preferably above 43%, more preferably above 50%, even more preferably above 55%, and particularly preferably above 60% to 80%. When the degree of crystallinity is within the above range, performances such as high strength and low thermal expansion are exhibited. In addition, the crystallinity refers to the abundance ratio of crystals (mainly cellulose type I crystals) in the entire cellulose, for example, in the case of cellulose nanofibers.

When the structure of the substrate is the form (i), the content of the nanofibers is preferably 5 parts by mass based on 100 parts by mass of the total content of the resin constituting the resin substrate and the nanofibers. 50 parts by mass, more preferably 10 parts by mass to 45 parts by mass, still more preferably 10 parts by mass to 40 parts by mass.

In addition, when the structure of the base material is the above-mentioned form (ii) or form (iii), with respect to the total of 100 parts by mass of the resin constituting the said resin layer and the content of the said nanofibers, the amount of said nanofibers The content is preferably from 5 parts by mass to 70 parts by mass, more preferably from 10 parts by mass to 60 parts by mass, still more preferably from 10 parts by mass to 50 parts by mass.

When the content of the nanofibers is within the above range, the effect exerted when the substrate is in the form (i) to form (iii) can be exhibited more clearly.

<Compound (A)> The compound (A) is not particularly limited as long as it has a maximum absorption wavelength in the wavelength range of 600 nm to 1200 nm. It is preferably a solvent-soluble pigment compound, more preferably a polymethine compound (for example, squarylium-based compounds, cyanine-based compounds, etc.), pyrrolopyrrole-based compounds, croconium-based compounds, diimonium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, Azaporphyrin-based compounds, porphyrin-based compounds, hexaphyrin-based compounds, metal dithiolate-based compounds, triarylmethane-based compounds, subphthalocyanine-based compounds, perylene-based compounds, semisquaric acid Onium compounds, styryl compounds, phenazine compounds, pyridomethylene-boron complex compounds, pyrazine-boron complex compounds, pyridone azo compounds, xanthene compounds , at least one of the group consisting of dipyrromethene compounds, more preferably selected from squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, pyrrolo At least one of the group consisting of pyrrole-based compounds, crotonium-based compounds, six-membered porphyrin-based compounds, metal dithiolate-based compounds, and ring-expanded boron-dipyrromethene (BODIPY)-based compounds One, and more preferably at least one selected from the group consisting of squarylium-based compounds, cyanine-based compounds, crotonium-based compounds, and pyrrolopyrrole-based compounds.

The maximum absorption wavelength of the compound (A) is 600 nm to 1200 nm, preferably 630 nm to 800 nm, further preferably 640 nm to 780 nm, particularly preferably 650 nm to 760 nm. When the absorption maximum wavelength of the compound (A) is in such a range, it can transmit light of a useful wavelength for near-infrared sensing and cut off unnecessary near-infrared rays, and reduce the incident angle dependence of the near-infrared transmission band.

Regarding the content of the compound (A), for example, a base material including a resin substrate containing the compound (A) or a base material obtained by laminating a resin layer such as an overcoat layer containing a curable resin or the like on the resin substrate is used as the target. In the case of the above base material, it is preferably 0.01 to 2.0 parts by mass, more preferably 0.02 to 1.5 parts by mass, and particularly preferably 0.03 to 1.0 parts by mass. In addition, when using a transparent resin layer such as an overcoat layer containing a curable resin or the like containing the compound (A) on a glass support or a resin support volume layer serving as a substrate as the substrate , preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 4.0 parts by mass, particularly preferably 0.3 to 3.0 parts by mass, relative to 100 parts by mass of the resin forming the transparent resin layer containing the compound (A) share. When the content of the compound (A) is within the above range, favorable near-infrared absorption characteristics can be achieved.

When the substrate is a form using the near-infrared-absorbing glass substrate in the form (ii), the compound (A) is CuO. The maximum absorption wavelength of CuO is in the wavelength range of about 850 nm to 900 nm. As the near-infrared-absorbing glass substrate, CuO-containing fluorophosphate glass or CuO-containing phosphate glass (hereinafter, these are collectively referred to as "CuO-containing glass") can be used. By using CuO-containing glass, it has high transmittance for visible light and high shielding property for near-infrared rays. In addition, phosphate glass includes silicon phosphate glass in which part of the glass skeleton contains SiO ₂ .

Commercially available products include, for example: NF50-E, NF50-EX (manufactured by Asahi Glass Co., Ltd.); BG-60, BG-61 (manufactured by SHOTT Corporation); BS-11 (manufactured by Matsunami Glass Industries); CD5000 (manufactured by HOYA), etc.

The thickness of CuO-containing fluorophosphate-based glass or CuO-containing phosphate-based glass is preferably in the range of 0.03 mm to 5 mm, and is more preferably 0.05 mm from the viewpoint of strength, weight reduction, and low profile. ~1 mm range.

＜Resin＞ The resin used for the (transparent) resin layer, the resin substrate, or the resin support of the base material is not particularly limited as long as it does not impair the effects of the present invention. For example, in order to ensure thermal stability and molding For the formability of the film, and to make a film that can form a dielectric multilayer film by high-temperature vapor deposition at a vapor deposition temperature of 100°C or higher, the glass transition temperature (Tg) is preferably 110°C to 380°C, More preferably, it is a resin at 110°C to 370°C, and still more preferably at 120°C to 360°C. In addition, if the glass transition temperature of the resin is 150° C. or higher, even when the glass transition temperature is lowered by adding a compound to the resin at a high concentration, it is possible to obtain a glass with a dielectric multilayer film that can be formed by high-temperature vapor deposition. Films with varying transition temperatures are therefore particularly preferred.

As the resin, when forming a resin plate with a thickness of 0.05 mm including the resin, the total light transmittance of the resin plate (Japanese Industrial Standards (JIS) K7105) is preferably 75% to 75%. 95%, more preferably 78% to 95%, particularly preferably 80% to 95% of the resin. When the resin whose total light transmittance is in such a range is used, the obtained board|substrate will show favorable transparency as an optical film.

The polystyrene-equivalent mass average molecular weight (Mw) of the resin measured by gel permeation chromatography (GPC) is usually 15,000-350,000, preferably 30,000-250,000, and the number average molecular weight (Mn ) is usually 10,000 to 150,000, preferably 20,000 to 100,000.

Examples of the resin include: cyclic polyolefin-based resins, aromatic polyether-based resins, polyimide-based resins, fluorene-polycarbonate-based resins, fluorene-polyester-based resins, polycarbonate-based resins, polyamide-based resins, Amide-based resins, aromatic polyamide-based resins, polyethylene-based resins, polyether-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorine Aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane UV curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyester Ether ether ketone resins, polyarylate resins, allyl ester curable resins, acrylic UV curable resins, vinyl UV curable resins, and silica-based resins formed by the sol-gel method resin. Among these, it is preferable to use a cyclic polyolefin resin, an aromatic polyether resin, a fluorene Polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyarylate resin.

"Commercially Available Items" As a commercial item of transparent resin, the following commercial item etc. are mentioned. Examples of commercially available cyclic polyolefin-based resins include Arton manufactured by JSR Co., Ltd., Zeonor manufactured by Zeon Co., Ltd., and Mitsui Chemicals Co., Ltd. ) manufactured APEL (APEL), Polyplastics (Polyplastics) (shares) manufactured TOPAS (TOPAS), etc. Examples of commercially available polyethersulfone-based resins include Sumikaexcel PES manufactured by Sumitomo Chemical Co., Ltd., and the like. Examples of commercially available polyimide-based resins include Neopulim L manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. Commercially available polycarbonate-based resins include PURE-ACE manufactured by Teijin Co., Ltd., and the like. As a commercial item of a fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. product Iupizeta (Iupizeta) EP-5000 etc. are mentioned. As a commercial item of a fluorene polyester type resin, OKP4HT etc. by the Osaka Gas Chemicals Co., Ltd. product are mentioned. Examples of commercially available acrylic resins include Acryviewa manufactured by Nippon Catalyst Co., Ltd., and the like. As commercially available products of the silsesquioxane-based ultraviolet curable resin, Silplus, manufactured by Nippon Steel Chemical Co., Ltd., and the like are exemplified.

＜Other ingredients＞ The substrate may further contain additives such as an antioxidant, a near-ultraviolet absorber, and a fluorescent matting agent within a range that does not impair the effect of the present invention. These other components may be used alone or in combination of two or more.

"Near UV Absorber" The near-ultraviolet absorber is not particularly limited as long as it has at least one absorption maximum wavelength in the wavelength range of 250 nm to 420 nm. Triazole compounds, triazine compounds, anthracene compounds, etc.

"Antioxidants" Examples of the antioxidant include: 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5' -Dimethyldiphenylmethane, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and tris(2,4-di-tert Butylphenyl) phosphite, etc.

The additive may be mixed with the resin or the like when the transparent resin is produced, or may be added when the resin is synthesized. Moreover, although the addition amount can be selected suitably according to desired characteristic, it is 0.01-5.0 mass parts normally with respect to 100 mass parts of said transparent resins, Preferably it is 0.05-2.0 mass parts.

＜Support＞ "Resin Support" The resin used for the resin substrate or the resin support is as described above.

"Glass Support" It does not specifically limit as said glass support body, For example, a borosilicate glass, a silicate glass, a soda-lime glass, a near-infrared absorption glass, etc. are mentioned.

<Manufacturing method of base material> When the base material is a base material including the resin-made substrate in the above-mentioned form (i) and form (ii), the said resin-made substrate can be formed, for example, by fusion molding or casting molding, and further, if necessary, it can also be Coating agents such as antireflective agents, hard coat agents, and/or antistatic agents are applied after molding.

When the base material is the base material of the form (iii), for example, by melting or casting a resin solution containing the compound (A) and nanofibers on a glass support or a resin support , preferably using methods such as spin coating, slit coating, inkjet, etc., and then drying and removing the solvent, and then performing light irradiation or heating if necessary, so that it can be manufactured on a glass support or a resin support. A substrate having a transparent resin layer comprising compound (A) and nanofibers.

"Molten Forming" As the melt molding, specifically, there may be mentioned: a method of melt molding pellets obtained by melting and kneading the resin and the compound (A) and/or nanofibers; A method of melt-molding a resin composition of nanofibers; or a method of melt-molding particles obtained by removing a solvent from a resin composition containing a compound (A) and/or nanofibers, a resin, and a solvent, and the like. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding, and the like.

"Casting and Forming" As the casting molding, it can also be produced by the following method: casting a resin composition containing compound (A) and/or nanofibers, resin and solvent on a suitable support and removing the solvent; or The curable composition of compound (A) and/or nanofibers, and photocurable resin and/or thermosetting resin is cast on a suitable support, and the solvent is removed, followed by ultraviolet irradiation or heating. hardening method, etc.

When the base material is a base material comprising a resin substrate containing the compound (A), the base material can be obtained by peeling off the coating film from the support after casting molding. In addition, when the base material is In the case of a substrate formed by laminating a transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A) on a support such as a glass support or a resin support, the substrate can be obtained by It is obtained without peeling off the coating film after casting.

As said support body, the support body made of a glass plate, a steel belt, a steel drum, and a transparent resin (for example, a polyester film, a cyclic olefin resin film) is mentioned, for example.

Furthermore, it is also possible to form a transparent resin layer on an optical part by a method such as applying the resin composition to an optical part made of glass plate, quartz or transparent plastic, and drying the solvent; A method for hardening and drying the curable composition.

The amount of residual solvent in the transparent resin layer (resin substrate) obtained by the method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less, based on the weight of the transparent resin layer (resin substrate). When the amount of the residual solvent is within the above range, a transparent resin layer (resin substrate) that is less likely to be deformed or changed in properties and can easily exhibit a desired function can be obtained.

When the base material is in the form (i), the web strength at the time of casting of the base material is improved, so that the following effects are exerted: (1) It can be peeled off from the support in the early stage of drying, (2) In the production of the base material, for example, it will not break midway when it is conveyed by rollers or pinched by a tenter, (3) The drying temperature can be increased without softening and yellowing during drying, Therefore, productivity improves. In addition, the base material can be further thinned, so the drying speed is improved, and as a result, the following effects are achieved: (4) Productivity can be improved by shortening the drying time, (5) Deterioration of resin and pigment caused by heating can be suppressed.

When the substrate is in the form (ii), when the resin layer containing nanofibers is formed by coating on the substrate, the physical properties of the coating liquid can be reduced as follows: (1) At the shearing part of the coating head, the coating liquid flows, (2) After coating, sinking can be suppressed by thickening or gelation caused by standing still.

When the substrate is in the form (iii), when the resin layer containing nanofibers and pigments is formed by coating on the substrate, the physical properties of the coating liquid can be reduced as follows: (1) At the shearing part of the coating head, the coating liquid flows, (2) After coating, sinking can be suppressed by thickening or gelation caused by standing still. In addition, even if the drying temperature is increased after thickening or gelation after coating, the unevenness of the coloring matter (pigment) can be suppressed, so the drying efficiency of the resin layer can be improved.

＜Dielectric Multilayer Film＞ This filter may have a dielectric multilayer film as needed. Examples of the dielectric multilayer film include laminates in which high-refractive-index material layers and low-refractive-index material layers are alternately laminated. The dielectric multilayer film may be provided on one side or both sides of the substrate. When provided on one side, the manufacturing cost and ease of manufacture are excellent, and when provided on both sides, an optical filter having high strength and less likely to be warped or twisted can be obtained. When this filter is used for a solid-state imaging device or the like, it is preferable that the filter has little warpage or twist, and therefore it is preferable to provide a dielectric multilayer film on both surfaces of the substrate.

Examples of the material constituting the high-refractive-index material layer include materials having a refractive index of 1.7 or more, and materials having a refractive index of 1.7 to 2.5 are usually selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as main components, and a small amount (for example, relatively A material such as tin oxide and/or cerium oxide whose main component is 0% to 10% by mass).

As the material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index of 1.2 to 1.6 is generally selected. Examples of such materials include silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The method of laminating the high-refractive-index material layer and the low-refractive-index material layer is not particularly limited as long as a dielectric multilayer film in which these materials are laminated is formed. For example, the high refractive index material layer and the Dielectric multilayer film in which low refractive index material layers are laminated alternately.

Generally, when the near-infrared wavelength to be blocked is λ (nm), the thickness of each of the high-refractive index material layer and the low-refractive index material layer is preferably 0.1λ˜0.5λ. The value of λ (nm) is, for example, 700 nm to 1400 nm, preferably 750 nm to 1300 nm in the case of a near infrared color filter (Near Infrared Ray-Color Filter, NIR-CF). When the thickness of each layer of the high-refractive-index material layer and the low-refractive-index material layer is within the above range, the optical film thickness that is the product (n×d) of the refractive index (n) and the film thickness (d) becomes equal to λ/4 The substantially same value tends to allow easy control of blocking and transmission of specific wavelengths, such as the relationship of optical characteristics of reflection and refraction.

The total number of laminated layers of the high-refractive-index material layer and the low-refractive-index material layer in the dielectric multilayer film is preferably 16 to 70 layers, more preferably 20 to 60 layers, for the optical filter as a whole. When the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, or the total number of laminated layers are within the above-mentioned ranges, sufficient manufacturing margin can be ensured, and warpage of the optical filter or torsion of the dielectric multilayer film can be reduced. crack.

In this filter, the types of materials constituting the high-refractive-index material layer and the low-refractive-index material layer, and the thickness of each layer of the high-refractive-index material layer and low-refractive-index material layer are appropriately selected in consideration of the absorption characteristics of the compound (A). , the order of lamination, and the number of laminations, thereby ensuring sufficient transmittance in the wavelength region to be transmitted (eg: visible region), and having sufficient light cut-off characteristics in the near-infrared wavelength region to be cut off, and can reduce near-infrared wavelengths. Reflectance when infrared rays are incident from an oblique direction.

Here, in order to optimize the conditions of the dielectric multilayer film, for example, it is only necessary to use optical film design software (for example, Essential Macleod, manufactured by Thin Film Center), so as to take into account the It is enough to set the parameters in such a way that the anti-reflection effect in the wavelength region (for example: visible region) and the light cutoff effect in the near-infrared region to be cut off. In the case of the above-mentioned soft body, for example, in the case of forming a NIR-CF dielectric multilayer film, set the target transmittance at a wavelength of 400 nm to 700 nm to 100%, and set the value of the target tolerance (Target Tolerance) to 1. , the parameter setting method of setting the target transmittance of wavelength 705 nm to 950 nm as 0%, setting the target tolerance value as 0.5, etc.

These parameters can also be combined with various characteristics of the substrate to divide the wavelength range more finely to change the value of the target tolerance (Target Tolerance).

＜Other functional films＞ The filter can be used on the base material and the dielectric multi-layer film for the purpose of improving the surface hardness of the base material or the dielectric multi-layer film, improving chemical resistance, antistatic, and eliminating damage within the scope of not impairing the effect of the present invention. Between the films, on the surface opposite to the surface of the substrate on which the dielectric multilayer film is provided, or on the surface opposite to the surface of the dielectric multilayer film on which the substrate is provided, it is suitable to provide an antireflection film, a hard coat film or an antireflection film. Electrostatic film and other functional films.

The filter may include one layer of the functional film, or more than two layers. When the present filter includes two or more layers of the functional film, it may include two or more layers of the same film, or may include two or more layers of different films.

The method of laminating the functional film is not particularly limited, and examples thereof include melt molding on a substrate or a coating agent such as an antireflective agent, a hard coat agent, and/or an antistatic agent on a substrate or a dielectric multilayer film in the same manner as described above. Or casting methods, etc.

In addition, it can also be produced by applying a curable composition containing the coating agent or the like to a substrate or a dielectric multilayer film using a bar coater or the like, and then curing it by ultraviolet irradiation or the like.

Examples of the coating agent include ultraviolet (Ultraviolet, UV)/electron beam (electron beam, EB) curable resins, thermosetting resins, and the like. Specifically, vinyl compounds and urethane Ester, urethane acrylate, acrylate, epoxy and epoxy acrylate resins, etc. One kind of coating agent may be used alone, or two or more kinds may be used.

Examples of the curable composition containing these coating agents include vinyl-based, urethane-based, acrylic-urethane-based, acrylate-based, epoxy-based, and epoxy-acrylate-based curable compositions. composition etc.

In addition, the curable composition may also contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator may be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. One kind of polymerization initiator may be used alone, or two or more kinds may be used.

In the curable composition, when the total amount of the curable composition is 100% by mass, the blending ratio of the polymerization initiator is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 10% by mass. % by mass, and more preferably 1% by mass to 5% by mass. When the blending ratio of the polymerization initiator is within the above range, a curable composition having excellent curability and workability can be easily obtained, and an antireflection film, hard coat film, or antireflection film having desired hardness can be easily obtained. Electrostatic film and other functional films.

Furthermore, an organic solvent may be added as a solvent to the curable composition, and a known solvent may be used as the organic solvent. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetic acid Ethyl ester, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other esters; ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc. Ethers; benzene, toluene, xylene and other aromatic hydrocarbons; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and other amides. These solvents may be used alone or in combination of two or more.

The thickness of the functional film is preferably 0.1 μm-20 μm, more preferably 0.5 μm-10 μm, particularly preferably 0.7 μm-5 μm.

In addition, for the purpose of improving the adhesion between the substrate and the functional film and/or the dielectric multilayer film, or the adhesion between the functional film and the dielectric multilayer film, the surface of the substrate, the functional film or the dielectric multilayer film may also be corona-treated. Surface treatment such as treatment or plasma treatment.

＜Applications of Optical Filters＞ For example, this filter is excellent in the ability to cut off light of the wavelength in the region to be cut and the ability to transmit light in the wavelength to be transmitted. Therefore, it is useful as a visibility correction application of a solid-state imaging device such as a CCD or a CMOS image sensor of a camera module. Especially in digital still cameras, cameras for smartphones, cameras for mobile phones, digital video cameras, cameras for wearable devices, personal computer (PC) cameras, surveillance cameras, automotive cameras, infrared cameras, televisions, automotive Useful in navigation, portable information terminals, video game consoles, portable game consoles, fingerprint authentication systems, digital music players, various sensor systems, infrared communications, etc. Furthermore, it is also useful as an infrared cut filter etc. which are attached to the glass plate of an automobile, a building, etc.

"Solid State Camera" The solid-state imaging device of the present invention includes the present filter. Here, the so-called solid-state imaging device is a device including a solid-state imaging element such as a CCD or a CMOS image sensor. Specifically, it can be used in digital still cameras, cameras for smartphones, cameras for mobile phones, cameras for wearable devices, Digital cameras, etc.

"Camera Module" The camera module of the present invention includes the optical filter of the present invention. Here, a camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, etc., and outputs an image or distance information as an electrical signal.

[Example] Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples at all.

＜Molecular Weight＞ The molecular weight of the resin is measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent and the like. (a) A gel permeation chromatography (GPC) device manufactured by WATERS (Type 150C, column: H-type column manufactured by Tosoh Co., Ltd., developing solvent: o-dichloro Benzene), the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured. (b) Using a GPC device manufactured by Tosoh Co., Ltd. (HLC-8220 type, column: TSKgel α-M, developing solvent: tetrahydrofuran (THF)), the weight average in terms of standard polystyrene was measured Molecular weight (Mw) and number average molecular weight (Mn).

In addition, about the resin synthesize|combined in the resin synthesis example 3 mentioned later, the molecular weight was not measured by the said method, but the logarithmic viscosity was measured by the following method (c). (c) A part of the polyimide solution was poured into anhydrous methanol to precipitate the polyimide, which was separated from unreacted monomers by filtration, and vacuum-dried at 80° C. for 12 hours. Dissolve 0.1 g of the obtained polyimide in 20 mL of N-methyl-2-pyrrolidone (dilute polyimide solution), and use a Cannon-Fenske viscometer according to the following formula Find the logarithmic viscosity (μ) at 30°C. μ={ln(ts/t0)}/C t0: Flow down time of solvent (N-methyl-2-pyrrolidone) ts: flow time of dilute polyimide solution C: 0.5 g/dL

＜Glass transition temperature (Tg)＞ The glass transition temperature of the resin was measured using a differential scanning calorimeter (DSC6200) manufactured by Hitachi High-Tech Science Co., Ltd. at a heating rate of 20° C. per minute under a nitrogen flow.

＜Spectral transmittance＞ The transmittance in each wavelength region of the base material and the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Co., Ltd. The transmittance is measured by using the spectrophotometer under the condition that the light is perpendicularly incident on the substrate or the optical filter.

＜Haze (%)＞ The haze value (%) was measured about the base material of the form (iii) using the haze meter ("Haze-guard II" by BYK-Gardner company).

＜Coefficient of linear expansion: CTE (ppm/℃)＞ With respect to the base material, the temperature was changed in the range of 40°C to 160°C, and the coefficient of linear expansion (unit: ppm/°C) was measured in the range of 40°C to 100°C. As a measuring device, "EXSTAR6000TMA/SS6100" manufactured by Seiko Instruments (SII) was used.

＜Tensile modulus of elasticity (GPa)＞ The base material was stamped with a JIS K6251-3 dumbbell, and a tensile test was performed at 5 mm/min to calculate the tensile modulus. As a measuring device, a small tabletop tester ("EZ-LX" manufactured by Shimadzu Corporation) was used.

<Martens Hardness (N/mm ² )> Using a micro-hardness measuring machine ("PICODENTOR HM500" manufactured by FISCHER Instruments Co., Ltd.) ), and the load (mN) when the surface of the base material of form (iii) is indented to a depth of 0.3 μm, and the Martens hardness is measured.

< ^Scratch resistance> For the substrates of the form (ii) and form (iii), it was confirmed visually in accordance with the following criteria. The state of occurrence of scratches on the coating film (resin layer) after the second time. 〇: No scratches △: Slight scratches (permissible level) ×: Scratches (unacceptable level)

<Confirmation method for dent defects on the coated surface> A coating film (resin layer) was formed on one side of the substrate, and then a 50 mm×50 mm area of the coating film (resin layer) formation surface was irradiated with light from a desk lamp (fluorescent lamp) in a dark room and the number of depressions was visually counted.

＜Thermal deformation of optical filters＞ An optical filter of 25 mm x 30 mm was cut from a sheet obtained by forming a dielectric multilayer film on both sides of the base material, and placed on a hot plate heated to 180°C so that the filter surface was in contact with the hot plate. Heat for 5 minutes. After heating, the filter was cooled, and the appearance of the filter surface was judged according to the following criteria. 〇: There is no change in the appearance of the surface ×: Changes in the appearance of the surface (bubbles or orange-peel fog)

＜Warpage of Optical Filter＞ An optical filter of 6 mm x 8 mm was cut out from a sheet formed by forming a dielectric multilayer film on both sides of the substrate, and the height of nine points in the plane of the optical filter was measured, and an approximate plane passing through the nine points was calculated by the least square method. The distance between each measurement point and the approximate plane was calculated, and the distance between the two points farthest from the plane was regarded as warpage, and it was judged according to the following criteria. ◎: Warpage≦30 μm ○: 30 μm<warping≦50 μm (permissible level) ×: 50 μm < warpage (unacceptable level)

＜Shock resistance of optical filters＞ The optical filter was incorporated into the camera module, the camera module was dropped from a height of 2 m, and the state of the optical filter was visually confirmed according to the following criteria. 〇: No change in optical filter ×: Frequent cracking (unacceptable level for high-definition camera module use)

＜Chip On Board (COB) Manufacturability＞ An optical filter wafer of 6 mm x 8 mm was cut out from a sheet formed by depositing a dielectric multilayer film on both sides of the substrate. Adhesive is applied to the end of the wafer and bonded to a resin board to produce a COB. Such as the state of the COB, and visually confirm it according to the following criteria. 〇: There is no chip bonding failure ×: The chip has poor bonding

＜Evaluation of color shading of camera images＞ Using the same method as in Japanese Patent Laid-Open No. 2016-110067, an optical filter is incorporated into a camera module, and the obtained camera module is used in a D65 light source (a standard light source manufactured by X-Rite Corporation) A white board with a size of 300 mm x 400 mm was photographed with the device "Macbeth Judge II"), and the difference in color tone between the center and edge of the white board in the camera image was evaluated using the following criteria . 〇: No problem at all ×: There is a clear difference in color tone (a level that cannot be tolerated even for normal camera module applications)

[Resin Synthesis Example 1] 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene represented by the following formula (a) (hereinafter Also referred to as "DNM") 100 parts by mass, 18 parts by mass of 1-hexene (molecular weight regulator), and 300 parts by mass of toluene (solvent for ring-opening polymerization reaction) were put into a reaction vessel replaced with nitrogen, and the solution Heat to 80°C. Next, 0.2 parts by mass of a toluene solution of triethylaluminum (0.6 mol/liter) as a polymerization catalyst, and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol/liter) were added to the solution in the reaction vessel 0.9 parts by mass, and the solution was heated and stirred at 80° C. for 3 hours to perform a ring-opening polymerization reaction to obtain a ring-opened polymer solution. The polymerization conversion rate in the polymerization reaction was 97%.

[chemical 1]

1,000 parts by mass of the obtained ring-opened polymer solution was put into an autoclave, and 0.12 parts by mass of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution. Under the conditions of a hydrogen pressure of 100 kg/cm ² and a reaction temperature of 165°C, the hydrogenation reaction was carried out by heating and stirring for 3 hours. After the obtained reaction solution (hydrogenated polymer solution) was cooled, the hydrogen gas was decompressed. The obtained reaction solution was poured into a large amount of methanol, the coagulated matter was separated and recovered, and dried to obtain a hydrogenated polymer (cyclic polyolefin-based resin; hereinafter also referred to as "resin A"). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165°C.

[Resin Synthesis Example 2] Add 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, and 41.46 g of potassium carbonate ( 0.300 mol), N,N-dimethylacetamide 443 g and toluene 111 g. Then, a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube, and a cooling tube were installed in the four-necked flask. Next, after nitrogen substitution was carried out in the flask, the obtained solution was reacted at 140°C for 3 hours, and the produced water was removed from the Dean Stark tube as needed. When generation of water was not confirmed, the temperature was gradually raised to 160° C., and the reaction was carried out at the temperature in the above state for 6 hours. Thereafter, it was cooled to room temperature (25° C.), the generated salt was removed with filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum-dried at 60° C. overnight to obtain a white powdery aromatic polyether-based resin (hereinafter also referred to as “resin B”) (yield: 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285°C.

[Resin Synthesis Example 3] Under nitrogen flow, put 1 ,4-bis(4-amino-α,α-dimethylbenzyl)benzene 27.66 g (0.08 mol) and 4,4'-bis(4-aminophenoxy)biphenyl 7.38 g (0.02 Mole), and dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide. The obtained solution was cooled to 5°C using an ice-water bath, kept isothermal, and 22.62 g (0.1 mole) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added at one time and used as imidization Catalyst triethylamine 0.50 g (0.005 mol). After completion of the addition, the temperature was raised to 180° C., and the distillate was distilled off as needed, and the mixture was refluxed for 6 hours. After the reaction was completed, it was air-cooled until the internal temperature reached 100°C, and then 143.6 g of N,N-dimethylacetamide was added to dilute, stirred and cooled to obtain a solid content concentration of 20% by mass. 264.16 g of polyimide solution. A part of the polyimide solution was poured into 1 L of methanol to precipitate polyimide. The polyimide separated by filtration was washed with methanol, and then dried in a vacuum dryer at 100° C. for 24 hours to obtain a white powder polyimide-based resin (hereinafter also referred to as “resin C”). As a result of measuring the infrared (IR) spectrum of the obtained resin C, absorptions at 1704 cm ^-1 and 1770 cm ^-1 peculiar to imide groups were observed. The glass transition temperature (Tg) of the resin C was 310° C., and the result of measuring the logarithmic viscosity was 0.87.

[Synthesis Example of Hydrophobic CNF] Sulfurous acid bleached pulp (cellulose fiber) obtained from coniferous trees was added to pure water at 0.1% by mass, and a stone mill (Pure Fine Mill) was used to KMG1-10; manufactured by Kurita Machinery Manufacturing Co., Ltd.) was subjected to 70 milling treatments (rotational speed: 1500 rpm) to defibrate the cellulose fibers. The aqueous dispersion was filtered, washed with pure water, and dried at 70° C. to obtain cellulose nanofibers A. Cellulose nanofiber A, 0.0125 g of 2,2,6,6-tetramethylpiperidine-N-oxyl (2,2,6,6-Tetramethylpiperidine- N-oxyl, TEMPO) and 0.125 g of sodium bromide were dispersed in 100 ml of water, and then a 13 mass % sodium hypochlorite aqueous solution was added so that the amount of sodium hypochlorite became 2.5 mmol to start the reaction. During the reaction, a 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10.5. The reaction was regarded as complete when no change in pH was observed. After filtering the reaction product with a glass filter, washing with a sufficient amount of water and filtering were repeated five times, and further, treatment was performed for 1 hour with an ultrasonic disperser. This was dried at 70°C to obtain cellulose nanofibers B. Furthermore, 10 parts by mass of cellulose nanofiber B was added to 500 parts by mass of a propionic anhydride/pyridine (molar ratio 1/1) solution, dispersed, and stirred at room temperature for 4 hours. Next, the dispersed cellulose nanofibers were filtered, washed five times with 500 parts by mass of water, and washed twice with 200 parts by mass of ethanol. Drying was carried out at 70°C to obtain hydrophobic CNF. As for the obtained hydrophobic CNF, the average fiber diameter was 4 nm and the average fiber length was 1 μm, as observed by a scanning electron microscope. In addition, the specific surface area obtained by the Brunauer-Emmett-Teller (BET) method is 270 m ² /g. The degree of crystallinity as obtained by X-ray diffraction method was 79%.

[Example A1] 〔Making of base material〕 90 parts by mass of resin A obtained in Resin Synthesis Example 1, 0.04 parts by mass of the following compound (a1) (absorption maximum wavelength in methylene chloride: 704 nm) as compound (A), and 0.04 parts by mass of the following 0.08 parts by mass of compound (a2) (absorption maximum wavelength in methylene chloride is 738 nm), 10 parts by mass of hydrophobic CNF obtained in Synthesis Example of Hydrophobic CNF as nanofibers, and tetrahydrofuran (THF), to prepare resin A solution with a concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried at 100 degreeC under reduced pressure for 8 hours, and the base material (A1) containing the resin-made board|substrate of thickness 0.1 mm, length 210 mm, and width 210 mm was obtained. The mechanical properties and optical properties of the obtained substrate (A1) were evaluated. The results are shown in Table 3.

[Chem 2]

[Chem 3]

[Production of optical filter] Dielectric multilayer film (I) was formed on one side of the obtained substrate (A1), and further, dielectric multilayer film (II) was formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.110 mm. filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 3. The dielectric multilayer film (I) is a laminate (26 layers in total) in which silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers are alternately laminated at a deposition temperature of 100°C. The dielectric multilayer film (II) is a laminate (a total of 20 layers) in which silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers are alternately laminated at a deposition temperature of 100°C.

In any one of the dielectric multilayer film (I) and the dielectric multilayer film (II), the silicon dioxide layer and the titanium dioxide layer are formed from the base material side into a titanium dioxide layer, a silicon dioxide layer, a titanium dioxide layer, ... silicon dioxide Layers, titanium dioxide layers, and silicon dioxide layers are stacked alternately in this order, and the outermost layer of the optical filter is set as the silicon dioxide layer.

Regarding the thickness and number of layers of each layer, the wavelength dependence of the refractive index of the base material or the absorption characteristics of the compound (A) used is combined so that good transmittance in the visible region and reflective performance in the near-infrared region can be achieved. Optimization was performed using Optical Film Design software (Essential Macleod, manufactured by Thin Film Center, Inc.). When performing optimization, in this embodiment, the input parameters (target (Target) values) for the software are set as shown in Table 1 below.

[Table 1] Table 1 Dielectric Multilayer Film wavelength (nm) Input parameters for software Incident Angle Required Value Target Tolerance type (I) 380～700 0 100 1 Transmittance 705～900 0 0 1 Transmittance 905～950 0 0 0.5 Transmittance (II) 420～700 0 100 0.8 Transmittance 940～1100 0 0 1 Transmittance 1105～1210 0 0 0.5 Transmittance

As a result of optimizing the film structure, the dielectric multilayer film (I) is formed by alternately laminating silicon dioxide layers with a film thickness of approximately 31 nm to 157 nm and titanium dioxide layers with a film thickness of approximately 10 nm to 95 nm. The number of laminated layers is 26 layers, and the dielectric multilayer film (II) is made by alternately laminating silicon dioxide layers with a film thickness of 37 nm to 194 nm and titanium dioxide layers with a film thickness of approximately 12 nm to 114 nm. Multilayer vapor-deposited film with 20 layers. An example of the optimized membrane structure is shown in Table 2 below.

Table 2 Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (I) 1 SiO ₂ 78.0 0.205λ 2 TiO ₂ 87.8 0.386λ 3 SiO ₂ 154.1 0.405λ 4 TiO ₂ 85.6 0.376λ 5 SiO ₂ 149.4 0.393 λ 6 TiO ₂ 83.1 0.365λ 7 SiO ₂ 147.4 0.388 λ 8 TiO ₂ 82.8 0.364λ 9 SiO ₂ 147.1 0.387λ 10 TiO ₂ 82.6 0.363 λ 11 SiO ₂ 147.0 0.387λ 12 TiO ₂ 82.5 0.362 λ 13 SiO ₂ 147.2 0.387λ 14 TiO ₂ 82.8 0.364λ 15 SiO ₂ 146.9 0.386λ 16 TiO ₂ 82.3 0.362 λ 17 SiO ₂ 147.6 0.388 λ 18 TiO ₂ 83.1 0.365λ 19 SiO ₂ 146.9 0.386λ 20 TiO ₂ 83.0 0.364λ twenty one SiO ₂ 150.7 0.396λ twenty two TiO ₂ 87.0 0.382λ twenty three SiO ₂ 156.9 0.413 λ twenty four TiO ₂ 95.0 0.417λ 25 SiO ₂ 31.2 0.082λ 26 TiO ₂ 10.3 0.045λ Substrate (II) 27 TiO ₂ 11.5 0.05λ 28 SiO ₂ 36.9 0.097λ 29 TiO ₂ 113.7 0.499 λ 30 SiO ₂ 187.2 0.492 λ 31 TiO ₂ 110.2 0.484λ 32 SiO ₂ 192.5 0.506 λ 33 TiO ₂ 113.3 0.498 λ 34 SiO ₂ 193.2 0.508 λ 35 TiO ₂ 112.6 0.494λ 36 SiO ₂ 193.5 0.509 λ 37 TiO ₂ 112.8 0.495 λ 38 SiO ₂ 191.6 0.504λ 39 TiO ₂ 110.7 0.486λ 40 SiO ₂ 188.3 0.495 λ 41 TiO ₂ 107.4 0.472 λ 42 SiO ₂ 181.1 0.476λ 43 TiO ₂ 102.9 0.452 λ 44 SiO ₂ 177.9 0.468 λ 45 TiO ₂ 102.2 0.449 λ 46 SiO ₂ 88.7 0.233 λ *λ=550nm

[Example A2] 〔Making of base material〕 Change the amount of resin A to 80 parts by mass, change the amount of compound (a1) to 0.10 parts by mass, change the amount of compound (a2) to 0.20 parts by mass, change the amount of hydrophobic CNF to 20 parts by mass, except Except for this, a solution having a resin concentration of 8% by mass was prepared in the same manner as in Example A1. Using the obtained solution, a substrate (A2) including a resin substrate having a dried thickness of 0.04 mm was obtained in the same manner as in Example A1. The mechanical properties and optical properties of the obtained substrate (A2) were evaluated. The results are shown in Table 3.

〔Production of optical filter〕 Except for using the obtained base material (A2), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (A2), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.050 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 3.

[Example A3] 〔Making of base material〕 Resin B was used instead of resin A in an amount of 90 parts by mass, and 0.075 parts by mass of compound (a2) and 0.075 parts by mass of the following compound (a3) were used as compound (A), and prepared in the same manner as in Example A1 A solution having a resin concentration of 16% by mass. Using the obtained solution, a resin substrate having a dried thickness of 0.08 mm was obtained in the same manner as in Example A1.

[chemical 4]

On one side of the obtained resin substrate, a resin composition (1) having the following composition was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 5 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (1) to form a resin layer on the resin substrate. Similarly, a resin layer containing the resin composition (1) was also formed on the other surface of the resin substrate to obtain a substrate (A3) having resin layers on both surfaces of the resin substrate. The mechanical properties and optical properties of the obtained substrate (A3) were evaluated. The results are shown in Table 3.

Resin composition (1): 60 parts by mass of tricyclodecane dimethanol diacrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, isopropyl alcohol (IPA) (Solvent, solid component concentration (Total Solid Concentration (TSC)): 30%)

〔Production of optical filter〕 Except for using the obtained base material (A3), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (A3), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.100 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 3.

[Example A4] 〔Making of base material〕 Change the amount of resin B to 70 parts by mass, change the amount of compound (a2) to 0.12 parts by mass, change the amount of compound (a3) to 0.12 parts by mass, change the amount of hydrophobic CNF to 30 parts by mass, except Except for this, a solution having a resin concentration of 10% by mass was prepared in the same manner as in Example A3. Using the obtained solution, a resin substrate having a dried thickness of 0.05 mm was obtained in the same manner as in Example A3.

On one side of the obtained resin substrate, a resin composition (2) having the following composition was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 5 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (2) to form a resin layer on the resin substrate. Similarly, a resin layer containing the resin composition (2) was also formed on the other surface of the resin substrate to obtain a substrate (A4) having resin layers on both surfaces of the resin substrate. The mechanical properties and optical properties of the obtained substrate (A4) were evaluated. The results are shown in Table 3.

Resin composition (2): 100 parts by mass of tricyclodecane dimethanol diacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (Methyl Ethyl Ketone, MEK) (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (A4), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (A4), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.070 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 3.

[Example A5] 〔Making of base material〕 Resin C was used in an amount of 90 parts by mass instead of resin A, 0.10 parts by mass of the following compound (a4) and 0.10 parts by mass of the following compound (a5) were used as compound (A), and methyl ethyl ketone was used instead of tetrahydrofuran as A solution having a resin concentration of 8% by mass was prepared in the same manner as in Example A1 except that the resin was dissolved in a solvent. Using the obtained solution, a resin substrate having a dried thickness of 0.04 mm was obtained in the same manner as in Example A1.

[chemical 5]

[chemical 6]

On one side of the obtained resin substrate, the resin composition (1) was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 5 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (1) to form a resin layer on the resin substrate. Similarly, a resin layer containing the resin composition (1) was also formed on the other surface of the resin substrate to obtain a substrate (A5) having resin layers on both surfaces of the resin substrate. The mechanical properties and optical properties of the obtained substrate (A5) were evaluated. The results are shown in Table 3.

〔Production of optical filter〕 Except for using the obtained base material (A5), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (A5), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.060 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 3.

[Comparative Example A1] 〔Making of base material〕 The amount of resin A was changed to 100 parts by mass, and instead of using hydrophobic CNF, dichloromethane was used instead of tetrahydrofuran as a solvent for dissolving the resin, and the base material (A6) was produced in the same manner as in Example A1. and optical properties were evaluated. The results are shown in Table 3.

〔Production of optical filter〕 Except for using the obtained substrate (A6), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the substrate (A6), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.110 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 3.

[Comparative Example A2] [Preparation of Substrate] A resin substrate was produced in the same manner as in Example A5 except that the compound (A) was not used. On one side of the obtained resin substrate, the resin composition (2) was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 5 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (2) to form a resin layer on the resin substrate. Similarly, a resin layer containing the resin composition (2) was also formed on the other surface of the resin substrate to obtain a substrate (A7) having resin layers on both surfaces of the resin substrate. The mechanical properties of the obtained base material (A7) were evaluated. The results are shown in Table 3.

〔Production of optical filter〕 Except for using the obtained base material (A7), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (A7), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.110 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 3.

[Table 3] Table 3 Comparative Example A1 Example A1 Example A2 Example A3 Example A4 Comparative example A2 Example A5 Substrate structure Compound (A) (parts by mass) Compound (a1) 0.04 0.04 0.10 - - - - Compound (a2) 0.08 0.08 0.20 0.075 0.12 - - Compound (a3) - - - 0.075 0.12 - - Compound (a4) - - - - - - 0.10 Compound (a5) - - - - - - 0.10 Resin (parts by mass) Resin A 100 90 80 - - - - Resin B - - - 90 70 - - Resin C - - - - - 90 90 Hydrophobic CNF (parts by mass) - 10 20 10 30 10 10 Solvent for Substrate Resin Dichloromethane THF THF THF THF MEK MEK Weight reduction of substrate after film formation (%) 0.4 0.4 0.1 0.3 0.2 0.6 0.3 coating layer resin - - - Composition (1) Composition (2) Composition (2) Composition (1) Solvent for Coating Layer Resin - - - IPA MEK MEK IPA Substrate film thickness (μm) 100 100 40 80 50 90 40 Coating layer film thickness (μm) - - - 5 5 5 5 Substrate film thickness (μm) 100 100 40 90 60 100 50 mechanical properties CTE (ppm/°C) 71 48 35 45 25 33 33 Tensile modulus of elasticity (GPa) 2.1 3.8 4.8 4.0 5.5 5.2 5.3 optical properties T ₁ (%) 0.7 0.7 0.5 0.6 0.5 - 0.5 Xc (nm) 637 637 635 640 639 - 633 optical filter Dielectric Multilayer Film structure total number of sides 26 26 26 26 26 26 26 Number of layers on one side 20 20 20 20 20 20 20 Warpage after evaporation on one side; radius of curvature (mm) 10 19 14 17 14 15 15 optical properties The average value of the transmittance at a wavelength of 430 nm to 580 nm (%) 87 88 86 86 85 92 86 The average value of the transmittance at a wavelength of 900 nm to 1050 nm (%) Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% ｜Xa-Xb｜（nm） 2 2 3 3 2 28 3 mechanical properties Shock Resistance of Optical Filters 〇 〇 〇 〇 〇 〇 〇 warping x ◎ 〇 ◎ 〇 ◎ 〇 Heat deformability x 〇 〇 〇 〇 〇 〇 Mod Evaluation COB production x 〇 〇 〇 〇 〇 〇 Image Evaluation Color Shading 〇 〇 〇 〇 〇 x 〇

[Example B1] 〔Making of base material〕 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.08 parts by mass of the compound (a1) (absorption maximum wavelength in dichloromethane is 704 nm) as the compound (A), 0.08 parts by mass of the Compound (a2) (absorption maximum wavelength in dichloromethane is 738 nm) 0.16 parts by mass and dichloromethane, and a solution having a resin concentration of 10 mass % was prepared. The obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried at 100 degreeC under reduced pressure for 8 hours, and the resin board|substrate of thickness 0.05 mm, length 210 mm, and width 210 mm was obtained.

On one side of the obtained resin substrate, a resin composition (3) having the following composition was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (3) to form a resin layer on the resin substrate. Similarly, a resin layer containing the resin composition (3) was also formed on the other surface of the resin substrate to obtain a substrate (B1) having resin layers containing hydrophobic CNF on both surfaces of the resin substrate. The mechanical properties and optical properties of the obtained substrate (B1) were evaluated. The results are shown in Table 4.

Resin composition (3): 20 parts by mass of the hydrophobic CNF, 48 parts by mass of tricyclodecane dimethanol diacrylate, 32 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, Isopropanol (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (B1), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (B1), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Example B2] 〔Making of base material〕 A substrate (B2) was obtained in the same manner as in Example B1 except that the resin composition (3) was changed to the following resin composition (4).

Resin composition (4): 40 parts by mass of the hydrophobic CNF, 36 parts by mass of tricyclodecane dimethanol diacrylate, 24 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, Isopropanol (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (B2), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (B2), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Example B3] 〔Making of base material〕 A substrate (B3) was obtained in the same manner as in Example B1 except that the resin composition (3) was changed to the following resin composition (5).

Resin composition (5): 60 parts by mass of the hydrophobic CNF, 24 parts by mass of tricyclodecane dimethanol diacrylate, 16 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, Isopropanol (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained substrate (B3), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the substrate (B3), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Example B4] 〔Making of base material〕 Resin B was used in an amount of 100 parts by mass instead of resin A, and 0.12 parts by mass of the compound (a2) and 0.12 parts by mass of the compound (a3) were used as the compound (A), in the same manner as in Example B1 A solution having a resin concentration of 10% by mass was prepared. Using the obtained solution, a resin substrate having a dried thickness of 0.05 mm was obtained in the same manner as in Example B1.

On one side of the obtained resin substrate, a resin composition (6) having the following composition was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (6) to form a resin layer on the resin substrate. Similarly, a resin layer containing the resin composition (6) was also formed on the other surface of the resin substrate to obtain a substrate (B4) having resin layers containing hydrophobic CNF on both surfaces of the resin substrate. The mechanical properties and optical properties of the obtained substrate (B4) were evaluated. The results are shown in Table 4.

Resin composition (6): 45 parts by mass of the hydrophobic CNF, 55 parts by mass of tricyclodecane dimethanol diacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, isopropanol (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (B4), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (B4), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Example B5] [Preparation of Substrate] A near-infrared-absorbing glass substrate ("BS-11" manufactured by Matsunami Glass Industry Co., Ltd., thickness 210 μm) was ground to a thickness of 150 μm, and coated with the following composition on both sides by a bar coater. The resin composition (14) was heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition ( 14 ) to form a resin layer on the glass support. Similarly, a resin layer containing the resin composition (14) was also formed on the other surface of the glass support to obtain a substrate (B5) having resin layers containing hydrophobic CNF on both surfaces of the glass support. The mechanical properties and optical properties of the obtained substrate (B5) were evaluated. The results are shown in Table 4.

Resin composition (14): 20 parts by mass of hydrophobic CNF, 48 parts by mass of tricyclodecane dimethanol diacrylate, 32 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl Ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (B5), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (B5), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.180 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Comparative Example B1] 〔Making of base material〕 A substrate (B6) having resin layers on both surfaces of a resin substrate was obtained in the same manner as in Example B1 except that the resin composition (3) was changed to the resin composition (2).

〔Production of optical filter〕 Except for using the obtained base material (B6), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (B6), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Comparative Example B2] 〔Making of base material〕 100 parts by mass of the resin A obtained in Resin Synthesis Example 1 and methylene chloride were put into the container to prepare a solution having a resin concentration of 10% by mass. The obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried at 100 degreeC under reduced pressure for 8 hours, and the resin-made support body of thickness 0.05 mm, length 210 mm, and width 210 mm was obtained.

On one side of the obtained resin support, the resin composition (1) having the above composition was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (1) to form a resin layer on the resin support. Similarly, a resin layer containing the resin composition (1) was also formed on the other surface of the resin support to obtain a substrate (B7) having resin layers on both surfaces of the resin support. The mechanical properties and optical properties of the obtained substrate (B7) were evaluated. The results are shown in Table 4.

〔Production of optical filter〕 Except for using the obtained base material (B7), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (B7), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Comparative Example B3] 〔Making of base material〕 100 parts by mass of the resin A obtained in Resin Synthesis Example 1 and methylene chloride were put into the container to prepare a solution having a resin concentration of 14% by mass. The obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried at 100 degreeC under reduced pressure for 8 hours, and the base material (B8) containing only the resin-made support body of 0.07 mm in thickness, 210 mm in length, and 210 mm in width was obtained.

〔Production of optical filter〕 Except for using the obtained base material (B8), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (B8), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Comparative Example B4] [Preparation of Substrate] A near-infrared-absorbing glass substrate ("BS-11" manufactured by Matsunami Glass Industry Co., Ltd., thickness 210 μm) was ground to a thickness of 120 μm, and coated with the following composition on both sides by a bar coater The resin composition (15) was heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition ( 15 ) to form a resin layer on the glass support. Similarly, a resin layer containing the resin composition (15) was also formed on the other surface of the glass support to obtain a substrate (B9) having resin layers containing the compound (A) on both surfaces of the glass support. The mechanical properties and optical properties of the obtained substrate (B9) were evaluated. The results are shown in Table 4.

Resin composition (15): 0.30 parts by mass of compound (a1), 0.30 parts by mass of compound (a2), 48 parts by mass of tricyclodecane dimethanol diacrylate, 32 parts by mass of dipentaerythritol hexaacrylate, 1-hydroxycyclohexyl 5 parts by mass of phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (B9), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (B9), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.150 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 4.

[Table 4] Table 4 Comparative Example B1 Example B1 Example B2 Example B3 Example B4 Example B5 Comparative Example B2 Comparative Example B3 Comparative Example B4 Substrate structure Support body Material Resin A Resin A Resin A Resin A Resin B Near Infrared Absorbing Glass Resin A Resin A Near Infrared Absorbing Glass Solvent for base resin Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane - Dichloromethane Dichloromethane - Compound (A) (parts by mass) Compound (a1) 0.08 0.08 0.08 0.08 - - - - - Compound (a2) 0.16 0.16 0.16 0.16 0.12 - - - - Compound (a3) - - - - 0.12 - - - - Compound (a4) - - - - - - - - - Compound (a5) - - - - - - - - - coating layer Coating layer resin Composition (2) Composition (3) Composition (4) Composition (5) Composition (6) Composition (14) Composition (1) - Composition (15) Hydrophobic CNF (parts by mass) - 20 40 60 45 20 - - - Solvent for Coating Layer Resin IPA IPA IPA IPA IPA MEK IPA - MEK Coated surface two sides two sides two sides two sides two sides two sides two sides - two sides Substrate or (or) support film thickness (μm) 50 50 50 50 50 150 50 70 120 Coating layer film thickness (μm) 10 10 10 10 10 10 10 - 10 Substrate film thickness (μm) 70 70 70 70 70 170 70 70 140 Properties when the resin layer is formed on one side The number of sunken defects on the coated surface 16 5 4 2 4 6 14 - 5 mechanical properties Martens Hardness (N/mm ² ) 190 213 221 232 220 200 230 165 225 Scratch resistance x 〇 〇 〇 〇 〇 〇 x x CTE (ppm/°C) 75 52 43 37 40 7 72 72 6 Tensile modulus of elasticity (GPa) 2 3.3 4.0 4.6 4.2 80 2 2 83 optical properties T ₁ (%) 0.6 0.4 0.5 0.6 0.6 15.0 - - 0.6 Xc (nm) 637 636 637 636 640 659 - - 637 optical filter Dielectric Multilayer Film structure total number of sides 26 26 26 26 26 26 26 26 26 Number of layers on one side 20 20 20 20 20 20 20 20 20 optical properties The average value of the transmittance at a wavelength of 430 nm to 580 nm (%) 87 86 86 86 87 89 91 91 88 The average value of the transmittance at a wavelength of 900 nm to 1050 nm (%) Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% ｜Xa-Xb｜（nm） 2 2 2 3 3 3 29 28 3 mechanical properties Shock Resistance of Optical Filters 〇 〇 〇 〇 〇 〇 〇 〇 x Warping of Optical Filters x 〇 〇 ◎ ◎ ◎ x x x Heat deformability x 〇 〇 〇 〇 〇 x x x Mod Evaluation COB production x 〇 〇 〇 〇 〇 x x x Image Evaluation Color Shading 〇 〇 〇 〇 〇 〇 x x 〇

[Example C1] 〔Making of base material〕 100 parts by mass of the resin A obtained in Resin Synthesis Example 1 and methylene chloride were put into the container to prepare a solution having a resin concentration of 10% by mass. The obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried at 100 degreeC under reduced pressure for 8 hours, and the resin-made support body of thickness 0.05 mm, length 210 mm, and width 210 mm was obtained.

On one side of the obtained resin support, a resin composition (7) having the following composition was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition ( 7 ) to form a resin layer on the resin support. Similarly, a resin layer containing the resin composition (7) was also formed on the other side of the resin support to obtain a substrate having resin layers containing the compound (A) and hydrophobic CNF on both sides of the resin support (C1 ). The mechanical properties and optical properties of the obtained substrate (C1) were evaluated. The results are shown in Table 5.

Resin composition (7): 0.20 parts by mass of compound (a1), 0.40 parts by mass of compound (a2), 20 parts by mass of hydrophobic CNF, pigment (1) ("CIR-FS265" manufactured by Nippon Carlit Co., Ltd. ) 0.65 parts by mass, 48 parts by mass of tricyclodecane dimethanol diacrylate, 32 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (C1), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (C1), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 5.

[Example C2] 〔Making of base material〕 A substrate having a resin layer containing compound (A) and hydrophobic CNF on both sides of a resin support was produced in the same manner as in Example C1, except that the following resin composition (8) was used instead of resin composition (7). (C2). The mechanical properties and optical properties of the obtained substrate (C2) were evaluated. The results are shown in Table 5.

Resin composition (8): 0.20 parts by mass of compound (a1), 0.40 parts by mass of compound (a2), 60 parts by mass of hydrophobic CNF, pigment (2) ("CIR-FS165" manufactured by Nippon Carlit Co., Ltd. ) 0.65 parts by mass, 24 parts by mass of tricyclodecane dimethanol diacrylate, 16 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (C2), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (C2), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 5.

[Example C3] 〔Making of base material〕 100 parts by mass of the resin B obtained in Resin Synthesis Example 2 and methylene chloride were put into the container to prepare a solution having a resin concentration of 10% by mass. The obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried at 100 degreeC under reduced pressure for 8 hours, and the resin-made support body of thickness 0.05 mm, length 210 mm, and width 210 mm was obtained.

On one side of the obtained resin support, a resin composition (9) having the following composition was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (9) to form a resin layer on the resin support. Similarly, a resin layer comprising the resin composition (9) was also formed on the other side of the resin support to obtain a substrate (C3) having a resin layer comprising the compound (A) and hydrophobic CNF on both sides of the resin support. ). The mechanical properties and optical properties of the obtained substrate (C3) were evaluated. The results are shown in Table 5.

Resin composition (9): 0.30 parts by mass of compound (a2), 0.30 parts by mass of compound (a3), 40 parts by mass of hydrophobic CNF, 0.65 parts by mass of pigment (1), 36 parts by mass of tricyclodecane dimethanol diacrylate , 24 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained substrate (C3), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the substrate (C3), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 5.

[Example C4] 〔Making of base material〕 100 parts by mass of the resin C obtained in Resin Synthesis Example 3 and methylene chloride were put into the container to prepare a solution having a resin concentration of 10% by mass. The obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried at 100 degreeC under reduced pressure for 8 hours, and the resin-made support body of thickness 0.05 mm, length 210 mm, and width 210 mm was obtained.

On one side of the obtained resin support, a resin composition (10) having the following composition was coated with a bar coater, and heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (10) to form a resin layer on the resin support. Similarly, a resin layer comprising the resin composition (10) was also formed on the other side of the resin support to obtain a substrate having resin layers comprising the compound (A) and hydrophobic CNF on both sides of the resin support (C4 ). The mechanical properties and optical properties of the obtained substrate (C4) were evaluated. The results are shown in Table 5.

Resin composition (10): 0.30 parts by mass of compound (a2), 0.30 parts by mass of compound (a3), 30 parts by mass of hydrophobic CNF, 0.65 parts by mass of pigment (2), 42 parts by mass of tricyclodecane dimethanol diacrylate , 28 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained substrate (C4), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the substrate (C4), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 5.

[Example C5] [Preparation of Substrate] On both sides of a glass support ("OA-10G" manufactured by NEC Glass, thickness 150 μm), a resin composition (11) having the following composition was coated with a bar coater , heated in an oven at 70° C. for 2 minutes to evaporate and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition (11) to form a resin layer on the glass support. Similarly, a resin layer containing the resin composition (11) is also formed on the other surface of the glass support, and a substrate having resin layers containing the compound (A) and hydrophobic CNF on both surfaces of the glass support is obtained (C5). The mechanical properties and optical properties of the obtained substrate (C5) were evaluated. The results are shown in Table 5.

Resin composition (11): 0.30 parts by mass of compound (a2), 0.30 parts by mass of compound (a3), 10 parts by mass of hydrophobic CNF, 0.65 parts by mass of pigment (2), 54 parts by mass of tricyclodecane dimethanol diacrylate , 36 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (C5), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (C5), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.180 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 5.

[Example C6] [Preparation of Substrate] On both sides of a near-infrared-absorbing glass substrate ("BS-11" manufactured by Matsunami Glass Industry Co., Ltd., thickness 120 μm), a resin composition having the following composition was coated with a bar coater ( 12) Heat in an oven at 70°C for 2 minutes to remove the solvent by volatilization. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 10 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition ( 12 ) to form a resin layer on the glass support. Similarly, a resin layer containing the resin composition (12) is also formed on the other surface of the glass support to obtain a substrate having a resin layer containing the compound (A) and hydrophobic CNF on both surfaces of the glass support (C6). The mechanical properties and optical properties of the obtained substrate (C6) were evaluated. The results are shown in Table 5.

Resin composition (12): 0.30 parts by mass of compound (a1), 0.30 parts by mass of compound (a2), 20 parts by mass of hydrophobic CNF, 48 parts by mass of tricyclodecane dimethanol diacrylate, 32 parts by mass of dipentaerythritol hexaacrylate parts, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained base material (C6), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (C6), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.150 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 5.

[Comparative Example C1] 〔Making of base material〕 Except that the resin composition (7) was changed to the following resin composition (13), a substrate (C7) having a resin layer containing the compound (A) on both sides of the resin support was obtained in the same manner as in Example C1. ). The mechanical properties and optical properties of the obtained substrate (C7) were evaluated. The results are shown in Table 5.

Resin composition (13): 0.20 parts by mass of compound (a1), 0.40 parts by mass of compound (a2), 0.65 parts by mass of pigment (1), 60 parts by mass of tricyclodecane dimethanol diacrylate, 40 parts by mass of dipentaerythritol hexaacrylate Parts by mass, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)

〔Production of optical filter〕 Except for using the obtained substrate (C7), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the substrate (C7), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 5.

[Comparative Example C2] 〔Making of base material〕 A substrate (C8) having resin layers containing hydrophobic CNFs on both surfaces of a resin support was obtained in the same manner as in Example C1 except that the resin composition (3) was used instead of the resin composition (7). The mechanical properties and optical properties of the obtained substrate (C8) were evaluated. The results are shown in Table 5.

〔Production of optical filter〕 Except for using the obtained base material (C8), in the same manner as in Example A1, a dielectric multilayer film (I) was formed on one side of the base material (C8), and a dielectric multilayer film (II) was formed on the other side to obtain a thickness of about 0.080 mm optical filter. The optical characteristics and properties of the obtained optical filter were evaluated. The results are shown in Table 5.

[Table 5] Table 5 Comparative example C1 Example C1 Example C2 Example C3 Example C4 Example C5 Example C6 Comparative example C2 Substrate structure Support body Material Resin A Resin A Resin A Resin B Resin C Glass Near Infrared Absorbing Glass Resin A Solvent for base resin Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane - - Dichloromethane coating layer Coating layer resin Composition (13) Composition (7) Composition (8) Composition (9) Composition (10) Composition (11) Composition (12) Composition (3) Hydrophobic CNF (parts by mass) - 20 60 40 30 10 20 20 Compound (a1) (parts by mass) 0.20 0.20 0.20 - - 0.20 - Compound (a2) (parts by mass) 0.40 0.40 0.40 0.30 0.30 0.30 0.40 - Compound (a3) (parts by mass) - - - 0.30 0.30 0.30 - - Pigment (1) (parts by mass) 0.65 0.65 - 0.65 - - - - Pigment (2) (parts by mass) - - 0.65 - 0.65 0.65 - - Pigment particle size (μm) 105 105 94 105 94 94 - - Solvent for Coating Layer Resin MEK MEK MEK MEK MEK MEK MEK MEK Coated surface two sides two sides two sides two sides two sides two sides two sides two sides Support film thickness (μm) 50 50 50 50 50 150 120 50 Coating layer film thickness (μm) 10 10 10 10 10 10 10 10 Substrate film thickness (μm) 70 70 70 70 70 170 140 70 mechanical properties Martens Hardness (N/mm ² ) 175 213 229 220 215 200 210 190 Scratch resistance x 〇 〇 〇 〇 △ 〇 〇 CTE (ppm/°C) 75 51 38 43 40 7 5 53 Tensile modulus of elasticity (GPa) 2 3.2 4.7 4 4.3 83 79 3.1 optical properties Haze (Haze) (%) 0.65 0.33 0.15 0.20 0.22 0.35 0.20 0.11 T ₁ (%) 0.7 0.6 0.7 0.5 0.5 0.7 0.6 - Xc (nm) 636 638 639 636 640 639 637 - optical filter Dielectric Multilayer Film structure total number of sides 26 26 26 26 26 26 26 26 Number of layers on one side 20 20 20 20 20 20 20 20 optical properties The average value of the transmittance at a wavelength of 430 nm to 580 nm (%) 81 81 80 80 80 81 88 90 The average value of the transmittance at a wavelength of 900 nm to 1050 nm (%) Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% Below 1% ｜Xa-Xb｜（nm） 3 2 2 3 3 3 3 28 mechanical properties Shock Resistance of Optical Filters 〇 〇 〇 〇 〇 〇 x 〇 Warping of Optical Filters x 〇 〇 〇 〇 ◎ ◎ 〇 Heat deformability x 〇 〇 〇 〇 〇 〇 〇 Mod Evaluation COB production x 〇 〇 〇 〇 〇 〇 〇 Image Evaluation Color Shading 〇 〇 〇 〇 〇 〇 〇 x

1a: Resin substrate 1b: Substrate 1c: Support body 2a: resin layer 2b: resin layer 2c: resin layer

FIG. 1( a ), FIG. 1( b ), and FIG. 1( c ) are schematic diagrams showing form examples of the base material of the present invention.

Claims (16)

A base material has a layer containing nanofibers, and the absorption maximum wavelength is in the wavelength range of 600 nm to 1200 nm. The substrate according to claim 1, wherein the nanofibers have an average fiber diameter of 3 nm to 200 nm, and an average fiber length of 0.2 μm to 10 μm. The substrate according to claim 1 or claim 2, wherein the nanofibers have a specific surface area of 70 m ² /g to 300 m ² /g. The substrate according to claim 1 or claim 2, wherein the crystallinity of the nanofibers is above 43%. The substrate according to claim 1 or claim 2, wherein the nanofibers are hydrophobic cellulose nanofibers that can be dispersed in an organic solvent. The base material according to claim 1 or claim 2, comprising a resin substrate containing the nanofibers and a compound (A) having a maximum absorption wavelength in a wavelength range of 600 nm to 1200 nm. The substrate according to claim 6, wherein the content of the nanofibers is 5 parts by mass when the total of the contents of the resin constituting the resin substrate and the nanofibers is 100 parts by mass ~50 parts by mass. The substrate according to claim 1 or claim 2, comprising: a substrate selected from resin substrates and near-infrared-absorbing glass substrates containing a compound (A) whose maximum absorption wavelength is in the range of 600 nm to 1200 nm; and a resin layer formed on both surfaces of the substrate and containing the nanofibers. The substrate according to claim 1 or claim 2, comprising: a support made of resin or glass; and a resin layer formed on both sides of the support and containing the nanofibers and absorbing a maximum wavelength at a wavelength Compound (A) in the range of 600 nm to 1200 nm. The base material according to claim 8, wherein when the total content of the resin constituting the resin layer and the content of the nanofibers is 100 parts by mass, the content of the nanofibers is 5 parts by mass to 5 parts by mass. 70 parts by mass. The substrate according to claim 6, wherein the resin constituting the resin substrate is selected from cyclic polyolefin resins, aromatic polyether resins, polyimide resins, and fluorene polycarbonate resins. , fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polyamide resin, polyether resin, polyparaphenylene resin, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane UV-curable resins, maleimide Amine resins, alicyclic epoxy thermosetting resins, polyether ether ketone resins, polyarylate resins, allyl ester curable resins, acrylic UV curable resins, vinyl UV curable resins and their applications At least one resin in the group consisting of resins formed by a sol-gel method and containing silica as a main component. The substrate as described in Claim 9, wherein the resin constituting the resin layer is selected from cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, Fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polyamide resins, polyether resins, polyparaphenylene resins, polyamide imides Resins, polyethylene naphthalate-based resins, fluorinated aromatic polymer-based resins, (modified) acrylic resins, epoxy-based resins, silsesquioxane-based UV-curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyether ether ketone resins, polyarylate resins, allyl ester curable resins, acrylic UV curable resins, vinyl UV curable resins and sols At least one resin in the group consisting of resins formed by a gel method and containing silica as a main component. An optical filter, comprising the substrate according to any one of claim 1 to claim 12, and a dielectric multilayer film. The optical filter according to claim 13, which has a thickness of 150 μm or less. An imaging device, characterized by comprising the optical filter described in Claim 13 or Claim 14. A camera module, characterized by comprising the optical filter as described in Claim 13 or Claim 14.

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