resin composition

Abstract

The present invention provides a resin composition which contains an alicyclic epoxy resin, a basic catalyst, a phenolic hydroxyl group-containing compound and a dye.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a cured resin product obtained by curing the resin composition, an optical filter formed from the cured resin product, and a sensor equipped with the optical filter. [Background technology]

[0002] Imaging devices such as mobile phone cameras, digital cameras, car cameras, video cameras, and display elements (LEDs, etc.) typically use imaging elements that convert light from a subject into electrical signals and output them. These imaging elements include a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor), a lens, and may also include an optical filter that selectively transmits only a portion of the incident light to improve performance.

[0003] When forming an optical filter from a resin composition, a dye is blended with a base resin to prepare a resin composition, which is then cured to form a cured resin, thereby producing an optical filter. By appropriately selecting a dye having an absorption range corresponding to the wavelength of incident light that is to be cut and blending it into the resin composition, light in the desired wavelength range can be transmitted or cut. Among such resin compositions, those using epoxy resins as the base resin are known (e.g., Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-040955 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-137401 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-214262 Summary of the Invention [Problem to be solved by the invention]

[0005] Cured resins formed from epoxy resins have high heat resistance and excellent shape stability at high temperatures. Among them, alicyclic epoxy resins are particularly suitable for optical filters because they have little coloring and excellent transparency. Epoxy resins can be cured, for example, by a thermosetting reaction. In this case, it is desirable that the pigment contained in the resin composition is not decomposed as much as possible, and that the resin composition has sufficient curability.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition containing an alicyclic epoxy resin and a dye, which resin composition suppresses decomposition of the dye during a thermal curing reaction and has excellent curability. The present invention also provides a cured resin obtained by curing the resin composition of the present invention, an optical filter including the cured resin, and a sensor equipped with the optical filter. [Means for solving the problem]

[0007] The present invention includes the following resin composition, cured resin, optical filter, and sensor. [1] A resin composition comprising an alicyclic epoxy resin, a basic catalyst, a phenolic hydroxyl group-containing compound, and a dye. [2] The resin composition according to [1], wherein the dye has an absorption maximum in the wavelength range of 200 nm to 1100 nm. [3] The resin composition according to [1] or [2], wherein the dye is an oxocarbon compound. [4] The resin composition according to [3], wherein the oxocarbon compound is a squarylium compound represented by the following formula (1) and / or a croconium compound represented by the following formula (2): [ka] [In formula (1) and formula (2), R 1 ~R 4each independently represents a group represented by the following formula (3) or (4): [ka] [In formula (3), Ring P represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing any of these ring structures, each of which may have a substituent; R 11 ~R 13 each independently represents a hydrogen atom, an organic group, or a polar functional group; R 12 and R 13 may be linked to each other to form a ring, * represents the bonding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2). [ka] [In formula (4), R 14 ~R 18 each independently represents a hydrogen atom, an organic group, or a polar functional group; R 14 and R 15 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 may be linked to each other to form a ring, * represents the bonding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2). [5] The resin composition according to any one of [1] to [4], wherein the dye is a compound having a styrene structure. [6] The resin composition according to [5], wherein the compound having a styrene structure is a compound represented by the following formula (6): [ka] [In formula (6), R 21 represents a cyano group, an acyl group, a carboxylic acid ester group, or an amide group, R22 represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group, or a heteroaryl group; R 21 and R 22 When both are acyl groups, carboxylic acid ester groups, or amide groups, R 21 and R 22 may be linked to each other to form a ring, R 23 represents a hydrogen atom or an alkyl group, R 24 represents a hydrogen atom, an organic group, or a polar functional group, and multiple R 24 may be the same or different from each other, X represents a sulfur atom or an oxygen atom; a represents an integer of 2 or more, L represents a divalent or higher valent linking group, The multiple groups bonded to L may be the same or different.] [7] The resin composition according to any one of [1] to [6], wherein the alicyclic epoxy resin has an epoxy equivalent of 200 g / eq or less. [8] A cured resin product obtained by curing the resin composition according to any one of [1] to [7]. [9] An optical filter comprising the cured resin according to [8].

[10] A sensor equipped with an optical filter as described in [9]. [Effects of the Invention]

[0008] The resin composition of the present invention is capable of suppressing decomposition of the dye during a heat curing reaction and also has excellent curability. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows the transmission spectrum of the optical filter produced in Example 2. [Figure 2] 1 shows the transmission spectrum of the optical filter produced in Example 3. [Figure 3] 1 shows the transmission spectrum of the optical filter produced in Example 5. [Figure 4] 1 shows the transmission spectrum of the optical filter produced in Comparative Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0010] The resin composition of the present invention contains (A) an alicyclic epoxy resin, (B) a basic catalyst, (C) a phenolic hydroxyl group-containing compound, and (D) a dye. The resin composition of the present invention contains the alicyclic epoxy resin (A) as the base resin and the dye (D). The cured resin obtained by curing the composition can be used as an optical filter that transmits or blocks light in a desired wavelength range due to the dye (D). The resin composition of the present invention contains the basic catalyst (B) and the phenolic hydroxyl group-containing compound (C) as a curing aid to cure the alicyclic epoxy resin (A). This prevents decomposition of the dye (D) even when the resin composition is thermally cured at high temperatures. Therefore, combined with the use of a highly transparent alicyclic epoxy resin as the base resin, the resulting cured resin can selectively transmit light in a desired wavelength range due to the dye (D). In addition, the resin composition of the present invention has excellent curability, and when thermally cured, the curing reaction proceeds sufficiently, so that the obtained cured resin product has excellent stability and solvent resistance. The resin composition of the present invention will be described in detail below.

[0011] The resin composition of the present invention uses an alicyclic epoxy resin as a base resin. By using an epoxy resin as a base resin, the resulting cured resin has high heat resistance and excellent shape stability at high temperatures. Furthermore, by using an alicyclic epoxy resin among epoxy resins, the heat resistance of the cured resin can be easily improved and it can be made less discolored.

[0012] Examples of alicyclic epoxy resins include oxirane compounds having an aliphatic hydrocarbon ring such as a cyclohexane ring. The alicyclic epoxy resin may be one in which the oxirane ring and the aliphatic hydrocarbon ring exist in a form sharing carbon atoms, such as in cycloalkene oxide, or one in which the oxirane ring and the aliphatic hydrocarbon ring exist independently without sharing carbon atoms.

[0013] Examples of alicyclic epoxy resins in which an oxirane ring and an aliphatic hydrocarbon ring share a carbon atom include 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, bis-(3,4-epoxycyclohexyl)adipate, and butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone.

[0014] In alicyclic epoxy resins in which the oxirane ring and the aliphatic hydrocarbon ring do not share carbon atoms, the aliphatic hydrocarbon ring is preferably contained in the main chain of the epoxy resin. That is, the alicyclic epoxy resin preferably has an alicyclic structure in the main chain. In alicyclic epoxy resins in which the oxirane ring and the aliphatic hydrocarbon ring share carbon atoms, the oxirane ring (epoxy group) may be directly bonded to the aliphatic hydrocarbon ring, as in cycloalkyloxirane, or the oxirane ring may be bonded to the aliphatic hydrocarbon ring via a linking group. In the latter case, examples of the linking group include alkylene groups, ether groups, thioether groups, carbonyl groups, amino groups, and combinations thereof. The number of atoms connecting the oxirane ring and the aliphatic hydrocarbon ring is preferably 5 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1 or less. It is particularly preferred that the oxirane ring is directly bonded to the aliphatic hydrocarbon ring.

[0015] Examples of alicyclic epoxy resins in which the oxirane ring and the aliphatic hydrocarbon ring do not share a carbon atom include aromatic epoxy resins in which the aromatic ring of an aromatic epoxy resin having an aromatic ring structure in the main chain has been hydrogenated (hydrogenated epoxy resins), and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol. Examples of aromatic epoxy resins before hydrogenation include bisphenol A type epoxy resins (bisphenol A diglycidyl ether); bisphenol F type epoxy resins (bisphenol F diglycidyl ether); biphenyl type epoxy resins; polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenylglycidyl etherethane; phenol novolac type epoxy resins; cresol novolac type epoxy resins; reaction products of epichlorohydrin with polyphenol compounds obtained by a condensation reaction of a phenolic compound such as phenol, o-cresol, m-cresol, or naphthol with an aromatic aldehyde having a phenolic hydroxyl group; and reaction products of epichlorohydrin with polyphenol compounds obtained by an addition reaction of a phenolic compound with a diolefin compound such as divinylbenzene or dicyclopentadiene.

[0016] The number of ring members in the aliphatic hydrocarbon ring contained in the alicyclic epoxy resin is preferably 5 or more, more preferably 6 or more, and is preferably 10 or less, more preferably 8 or less. The aliphatic hydrocarbon ring is preferably an aliphatic saturated hydrocarbon ring, i.e., a cycloalkane.

[0017] The epoxy equivalent of the alicyclic epoxy resin is preferably 200 g / eq or less, more preferably 180 g / eq or less, and even more preferably 150 g / eq or less. The epoxy equivalent refers to the mass of the epoxy resin containing 1 gram equivalent of epoxy groups; the smaller the epoxy equivalent value, the greater the number of epoxy groups contained per unit mass of the epoxy resin. Using an alicyclic epoxy resin with an epoxy equivalent of 200 g / eq or less facilitates enhancing the curability of the resin composition. The lower limit of the epoxy equivalent of the alicyclic epoxy resin is not particularly limited, and may be, for example, 80 g / eq or more, or 100 g / eq or more.

[0018] Alicyclic epoxy resins usually contain two or more oxirane rings in one molecule, but preferably contain three or more oxirane rings in one molecule (multifunctional type).

[0019] The alicyclic epoxy resin is preferably one in which the oxirane ring and the aliphatic hydrocarbon ring do not share a carbon atom. Epoxy resins are usually handled as resin compositions containing a curing agent and a curing catalyst, but the use of an alicyclic epoxy resin in which the oxirane ring and the aliphatic hydrocarbon ring do not share a carbon atom makes it easier to use various types of curing agents and curing catalysts during curing.

[0020] The molecular weight of the alicyclic epoxy resin is not particularly limited, and may be a low molecular weight compound of about 120 to 500, or a high molecular weight compound exceeding 500. Use of a high molecular weight alicyclic epoxy resin facilitates improving the film-forming properties of the resin composition. When the alicyclic epoxy resin is a high molecular weight compound, its number average molecular weight is preferably 600 or more, more preferably 1000 or more, and even more preferably 2000 or more, and is preferably 5000 or less, more preferably 4000 or less, and even more preferably 3500 or less.

[0021] The content of the alicyclic epoxy resin as component (A) in the resin composition is preferably 15 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more, per 100 parts by mass of the solid content of the resin composition. The content of component (A) in the resin composition may be 40 parts by mass or more, or even 45 parts by mass or more, per 100 parts by mass of the solid content of the resin composition. On the other hand, the content of component (A) in the resin composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 65 parts by mass or less, per 100 parts by mass of the solid content of the resin composition. The solid content of the resin composition refers to the amount of the resin composition excluding the solvent.

[0022] The resin composition contains an alicyclic epoxy resin (A), a basic catalyst (B), and a phenolic hydroxyl group-containing compound (C). The resin composition contains a basic catalyst and a phenolic hydroxyl group-containing compound as a curing aid, which allows the curing reaction of the alicyclic epoxy resin to proceed. The O produced by the basic catalyst abstracting a proton from the hydroxyl group of the phenolic hydroxyl group-containing compound is then converted into a hydroxyl group. - The reaction is initiated by the nucleophilic attack of the epoxy group by the hydroxyl group, and the O - It is thought that the curing reaction proceeds as a result of successive reactions in which the nucleophilic attack of the epoxy group occurs on another epoxy group.

[0023] As described below, the resin composition contains a dye as component (D) in addition to an alicyclic epoxy resin, a basic catalyst, and a phenolic hydroxyl group-containing compound. This resin composition configuration suppresses dye decomposition during the thermosetting reaction of the resin composition. Furthermore, the curing reaction proceeds smoothly, resulting in excellent curability of the resin composition. Consequently, the cured resin obtained by curing the resin composition exhibits excellent solvent resistance. For example, alicyclic epoxy resins can undergo curing reaction in the presence of a basic catalyst but in the absence of a phenolic hydroxyl group-containing compound. However, in this case, the curability of the resin composition decreases, and the resulting cured resin tends to have poor solvent resistance. Furthermore, alicyclic epoxy resins can be cured using Lewis acid catalysts, but this method tends to cause dye decomposition. However, the resin composition of the present invention suppresses dye decomposition even during the thermosetting reaction at high temperatures. Furthermore, because a highly transparent alicyclic epoxy resin is used as the base resin, the resulting cured resin selectively transmits light in the desired wavelength range due to the dye, making it suitable for use in optical filters. Furthermore, because of its excellent curability, the resulting cured resin exhibits excellent stability.

[0024] The basic catalyst of component (B) is not particularly limited as long as it acts as a base and can abstract a proton from a phenolic hydroxyl group, and may be an inorganic base or an organic base. Examples of inorganic bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; and alkali metal carbonates such as sodium carbonate, potassium carbonate, and sodium hydrogencarbonate. Examples of organic bases include tertiary amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; nitrogen-containing aromatic ring compounds having a nitrogen atom bonded only to an intracyclic carbon atom, such as pyridine compounds, pyrazine compounds, pyrimidine compounds, pyridazine compounds, triazine compounds, imidazole compounds, and pyrazole compounds; amidine compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and diazabicyclononene (DBN); and guanidine compounds such as 7-methyl-1,5,7-triazabicyclo[4.4.0]decene (MTBD) and 1,5,7-triazabicyclo[4.4.0]decene (TBD). These basic catalysts may be used alone or in combination of two or more. Among these, organic bases are preferred as basic catalysts, nitrogen-containing aromatic ring compounds are preferred, and imidazole compounds are more preferred. This makes it easier to improve the stability of the resin composition and to obtain a resin composition with less coloration.Preferred imidazole compounds include 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole.

[0025] The phenolic hydroxyl group-containing compound of component (C) is not particularly limited as long as it is a compound in which a hydroxyl group is bonded to an aromatic ring, and examples thereof include compounds having one phenolic hydroxyl group per molecule, such as phenol, cresol, dimethylphenol, trimethylphenol, methoxyphenol, phenylphenol, naphthylphenol, naphthol, anthracenol, and phenanthrenol, and compounds having two or more phenolic hydroxyl groups per molecule, such as hydroquinone, resorcinol, methylresorcinol, catechol, pyrogallol, bisphenol A, bisphenol F, bisphenol S, and bisphenol Z. The phenolic hydroxyl group-containing compound may be a compound in which two or more aromatic rings are bonded via a divalent linking group such as an alkylene group, a cycloalkylene group, -O-, -CO-, -CO2-, -S-, -SO2-, SO2-, or -NH-. The compound may have one or more hydroxyl groups bonded to an aromatic ring, preferably two or more, and more preferably two or more aromatic rings to which hydroxyl groups are bonded. The phenolic hydroxyl group-containing compound preferably has three or more aromatic rings bonded via a divalent linking group. As such a compound, for example, aromatic polyether ketone may be used. By using a compound in which three or more aromatic rings are bonded via a linking group, the heat resistance of the cured resin obtained by curing the resin composition can be improved.

[0026] The phenolic hydroxyl group-containing compound may be any compound having one or more phenolic hydroxyl groups per molecule, but is preferably a compound having two or more phenolic hydroxyl groups per molecule, which allows the alicyclic epoxy resin polymer to be crosslinked by the phenolic hydroxyl group-containing compound, thereby producing a stronger cured resin product.

[0027] The OH equivalent of the phenolic hydroxyl group-containing compound is preferably 2500 g / eq or less, more preferably 2000 g / eq or less, and even more preferably 1700 g / eq or less. The OH equivalent refers to the mass of the phenolic hydroxyl group-containing compound containing 1 gram equivalent of hydroxyl groups. The smaller the OH equivalent value, the greater the number of hydroxyl groups contained per unit mass of the phenolic hydroxyl group-containing compound. Using a phenolic hydroxyl group-containing compound with an OH equivalent of 2500 g / eq or less facilitates enhancing the curability of the resin composition. The lower limit of the OH equivalent of the phenolic hydroxyl group-containing compound is not particularly limited, and may be, for example, 80 g / eq or more, 100 g / eq or more, 200 g / eq or more, 300 g / eq or more, or 400 g / eq or more.

[0028] The molecular weight of the phenolic hydroxyl group-containing compound is not particularly limited, but is preferably 150 or more, more preferably 180 or more, and even more preferably 200 or more, from the viewpoint of suppressing volatilization of the phenolic hydroxyl group-containing compound from the resin composition and ensuring the coatability of the resin composition. The upper limit of the molecular weight of the phenolic hydroxyl group-containing compound may be, for example, 10,000 or less, 8,000 or less, 6,000 or less, 4,000 or less, 3,500 or less, or 1,500 or less. The molecular weight of the phenolic hydroxyl group-containing compound may be 400 or more, 600 or more, or 800 or more. Using a phenolic hydroxyl group-containing compound with a relatively high molecular weight can improve the film-forming properties of the resin composition, making it easier to form a uniform coating film, and can reduce distortion and defects in the cured resin obtained by curing the resin composition. For example, the curing shrinkage during curing of the resin composition is small, reducing distortion in the cured resin, and reducing optical anisotropy when used as an optical filter. Furthermore, toughness is imparted to the cured resin, making defects such as cracks less likely to occur, and when the resin is used as an optical filter, the appearance of the filter is less likely to be poor due to microcracks.

[0029] The content of component (B) in the resin composition is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, even more preferably 0.1 part by mass or more, and preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the solid content of the resin composition. The content of component (B) based on the alicyclic epoxy resin of component (A) is preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, even more preferably 0.2 part by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, per 100 parts by mass of the resin.

[0030] The content of component (C) in the resin composition is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, and even more preferably 35 parts by mass or more, per 100 parts by mass of the solid content of the resin composition. The content of component (C) in the resin composition may be 40 parts by mass or more, or even 50 parts by mass or more, per 100 parts by mass of the solid content of the resin composition. Meanwhile, the content of component (C) in the resin composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, per 100 parts by mass of the solid content of the resin composition. The content of component (C) based on the alicyclic epoxy resin of component (A) is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 70 parts by mass or more, and is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 150 parts by mass or less, per 100 parts by mass of the resin.

[0031] The resin composition contains a dye as component (D). The dye contained in the resin composition may be a dye that absorbs visible light, a dye that absorbs near-infrared light, which has a wavelength longer than that of visible light, or a dye that absorbs ultraviolet light, which has a wavelength shorter than that of visible light. The dye preferably has an absorption maximum in the wavelength range of 200 nm to 1100 nm. This allows the cured resin obtained by curing the resin composition of the present invention to be suitably used in optical components having selective light transmission properties (for example, selective light transmission filters).

[0032] When the dye of component (D) is a visible light-absorbing dye, the dye may have a maximum absorption in the visible light region (for example, a wavelength range of more than 420 nm and less than 680 nm), and preferably has a maximum absorption in the wavelength range of 500 nm or more and less than 680 nm, where visibility is high. A resin composition containing a visible light-absorbing dye can be cured to obtain a cured resin, which can be used in optical filters such as colored filters and blue light reduction filters.

[0033] When the dye of component (D) is a near-infrared absorbing dye, the dye preferably has an absorption maximum in the wavelength range of 680 nm to 1100 nm. A resin composition containing a near-infrared absorbing dye can be cured to produce a cured resin that is suitable for use in optical filters that suppress transmission of light in the near-infrared region and preferentially transmit light in the visible region. It can also be used in near-infrared cut filters that cut light in the red to near-infrared region.

[0034] The near-infrared absorbing dye preferably has an absorption peak in the wavelength range of 200 nm to 1100 nm, with the absorption peak having a maximum value in the wavelength range of 200 nm to 1100 nm, more preferably 685 nm or more, even more preferably 690 nm or more, more preferably 1000 nm or less, even more preferably 900 nm or less, and even more preferably 800 nm or less.

[0035] When the dye of component (D) is an ultraviolet-absorbing dye, the dye preferably has an absorption maximum in the range of, for example, 200 nm or more and 420 nm or less. A resin composition containing an ultraviolet-absorbing dye can be cured to obtain a cured resin that can be used in an optical filter that suppresses transmission of light in the violet to ultraviolet region and preferentially transmits light in the visible region. It can also be used in an ultraviolet-cutting filter that cuts light in the ultraviolet region. Furthermore, even if the resin composition is exposed to ultraviolet light during storage or during the production and processing of the optical filter (e.g., vapor deposition or mounting), the resin component and other components contained in the resin composition can be protected from the ultraviolet light, thereby suppressing deterioration of these components.

[0036] The ultraviolet absorbing dye preferably has an absorption peak in the wavelength range of 200 nm to 420 nm in its absorption spectrum in the wavelength range of 200 nm to 1100 nm, and the absorption peak preferably has a maximum value in the wavelength range of 200 nm to 1100 nm, more preferably 250 nm or more, even more preferably 300 nm or more, and more preferably 400 nm or less.

[0037] The dye of component (D) is not particularly limited and may be an organic dye, an inorganic dye, or an organic-inorganic composite dye (for example, an organic compound with coordinated metal atoms or ions).

[0038] Examples of near-infrared absorbing dyes and visible light absorbing dyes include squarylium dyes, croconium dyes, cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, naphthalocyanines, cholines, etc.) that may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as a central metal ion, cyanine dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethane dyes, quaterrylene dyes, diimonium dyes, perylene dyes, quinacrylonitrile dyes, oxazine dyes, dipyrromethene dyes, nickel complex dyes, and copper ion dyes. These dyes may be used alone or in combination of two or more.

[0039] Examples of ultraviolet absorbing dyes that can be used include known compounds known as ultraviolet absorbers, such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazinone compounds, methine compounds (e.g., cyanoacrylate compounds and merocyanine compounds), benzoxazole compounds, and triazine compounds. Only one type of ultraviolet absorbing dye may be used, or two or more types may be used.

[0040] The content of component (D) in the resin composition is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, even more preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the solid content of the resin composition. The content of component (D) based on the alicyclic epoxy resin of component (A) is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, based on 100 parts by mass of the resin.

[0041] The resin composition preferably contains a near-infrared absorbing dye and / or an ultraviolet absorbing dye as the dye component (D), which results in a cured resin product obtained by curing the resin composition that suppresses transmission of light in the near-infrared and / or ultraviolet regions and preferentially transmits light in the visible region, making it suitable for use in optical filters such as near-infrared cut filters and ultraviolet cut filters.

[0042] Some optical filters are provided with a dielectric multilayer film composed of alternating layers of high-refractive index material and low-refractive index material. The dielectric multilayer film can cut off light in a desired wavelength range by adjusting the thickness and number of each high-refractive index material layer and low-refractive index material layer. In optical filters equipped with such a dielectric multilayer film, when the dielectric multilayer film cuts off light in the near-infrared and / or ultraviolet regions, the cutoff wavelength range or transmission wavelength range varies depending on the incident angle. When the incident angle changes from perpendicular to oblique, the cutoff wavelength range or transmission wavelength range shifts to shorter wavelengths. Therefore, for obliquely incident light, the dielectric multilayer film may not be able to adequately cut off light in the near-infrared or ultraviolet regions, or may even cut off light in the visible region, resulting in a change in color. However, by applying a cured resin obtained from a resin composition containing a near-infrared absorbing dye and / or an ultraviolet absorbing dye to an optical filter, the incidence angle dependence of optical properties can be reduced. In this case, the optical filter preferably has an absorption layer made of a cured resin formed from the resin composition of the present invention and further has a dielectric multilayer film.

[0043] For example, an oxocarbon compound can be suitably used as the dye of component (D). The oxocarbon compound is not particularly limited as long as it contains a carbon oxide as a basic skeleton. However, squarylium compounds or croconium compounds are preferred, which are widely known as compounds with absorption wavelengths in the red to near-infrared region and relatively high light transmittance in the visible light region. If the resin composition contains such an oxocarbon compound, the cured resin obtained by curing the resin composition can be suitably used in optical filters that cut light in the red to near-infrared region. Furthermore, when such a dye is used, the inclusion of components (B) and (C) in the resin layer can suppress decomposition of the dye when the resin composition is subjected to a thermal curing reaction at high temperatures.

[0044] The squarylium compound is specifically a compound having a squarylium skeleton represented by the following formula (1), and the croconium compound is specifically a compound having a croconium skeleton represented by the following formula (2). In the following formulas (1) and (2), R 1 ~R 4 each independently represents an organic group.

[0045] [ka]

[0046] The oxocarbon compounds include those represented by the formula (1) and the formula (2), where R 1 ~R 4 are each independently a group represented by the following formula (3) or (4): A squarylium compound or croconium compound having a group represented by the following formula (3) forms a broad absorption peak in the red to near-infrared region and can cut light in a relatively wide wavelength region. On the other hand, a squarylium compound or croconium compound having a group represented by the following formula (4) forms a sharp absorption peak in the red to near-infrared region and can selectively cut light in the wavelength region corresponding to this absorption peak.

[0047] [ka]

[0048] [ka]

[0049] In formula (3), ring P represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing these ring structures, which may have a substituent; R 11 ~R 13 each independently represents a hydrogen atom, an organic group, or a polar functional group; R 12 and R 13 may be linked to each other to form a ring.14 ~R 18 each independently represents a hydrogen atom, an organic group, or a polar functional group; R 14 and R 15 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 may be linked to each other to form a ring. * represents the bonding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2).

[0050] There are cases where squarylium compounds and croconium compounds have a resonance relationship, and the squarylium compounds represented by the above formula (1) and the croconium compounds represented by the above formula (2) also include compounds having such a resonance relationship.

[0051] In the above formula (1), the groups bonded to one side and the other side of the squarylium skeleton may be the same or different. In the above formula (2), the groups bonded to one side and the other side of the croconium skeleton may be the same or different. When the groups bonded to one side and the other side of the squarylium skeleton or the croconium skeleton are the same, the squarylium compound or the croconium compound is expected to have improved durability against heat and light. When the groups bonded to one side and the other side of the squarylium skeleton or the croconium skeleton are different, association and aggregation between molecules of the squarylium compound or the croconium compound is suppressed, and improved solubility in solvents and resins is expected.

[0052] R 11 ~R 18 Examples of the organic group in R include an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an aryloxycarbonyl group, an arylsulfonyl group, an arylsulfinyl group, a heteroaryl group, an amino group, an amido group, a sulfonamide group, a carboxy group (a carboxylic acid group), and a cyano group. 11 ~R18 Examples of the polar functional group include a halogeno group, a hydroxyl group, a nitro group, and a sulfo group (sulfonic acid group).

[0053] R 11 ~R 18 Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl; and cyclic (alicyclic) alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. The alkyl group may have a substituent, and examples of such a substituent include an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxyl group, an alkoxyl group, a cyano group, a nitro group, an amino group, and a sulfo group. Examples of the alkyl group having a halogeno group include a monohalogenoalkyl group, a dihalogenoalkyl group, an alkyl group having a trihalomethyl unit, and a perhalogenoalkyl group. As the halogeno group, a fluorine atom, a chlorine atom, or a bromine atom is preferred, with a fluorine atom being particularly preferred. The number of carbon atoms in the alkyl group (the number of carbon atoms excluding substituents) is preferably 1 to 20. Specifically, if the alkyl group is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5, and if the alkyl group is a cyclic alkyl group, the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8.

[0054] R 11 ~R 18 For specific examples of the alkyl groups contained in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group and alkylsulfinyl group, see the above description of the alkyl group.

[0055] R 11 ~R 18Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and an indenyl group. The aryl group may have a substituent, and examples of the substituent that the aryl group has include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The number of carbon atoms in the aryl group (the number of carbon atoms excluding the substituent) is preferably 6 to 20, and more preferably 6 to 12.

[0056] R 11 ~R 18 Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a naphthylmethyl group. The aralkyl group may have a substituent, and examples of the substituent that the aralkyl group has include an alkyl group, an alkoxy group, a halogeno group, a halogenoalkyl group, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The number of carbon atoms in the aralkyl group (the number of carbon atoms excluding the substituent) is preferably 7 to 25, and more preferably 7 to 15.

[0057] R 11 ~R 18 For specific examples of the aryl group contained in the aryloxy group, arylthio group, aryloxycarbonyl group, arylsulfonyl group and arylsulfinyl group, see the above description of the aryl group.

[0058] R 11 ~R 18Examples of heteroaryl groups include thienyl, thiopyranyl, isothiochromenyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyraridinyl, pyrimidinyl, pyridazinyl, thiazolyl, isothiazolyl, furanyl, and pyranyl. The heteroaryl group may have a substituent, and examples of the substituent include alkyl, alkoxy, aryl, halogeno, halogenoalkyl, hydroxyl, cyano, amino, nitro, thiocyanate, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and sulfamoyl. The number of carbon atoms in the heteroaryl group (excluding the number of carbon atoms in the substituent) is preferably 2 to 20, and more preferably 3 to 15.

[0059] R 11 ~R 18 The amino group of the formula: -NR a1 R a2 and R a1 and R a2 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group are described above, and examples of the alkenyl group and the alkynyl group include the alkyl groups exemplified above in which some of the carbon-carbon single bonds have been replaced with double bonds or triple bonds. a1 and R a2 may be linked to each other to form a ring.

[0060] R 11 ~R 18 The amide group of the formula: -NH-C(=O)-R a3 and R a3 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group are described above.

[0061] R 11 ~R 18 The sulfonamide group of the formula: -NH-SO2-R a4 and R a4 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group are described above.

[0062] R 11 ~R 18 Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0063] R 12 ~R 18 Examples of the ring structures formed from the above include hydrocarbon rings and heterocycles. These ring structures may or may not have aromaticity, but are preferably non-aromatic hydrocarbon rings or non-aromatic heterocycles. Examples of non-aromatic hydrocarbon rings include cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane; and cycloalkenes such as cyclopentene, cyclohexene, cyclohexadiene (e.g., 1,3-cyclohexadiene), cycloheptene, and cycloheptadiene. Examples of non-aromatic heterocycles include rings in which one or more carbon atoms constituting the non-aromatic hydrocarbon ring as described above are replaced with at least one atom selected from N (nitrogen atom), S (sulfur atom), and O (oxygen atom). Examples of non-aromatic heterocycles include a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a tetrahydropyran ring, a tetrahydrothiopyran ring, a morpholine ring, a hexamethyleneimine ring, a hexamethylene oxide ring, a hexamethylene sulfide ring, and a heptamethyleneimine ring.

[0064] In equation (3), R 11 ~R 13 is an independent group, R 11 ~R 13are each independently preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, or an aralkyl group, and more preferably a hydrogen atom, an alkyl group, or an aryl group. 11 ~R 13 Preferred examples of the alkyl group and aryl group include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group.

[0065] In equation (3), R 12 and R 13 The ring structure formed by linking the groups is preferably a 4- to 9-membered unsaturated hydrocarbon ring, and among these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are more preferred. When the group of formula (3) is configured in this way, the shoulder peak of the absorption waveform in the red to near-infrared region is reduced, and the absorption peak becomes sharper.

[0066] Examples of the aromatic hydrocarbon ring of ring P in formula (3) include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, and a cyclotetradecaheptaene ring. The aromatic hydrocarbon ring may have only one ring structure, or two or more ring structures fused together. The aromatic heterocycle of ring P contains one or more atoms selected from N (nitrogen atom), O (oxygen atom), and S (sulfur atom) in the ring structure and has aromaticity, such as a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a purine ring, and a pteridine ring. The aromatic heterocycle may have only one ring structure, or two or more ring structures fused together. The fused ring containing these ring structures of ring P has a structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are fused together, and examples thereof include an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, a benzopyran ring, an acridine ring, a xanthene ring, a carbazole ring, etc. By appropriately setting the π-conjugated system of ring P, the absorption wavelength in the red to near-infrared region can be easily adjusted.

[0067] The ring P may have a substituent, and examples of the substituent include the organic groups and polar functional groups explained above. When the ring P has a substituent, the number of the substituents is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The ring P may not have a substituent.

[0068] For details of the squarylium compound and croconium compound having a group represented by formula (3), see, for example, the description in JP-A-2016-74649.

[0069] In equation (4), R 14 ~R 18 is an independent group, R 14 ~R 18 are each preferably independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, an amide group, or a hydroxyl group. 14 ~R 18By appropriately selecting R, it is possible to control the absorption maximum wavelength of the squarylium compound or croconium compound to a desired value. In particular, from the viewpoint of the stability and ease of production of the squarylium compound or croconium compound, R 14 ~R 18 are each preferably independently a hydrogen atom, an alkyl group, or an amide group. In this case, the alkyl group is preferably linear or branched, and preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0070] In equation (4), R 15 and R 16 and / or R 16 and R 17 are preferably linked to form a ring. In this case, at least R 14 and R 18 becomes an independent group. If the group of formula (4) is configured in this way, the absorption peak in the red to near-infrared region becomes sharp. 15 and R 16 Ring structures formed from R 16 and R 17 The number of ring members in the ring structure formed by is preferably 5 or more, more preferably 6 or more, and is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0071] In the group represented by formula (4), R 16 is an amino group or R is an amino group 16 R 15 and / or R 17 It is preferable that R is linked to R to form a ring. In this case, the absorption maximum wavelength shifts to the long wavelength side (for example, 685 nm or more), the transmittance of light in the red region is increased, and the color of the transmitted light can be made closer to the actual color. 14 or R 18 is preferably an amide group.

[0072] The group represented by formula (4) is preferably a group represented by the following formula (5): In formula (5), R 14 , R15 , R 18 represents the same meaning as above, and each is preferably an independent group. Ring Q represents a nitrogen-containing heterocycle, and R 19 represents an alkyl group which may have a substituent. Ring Q has at least one nitrogen atom (specifically, a nitrogen atom bonded to a carbon atom of a benzene ring to which ring Q is fused) as a heteroatom constituting the ring, and this nitrogen atom is bonded to R 19 The alkyl group R 19 Specific examples of alkyl groups are those listed above for R 11 ~R 18 Reference is made to the description of alkyl groups given above.

[0073] [ka]

[0074] The nitrogen-containing heterocycle of ring Q may have only one nitrogen atom as a ring-constituting atom, or may have two or more heteroatoms. When having two or more heteroatoms, it must have at least one nitrogen atom and further have at least one atom selected from N (nitrogen atom), S (sulfur atom), and O (oxygen atom). Examples of the nitrogen-containing heterocycle of ring Q include a pyrrolidine ring, a piperidine ring, a hexamethyleneimine ring, a heptamethyleneimine ring, a morpholine ring, a thiomorpholine ring, and a piperazine ring. From the viewpoint of ease of production of the oxocarbon compound, the nitrogen-containing heterocycle of ring Q preferably has only one nitrogen atom as a ring-constituting heteroatom. Furthermore, ring Q is preferably a non-aromatic nitrogen-containing heterocycle, and more preferably, a ring is formed by a carbon atom and a nitrogen atom or by carbon atoms bonded together by a single bond, except for the carbon-carbon bond fused to the benzene ring.

[0075] R 19 The alkyl group R is preferably a branched alkyl group, which can enhance the solubility of the oxocarbon compound in the resin. 19The branched alkyl group is not particularly limited as long as it has 3 or more carbon atoms. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a sec-pentyl group, a 1-ethylpropyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, a sec-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a tert-hexyl group, and a 2-ethylhexyl group. The upper limit of the carbon number of the branched alkyl group (the number of carbon atoms excluding the substituent) is not particularly limited, but is preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and even more preferably 6 or less. R 19 The branched alkyl group may have a substituent, and examples of the substituent include an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and a sulfo group. 19 The branched alkyl group preferably has no substituent.

[0076] The nitrogen-containing heterocycle of ring Q is R 19 In other words, the nitrogen-containing heterocycle of ring Q may have a substituent bonded to a ring-constituting atom other than the nitrogen atom, and examples of such a substituent include the organic groups and polar functional groups described above. 19 The substituents that ring Q may have other than R are preferably an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a halogeno group, a halogenoalkyl group, or a hydroxyl group, and more preferably an alkyl group, an aryl group, an aralkyl group, or a halogenoalkyl group. In this case, the alkyl group, alkoxy group, or halogenoalkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3 carbon atoms, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and the aralkyl group preferably has 7 to 13 carbon atoms, more preferably 7 to 11 carbon atoms. The alkyl group may be linear or branched. Ring Q may be R 19 It may not have any other substituents.

[0077] The number of ring members in ring Q is preferably 5 or more, more preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. In particular, when the number of ring members in ring Q is 6 or more, the absorption peak having the maximum absorption in the red to near-infrared region can be made particularly sharp, and the slope of the slope on the short wavelength side of the absorption peak can be made to be absorption. Therefore, the boundary between the transmission wavelength region and the absorption wavelength region is formed sharply, and it becomes possible to selectively cut light in the wavelength region corresponding to the absorption peak.

[0078] In equation (5), R 14 is represented by the formula: -NH-C(=O)-R a3 Preferably, the R contained in the amide group is an amide group represented by a3 is preferably an alkyl group having 3 or more carbon atoms, which may have a substituent. This can increase the solubility of the oxocarbon compound in resins and organic solvents. This makes it possible to incorporate a high concentration of the oxocarbon compound into the resin composition. When forming an optical filter from the resin composition, even if the filter is formed to a thin thickness, the oxocarbon compound can effectively absorb light in the red to near-infrared region.

[0079] R a3 The number of carbon atoms in the alkyl group (excluding the number of carbon atoms in the substituent) is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more, from the viewpoint of improving solubility in resins and organic solvents. a3 The upper limit of the number of carbon atoms in the alkyl group R is not particularly limited, but is preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, and even more preferably 18 or less. a3 In the case where the alkyl group has a substituent, examples of the substituent include an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, and a sulfo group. a3 The alkyl group preferably has no substituent.

[0080] R a3 The alkyl group in R is preferably linear. a3If R is a linear alkyl group, the heat resistance of the oxocarbon compound tends to be enhanced, and decomposition of the oxocarbon compound is easily suppressed when the oxocarbon compound is blended with a resin and cured by heating. Therefore, it is possible to maintain a high concentration of the oxocarbon compound in the cured resin after heating. In addition, in formula (5), R 15 and R 18 is preferably not an amide group, and is preferably, for example, a hydrogen atom or an alkyl group.

[0081] In the squarylium compound and croconium compound having the group represented by formula (4) and formula (5), the benzene rings on both sides of the squarylium skeleton or the croconium skeleton may be linked by a linking group. Examples of such compounds include the squarylium compounds disclosed in JP 2015-176046 A.

[0082] It is also preferable to use a compound having a styrene structure (hereinafter referred to as a "styrene-based compound") as the dye of component (D). In this case, decomposition of the dye can be suppressed when the resin composition is subjected to a thermal curing reaction at high temperatures. As the styrene-based compound, it is preferable to use a styrene-based compound represented by the following formula (6). The styrene-based compound represented by the following formula (6) forms an absorption wavelength range in the wavelength range of 350 nm to 395 nm, and can form a sharp boundary between the absorption wavelength range and the transmission wavelength range on the long wavelength side of this absorption wavelength range. Therefore, if a resin composition contains such a styrene-based compound, the cured resin obtained by curing the resin composition can be suitably used in optical filters that cut light in the violet to ultraviolet range.

[0083] [ka]

[0084] In the above formula (6), R 21 represents a cyano group, an acyl group, a carboxylic acid ester group, or an amide group, and R 22represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group, or a heteroaryl group; R 21 and R 22 When both are acyl groups, carboxylic acid ester groups, or amides, R 21 and R 22 may be linked to each other to form a ring, and R 23 represents a hydrogen atom or an alkyl group, and R 24 represents a hydrogen atom, an organic group, or a polar functional group, and multiple R 24 may be the same or different from each other, X represents a sulfur atom or an oxygen atom, L represents a divalent or higher valent linking group, a represents an integer of 2 or more, and the multiple groups bonded to L may be the same or different from each other. 21 (or R 22 ) is R 23 It may be in the cis position or the trans position relative to the

[0085] R 21 and R 22 Examples of the acyl group (alkanoyl group) include a methanoyl group, an ethanoyl group, a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a tridecanoyl group, a tetradecanoyl group, a pentadecanoyl group, a hexadecanoyl group, a heptadecanoyl group, an octadecanoyl group, a nonadecanoyl group, and an eicosanoyl group. The acyl group may have some of its hydrogen atoms substituted with an aryl group, an alkoxy group, a halogeno group, a hydroxyl group, or the like. The alkyl group in the acyl group may be linear or branched. The number of carbon atoms in the acyl group (excluding the number of carbon atoms in the substituent) is preferably 2 to 21, more preferably 2 to 11, and even more preferably 2 to 6.

[0086] R 21 and R 22 The carboxylic acid ester group of the formula: -C(=O)-OR b1 and R b1is an alkyl group, an aryl group, or an aralkyl group. Specific examples of the alkyl group, aryl group, and aralkyl group include those described above for R 11 ~R 18 Reference is made to the description of these groups in

[0087] R 21 and R 22 The amide group of the formula: -C(=O)-NR b2 R b3 and R b2 is a hydrogen atom or an alkyl group, and R b3 is an alkyl group, an acyl group, an aryl group, or an aralkyl group. b2 and R b3 Specific examples of the alkyl group, aryl group, and aralkyl group are those listed above for R 11 ~R 18 and R b3 Specific examples of the acyl group are those listed above for R 21 and R 22 Reference is made to the description of the acyl group in

[0088] R 21 and R 22 are both acyl groups and are linked together to form a ring, 21 and R 22 Examples of the group formed from the formula: -C(=O)-R b4 A group represented by -C(=O)- is shown. R 21 and R 22 are both carboxylic acid ester groups and are linked together to form a ring, 21 and R 22 Examples of groups formed from the formula: -C(=O)-OR b5 A group represented by -OC(=O)- is shown. R 21 and R 22 are both amide groups and are linked together to form a ring, 21 and R 22 Examples of the group formed from the formula: -C(=O)-NR b6 -R b7 -NR b8 In these formulas, Rb4 , R b5 and R b7 each independently represents a linear or branched alkylene group, R b6 and R b8 R each independently represents a hydrogen atom or a hydrocarbon group, and the carbon atoms of the carbonyl groups at both ends of the structures shown in these formulas are bonded to the carbon atom of the ethylene double bond in formula (6). b4 , R b5 and R b7 In the alkylene group of R, some of the hydrogen atoms may be substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or the like. b4 , R b5 and R b7 The number of carbon atoms in the alkylene group (excluding the number of carbon atoms in the substituent) is preferably 2 to 10, and more preferably 3 to 8. b6 and R b8 The hydrocarbon group is preferably an alkyl group, an aryl group or an aralkyl group, and specific examples of these groups are the same as those of the above R 11 ~R 18 Reference is made to the description of alkyl, aryl and aralkyl groups in the above.

[0089] R 22 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group). The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples of the saturated aliphatic hydrocarbon group include the above-mentioned R 11 ~R 18 The description of the alkyl group in the above is referred to, and specific examples of the aliphatic unsaturated hydrocarbon group are the R 11 ~R 18 Examples of the aromatic hydrocarbon group (aryl group) include those in which some of the carbon-carbon single bonds in the alkyl group are replaced with double or triple bonds. 11 ~R 18 Reference is made to the description of aryl groups in the above.

[0090] R 22 Specific examples of heteroaryl groups are those listed above for R 11 ~R 18Please refer to the explanation of the heteroaryl group in 1. It is preferable that the carbon atom of the heteroaryl group is bonded to the carbon atom of the ethylene double bond of formula (6), and it is more preferable that the carbon atom adjacent to the heteroatom is bonded to the carbon atom of the ethylene double bond of formula (6), which facilitates the synthesis of the styrene-based compound.

[0091] R in equation (6) 23 represents a hydrogen atom or an alkyl group, and specific examples of the alkyl group are the same as those of R 11 ~R 18 The description of alkyl groups is given in R. 23 The alkyl group in R preferably has 1 to 3 carbon atoms, and more preferably has 1 to 2 carbon atoms. 23 A hydrogen atom is particularly preferred as .

[0092] R in equation (6) 24 For details of the organic groups and polar functional groups, see above R 11 ~R 18 Please refer to the explanation of organic groups and polar functional groups in R. 24 is preferably one or more selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group, and an arylthio group, and is preferably a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 to 3. In particular, the four R bonded to the benzene ring in formula (6) 24 Among these, preferably two or more are hydrogen atoms, more preferably three or more are hydrogen atoms, and particularly preferably all four are hydrogen atoms.

[0093] In formula (6), X represents a sulfur atom or an oxygen atom. 21 ~R 23 It may be bonded to the ortho-position, meta-position, or para-position relative to the ethylene structural unit containing the formula (I). From the viewpoint of ease of production of the styrene-based compound, it is preferable that X is bonded to the para-position relative to the ethylene structural unit. It is also preferable that X is a sulfur atom.

[0094] In formula (6), L represents a divalent or higher linking group. The linking group L may be a divalent, trivalent, tetravalent, pentavalent, or hexavalent organic group for linking groups alone, or an n-valent group formed by combining these divalent, trivalent, tetravalent, pentavalent, or hexavalent organic groups for linking groups.

[0095] The divalent organic group for linking includes an alkylene group, a cycloalkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, SO2-, -NH-, etc. The alkylene group, cycloalkylene group, arylene group, and heteroarylene group may have a hydroxyl group and / or a thiol group.

[0096] Examples of the alkylene group include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms, such as a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, and octadecylene group.

[0097] Examples of the cycloalkylene group include cycloalkylene groups having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms, such as a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, and a cyclohexane-1,4-diyl group.

[0098] Examples of the arylene group include arylene groups having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms, such as a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-naphthylene group, a 1,3-naphthylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,7-naphthylene group, a 1,8-naphthylene group, a 2,3-naphthylene group, a 2,4-naphthylene group, a 2,5-naphthylene group, a 2,6-naphthylene group, and a 2,7-naphthylene group.

[0099] Examples of the heteroarylene group include heteroarylene groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms, such as a furan-2,3-diyl group, a furan-2,4-diyl group, a furan-2,5-diyl group, and a furan-3,4-diyl group.

[0100] As the divalent organic group for a linking group, the alkylene group, the cycloalkylene group, the arylene group, and the like are preferred.

[0101] When the divalent linking group L is a divalent group formed by linking organic groups, examples thereof include a group in which an alkylene group, -O-, and an alkylene group are bonded in this order; a group in which an alkylene group, -S-, and an alkylene group are bonded in this order; a group in which an alkylene group, -CO, -O-, and an alkylene group are bonded in this order; a group in which an alkylene group, -CO-, -NH-, and an alkylene group are bonded in this order; a group in which an alkylene group, -O-, an alkylene group, -O-, and an alkylene group are bonded in this order; and a group in which an arylene group, an alkylene group, and an arylene group are bonded in this order.

[0102] Examples of the group in which an alkylene group, -O-, and another alkylene group are bonded in this order include di-C alkyl ether residues having bonds on the alkyl moiety, such as a group in which methylene, -O-, and another methylene are bonded in this order; a group in which ethylene, -O-, and another ethylene are bonded in this order; and a group in which propylene, -O-, and another propylene are bonded in this order.

[0103] Examples of the group in which an alkylene group, -S-, and another alkylene group are bonded in this order include di-C alkylthiol residues having bonds on the alkyl moiety, such as a group in which methylene, -S-, and another methylene are bonded in this order; a group in which ethylene, -S-, and another ethylene are bonded in this order; and a group in which propylene, -S-, and another propylene are bonded in this order.

[0104] Examples of the group in which an alkylene group, -CO, -O-, and an alkylene group are bonded in this order include C2-4 alkanoic acid C1-4 alkyl ester residues having bonds on the alkyl moiety such as: a group in which methylene, -CO-, -O-, and methylene are bonded in this order; a group in which methylene, -CO-, -O-, and ethylene are bonded in this order; a group in which ethylene, -CO-, -O-, and methylene are bonded in this order; or a group in which ethylene, -CO-, -O-, and ethylene are bonded in this order.

[0105] Examples of the group in which an alkylene group, -CO-, -NH-, and an alkylene group are bonded in this order include a C2-4 alkanoic acid C1-4 alkylamide residue having bonds on the alkyl moiety such as a group in which methylene, -CO-, -NH-, and methylene are bonded in this order; a group in which methylene, -CO-, -NH-, and ethylene are bonded in this order; a group in which ethylene, -CO-, -NH-, and methylene are bonded in this order; or a group in which ethylene, -CO-, -NH-, and ethylene are bonded in this order.

[0106] Examples of the group in which an alkylene group, -O-, an alkylene group, -O-, and an alkylene group are bonded in this order include a C1-4 alkylene glycol di-C1-4 alkyl ether residue having bonds on the alkyl moiety such as a group in which methylene, -O-, methylene, -O-, and methylene are bonded in this order; or a group in which ethylene, -O-, ethylene, -O-, and ethylene are bonded in this order.

[0107] Examples of the group in which an arylene group, an alkylene group, and an arylene group are bonded in this order include a diphenyl C1-6 alkane residue having a bond to a benzene ring carbon, such as a group in which a 1,4-phenylene group, a methylene group, and a 1,4-phenylene group are bonded in this order; a group in which a 1,4-phenylene group, an ethylene group, and a 1,4-phenylene group are bonded in this order; a group in which a 1,4-phenylene group, a propylene group, and a 1,4-phenylene group are bonded in this order; and a group in which a 1,4-phenylene group, an n-propane-2,2-diyl group, and a 1,4-phenylene group are bonded in this order.

[0108] The trivalent organic group for linking group includes a methine group (-C<) which may have an alkyl group, -N<, a trivalent benzene ring, a trivalent naphthalene ring, etc. Examples of the alkyl group possessed by the methine group include the above-mentioned R 11 ~R 18 The explanation for the alkyl group in (1) is referred to. Examples of the trivalent benzene ring include a benzene-1,2,3-triyl group and a benzene-1,3,5-triyl group. Examples of the trivalent naphthalene ring include a naphthalene-1,2,3-triyl group and a naphthalene-1,3,6-triyl group. As the trivalent organic group for the linking group, a trivalent benzene ring is preferred.

[0109] When the trivalent linking group L is a trivalent group formed by linking organic groups for use as a linking group, examples include C3-20 alkanetriyl groups such as a group in which a methylene group, a methine group, and a methylene group are linked in that order (n-propane-1,2,3-triyl group), and a group in which an ethylene group, a methine group, and an ethylene group are linked in that order (n-hexane-1,3,6-triyl group); cycloC3-10 alkanetriyl groups such as a trivalent group formed by cyclically bonding three methine groups together with one or more methylene groups as necessary; a group in which a >C< having an alkyl group is bonded to three of the above-mentioned divalent organic groups for use as a linking group, for example, a group in which a >C< having a C1-4 alkyl group is bonded to three of the above-mentioned C2-4 alkanoic acid C1-4 alkyl ester residues (divalent groups) are bonded to each other.

[0110] Tetravalent organic groups for linking groups include >C<, tetravalent benzene rings, and tetravalent naphthalene rings. Examples of tetravalent benzene rings include benzene-1,2,3,4-tetrayl groups and benzene-1,2,4,5-tetrayl groups. Examples of tetravalent naphthalene rings include naphthalene-1,2,3,4-tetrayl groups, naphthalene-2,3,6,7-tetrayl groups, and naphthalene-1,4,5,6-tetrayl groups.

[0111] When the tetravalent linking group L is a tetravalent group formed by linking organic groups for linking groups, examples include C4-20 alkanetetrayl groups such as a group in which a methylene group, a methine group, a methine group, and a methylene group are linked in this order (n-butane-1,2,3,4-tetrayl group), and a group in which an ethylene group, a methine group, a methine group, and an ethylene group are linked in this order (n-hexane-1,3,4,6-tetrayl group); a group in which a >C< having an alkyl group is linked to four of the above-mentioned divalent organic groups for linking groups, such as a group in which a >C< having a C1-4 alkyl group is linked to four of the above-mentioned C2-4 alkanoic acid C1-4 alkyl ester residues (divalent groups) are linked to each other; and the like.

[0112] Pentavalent organic groups for linking groups include pentavalent benzene rings and pentavalent naphthalene rings. Examples of pentavalent benzene rings include benzene-1,2,3,4,5-pentyl groups. Examples of pentavalent naphthalene rings include naphthalene-1,2,3,4,5-pentyl groups, naphthalene-1,2,3,5,6-pentyl groups, and naphthalene-1,2,3,6,7-pentyl groups.

[0113] The hexavalent organic group for linking group includes a hexavalent benzene ring, a hexavalent naphthalene ring, etc. Examples of the hexavalent naphthalene ring include a naphthalene-1,2,3,4,5,6-hexyl group and a naphthalene-1,2,3,5,6,7-hexyl group.

[0114] When the hexavalent linking group L is a hexavalent group formed by linking organic groups, examples include >C< in which three of the C2-4 alkanoic acid C1-4 alkyl ester residues (divalent groups) are bonded together, followed by a methylene group, -O-, a methylene group, and a group in which three of the C2-4 alkanoic acid C1-4 alkyl ester residues (divalent groups) are bonded together in >C<, an alkylene group, -O-, an alkylene group, and a group in which three of the divalent organic groups for linking groups are bonded together in >C<, in this order.

[0115] The divalent, trivalent, tetravalent, pentavalent, or hexavalent organic group for use as a linking group may optionally have a substituent such as a halogeno group, a cyano group, an amino group, or a nitro group. As the organic group for use as a linking group having a substituent, a trivalent to hexavalent benzene ring having a cyano group, a trivalent to hexavalent naphthalene ring having a cyano group, or the like is preferred, a trivalent to hexavalent benzene ring having a cyano group is more preferred, and a tetravalent benzene ring having a cyano group is more preferred. Examples of the tetravalent benzene ring having a cyano group include a 5,6-dicyanobenzene-1,2,3,4-tetrayl group and a 3,6-dicyanobenzene-1,2,4,5-tetrayl group.

[0116] From the viewpoint of improving the heat resistance of the styrene-based compound, the linking group L is preferably an alkylene group in which some of the hydrogen atoms may be replaced with hydroxyl groups and / or thiol groups, a cycloalkylene group in which some of the hydrogen atoms may be replaced with hydroxyl groups and / or thiol groups, an arylene group in which some of the hydrogen atoms may be replaced with hydroxyl groups and / or thiol groups, -O-, -S-, or a linking group combining these groups (however, the ether bond and the thioether bond are not consecutive). The number of consecutive carbon atoms in the alkylene group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The number of carbon atoms in the cycloalkylene group is preferably 4 or more, more preferably 5 or more, and also preferably 10 or less, and more preferably 8 or less. The number of carbon atoms in the arylene group is preferably 5 or more, more preferably 6 or more, and also preferably 10 or less, and more preferably 8 or less.

[0117] As the styrene-based compound, a styrene-based compound represented by the following formula (7) is particularly preferred. Such a styrene-based compound has an absorption maximum peak in the wavelength range of, for example, 300 nm to 420 nm, and can effectively absorb light in the ultraviolet (UVA) to violet region, and is also excellent in stability and easy to produce. In the following formula (7), R 21a and R 21b The explanation of R above 21 The explanation of R 22a and R 22b The explanation of R above 22 The explanation of R 23a and R 23b The explanation of R above 23 The explanation of X is referred to. a and X b For an explanation of X, please refer to the explanation of X above.

[0118] [ka]

[0119] For details of the styrene-based compounds represented by formula (6) or formula (7), see WO 2019 / 009093.

[0120] The resin composition preferably further contains, as component (E), at least one selected from a silane coupling agent, a hydrolyzate of a silane coupling agent, and a hydrolysis condensate of a silane coupling agent. By including component (E) in the resin composition, when the resin composition is applied to a substrate and cured to form a resin layer, the adhesion of the resin layer to the substrate can be improved. A resin layer laminated substrate formed from such a resin composition can be suitably used in optical filters. Hereinafter, the silane coupling agent, the hydrolyzate of a silane coupling agent, and the hydrolysis condensate of a silane coupling agent may be collectively referred to as a "specific silane compound."

[0121] The silane coupling agent preferably has an epoxy group-containing group, an amino group-containing group, a mercapto group-containing group or a polymerizable double bond-containing group, and it is preferable to use a compound having such a functional group and an alkoxysilyl group.The silane coupling agent may contain only one or more of the above-mentioned functional groups, and may contain only one or more alkoxysilyl groups.

[0122] When the silane coupling agent contains only one alkoxysilyl group, the silane coupling agent is preferably an alkoxysilane represented by the following formula (8): Therefore, it is preferable to use, as component (E), at least one selected from the silane coupling agent represented by the following formula (8), its hydrolysate, and its hydrolysis condensate. SiR 31 k R 32 m (OR 33 ) n (OH) 4-k-m-n (8)

[0123] In formula (8), R 31 represents an epoxy group-containing group, an amino group-containing group, a mercapto group-containing group, or a polymerizable double bond-containing group; R 32 and R 33 each independently represents an alkyl group, k represents an integer of 1 to 3, m represents an integer of 0 to 2, and n represents an integer of 1 to 3. When k is 2 or more, multiple R 31 may be the same or different, and when m is 2, a plurality of R 32 may be the same or different, and when n is 2 or more, a plurality of OR 33 may be the same or different. 31 and R 32 and OR 33 and OH are groups that bond directly to Si.

[0124] R 31The epoxy group-containing group in R is not particularly limited as long as it contains an epoxy group, and examples thereof include a glycidoxy group-containing group and a cycloalkene oxide (alicyclic epoxy group)-containing group. The glycidoxy group or cycloalkene oxide may be bonded to a silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). 31 Preferably, R contains only one epoxy group. 31 Examples of the epoxy group-containing group include a glycidoxy group, a 3-glycidoxypropyl group, an 8-(glycidoxy)-n-octyl group, a 3,4-epoxycyclohexyl group, and a 2-(3,4-epoxycyclohexyl)ethyl group.

[0125] R 31 The amino group-containing group in R is not particularly limited as long as it has an amino group, and may have a primary amino group, a secondary amino group, a tertiary amino group, or a plurality of amino groups (for example, a primary amino group and a secondary amino group). The amino group is preferably bonded to the silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). 31 Examples of the amino group-containing group include a 3-aminopropyl group, a 3-(2-aminoethyl)aminopropyl group, a 3-(6-aminohexyl)aminopropyl group, a 3-(N,N-dimethylamino)propyl group, an N-phenylaminomethyl group, an N-phenyl-3-aminopropyl group, an N-benzyl-3-aminopropyl group, and an N-cyclohexylaminomethyl group.

[0126] R 31 The mercapto group-containing group of R is not particularly limited as long as it has a mercapto group, but a mercaptoalkyl group is preferred. The alkyl group in the mercaptoalkyl group may be linear or branched, and preferably has 1 to 12 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 6 carbon atoms. 31 Preferably, R contains only one mercapto group. 31Examples of the mercapto group-containing group include a 3-mercaptopropyl group, a 2-mercaptoethyl group, a 2-mercaptopropyl group, and a 6-mercaptohexyl group.

[0127] R 31 The polymerizable double bond-containing group of R is not particularly limited as long as it has a polymerizable double bond group, and examples of the polymerizable double bond group include a vinyl group, a styryl group, and a (meth)acrylic group. The polymerizable double bond group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). 31 Examples of the polymerizable double bond-containing group include a vinyl group, a 2-propenyl group, a styryl group, and a 3-(meth)acryloxypropyl group.

[0128] In order to improve the adhesion of the resin layer to the substrate, R 31 It is preferable that the epoxy group, amino group, mercapto group or polymerizable double bond group contained in is not too far from the silicon atom, and these groups are preferably bonded to the silicon atom directly or via an alkylene group having 1 to 6 carbon atoms.

[0129] R 32 and R 33 The alkyl group in R preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms. 32 Preferred examples of the OR include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 33 Preferred examples of the alkyl group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.

[0130] In formula (8), k is preferably 1 or 2, more preferably 1, which facilitates improving the adhesion of the resin layer to the substrate. Also, m is preferably 0 or 1, more preferably 0, and n is preferably 2 or 3.

[0131] When the silane coupling agent contains multiple alkoxysilyl groups, a polymeric polyfunctional silane coupling agent can be used as the silane coupling agent. The polymeric polyfunctional silane coupling agent has a structure in which a group and an alkoxysilyl group-containing group are bonded to an organic polymer chain, and in addition to containing multiple alkoxysilyl groups in one molecule, it can also contain multiple functional groups such as epoxy groups, amino groups, mercapto groups, and polymerizable double bond groups. The organic chain of the polymeric polyfunctional silane coupling agent does not contain polysiloxane. This configuration of the polymeric polyfunctional silane coupling agent forms many reaction sites with the resin and the substrate, thereby improving the adhesion of the resin layer to the substrate.

[0132] The hydrolyzate of the silane coupling agent used as component (E) can be obtained by converting the alkoxysilyl groups contained in the silane coupling agent into silanol groups through hydrolysis. The hydrolyzed condensate of the silane coupling agent can also be obtained by dehydrating and condensing the silanol groups contained in the hydrolyzed silane coupling agent to form a siloxane bond (-Si-O-Si-). Typically, hydrolysis of a silane coupling agent produces a hydrolyzed silane coupling agent, and the silanol groups contained in the hydrolyzed silane coupling agent also undergo a dehydration and condensation reaction, easily producing a hydrolyzed condensate of the silane coupling agent. The hydrolyzed condensate of the silane coupling agent may be a dehydration and condensate of the hydrolyzed silane coupling agent of the same type, or may be a dehydration and condensate of the hydrolyzed silane coupling agent of a different type.

[0133] As the component (E), it is preferable to use at least one selected from the group consisting of an epoxy group-containing silane coupling agent, its hydrolyzate, and its hydrolysis condensate. 31 is preferably an epoxy group-containing group, which makes it easier to improve the adhesion between the resin layer formed by curing the alicyclic epoxy resin and the substrate.

[0134] The resin composition may contain only one type of component (E), or two or more types. The resin composition preferably contains at least a hydrolyzate and / or hydrolysis condensate of a silane coupling agent as component (E), which can improve the adhesion of the resin layer to the substrate, particularly the adhesion after boiling in water, which is a severe condition. More preferably, component (E) contains at least a hydrolyzate or hydrolysis condensate of an epoxy group-containing silane coupling agent.

[0135] Component (E) more preferably contains a hydrolysis condensate of a silane coupling agent. In this case, the dehydration condensate preferably contains at least a dimer or trimer of an alkoxysilane (e.g., an alkoxysilane represented by the above formula (8)). For example, when the weight-average molecular weight of the specific silane compound used as component (E) is measured, it is preferably equal to or less than the molecular weight of a pentamer (assuming that all alkoxy groups are converted to hydroxyl groups), and more preferably equal to or less than the molecular weight of a tetramer. Specific values ​​for the weight-average molecular weight are, for example, preferably 300 or more, and preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.

[0136] The content of component (E) in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the solid content of the resin composition. When component (E) is contained in an amount of 0.1 parts by mass or more per 100 parts by mass of the solid content of the resin composition, the adhesion of the resin layer to the substrate is easily improved when the resin composition is used to form a resin layer on the substrate. On the other hand, even if the resin composition contains an excess of component (E), the effect of improving the adhesion of the resin layer to the substrate is not significantly improved. Therefore, the content of component (E) is preferably 20 parts by mass or less per 100 parts by mass of the solid content of the resin composition. The content of component (E) relative to 100 parts by mass of the alicyclic epoxy resin of component (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 3 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[0137] The resin composition may contain a solvent. For example, when the resin composition is a paint-formed resin composition, the inclusion of a solvent makes it easier to apply the resin composition.

[0138] The solvent may function to dissolve each component contained in the resin composition or may function as a dispersion medium. Examples of the solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycol derivatives (ether compounds, ester compounds, ether ester compounds, etc.) such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol ethyl ether acetate; amides such as N,N-dimethylacetamide; esters such as ethyl acetate, propyl acetate, and butyl acetate; pyrrolidones such as N-methyl-pyrrolidone (specifically, 1-methyl-2-pyrrolidone); aromatic hydrocarbons such as toluene, xylene, and trimethylbenzene; aliphatic hydrocarbons such as cyclohexane and heptane; and ethers such as tetrahydrofuran, dioxane, diethyl ether, and dibutyl ether. These solvents may be used alone or in combination of two or more.

[0139] The content of the solvent is, for example, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 70 parts by mass or more, per 100 parts by mass of the resin composition, and is preferably less than 100 parts by mass, more preferably 95 parts by mass or less. By adjusting the content of the solvent within such a range, it becomes easy to obtain a resin composition with a high concentration of each component.

[0140] The resin composition may contain a surface conditioner, which can prevent appearance defects such as striations and dents from occurring in the resin layer when the resin composition is cured to form a resin layer. The type of surface conditioner is not particularly limited, and siloxane-based surfactants, acetylene glycol-based surfactants, fluorine-based surfactants, acrylic leveling agents, etc. can be used. Examples of surface conditioners that can be used include the BYK (registered trademark) series manufactured by BYK-Chemie and the KF series manufactured by Shin-Etsu Chemical Co., Ltd.

[0141] The resin composition may contain a dispersant, which stabilizes the dispersibility of the resin composition and suppresses re-aggregation. The type of dispersant is not particularly limited, and examples that can be used include the EFKA series manufactured by EFKA Additives, the BYK (registered trademark) series manufactured by BYK-Chemie, the Solsperse (registered trademark) series manufactured by The Lubrizol Corporation, the Disparlon (registered trademark) series manufactured by Kusumoto Chemicals, Ltd., the Ajisper (registered trademark) series manufactured by Ajinomoto Fine-Techno Co., Ltd., the KP series manufactured by Shin-Etsu Chemical Co., Ltd., the Polyflow series manufactured by Kyoeisha Chemical Co., Ltd., the Megafac (registered trademark) series manufactured by DIC Corporation, and the Disper Aid series manufactured by San Nopco.

[0142] The resin composition may contain various additives, such as a plasticizer, a surfactant, a viscosity modifier, an antifoaming agent, a preservative, a resistivity modifier, a stability improver such as a polyvalent mercaptan, and an adhesion improver, as needed.

[0143] The resin composition can be cured to form a cured resin. The curing reaction of the resin composition is preferably accelerated by heating. The heating temperature when curing the resin composition is, for example, preferably 130°C or higher, more preferably 150°C or higher, and even more preferably 170°C or higher, and is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 250°C or lower.

[0144] The resin composition may be cured and molded into a predetermined shape. The shape of the molded product is not particularly limited, and examples thereof include plate-like, sheet-like, granular, powder-like, lump-like, particle aggregate-like, spherical, oval-spherical, lenticular, cubic, columnar, rod-like, conical, cylindrical, needle-like, fibrous, hollow fiber-like, and porous shapes.

[0145] The resin composition may be prepared as a paint so that it can be applied by spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, slit coating, screen printing, flexographic printing, inkjet printing, or the like. In this case, a liquid or paste-like resin composition can be applied to a substrate (e.g., a resin plate, a film, a glass plate, or the like) to obtain a film-like cured resin product having a thickness of 200 μm or less or a sheet-like resin product having a thickness of more than 200 μm. The cured resin product thus obtained can be handled as an integral part of the substrate.

[0146] The resin composition of the present invention can be preferably used as a resin composition for forming filters used in various applications such as optical devices, display devices, mechanical parts, and electric / electronic parts. The resin composition can be suitably applied to optical filters such as near-infrared cut filters and ultraviolet cut filters. For example, an optical filter can be formed by curing the resin composition to form a resin molded product or by forming a resin layer on a substrate.

[0147] The optical filter preferably has a substrate and a resin layer formed from the resin composition of the present invention, with the resin layer being formed on the substrate. This results in an optical filter in which the substrate and the resin layer are laminated together. The resin layer can be formed by curing the resin composition of the present invention. The resin layer may be provided on only one side of the substrate, or on both sides.

[0148] The thickness of the resin layer is not particularly limited, but from the viewpoint of ensuring the desired light selective transmission performance, it is preferably, for example, 0.5 μm or more, more preferably 1 μm or more. The upper limit of the thickness of the resin layer may be, for example, 1 mm or less, or may be 500 μm or less, 200 μm or less, or 50 μm or less. When the resin composition in the form of a paint is applied to a substrate by spin coating, the resin layer can be formed even thinner. From the viewpoint of forming a thinner optical filter, the resin layer is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 2 μm or less.

[0149] As the substrate, it is preferable to use a transparent substrate such as a resin plate, a resin film, or a glass plate. Among these, it is preferable to use a glass substrate as the substrate. By providing a resin layer on a glass substrate, an optical filter with excellent heat resistance can be obtained. The optical filter obtained in this manner can be mounted on an electronic component, for example, by solder reflow, thereby enabling the miniaturization of the electronic component. Furthermore, since a glass substrate is less likely to crack or warp even when exposed to high temperatures, it is easier to ensure adhesion with the resin layer.

[0150] The glass used for the glass substrate may be any known glass, such as silicate glass, borosilicate glass, borate glass, or phosphate glass. In these glasses, silicon atoms, boron atoms, or phosphorus atoms form a network structure with oxygen atoms to form the main skeleton of the glass, and in addition to these atoms, atoms or ions of sodium, potassium, calcium, magnesium, barium, aluminum, iron, silver, copper, cobalt, nickel, lead, zinc, fluorine, etc. may also be present in the glass. The glass may be colorless and transparent, or colored glass, such as blue glass, may be used depending on the application.

[0151] The thickness of the substrate is, for example, preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoint of ensuring strength, and is preferably 0.4 mm or less, more preferably 0.3 mm or less, from the viewpoint of thinning.

[0152] A protective layer made of the same or a different resin as the resin layer may be laminated as a second resin layer on the resin layer formed from the resin composition of the present invention. By providing a protective layer, the durability (decomposition resistance) of each component contained in the resin layer can be improved. The protective layer may be provided on only one side of the resin layer or on both sides.

[0153] The optical filter may have an anti-reflection or anti-glare layer (anti-reflection film) that reduces reflections from fluorescent lights, etc., a layer with scratch resistance, a transparent substrate with other functions, etc. The optical filter may have an ultraviolet reflective film or near-infrared reflective film on the resin layer. The ultraviolet reflective film or near-infrared reflective film is preferably provided on the light incident side of the resin layer. If the optical filter has an ultraviolet reflective film or near-infrared reflective film, ultraviolet and near-infrared rays can be further blocked from the light transmitted through the optical filter. The ultraviolet reflective film and near-infrared reflective film may have both ultraviolet and near-infrared reflective functions in one film.

[0154] Ultraviolet reflective films, near-infrared reflective films, and anti-reflection films (visible light anti-reflection films) can be composed of a dielectric multilayer film in which high-refractive index material layers and low-refractive index material layers are alternately stacked. Therefore, when imparting such functions to an optical filter, it is preferable that the optical filter has a dielectric multilayer film. Materials having a refractive index of 1.7 or higher can be used as materials for the high-refractive index material layer, and materials with a refractive index ranging from 1.7 to 2.5 are typically selected. Examples of materials for the high-refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; nitrides such as silicon nitride; mixtures of these oxides and nitrides, and mixtures thereof doped with metals such as aluminum and copper or carbon (e.g., tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO)). Materials having a refractive index of 1.6 or lower can be used as materials for the low-refractive index material layer, and materials with a refractive index ranging from 1.2 to 1.6 are typically selected. Examples of materials that can be used to form the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

[0155] The optical filter may also have an aluminum vapor deposition film, a thin film of a noble metal, or a resin film in which metal oxide fine particles containing indium oxide as the main component and a small amount of tin oxide are dispersed.

[0156] The thickness of the optical filter is preferably, for example, 1 mm or less. This makes it possible to fully meet the demand for miniaturization of imaging elements, for example. The thickness of the optical filter is more preferably 500 μm or less, even more preferably 300 μm or less, and even more preferably 150 μm or less, and is preferably 30 μm or more, and even more preferably 50 μm or more.

[0157] Optical filters can be used as one of the components of sensors such as image sensors (imaging elements), illuminance sensors, and proximity sensors. For example, image sensors are used as electronic components that convert light from a subject into electrical signals and output the signals, and examples of such sensors include CCDs (Charge Coupled Devices) and CMOSs ​​(Complementary Metal-Oxide Semiconductors). Image sensors can be used in mobile phone cameras, digital cameras, in-vehicle cameras, surveillance cameras, display elements (LEDs, etc.), and the like. The sensor includes one or more of the optical filters described above and may further include other filters and lenses as necessary.

[0158] This application claims the benefit of priority based on Japanese Patent Application No. 2022-118243, filed on July 25, 2022. The entire contents of the specification of Japanese Patent Application No. 2022-118243, filed on July 25, 2022, are incorporated herein by reference. [Example]

[0159] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples, and can be practiced with appropriate modifications within the scope of the above and below-described aims, and all such modifications are included in the technical scope of the present invention.

[0160] (1) Pigment synthesis (1-1) Synthesis Example 1: Synthesis of Dye A A 300 mL four-neck flask was charged with 110 g of chloroform, 1.8 g of acetic acid, 5.4 g (0.0303 mol) of 7-nitro-1,2,3,4-tetrahydroquinoline, and 12.84 g (0.0606 mol) of sodium triacetoxyborohydride. Under nitrogen flow (10 mL / min), 4.37 g (0.0606 mol) of isobutyraldehyde was added dropwise over 10 minutes while stirring with a stirring blade. After the addition was complete, the resulting reaction solution was added to 300 g of water and neutralized with hydrochloric acid. 300 g of ethyl acetate was added, and the organic phase was extracted using a separatory funnel. The extracted organic phase was dehydrated by adding anhydrous magnesium sulfate. After filtering off the solid matter (inorganic matter) from this organic phase, the solvent was concentrated using an evaporator, and then 1-isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline was obtained by appropriately using silica gel column chromatography (developing solvent: chloroform), concentration, and vacuum drying.

[0161] Next, 2.8 g (0.012 mol) of 1-isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline and 9.0 g of concentrated hydrochloric acid (36 wt%) were added to the mixture. While stirring under a nitrogen flow (5 mL / min) using a magnetic stirrer, a solution containing 9.1 g of tin chloride dihydrate and 9.1 g of concentrated hydrochloric acid (36 wt%) was gradually added, taking care to avoid the heat of reaction. After the addition, the mixture was stirred at room temperature for approximately 3 hours. The resulting reaction mixture was then added to a beaker containing 100 g of purified water and 100 g of ethyl acetate, with stirring. Potassium hydroxide solution was gradually added to the mixture. Once the pH of the solution reached approximately 10, the mixture was stirred for a while, after which the organic phase was extracted using a separatory funnel. The extracted organic phase was dehydrated by adding anhydrous magnesium sulfate. After filtering off the solid matter (inorganic matter) from this organic phase, the solvent was concentrated using an evaporator, and then 1-isobutyl-7-amino-1,2,3,4-tetrahydroquinoline was obtained by appropriately using silica gel column chromatography (developing solvent: chloroform), concentration, and vacuum drying.

[0162] Next, 2.86 g (0.0143 mol) of 1-isobutyl-7-amino-1,2,3,4-tetrahydroquinoline and 50 g of ultra-dehydrated chloroform were placed in a 100 mL three-neck flask. Under nitrogen flow (5 mL / min), 4.34 g (0.0429 mol) of triethylamine and 7.86 g (0.0286 mol) of palmitoyl chloride (n-hexadecanoyl chloride) were added while stirring using a magnetic stirrer. The mixture was allowed to react at room temperature for 12 hours. After the reaction was complete, the resulting reaction solution was added to ion-exchanged water and extracted with ethyl acetate. The extracted organic phase was dehydrated by adding magnesium sulfate (anhydrous). After filtering off the solid matter (inorganic matter) from this organic phase, the solvent was concentrated using an evaporator, and then the residue was purified by silica gel column chromatography (developing solvent: chloroform), followed by concentration and vacuum drying to obtain 1-isobutyl-7-(N-palmitoylamino)-1,2,3,4-tetrahydroquinoline.

[0163] Next, 6.3 g (0.0143 mol) of 1-isobutyl-7-(N-palmitoylamino)-1,2,3,4-tetrahydroquinoline, 0.82 g (0.0072 mmol) of squaric acid, 30 g of 1-butanol, and 30 g of toluene were placed in a 300 mL two-neck flask. The mixture was stirred using a magnetic stirrer under a nitrogen flow (10 mL / min) and the resulting mixture was reacted under reflux conditions for 3 hours while removing the eluted water using a Dean-Stark apparatus. After the reaction was completed, the mixture was cooled to room temperature and the precipitate was filtered off. The filtered precipitate was washed with methanol and filtered again. The resulting cake (solid) was purified by alumina column chromatography (eluent: chloroform). The resulting purified product was dried in a vacuum dryer at 60 °C for 12 hours to obtain Dye A (squarylium compound) shown in Table 1. When the transmission spectrum of dye A in toluene was measured, the absorption maximum wavelength was 700 nm.

[0164] (1-2) Synthesis Example 2: Synthesis of Dye B A 200 mL four-neck flask was charged with 4.98 g (0.039 mol) of 4-fluorobenzaldehyde, 3.57 g (0.020 mol) of ethylene glycol bis(2-mercaptoethyl) ether, 10.86 g (0.079 mol) of potassium carbonate, and 74 g of acetonitrile. The mixture was reacted at 60 °C for 12 hours under nitrogen flow (10 mL / min) with stirring using a stirring blade. After completion of the reaction, the insoluble matter was filtered off by vacuum filtration, and the solvent was removed using an evaporator. The resulting concentrate was placed in a 200 mL four-neck flask, to which 11.09 g (0.079 mol) of isobutyl cyanoacetate, 3.32 g (0.039 mol) of piperidine, and 68 g of methanol were added. The mixture was reacted under reflux for 4 hours. After the reaction was completed, the solvent was removed using an evaporator, and the resulting concentrate was purified by column chromatography (developing solvent: chloroform) to obtain dye B (a compound having a styrene structure) shown in Table 1. When the transmission spectrum of dye B in toluene was measured, the maximum absorption wavelength was 364 nm.

[0165] [Table 1]

[0166] (2) Preparation of Lewis acid catalyst (for comparison) According to the synthesis method described in International Publication No. 1997 / 031924, 255 g of Isopar (registered trademark) E solution manufactured by Ando Parachemie Co., Ltd., containing 7% TPB (tris(pentafluorophenyl)borane), was prepared. Water was added dropwise to this solution at 60°C, and white crystals precipitated during the addition. After cooling this reaction solution to room temperature, the resulting slurry was suction filtered and washed with n-heptane. The resulting cake was dried under reduced pressure at 60°C, yielding 18.7 g of a white crystalline TPB-water complex (TPB-containing powder). This TPB-containing powder had a water content of 9.2% (Karl Fischer moisture meter) and a TPB content of 90.8%. The dried complex had a water content of 9.2% (Karl Fischer moisture meter) and a TPB content of 90.8%. 19F-NMR analysis and gas chromatography analysis revealed no peaks other than those of TPB. 2.0 g of the resulting TPB-containing powder (1.82 g pure TPB, 0.18 g water) was mixed with 1.1 g of toluene at room temperature for 10 minutes, followed by the addition of 2.6 g of a 2 mol / L ammonia-ethanol solution and mixing at room temperature for 60 minutes, yielding a homogeneous solution of the TPB catalyst, a Lewis acid catalyst.

[0167] (3) Synthesis of phenolic hydroxyl group-containing compounds (3-1) Synthesis of phenolic hydroxyl group-containing compound A 4,4'-bis(2,3,4,5,6-pentafluorobenzoyl)diphenyl ether (BPDE) was synthesized according to the method described in JP 2005-41950 A. A 100 mL flask was charged with 0.50 g (2.19 mmol) of bisphenol A, 0.318 g (2.30 mmol) of potassium carbonate, and 4.5 g of N,N-dimethylacetamide as a solvent, and the mixture was stirred at 60°C for 1 hour under a nitrogen atmosphere. The reaction mixture was returned to room temperature, and 0.612 g (1.10 mmol) of BPDE was added. The mixture was then heated to 60°C and stirred for 3 hours. After completion of the reaction, the reaction mixture was added dropwise to 50 mL of purified water, and the precipitate was collected. The precipitate was immersed in a 1% aqueous solution of acetic acid for 10 hours, then filtered, washed with pure water, and dried in a vacuum dryer at 80°C for 24 hours to obtain 0.888 g of phenolic hydroxyl group-containing compound A (molecular weight 974, OH equivalent 487 g / eq) shown in Table 2. The yield was 83%. The structural formulas shown in Table 2 are based on the ratios of the raw materials used.

[0168] (3-2) Synthesis of phenolic hydroxyl group-containing compound B A 100 mL flask was charged with 0.50 g (2.19 mmol) of bisphenol A, 0.318 g (2.30 mmol) of potassium carbonate, and 4.5 g of N,N-dimethylacetamide (as solvent) and stirred at 60 °C for 1 hour under a nitrogen atmosphere. The reaction mixture was returned to room temperature, and 0.979 g (1.75 mmol) of BPDE was added. The mixture was heated to 60 °C and stirred for 3 hours. After completion of the reaction, the reaction mixture was added dropwise to 50 mL of purified water, and the precipitate was collected. The precipitate was immersed in a 1% aqueous acetic acid solution for 10 hours, filtered, washed with purified water, and dried in a vacuum oven at 80 °C for 24 hours to obtain 0.736 g of phenolic hydroxyl group-containing compound B (molecular weight 3212, OH equivalent 1606 g / eq) shown in Table 2. The yield was 52%. The structural formulas shown in Table 2 are based on the raw material charge ratios.

[0169] [Table 2]

[0170] (4) Preparation of hydrolyzed solution of silane coupling agent 4.0 g of 3-glycidoxypropyltrimethoxysilane (Dow-Toray, OFS-6040), 5.7 g of 2-propanol, and 0.1 g of distilled water were blended and mixed uniformly at 25°C. 0.2 g of formic acid was added and mixed for 90 minutes to promote the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane, thereby preparing a 3-glycidoxypropyltrimethoxysilane hydrolysate.

[0171] (5) Preparation of resin composition (5-1) Preparation Example 1 0.10 g of an alicyclic epoxy resin, CELLOXIDE® 2021P (3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, epoxy equivalent: 126.15 g / eq) manufactured by Daicel Corporation, and 0.090 g of bisphenol A (OH equivalent: 114.14 g / eq) were added to 0.76 g of toluene, heated to 40°C, and dissolved by applying ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the resulting filtrate was mixed with 0.003 g of the dye A obtained in Synthesis Example 1 and 0.0005 g of Shikoku Chemicals' Curesol® 2E4MZ (2-ethyl-4-methylimidazole) as a basic catalyst to obtain Resin Composition 1.

[0172] (5-2) Preparation Example 2 0.10 g of Daicel Corporation's EHPE3150 alicyclic epoxy resin (2,2-bis(hydroxymethyl)-1-butanol to 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct, epoxy equivalent 117 g / eq) and 0.097 g of bisphenol A (OH equivalent 114.14 g / eq) were added to 0.95 g of toluene, heated to 40°C, and dissolved by application of ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the resulting filtrate was mixed with 0.003 g of the dye A obtained in Synthesis Example 1 and 0.0005 g of Shikoku Chemicals Corporation's Curesol® 2E4MZ basic catalyst to obtain Resin Composition 2.

[0173] (5-3) Preparation Example 3 0.10 g of Daicel Corporation's EHPE3150 (epoxy equivalent: 117 g / eq) alicyclic epoxy resin and 0.097 g of bisphenol A (OH equivalent: 114.14 g / eq) were added to 0.95 g of toluene, heated to 40°C, and dissolved by application of ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the obtained filtrate was mixed with 0.005 g of dye B obtained in Synthesis Example 2 and 0.0005 g of Shikoku Chemicals Corporation's Curesol (registered trademark) 2E4MZ as a basic catalyst to obtain Resin Composition 3.

[0174] (5-4) Preparation Example 4 0.10 g of Daicel Corporation's EHPE3150 alicyclic epoxy resin (epoxy equivalent: 117 g / eq) and 0.416 g of phenolic hydroxyl group-containing compound A (OH equivalent: 487 g / eq) were added to 0.95 g of toluene, heated to 40°C, and dissolved by application of ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the resulting filtrate was mixed with 0.003 g of dye A obtained in Synthesis Example 1 and 0.0005 g of Shikoku Chemicals Corporation's Curesol (registered trademark) 2E4MZ as a basic catalyst to obtain Resin Composition 4.

[0175] (5-5) Preparation Example 5 0.10 g of Daicel Corporation's EHPE3150 alicyclic epoxy resin (epoxy equivalent: 117 g / eq) and 1.373 g of phenolic hydroxyl group-containing compound B (OH equivalent: 1606 g / eq) were added to 0.95 g of toluene, heated to 40°C, and dissolved by application of ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the resulting filtrate was mixed with 0.003 g of dye A obtained in Synthesis Example 1 and 0.0005 g of Shikoku Chemicals Corporation's Curesol® 2E4MZ basic catalyst to obtain Resin Composition 5.

[0176] (5-6) Preparation Example 6 0.10 g of an alicyclic epoxy resin, CELLOXIDE (registered trademark) 2021P (epoxy equivalent: 126.15 g / eq) manufactured by Daicel Corporation, was added to 0.30 g of toluene, heated to 40°C, and dissolved by application of ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the obtained filtrate was mixed with 0.003 g of dye A obtained in Synthesis Example 1 and 0.0025 g of TPB catalyst, a Lewis acid catalyst, to obtain Resin Composition 6.

[0177] (5-7) Preparation Example 7 0.10 g of Daicel Corporation's Celloxide (registered trademark) 2021P (epoxy equivalent: 126.15 g / eq) as an alicyclic epoxy resin and 0.090 g of bisphenol A (OH equivalent: 114.14 g / eq) were added to 0.76 g of toluene, heated to 40 ° C, and dissolved by applying ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the obtained filtrate was mixed with 0.003 g of dye A obtained in Synthesis Example 1 and 0.0025 g of TPB catalyst, a Lewis acid catalyst, to obtain Resin Composition 7.

[0178] (5-8) Preparation Example 8 0.10 g of an alicyclic epoxy resin, CELLOXIDE (registered trademark) 2021P (epoxy equivalent: 126.15 g / eq) manufactured by Daicel Corporation, was added to 0.30 g of toluene, heated to 40°C, and dissolved by application of ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the obtained filtrate was mixed with 0.003 g of Dye A obtained in Synthesis Example 1 and 0.0005 g of Curesol (registered trademark) 2E4MZ (a basic catalyst manufactured by Shikoku Chemical Industries, Ltd.), to obtain Resin Composition 8.

[0179] (5-9) Preparation Example 9 0.10 g of Daicel Corporation's EHPE3150 (epoxy equivalent: 117 g / eq) alicyclic epoxy resin was added to 0.30 g of toluene, heated to 40°C, and dissolved by application of ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the obtained filtrate was mixed with 0.003 g of dye A obtained in Synthesis Example 1 and 0.0005 g of Shikoku Chemical Industries' Curesol (registered trademark) 2E4MZ as a basic catalyst to obtain Resin Composition 9.

[0180] (5-10) Preparation Example 10 0.10 g of alicyclic epoxy resin CELLOXIDE (registered trademark) 2021P (epoxy equivalent: 126.15 g / eq) manufactured by Daicel Corporation and 0.060 g of triethylene glycol (OH equivalent: 75.08 g / eq) were added to 0.50 g of toluene, heated to 40°C, and dissolved by applying ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the resulting filtrate was mixed with 0.003 g of dye A obtained in Synthesis Example 1 and 0.0005 g of Shikoku Chemicals Corporation's Curesol (registered trademark) 2E4MZ as a basic catalyst to obtain Resin Composition 10.

[0181] (5-11) Preparation Example 11 0.10 g of Daicel Corporation's EHPE3150 alicyclic epoxy resin (epoxy equivalent: 117 g / eq) and 0.064 g of triethylene glycol (OH equivalent: 75.08 g / eq) were added to 0.50 g of toluene, heated to 40°C, and dissolved by application of ultrasound to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter, and the resulting filtrate was mixed with 0.003 g of the dye A obtained in Synthesis Example 1 and 0.0005 g of Shikoku Chemicals Corporation's Curesol (registered trademark) 2E4MZ as a basic catalyst to obtain Resin Composition 11.

[0182] (6) Preparation of optical filters To each of Resin Compositions 1-11, 8.3 parts by weight of a hydrolyzed solution of a silane coupling agent and 0.25 parts by weight of BYK-310 (polyether-modified polydimethylsiloxane) as a surface modifier were added to 100 parts by weight of the alicyclic epoxy resin, and the mixture was homogeneously mixed. 1 cc of this mixture was dispensed onto a glass substrate (Schott, D263Teco), and then a film was formed on the glass substrate using a spin coater (Mikasa, 1H-D7) by rotating the spin coater at 300 rpm over 0.3 seconds and holding the rotation speed for 1 second. The glass substrate with the resin composition film was then heated to 190°C in approximately 15 minutes under nitrogen purging in an inert oven (Yamato Scientific, DN610I). The resin composition film was then cured by heating at 190°C for 60 minutes under a nitrogen atmosphere to form a resin layer (absorption layer), and an optical filter was fabricated. The optical filters produced using resin compositions 1 to 5 were designated as Examples 1 to 5, respectively, and the optical filters produced using resin compositions 6 to 11 were designated as Comparative Examples 1 to 6, respectively.

[0183] (7) Evaluation (7-1) Measurement of the transmission spectrum of the optical filter before and after curing For each optical filter, the transmission spectrum was measured at a measurement interval of 1 nm using a spectrophotometer (Agilent Technologies, Spectrophotometer 8454), and the light transmittance at wavelengths of 200 nm to 1100 nm was determined. The transmission spectra were measured for the optical filters before and after curing of the resin layer. Spectral changes during curing were evaluated as follows: a change in transmittance at the absorption maximum wavelength before and after curing of 5% or less was evaluated as A, a change in transmittance of 6% to 50% was evaluated as B, and a change in transmittance of 51% or more was evaluated as C. Specific examples of transmission spectra are shown in Figures 1 to 4 for the optical filters prepared in Examples 2, 3, and 5, and Comparative Example 4.

[0184] (7-2) Solvent resistance To evaluate the progress of curing of the epoxy resin in the resin layer, the cured optical filter was immersed in toluene and observed to see if the resin layer would dissolve in toluene. Resin layers that showed solvent resistance to toluene were rated A, and those that dissolved in toluene were rated C.

[0185] (8) Results Table 3 shows the composition of the resin compositions used in each example and comparative example, as well as the evaluation results of spectral change upon curing and solvent resistance. The resin compositions used in examples 1 to 3 contained an alicyclic epoxy resin as component (A), a basic catalyst as component (B), bisphenol A, a phenolic hydroxyl group-containing compound, as component (C), and dye A or dye B as component (D). Therefore, optical filters obtained by curing these resin compositions on glass substrates showed almost no spectral change before and after curing and exhibited excellent solvent resistance. The resin compositions of examples 1 to 5 exhibited excellent curability, with suppressed decomposition of the dye during the thermal curing reaction.

[0186] On the other hand, the resin compositions used in Comparative Examples 1 and 2 contained a Lewis acid catalyst instead of the basic catalyst (B), but the optical filters produced from these resin compositions showed large spectral changes before and after curing, and the dye absorption characteristics were impaired. The resin compositions used in Comparative Examples 3 and 4 did not contain the phenolic hydroxyl group-containing compound (C), and the resin compositions used in Comparative Examples 5 and 6 contained triethylene glycol, an alcoholic hydroxyl group-containing compound, instead of the phenolic hydroxyl group-containing compound (C). However, the optical filters produced from these resin compositions showed some spectral changes before and after curing, were insufficient in curing, and had poor solvent resistance.

[0187] When an AR film (five layers of TiO2 and SiO2 films alternately laminated by vapor deposition) was laminated on the resin layer formed on the glass substrate prepared in Examples 1 to 5, an optical filter with high visible light transmittance and the desired absorption peak of the dye was obtained. This optical filter showed no change in spectrum, appearance, or adhesion even after being stored for 1000 hours under high temperature and humidity conditions of 85°C and 85% RH, demonstrating high durability.

[0188] [Table 3] [Industrial Applicability]

[0189] The resin composition of the present invention can be applied to a substrate and cured to form a resin layer, and can be used as an optical filter useful for optical devices, display devices, mechanical parts, electrical and electronic parts, etc.

Claims

1. A resin composition containing an alicyclic epoxy resin, a basic catalyst, a phenolic hydroxyl group-containing compound, and a dye, the basic catalyst is an imidazole compound; The resin composition is characterized in that the dye is at least one selected from the group consisting of oxocarbon compounds and compounds having a styrene structure represented by formula (6). 【Chemistry 1】 [In formula (6), R 21 represents a cyano group, an acyl group, a carboxylic acid ester group, or an amide group; R 22 represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group, or a heteroaryl group; When R 21 and R 22 are both an acyl group, a carboxylic acid ester group, or an amide group, R 21 and R 22 may be bonded to each other to form a ring; R 23 represents a hydrogen atom or an alkyl group; R 24 represents a hydrogen atom, an organic group, or a polar functional group, and multiple R 24 s may be the same or different from each other; X represents a sulfur atom or an oxygen atom; a represents an integer of 2 or more; L represents a divalent or higher valent linking group; The multiple groups bonded to L may be the same or different.

2. 2. The resin composition according to claim 1, wherein the dye has an absorption maximum in a wavelength range of 200 nm to 1100 nm.

3. 2. The resin composition according to claim 1, wherein the oxocarbon compound is a squarylium compound represented by the following formula (1) and / or a croconium compound represented by the following formula (2): 【Chemistry 2】 [In formula (1) and formula (2), R １ ~R ４ each independently represents a group represented by the following formula (3) or (4): 【Transformation 3】 [In formula (3), Ring P represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing any of these ring structures, each of which may have a substituent; R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a polar functional group; R １２ and R １３ may be linked to each other to form a ring, * represents the bonding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2). 【Chemistry 4】 [In formula (4), R １４ ~R １８ each independently represents a hydrogen atom, an organic group, or a polar functional group; R １４ and R １５ , R １５ and R １６ , R １６ and R １７ , R １７ and R １８ may be linked to each other to form a ring, * represents the bonding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2).

4. 2. The resin composition according to claim 1, wherein the alicyclic epoxy resin has an epoxy equivalent of 200 g / eq or less.

5. A resin composition described in claim 1, wherein the phenolic hydroxyl group-containing compound has one or two phenolic hydroxyl groups per molecule and has a molecular weight of 400 or more and 10,000 or less.

6. A resin composition described in claim 1, wherein the phenolic hydroxyl group-containing compound has an OH equivalent of 80 g / eq or more and 2500 g / eq or less.

7. A cured resin product obtained by curing the resin composition according to any one of claims 1 to 6.

8. An optical filter comprising the cured resin according to claim 7.

9. A sensor comprising the optical filter according to claim 8.

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