Resin composition

Abstract

A resin composition containing 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 obtained by curing the resin composition, an optical filter formed of the cured resin, and a sensor including the optical filter. Background Art

[0002] In camera devices such as mobile phone cameras, digital cameras, car cameras, video cameras, and display elements (LEDs, etc.), an image sensor that converts the light of a subject into an electrical signal and outputs it is generally used. Such an image sensor includes a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) and a lens, and sometimes includes a filter for selectively transmitting only a portion of the incident light in order to improve performance.

[0003] When forming an optical filter from a resin composition, a pigment can be added to a base resin to prepare the resin composition, which is cured to form a resin cured product, thereby forming an optical filter. By appropriately selecting a pigment having an absorption region at a wavelength to be cut off in incident light and adding it to the resin composition, light of the desired wavelength band can be transmitted or cut off. Among such resin compositions, resin compositions using epoxy resin as a base resin are known (e.g., Patent Documents 1 to 3).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2018-040955

[0007] Patent Document 2: Japanese Patent Application Publication No. 2017-137401

[0008] Patent Document 3: Japanese Patent Application Publication No. 2014-214262 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] The cured resin formed by epoxy resin has high heat resistance and excellent shape stability at high temperature. Among them, alicyclic epoxy resin has little coloration and excellent transparency, so it can be particularly preferably used in optical filters. Epoxy resin can be cured by, for example, a thermal curing reaction, but in this case, it is desirable that the pigment contained in the resin composition is not decomposed as much as possible, and it is desirable that it has sufficient curability.

[0011] The present invention is made in view of the above circumstances, and its object is to provide a resin composition containing an alicyclic epoxy resin and a pigment, wherein the decomposition of the pigment is suppressed during the thermal curing reaction of the resin composition, and the curing property is excellent. 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 having the optical filter.

[0012] Technical Solution

[0013] The present invention includes the following resin composition, resin cured product, optical filter and sensor.

[0014] [1] A resin composition, characterized in that the resin composition contains an alicyclic epoxy resin, a basic catalyst, a phenolic hydroxyl group-containing compound, and a pigment.

[0015] [2] The resin composition according to [1], wherein the pigment has a maximum absorption in a wavelength range of 200 nm to 1100 nm.

[0016] [3] The resin composition according to [1] or [2], wherein the pigment is a carbon oxide-based compound.

[0017] [4] The resin composition according to [3], wherein the carbon oxide-based compound is a squarylium compound represented by the following formula (1) and / or a cresone compound represented by the following formula (2).

[0018] [Chemical formula 1]

[0019]

[0020] [In formula (1) and formula (2), R 1 ~R 4 Each independently represents a group represented by the following formula (3) or the following formula (4).]

[0021] [Chemical formula 2]

[0022]

[0023] [In formula (3),

[0024] Ring P represents an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures, which may have a substituent.

[0025] R 11 ~R 13 Each independently represents a hydrogen atom, an organic group or a polar functional group, R 12 With R 13 can be linked together to form a ring,

[0026] * represents the bonding site to the four-membered ring in formula (1) or the five-membered ring in formula (2).]

[0027] [Chemical formula 3]

[0028]

[0029] [In formula (4),

[0030] R 14 ~R 18 Each independently represents a hydrogen atom, an organic group or a polar functional group, R 14 With R 15 , R 15 With R 16 , R 16 With R 17 , R 17 With R 18 They can be connected to each other to form a ring.

[0031] * represents the bonding site to the four-membered ring in formula (1) or the five-membered ring in formula (2).]

[0032] [5] The resin composition according to any one of [1] to [4], wherein the pigment is a compound having a styrene structure.

[0033] [6] The resin composition according to [5], wherein the compound having a styrene structure is a compound represented by the following formula (6).

[0034] [Chemical formula 4]

[0035]

[0036] [In formula (6),

[0037] R 21 represents a cyano group, an acyl group, a carboxylate group or an amide group,

[0038] R 22 represents a hydrogen atom, a cyano group, an acyl group, a carboxylate group, an amide group, a hydrocarbon group or a heteroaryl group,

[0039] In R 21 and R 22 When all R 21 With R 22 can be linked together to form a ring,

[0040] R 23 represents a hydrogen atom or an alkyl group,

[0041] R 24 Represents a hydrogen atom, an organic group or a polar functional group.24 can be the same or different from each other,

[0042] X represents a sulfur atom or an oxygen atom,

[0043] a represents an integer greater than or equal to 2,

[0044] L represents a divalent or higher valent linking group,

[0045] The multiple groups bonded to L may be the same as or different from each other.]

[0046] [7] The resin composition according to any one of [1] to [6], wherein the epoxy equivalent of the alicyclic epoxy resin is 200 g / eq or less.

[0047] [8] A cured resin product obtained by curing the resin composition according to any one of [1] to [7].

[0048] [9] An optical filter comprising the cured resin according to [8].

[0049]

[10] A sensor comprising the optical filter described in [9].

[0050] Beneficial Effects

[0051] The resin composition of the present invention suppresses decomposition of a pigment during a thermal curing reaction and has excellent curability. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 The transmission spectrum of the optical filter produced in Example 2 is shown.

[0053] Figure 2 The transmission spectrum of the optical filter produced in Example 3 is shown.

[0054] Figure 3 The transmission spectrum of the optical filter produced in Example 5 is shown.

[0055] Figure 4 The transmission spectrum of the optical filter produced in Comparative Example 4 is shown. DETAILED DESCRIPTION

[0056] The resin composition of the present invention contains (A) alicyclic epoxy resin, (B) an alkaline catalyst, (C) a compound containing a phenolic hydroxyl group, and (D) a pigment. The resin composition of the present invention contains the alicyclic epoxy resin (A) as a matrix resin, and also contains the pigment (D), so the resin cured product obtained by curing them can be used in an optical filter, which transmits or cuts off the light of the desired wavelength due to the pigment (D). At this time, the resin composition of the present invention contains the alkaline catalyst (B) and the compound containing the phenolic hydroxyl group as a curing aid in order to cure the alicyclic epoxy resin (A). Thus, even if the resin composition is subjected to a heat curing reaction at a high temperature, the decomposition of the pigment (D) can be suppressed. Therefore, by interacting with the alicyclic epoxy resin with high transparency used as the matrix resin, the obtained resin cured product can selectively transmit the light of the desired wavelength due to the pigment (D). In addition, the resin composition of the present invention has excellent curability, and it is easy to fully perform the curing reaction during heat curing, so the obtained resin cured product has excellent stability and excellent solvent resistance. Hereinafter, the resin composition of the present invention will be described in detail.

[0057] The resin composition of the present invention uses an alicyclic epoxy resin as a base resin. By using the epoxy resin as the base resin, the obtained resin cured product has high heat resistance and excellent shape stability at high temperatures. In addition, by using the alicyclic epoxy resin among the epoxy resins, the heat resistance of the resin cured product can be easily improved and less coloring can be achieved.

[0058] Examples of the alicyclic epoxy resin include oxirane compounds having an aliphatic hydrocarbon ring such as a cyclohexane ring. The alicyclic epoxy resin may be a substance in which an oxirane ring and an aliphatic hydrocarbon ring share a carbon atom, such as in cycloolefin oxide, or a substance in which an oxirane ring and an aliphatic hydrocarbon ring exist independently without sharing a carbon atom.

[0059] Examples of the alicyclic epoxy resin in which an oxirane ring and an aliphatic hydrocarbon ring share a carbon atom include 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, ε-caprolactone-modified-3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, bis-(3,4-epoxycyclohexyl) adipate, and butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone.

[0060] The alicyclic epoxy resin in which the oxirane ring and the aliphatic hydrocarbon ring do not share carbon atoms preferably contains an aliphatic hydrocarbon ring in the main chain of the epoxy resin. That is, the alicyclic epoxy resin is preferably an alicyclic epoxy resin having an alicyclic structure on the main chain. The alicyclic epoxy resin in which the oxirane ring and the aliphatic hydrocarbon ring share carbon atoms can be bonded directly to the aliphatic hydrocarbon ring by the oxirane ring (epoxy group) as cycloalkyl oxirane, or the oxirane ring can be bonded to the aliphatic hydrocarbon ring via a linking group. In the latter case, as the linking group, alkylene, ether, thioether, carbonyl, amino and a group composed of them can be listed. The number of atoms connecting the oxirane ring and the aliphatic hydrocarbon ring is preferably 5 or less, more preferably 3 or less, further preferably 2 or less, and further preferably 1 or less. The oxirane ring is particularly preferably directly bonded to the aliphatic hydrocarbon ring.

[0061] Examples of the alicyclic epoxy resin in which the oxirane ring and the aliphatic hydrocarbon ring do not share a common carbon atom include a product obtained by hydrogenating the aromatic ring of an aromatic epoxy resin having an aromatic ring structure in the main chain (hydrogenated epoxy resin), and a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Examples of the aromatic epoxy resin before hydrogenation include: bisphenol A type epoxy resin (bisphenol A diglycidyl ether); bisphenol F type epoxy resin (bisphenol F diglycidyl ether); biphenyl type epoxy resin; polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenylglycidyl ether ethane; phenol novolac type epoxy resin; cresol novolac type epoxy resin; a reaction product of epichlorohydrin with a polyphenol compound obtained by a condensation reaction of a phenol compound such as phenol, o-cresol, m-cresol, naphthol, etc., with an aromatic aldehyde having a phenolic hydroxyl group; a reaction product of epichlorohydrin with a polyphenol compound obtained by an addition reaction of a phenol compound with a diene compound such as divinylbenzene and dicyclopentadiene, etc.

[0062] The number of ring members of 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. Furthermore, the aliphatic hydrocarbon ring is preferably an aliphatic saturated hydrocarbon ring, that is, a cycloalkane.

[0063] The epoxy equivalent of the alicyclic epoxy resin is preferably 200 g / eq or less, more preferably 180 g / eq or less, and further preferably 150 g / eq or less. Epoxy equivalent refers to the mass of an epoxy resin containing 1 gram equivalent of epoxy groups. The smaller the value of epoxy equivalent, the more epoxy groups contained per unit mass of epoxy resin. By using an alicyclic epoxy resin having an epoxy equivalent of 200 g / eq or less, it is easy to improve the curability of the resin composition. The lower limit of the epoxy equivalent of the alicyclic epoxy resin is not particularly limited, for example, it can be 80 g / eq or more, or it can be 100 g / eq or more.

[0064] The alicyclic epoxy resin generally contains two or more ethylene oxide rings in one molecule, and the alicyclic epoxy resin preferably contains three or more ethylene oxide rings in one molecule (polyfunctional type).

[0065] As the alicyclic epoxy resin, an alicyclic epoxy resin in which the oxirane ring and the aliphatic hydrocarbon ring do not share a carbon atom is preferred. The epoxy resin is usually treated as a resin composition containing a curing agent and a curing catalyst, but if an alicyclic epoxy resin in which the oxirane ring and the aliphatic hydrocarbon ring do not share a carbon atom is used, various curing agents and curing catalysts can be easily used during curing.

[0066] 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. If a high molecular weight alicyclic epoxy resin is used, it is easy to improve the film forming property of the resin composition. If the alicyclic epoxy resin is a high molecular weight compound, the number average molecular weight is preferably 600 or more, more preferably 1000 or more, and further preferably 2000 or more, and preferably 5000 or less, more preferably 4000 or less, and further preferably 3500 or less.

[0067] The content of the alicyclic epoxy resin of the (A) component in the resin composition is preferably 15 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 35 parts by mass or more, in 100 parts by mass of the solid content of the resin composition. The content of the (A) component in the resin composition can be 40 parts by mass or more, or 45 parts by mass or more, in 100 parts by mass of the solid content of the resin composition. On the other hand, the content of the (A) component in the resin composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and further preferably 65 parts by mass or less, in 100 parts by mass of the solid content of the resin composition. It should be noted that the solid content of the resin composition refers to the amount of the resin composition after removing the solvent.

[0068] The resin composition contains (A) alicyclic epoxy resin, (B) a basic catalyst and (C) a phenolic hydroxyl group-containing compound. The resin composition can perform a curing reaction of the alicyclic epoxy resin by containing a basic catalyst and a phenolic hydroxyl group-containing compound as a curing aid. It is believed that the O-type epoxy resin generated by the basic catalyst taking a proton from the hydroxyl group of the phenolic hydroxyl group-containing compound - The partial nucleophilic attack on the epoxy group initiates the reaction, and the O generated by the ring-opening reaction of the epoxy group - The reaction continues by nucleophilic attack on other epoxy groups, thereby causing the curing reaction to proceed.

[0069] As described below, the resin composition contains a pigment as component (D) in addition to alicyclic epoxy resin, alkaline catalyst and phenolic hydroxyl-containing compound. By constituting the resin composition in this way, the decomposition of the pigment can be suppressed when the resin composition is subjected to a heat curing reaction. In addition, the curing reaction becomes easy to be fully carried out, and the curability of the resin composition is excellent. Therefore, the solvent resistance of the resin cured product obtained by curing the resin composition is excellent. For example, even if alicyclic epoxy resin is subjected to a curing reaction in the presence of an alkaline catalyst and the absence of a phenolic hydroxyl-containing compound, the curability of the resin composition is reduced, and the solvent resistance of the obtained resin cured product is easy to deteriorate. In addition, with respect to alicyclic epoxy resin, even if a Lewis acid catalyst is used, it can be cured, but in this case, it is easy to cause the decomposition of the pigment. However, even if the resin composition of the present invention is subjected to a heat curing reaction at high temperature, the decomposition of the pigment can be suppressed, and, using alicyclic epoxy resin with high transparency as a matrix resin, the resin cured product obtained can be preferably used for an optical filter because the pigment can selectively transmit the light of the desired wavelength. Furthermore, since the curing property is excellent, the obtained resin cured product is excellent in stability.

[0070] The basic catalyst as component (B) is not particularly limited as long as it functions as a base and can extract a proton from the phenolic hydroxyl group, and may be an inorganic base or an organic base. Examples of the inorganic base 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 hydrogen carbonate. As an organic base, for example, tertiary amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine can be listed; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; nitrogen-containing aromatic ring compounds having nitrogen atoms bonded only to carbon atoms in the ring, 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); 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 can be used alone or in combination of two or more. Among them, the basic catalyst is preferably an organic base, preferably a nitrogen-containing aromatic ring compound, and more preferably an imidazole compound. As a result, it is easy to improve the stability of the resin composition and to obtain a resin composition with less coloration. As the imidazole compound, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole and the like are preferred.

[0071] (C) The compound containing phenolic hydroxyl group of component is not particularly limited as long as it is a compound with hydroxyl group bonded to the aromatic ring, and examples thereof include: compounds having one phenolic hydroxyl group in one molecule such as phenol, cresol, dimethylphenol, trimethylphenol, methoxyphenol, phenylphenol, naphthylphenol, naphthol, anthracenol, phenanthrol, etc.; compounds having two or more phenolic hydroxyl groups in one molecule such as hydroquinone, resorcinol, methylresorcinol, catechol, pyrogallol, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, etc. The compound containing phenolic hydroxyl group can use 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-, -SO-, SO2-, -NH-, etc. The compound only needs to have one or more hydroxyl groups bonded to the aromatic ring, preferably two or more hydroxyl groups bonded to the aromatic ring, and preferably two or more aromatic rings bonded with hydroxyl groups. The compound containing phenolic hydroxyl group preferably has three or more aromatic rings bonded via a divalent linking group. As such a compound, for example, an aromatic polyether ketone can be used. By using a compound in which three or more aromatic rings are bonded via a linking group, the heat resistance of a cured resin obtained by curing the resin composition can be improved.

[0072] The phenolic hydroxyl group-containing compound may be any compound having one or more phenolic hydroxyl groups in one molecule, and preferably a compound having two or more phenolic hydroxyl groups in one molecule. Thus, the polymer of the alicyclic epoxy resin is cross-linked by the phenolic hydroxyl group-containing compound, and a stronger cured resin can be obtained.

[0073] The OH equivalent of the compound containing phenolic hydroxyl groups is preferably less than 2500g / eq, more preferably less than 2000g / eq, and further preferably less than 1700g / eq. OH equivalent refers to the mass of the compound containing phenolic hydroxyl groups containing 1 gram equivalent of hydroxyl groups, and the smaller the value of OH equivalent, the more the number of hydroxyl groups contained in the compound containing phenolic hydroxyl groups per unit mass. By using a phenolic hydroxyl group-containing compound having an OH equivalent of less than 2500g / eq, it is easy to improve the curability of the resin composition. The lower limit of the OH equivalent of the compound containing phenolic hydroxyl groups is not particularly limited, for example, it can be more than 80g / eq, more than 100g / eq, more than 200g / eq, more than 300g / eq or more than 400g / eq.

[0074] The molecular weight of the compound containing phenolic hydroxyl group is not particularly limited. From the viewpoint of suppressing the volatilization of the compound containing phenolic hydroxyl group from the resin composition and ensuring the coating property of the resin composition, it is preferably 150 or more, more preferably 180 or more, and further preferably 200 or more. The upper limit of the molecular weight of the compound containing phenolic hydroxyl group can be, for example, less than 10000, less than 8000, less than 6000, less than 4000, less than 3500 or less than 1500. The molecular weight of the compound containing phenolic hydroxyl group can be more than 400, more than 600 or more than 800. By using a compound containing phenolic hydroxyl group with a larger molecular weight, the film-forming property of the resin composition can be improved, it is easy to form a uniform coating film, and the strain and defects of the resin cured product obtained by curing the resin composition can be reduced. For example, the curing shrinkage when the resin composition is cured is small, the resin cured body is not easy to produce strain, and optical anisotropy is not easy to occur when making an optical filter. In addition, toughness is given to the resin cured body, defects such as cracks are not easy to occur, and poor appearance caused by microcracks is not easy to occur when making an optical filter.

[0075] The content of the component (B) in the resin composition is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and more preferably 1 part by mass or less, in 100 parts by mass of the solid content of the resin composition. As the content of the component (B) based on the alicyclic epoxy resin of the component (A), the content of the component (B) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and more preferably 2 parts by mass or less.

[0076] The content of the (C) component in the resin composition is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, and more preferably 35 parts by mass or more, in 100 parts by mass of the solid content of the resin composition. The content of the (C) component in the resin composition can be 40 parts by mass or more, or 50 parts by mass or more, in 100 parts by mass of the solid content of the resin composition. On the other hand, the content of the (C) component in the resin composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and more preferably 60 parts by mass or less, in 100 parts by mass of the solid content of the resin composition. As the content of the (C) component based on the alicyclic epoxy resin of the (A) component, relative to 100 parts by mass of the resin, the content of the (C) component is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and more preferably 70 parts by mass or more, and preferably 400 parts by mass or less, more preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and more preferably 150 parts by mass or less.

[0077] The resin composition has a pigment as component (D). The pigment contained in the resin composition may be a pigment that absorbs visible light, or a pigment that absorbs near infrared light having a wavelength longer than visible light, or a pigment that absorbs ultraviolet light having a wavelength shorter than visible light. The pigment preferably has a maximum absorption in the range of a wavelength of 200nm to 1100nm. Thus, the cured resin obtained by curing the resin composition of the present invention can be preferably used for an optical component having light selective transmittance (e.g., a light selective transmission filter).

[0078] When the pigment of component (D) is a visible light absorbing pigment, the pigment may be a pigment having maximum absorption in the visible light region (e.g., a wavelength greater than 420 nm and less than 680 nm), and preferably a pigment having maximum absorption in a wavelength range of 500 nm or more and less than 680 nm with high visibility. The resin composition containing the visible light absorbing pigment can be cured to obtain a cured resin material that can be used in filters such as color filters and blue light reduction filters.

[0079] When the component pigment (D) is a near-infrared absorbing pigment, the pigment is preferably a pigment having a maximum absorption in a range of more than 680 nm and less than 1100 nm in wavelength. If it is a resin composition containing a near-infrared absorbing pigment, the cured resin obtained by curing it can be preferably used for an optical filter that suppresses the transmission of light in the near-infrared region and preferentially transmits light in the visible light region. In addition, it can be applied to a near-infrared cutoff filter that cuts off light in the red to near-infrared region.

[0080] The near-infrared absorbing pigment has a peak with maximum absorption in the range of 680 nm to 1100 nm in the absorption spectrum in the range of 200 nm to 1100 nm, and the maximum absorption of the absorption peak preferably takes a maximum value in the range of 200 nm to 1100 nm. The maximum absorption wavelength is more preferably 685 nm or more, further preferably 690 nm or more, and more preferably 1000 nm or less, further preferably 900 nm or less, and further preferably 800 nm or less.

[0081] When (D) component pigment is ultraviolet absorbing pigment, pigment is preferably a pigment with maximum absorption in the range of more than 200nm and less than 420nm. As long as it is a resin composition containing ultraviolet absorbing pigment, the resin cured product obtained by curing it can be applied to an optical filter that suppresses the transmission of light in the purple-ultraviolet region and preferentially transmits light in the visible light region. In addition, it can be applied to an ultraviolet cut-off filter that cuts off light in the ultraviolet region. And, even when exposed to ultraviolet light during the storage of the resin composition, the manufacture / processing (such as evaporation, installation, etc.) of the filter, the resin component and other components contained in the resin composition can be protected from the influence of the ultraviolet light, and the degradation of their components can be suppressed.

[0082] The ultraviolet absorbing pigment has a peak with maximum absorption in the range of wavelength 200nm to 420nm in the absorption spectrum in the range of wavelength 200nm to 1100nm, and preferably the maximum absorption of the absorption peak takes a maximum value in the range of wavelength 200nm to 1100nm. The maximum absorption wavelength is more preferably 250nm or more, further preferably 300nm or more, and more preferably 400nm or less.

[0083] The component (D) dye may be an organic dye, an inorganic dye, or an organic-inorganic composite dye (for example, an organic compound coordinated with a metal atom or ion), and is not particularly limited.

[0084] As near-infrared absorbing pigments and visible light absorbing pigments, for example, squarylium pigments, croconium pigments, cyclic tetrapyrrole pigments (porphyrins, chlorins, phthalocyanines, naphthalocyanines, cholines, etc.) which may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as central metal ions, anthocyanin pigments, azo pigments, quinone pigments, xanthene pigments, indoline pigments, arylmethane pigments, quaterrylene pigments, diimonium pigments, perylene pigments, quinacridone pigments, oxazine pigments, dipyrromethene pigments, nickel complex pigments, copper ion pigments, etc. These pigments may be used alone or in combination.

[0085] As the ultraviolet absorbing pigment, known compounds known as ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazinone compounds, methine compounds (e.g., cyanoacrylate compounds, merocyanidin compounds), benzoxazole compounds, and triazine compounds can be used. The ultraviolet absorbing pigment can be used alone or in combination of two or more.

[0086] As for the content of the component (D) in the resin composition, in 100 parts by mass of the solid content of the resin composition, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 1 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. As the content of the component (D) based on the alicyclic epoxy resin of the component (A), relative to 100 parts by mass of the resin, the content of the component (D) is preferably 0.5 parts by mass or more, more preferably 1 parts by mass or more, 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 more preferably 15 parts by mass or less.

[0087] The resin composition preferably contains near infrared absorbing pigment and / or ultraviolet absorbing pigment as component (D) pigment. Thus, the resin cured product obtained by curing the resin composition suppresses the transmission of light in the near infrared region and / or ultraviolet region, preferentially transmits light in the visible light region, and can be preferably used in filters such as near infrared cut-off filters and ultraviolet cut-off filters.

[0088] In the optical filter, there is a dielectric multilayer film formed by alternately stacking high refractive index material layers and low refractive index material layers. The dielectric multilayer film can cut off the incident light of the desired band by adjusting the thickness and number of each layer of the high refractive index material layer and the low refractive index material layer. In the optical filter with such a dielectric multilayer film, when the incident light of the near infrared region and / or the ultraviolet region is cut off by the dielectric multilayer film, the cut-off band or the transmission band of the dielectric multilayer film changes according to the incident angle. If the incident angle changes from the vertical direction to the inclined direction, the cut-off band or the transmission band moves toward the short wavelength side. Therefore, in the dielectric multilayer film, it may happen that for the incident light in the inclined direction, the light of the near infrared region and the ultraviolet region cannot be fully cut off, or the light of the visible light region is also cut off, so that the color tone changes. However, by using a resin cured product obtained by a resin composition having a near infrared absorbing pigment and / or an ultraviolet absorbing pigment for an optical filter, the incidence angle dependence of the optical properties can be reduced. In this case, the optical filter has a resin cured product formed from the resin composition of the present invention as an absorption layer, and preferably further has a dielectric multilayer film.

[0089] As (D) component pigment, for example, carbon oxide compounds can be preferably used. Carbon oxide compounds are not particularly limited as long as they are compounds containing carbon oxides as basic skeletons, but preferably are well-known squarylium compounds or keto acid compounds as compounds having absorption wavelengths in the red to near-infrared region and higher transmittance in the visible light region. If the resin composition contains such carbon oxide compounds, the resin cured product obtained by curing the resin composition can be preferably used for a filter that cuts off light in the red to near-infrared region. In addition, if such a pigment is used, by including (B) component and (C) component in the resin layer, the decomposition of the pigment can be suppressed when the resin composition is subjected to a heat curing reaction at high temperature.

[0090] As the squarylium compound, a compound having a squarylium skeleton represented by the following formula (1) is specifically shown, and as the croconic acid compound, a compound having a croconic acid skeleton represented by the following formula (2) is specifically shown. In the following formulas (1) and (2), R 1 ~R 4 Each independently represents an organic group.

[0091] [Chemical formula 5]

[0092]

[0093] As the carbon oxide compound, it is preferred that in the above formula (1) and formula (2), R 1 ~R 4 A carbon oxide compound which is independently a group represented by the following formula (3) or the following formula (4). The squarylium cyanine compound or the crotonic acid compound having the group represented by the following formula (3) forms a broad absorption peak in the red to near-infrared region and can cut off light in a relatively wide wavelength band. On the other hand, the squarylium cyanine compound or the crotonic acid compound having the group represented by the following formula (4) forms a sharp absorption peak in the red to near-infrared region and can selectively cut off light in the wavelength band corresponding to the absorption peak.

[0094] [Chemical formula 6]

[0095]

[0096] [Chemical formula 7]

[0097]

[0098] In formula (3), ring P represents an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures, which may have a substituent, and R 11 ~R 13 Each independently represents a hydrogen atom, an organic group or a polar functional group, R 12 With R 13They 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 With R 15 , R 15 With R 16 , R 16 With R 17 , R 17 With R 18 They may be linked to each other to form a ring. * represents a bonding site to the four-membered ring in formula (1) or the five-membered ring in formula (2).

[0099] There are some compounds having a resonance relationship among the squarylium compounds and the croconic acid compounds, and these compounds having a resonance relationship are also included in the squarylium compounds represented by the above formula (1) and the croconic acid compounds represented by the above formula (2).

[0100] In the above formula (1), the groups bonded to one side and the other side of the squaryl cyanide skeleton may be the same or different from each other. In the above formula (2), the groups bonded to one side and the other side of the keto acid skeleton may be the same or different from each other. In the case where the groups bonded to one side and the other side of the squaryl cyanide skeleton or the keto acid skeleton are the same, it is expected that the durability of the squaryl cyanide compound or the keto acid compound to heat and light will be improved. In the case where the groups bonded to one side and the other side of the squaryl cyanide skeleton or the keto acid skeleton are different from each other, the association and agglomeration of the molecules of the squaryl cyanide compound or the keto acid compound are suppressed, and it is expected that the solubility in solvents and resins will be improved.

[0101] As R 11 ~R 18 Examples of the organic group include alkyl, alkoxy, alkylthio, alkoxycarbonyl, alkylsulfonyl, alkylsulfinyl, aryl, aralkyl, aryloxy, arylthio, aryloxycarbonyl, arylsulfonyl, arylsulfinyl, heteroaryl, amino, amide, sulfonamide, carboxyl (carboxylic acid), and cyano. 11 ~R 18 The polar functional group includes a halide group, a hydroxyl group, a nitro group, a sulfo group (sulfonic acid group) and the like.

[0102] As R 11 ~R 18Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and other linear or branched alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and other cyclic (alicyclic) alkyl groups. The alkyl group may have a substituent, and examples of such a substituent include aryl, heteroaryl, halo, hydroxyl, carboxyl, alkoxy, cyano, nitro, amino, sulfo and the like. Examples of the alkyl group having a halo group include monohaloalkyl, dihaloalkyl, alkyl having a trihalomethyl unit, and perhaloalkyl. As the halo group, a fluorine atom, a chlorine atom, and a bromine atom are preferred, and a fluorine atom is particularly preferred. The number of carbon atoms of the alkyl group (excluding the number of carbon atoms of the substituent) is preferably 1 to 20. Specifically, if it is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 5. If it is a cyclic alkyl group, the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8.

[0103] R 11 ~R 18 For specific examples of the alkyl group contained in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group and alkylsulfinyl group, refer to the above description of the alkyl group.

[0104] As R 11 ~R 18 The aryl group includes phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, indenyl, etc. The aryl group may have a substituent, and examples of the substituents of the aryl group include alkyl, alkoxy, heteroaryl, halo, haloalkyl, hydroxy, cyano, nitro, amino, thiocyanate, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfamoyl, etc. The number of carbon atoms of the aryl group (excluding the number of carbon atoms of the substituent) is preferably 6 to 20, and more preferably 6 to 12.

[0105] As R 11 ~R 18 Examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl, naphthylmethyl, etc. The aralkyl group may have a substituent, and examples of the substituents possessed by the aralkyl group include alkyl, alkoxy, halo, haloalkyl, cyano, nitro, thiocyanate, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfamoyl, etc. The number of carbon atoms of the aralkyl group (excluding the number of carbon atoms of the substituent) is preferably 7 to 25, and more preferably 7 to 15.

[0106] R 11 ~R 18 As for specific examples of the aryl group contained in the aryloxy group, arylthio group, aryloxycarbonyl group, arylsulfonyl group and arylsulfinyl group, refer to the above description of the aryl group.

[0107] As R 11 ~R 18 Examples of the heteroaryl group include thienyl, thiopyranyl, isothiobenzopyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrrolidinyl, pyrimidinyl, pyridazinyl, thiazolyl, isothiazolyl, furanyl, and pyranyl. The heteroaryl group may have a substituent, and examples of the substituents possessed by the heteroaryl group include alkyl, alkoxy, aryl, halo, haloalkyl, hydroxy, cyano, amino, nitro, thiocyanate, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and sulfamoyl. The number of carbon atoms (excluding the number of carbon atoms of the substituent) of the heteroaryl group is preferably 2 to 20, and more preferably 3 to 15.

[0108] As R 11 ~R 18 The amino group can be exemplified by the formula: -NR a1 R a2 The amino group shown in FIG. a1 and R a2 Each independently represents 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 refer to the description of these groups above. As the alkenyl group and the alkynyl group, there can be cited groups in which a part of the carbon-carbon single bonds of the alkyl groups exemplified above are replaced by double bonds or triple bonds. a1 With R a2 Can be linked to each other to form a ring.

[0109] As R 11 ~R 18 The amide group may be of the formula: -NH-C(=O)-R a3 The amide group shown, wherein R a3 The specific examples of the alkyl group, aryl group, aralkyl group and heteroaryl group can refer to the description of these groups above.

[0110] As R 11 ~R 18 The sulfonamide group may be of the formula: -NH-SO2-R a4 The sulfonamide group shown in FIG. a4 The specific examples of the alkyl group, aryl group, aralkyl group and heteroaryl group can refer to the description of these groups above.

[0111] As R 11 ~R 18 Examples of the halogenated group include fluoro, chloro, bromo, and iodo.

[0112] As R 12 ~R 18 The ring structures formed include hydrocarbon rings and heterocyclic rings, which may or may not be aromatic, and are preferably non-aromatic hydrocarbon rings or non-aromatic heterocyclic rings. As non-aromatic hydrocarbon rings, for example, cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane; cycloalkenes such as cyclopentene, cyclohexene, cyclohexadiene (such as 1,3-cyclohexadiene), cycloheptene, and cycloheptadiene, etc. As non-aromatic heterocyclic rings, rings in which one or more carbon atoms constituting the non-aromatic hydrocarbon rings described above are replaced by at least one atom selected from N (nitrogen atom), S (sulfur atom) and O (oxygen atom) can be listed. As non-aromatic heterocyclic rings, for example, pyrrolidine rings, tetrahydrofuran rings, tetrahydrothiophene rings, piperidine rings, tetrahydropyran rings, tetrahydrothiopyran rings, morpholine rings, hexamethyleneimine rings, oxirane rings, hexamethylenesulfide rings, heptamethyleneimine rings, etc. can be listed.

[0113] In formula (3), R 11 ~R 13 When R is an independent group, 11 ~R 13 Preferably, each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group or an aralkyl group, and more preferably represents a hydrogen atom, an alkyl group or an aryl group. 11 ~R 13 Preferred examples of the alkyl group and the aryl group include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group.

[0114] In formula (3), as R 12 With R 13 The ring structure formed by the connection is preferably a 4- to 9-membered unsaturated hydrocarbon ring, and more preferably a cycloalkane monoene such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene. When the group of formula (3) is constructed in this way, the shoulder peak of the absorption waveform in the red to near infrared region decreases, and the absorption peak becomes sharp.

[0115] As the aromatic hydrocarbon ring of ring P of formula (3), benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, fluoranthene ring, cyclotetradecene ring, etc. can be listed. The aromatic hydrocarbon ring may have only one ring structure, or it may be formed by condensation of two or more ring structures. The aromatic heterocyclic ring of ring P is an aromatic heterocyclic ring having one or more atoms selected from N (nitrogen atom), O (oxygen atom) and S (sulfur atom) in the ring structure, and having aromaticity, for example, furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, purine ring, pteridine ring, etc. The aromatic heterocyclic ring may have only one ring structure, or it may be formed by condensation of two or more ring structures. The condensed ring of these ring structures including the ring P has a structure in which an aromatic hydrocarbon ring and an aromatic heterocyclic ring are condensed, 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, and a carbazole ring. By appropriately setting the π-conjugated system of the ring P, the absorption wavelength in the red to near-infrared region can be easily adjusted.

[0116] Ring P may have a substituent, and examples of the substituent include the organic groups and polar functional groups described above. When ring P has a substituent, the number of the substituent is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. Ring P may not have a substituent.

[0117] For details of the squarylium compound and the crotonic acid compound having a group represented by formula (3), reference can be made to the description of, for example, JP-A-2016-74649.

[0118] In formula (4), R 14 ~R 18 When R is an independent group, it is preferred that 14 ~R 18 Each is 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 18 , the maximum absorption wavelength of the squarylium compound and the crotonic acid compound can be controlled to a desired value. Among them, from the perspective of the stability and ease of manufacture of the squarylium compound and the crotonic acid compound, R 14 ~R 18 Each independently represents a hydrogen atom, an alkyl group or an amide group. In this case, the alkyl group is preferably linear or branched, and has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0119] In formula (4), preferably R 15 With R 16 and / or R 16 With R 17 In this case, at least R 14and R 18 If the group of formula (4) is constructed in this way, the absorption peak in the red to near-infrared region becomes sharp. 15 and R 16 The ring structure formed by R 16 and R 17 The number of ring members of the formed ring structure is preferably 5 or more, more preferably 6 or more, and is preferably 12 or less, more preferably 10 or less, and further preferably 8 or less.

[0120] Among the groups represented by formula (4), R 16 is an amino group, or R 16 With R 15 and / or R 17 In this case, the maximum absorption wavelength moves to the long wavelength side (for example, above 685nm), the transmittance of light in the red region is increased, and the hue of the transmitted light can be made close to the actual hue. In addition, from the same point of view, it is preferred that R 14 or R 18 It is an amide group.

[0121] The group represented by formula (4) is preferably a group represented by the following formula (5). In formula (5), R 14 , R 15 , R 18 represents the same meaning as above, and preferably is an independent group. Ring Q represents a nitrogen-containing heterocyclic ring, R 19 represents an alkyl group optionally having a substituent. Ring Q has at least one nitrogen atom (specifically, a nitrogen atom bonded to a carbon atom of the benzene ring of ring Q) as a heteroatom constituting the ring, and R 19 An alkyl group is bonded to the nitrogen atom. 19 For specific examples of the alkyl group, refer to the above R 11 ~R 18 Description of the alkyl group.

[0122] [Chemical formula 8]

[0123]

[0124] The nitrogen-containing heterocyclic ring of ring Q may have only one nitrogen atom as a ring-constituting atom, or may have two or more heteroatoms. In the case of having two or more heteroatoms, it is necessary to have at least one nitrogen atom, and also have one or more atoms selected from N (nitrogen atom), S (sulfur atom) and O (oxygen atom). As the nitrogen-containing heterocyclic ring of ring Q, for example, pyrrolidine ring, piperidine ring, hexamethyleneimine ring, heptamethyleneimine ring, morpholine ring, thiomorpholine ring, piperazine ring, etc. can be cited. From the aspect of the ease of manufacturing of carbon oxide-based compounds, the nitrogen-containing heterocyclic ring of ring Q preferably has only one nitrogen atom as a heteroatom constituting the ring. In addition, ring Q is preferably a non-aromatic nitrogen-containing heterocyclic ring, and in addition to the carbon-carbon bond of the benzene ring contraction, it is more preferred that carbon atoms are bonded to nitrogen atoms or carbon atoms through single bonds to form a ring.

[0125] R 19 The alkyl group is preferably a branched alkyl group. This can improve the solubility of the carbon oxide compound in the resin. 19 The branched alkyl group is not particularly limited as long as the number of carbon atoms is 3 or more. Examples of the branched alkyl group include isopropyl, isobutyl, tert-butyl, isopentyl, sec-pentyl, 1-ethylpropyl, neopentyl, tert-pentyl, isohexyl, sec-hexyl, 2-methylpentyl, 3-methylpentyl, tert-hexyl, and 2-ethylhexyl. The upper limit of the number of carbon atoms of the branched alkyl group (excluding the number of carbon atoms of the substituent) is not particularly limited, but is preferably 20 or less, more preferably 12 or less, further preferably 8 or less, and further 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 halide 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.

[0126] The nitrogen-containing heterocyclic ring of ring Q, except R 19 That is, in the case of the nitrogen-containing heterocyclic ring of ring Q, a substituent may be 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 alkyl, alkoxy, aryl, aralkyl, halo, haloalkyl, and hydroxyl, and more preferably alkyl, aryl, aralkyl, and haloalkyl. In this case, the number of carbon atoms of the alkyl, alkoxy, and haloalkyl is preferably 1 to 8, more preferably 1 to 5, and further preferably 1 to 3, the number of carbon atoms of the aryl is preferably 6 to 12, more preferably 6 to 10, and the number of carbon atoms of the aralkyl is preferably 7 to 13, and more preferably 7 to 11. The alkyl group may be straight-chain or branched. It should be noted that ring Q, except for R 19 In addition, it may not have a substituent.

[0127] The number of ring members of ring Q is preferably 5 or more, more preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and further preferably 8 or less. In particular, when the number of ring members of ring Q is 6 or more, the absorption peak having maximum absorption in the red to near-infrared region can be made particularly sharp, and the inclination of the inclined portion on the short-wavelength side of the absorption peak can be made absorptive. Therefore, the boundary between the transmission band and the absorption band is clearly formed, and light in the band corresponding to the absorption peak can be selectively cut off.

[0128] In formula (5), R 14 Preferably, the formula is: -NH-C(=O)-R a3 The amide group shown in FIG. a3 Preferably, it is an alkyl group having 3 or more carbon atoms which may have a substituent. Thus, the solubility of the carbon oxide compound in the resin and the organic solvent can be improved. Therefore, the carbon oxide compound can be contained in the resin composition at a high concentration, and in the case where the resin composition is used to form an optical filter, even if the thickness is formed to be relatively thin, the carbon oxide compound can preferably absorb light in the red to near-infrared region.

[0129] From the perspective of improving solubility in resins and organic solvents, R a3 The number of carbon atoms of the alkyl group (excluding the number of carbon atoms of the substituent) is preferably 6 or more, more preferably 7 or more, and further preferably 8 or more. a3 The upper limit of the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 30 or less, more preferably 25 or less, further preferably 20 or less, and further preferably 18 or less. a3 When the alkyl group has a substituent, the substituent includes an aryl group, a heteroaryl group, a halide group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a sulfo group, and the like. a3 The alkyl group preferably has no substituent.

[0130] R a3 The alkyl group is preferably straight-chain. a3 If the carbon oxide compound is a straight-chain alkyl group, the heat resistance of the carbon oxide compound tends to be improved, and the decomposition of the carbon oxide compound is easily suppressed when the carbon oxide compound is added to a resin for heat curing. Therefore, even in the heated resin cured product, the carbon oxide compound can be present in a high concentration. It should be noted that in formula (5), R 15 and R 18 It is preferably not an amide group, and is, for example, preferably a hydrogen atom or an alkyl group.

[0131] In the squaryl acid compound and the crotonyl acid compound having the groups represented by formula (4) and formula (5), the benzene rings on both sides of the squaryl acid skeleton or the crotonyl acid skeleton can be linked by a linking group. As such a compound, for example, the squaryl acid compound disclosed in Japanese Patent Application Laid-Open No. 2015-176046 is shown.

[0132] As the pigment of component (D), it is also preferred to use a compound having a styrene structure (hereinafter referred to as a "styrene-based compound"). In this case, when the resin composition is subjected to a heat curing reaction at a high temperature, the decomposition of the pigment can also be suppressed. As the styrene-based compound, it is preferred 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 band within the range of a wavelength of 350nm to 395nm, and on the long wavelength side of the absorption band, the boundary between the absorption band and the transmission band can be clearly formed. Therefore, if the resin composition contains such a styrene-based compound, the resin cured product obtained by curing the resin composition can be preferably used for filters that cut off light in the purple to ultraviolet region, etc.

[0133] [Chemical formula 9]

[0134]

[0135] In the above formula (6), R 21 represents a cyano group, an acyl group, a carboxylate group or an amide group, R 22 represents a hydrogen atom, a cyano group, an acyl group, a carboxylate group, an amide group, a hydrocarbon group or a heteroaryl group, and in R 21 and R 22 When all R 21 With R 22 Can 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. 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 greater than 2, and a plurality of groups bonded to L may be the same or different from each other. In formula (6), R 21 (or R 22 ) relative to R 23 It can be located in the cis position or the trans position.

[0136] As R 21 and R 22The acyl group (alkanoyl group) may include formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, eicosanoyl, etc. A portion of the hydrogen atoms of the acyl group may be substituted by an aryl group, an alkoxy group, a halide group, a hydroxyl group, etc. The alkyl group in the acyl group may be linear or branched. The number of carbon atoms of the acyl group (excluding the number of carbon atoms of the substituent) is preferably 2 to 21, more preferably 2 to 11, and further preferably 2 to 6.

[0137] As R 21 and R 22 The carboxylate group may be of the formula: -C(=O)-OR b1 As shown, R b1 Specific examples of alkyl, aryl and aralkyl groups can be referred to the above R 11 ~R 18 Description of these groups.

[0138] As R 21 and R 22 The amide group may be of the formula: -C(=O)-NR b2 R b3 The amide group shown, wherein R b2 is a hydrogen atom or an alkyl group, R b3 is an alkyl group, an acyl group, an aryl group or an aralkyl group. b2 and R b3 For specific examples of alkyl, aryl, and aralkyl groups, refer to the above R 11 ~R 18 Description of these groups, R b3 For specific examples of the acyl group, refer to the above R 21 and R 22 Description of the acyl group.

[0139] As R 21 and R 22 are all acyl groups, and when they are linked to form a ring, R 21 and R 22 The group formed is shown in the formula: -C(=O)-R b4 -C(=O)-. 21 and R 22 are carboxylate groups, and when they are linked to form a ring, R 21 and R 22 The group formed is shown in the formula: -C(=O)-OR b5 -OC(=O)-. 21 and R 22are amide groups, and when they are linked to form a ring, R 21 and R 22 The group formed is shown in the formula: -C(=O)-NR b6 -R b7 -NR b8 -C(=O)-. In these formulas, R b4 , R b5 and R b7 Each independently represents a linear or branched alkylene group, R b6 and R b8 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 formulae are bonded to the carbon atoms of the ethylene double bond of formula (6). b4 , R b5 and R b7 Some of the hydrogen atoms in the alkylene group may be substituted by an aryl group, an alkoxy group, a cyano group, a halide group, a hydroxyl group, a nitro group, or the like. b4 , R b5 and R b7 The number of carbon atoms of the alkylene group (excluding the number of carbon atoms of the substituent) is preferably 2 to 10, more preferably 3 to 8. b6 and R b8 The hydrocarbon group may be an alkyl group, an aryl group or an aralkyl group. Specific examples of these groups can refer to the above R 11 ~R 18 Description of the alkyl group, aryl group and aralkyl group.

[0140] As R 22 Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups (aryl groups). Aliphatic hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples of aliphatic saturated hydrocarbon groups are shown in the R 11 ~R 18 Specific examples of the aliphatic unsaturated hydrocarbon group include the R 11 ~R 18 A group in which a portion of the carbon-carbon single bonds of an alkyl group are replaced by double bonds or triple bonds. Specific examples of aromatic hydrocarbon groups (aryl groups) can be found in the R 11 ~R 18 Description of the aromatic group.

[0141] R 22 Specific examples of heteroaryl groups can refer to the above R 11 ~R 18It should be noted that the heteroaryl group preferably has a carbon atom bonded to the carbon atom of the ethylene double bond of formula (6), and more preferably has a carbon atom adjacent to the heteroatom bonded to the carbon atom of the ethylene double bond of formula (6), thereby facilitating the synthesis of styrene-based compounds.

[0142] R in formula (6) 23 represents a hydrogen atom or an alkyl group. For specific examples of the alkyl group, refer to the above R 11 ~R 18 Description of the alkyl group. 23 The alkyl group preferably has 1 to 3 carbon atoms, and more preferably has 1 to 2 carbon atoms. 23 , a hydrogen atom is particularly preferred.

[0143] R in formula (6) 24 For details of the organic groups and polar functional groups, please refer to the above R 11 ~R 18 Description of the organic group and polar functional group. 24 , preferably one or more selected from hydrogen atom, alkyl group, alkoxy group, alkylthio group, aralkyl group, aryloxy group and arylthio group, preferably hydrogen atom or alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 to 3. Among them, the four R bonded to the benzene ring of formula (6) 24 Among them, preferably two or more are hydrogen atoms, more preferably three or more are hydrogen atoms, and particularly preferably all four are hydrogen atoms.

[0144] In formula (6), X represents a sulfur atom or an oxygen atom. 21 ~R 23 The ethylene structure of X may be bonded at the ortho position, at the meta position, or at the para position. It should be noted that, from the perspective of the ease of manufacturing the styrene-based compound, X is preferably bonded at the para position relative to the ethylene structure. In addition, X is preferably a sulfur atom.

[0145] In formula (6), L represents a divalent or higher linking group. The linking group L may be a single divalent, trivalent, tetravalent, pentavalent or hexavalent organic group for linking groups, or an n-valent group formed by bonding these divalent, trivalent, tetravalent, pentavalent or hexavalent organic groups for linking groups.

[0146] The divalent organic group for linking groups includes alkylene, cycloalkylene, arylene, heteroarylene, -O-, -CO-, -S-, -SO-, SO2-, -NH-, etc. The alkylene, cycloalkylene, arylene, heteroarylene may have a hydroxyl group and / or a thiol group.

[0147] 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 methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene and octadecylene.

[0148] 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 cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,4-diyl.

[0149] Examples of the arylene group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 2,4-naphthylene, 2,5-naphthylene, 2,6-naphthylene, and 2,7-naphthylene, which have 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.

[0150] Examples of the heteroarylene group include a heteroarylene group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms, such as furan-2,3-diyl, furan-2,4-diyl, furan-2,5-diyl, and furan-3,4-diyl.

[0151] As the divalent organic group for the linking group, the above-mentioned alkylene group, the above-mentioned cycloalkylene group, the above-mentioned arylene group, etc. are preferable.

[0152] When the divalent linking group L is a divalent group formed by bonding an organic group for a linking group, examples thereof include: a group in which an alkylene group, -O-, and an alkylene group are bonded in sequence; a group in which an alkylene group, -S-, and an alkylene group are bonded in sequence; a group in which an alkylene group, -CO, -O-, and an alkylene group are bonded in sequence; a group in which an alkylene group, -CO-, -NH-, and an alkylene group are bonded in sequence; a group in which an alkylene group, -O-, an alkylene group, -O-, and an alkylene group are bonded in sequence; a group in which an arylene group, an alkylene group, and an arylene group are bonded in sequence, etc.

[0153] Examples of the group formed by sequentially bonding an alkylene group, -O-, and an alkylene group include a group formed by sequentially bonding a methylene group, -O-, and a methylene group; a group formed by sequentially bonding an ethylene group, -O-, and an ethylene group; a group formed by sequentially bonding a propylene group, -O-, and a propylene group; and the like, which are diC1-4 alkyl ether residues having a bonding bond in the alkyl portion.

[0154] Examples of the group in which an alkylene group, -S-, and an alkylene group are bonded in sequence include a group in which a methylene group, -S-, and a methylene group are bonded in sequence; a group in which an ethylene group, -S-, and an ethylene group are bonded in sequence; a group in which a propylene group, -S-, and a propylene group are bonded in sequence, and the like, have a diC1-4 alkylthiol residue having a bond in the alkyl portion.

[0155] Examples of the group formed by sequentially bonding an alkylene group, -CO, -O-, and an alkylene group include: a group formed by sequentially bonding a methylene group, -CO-, -O-, and a methylene group; a group formed by sequentially bonding a methylene group, -CO-, -O-, and an ethylene group; a group formed by sequentially bonding an ethylene group, -CO-, -O-, and a methylene group; a group formed by sequentially bonding an ethylene group, -CO-, -O-, and an ethylene group, and the like, which are C2-4 alkyl acid C1-4 alkyl ester residues having a bonding bond in the alkyl portion.

[0156] Examples of the group in which an alkylene group, -CO-, -NH-, and an alkylene group are bonded in sequence include a group in which a methylene group, -CO-, -NH-, and a methylene group are bonded in sequence; a group in which a methylene group, -CO-, -NH-, and an ethylene group are bonded in sequence; a group in which an ethylene group, -CO-, -NH-, and a methylene group are bonded in sequence; a group in which an ethylene group, -CO-, -NH-, and an ethylene group are bonded in sequence, and the like are C2-4 alkyl acid C1-4 alkylamide residues having a bond in the alkyl portion.

[0157] Examples of the group formed by sequentially bonding alkylene, -O-, alkylene, -O-, alkylene include a group formed by sequentially bonding methylene, -O-, methylene, -O-, methylene; a group formed by sequentially bonding ethylene, -O-, ethylene, -O-, ethylene; and the like, which are C1-4 alkylene glycol di-C1-4 alkyl ether residues having a bonding bond in the alkyl part.

[0158] Examples of the group formed by sequentially bonding an arylene group, an alkylene group, and an arylene group include: a group formed by sequentially bonding a 1,4-phenylene group, a methylene group, and a 1,4-phenylene group; a group formed by sequentially bonding a 1,4-phenylene group, an ethylene group, and a 1,4-phenylene group; a group formed by sequentially bonding a 1,4-phenylene group, a propylene group, and a 1,4-phenylene group; a group formed by sequentially bonding a 1,4-phenylene group, a n-propane-2,2-diyl group, and a 1,4-phenylene group; and the like, which are diphenyl C1-6 alkane residues having a bond to a benzene ring carbon.

[0159] The trivalent organic group for the linking group includes a methine group (-C<), -N<, a trivalent benzene ring, a trivalent naphthalene ring, etc. which may have an alkyl group. As the alkyl group possessed by the methine group, refer to the above R 11 ~R 18 The description of the alkyl group of the present invention. Examples of the trivalent benzene ring include benzene-1,2,3-triyl and benzene-1,3,5-triyl. Examples of the trivalent naphthalene ring include naphthalene-1,2,3-triyl and naphthalene-1,3,6-triyl. A trivalent benzene ring is preferably used as the trivalent organic group for the linking group.

[0160] When the trivalent linking group L is a trivalent group formed by bonding an organic group for a linking group, examples thereof include: a C3-20 alkane triyl group such as a group formed by bonding a methylene group, a methine group, and a methylene group in sequence (n-propane-1,2,3-triyl), a group formed by bonding an ethylene group, a methine group, and an ethylene group in sequence (n-hexane-1,3,6-triyl); a cyclo C3-10 alkane triyl group such as a trivalent group formed by bonding three methine groups to one or more methylene groups as needed to form a ring; a group formed by bonding >C< having a hydrocarbon group to three of the above-mentioned divalent organic groups for a linking group, for example, a group formed by bonding >C< having a C1-4 hydrocarbon group to three of the above-mentioned C2-4 alkyl acid C1-4 alkyl ester groups (divalent groups); and the like.

[0161] The tetravalent organic group for linking groups includes >C<, a tetravalent benzene ring, a tetravalent naphthalene ring, etc. Examples of the tetravalent benzene ring include benzene-1,2,3,4-tetrayl and benzene-1,2,4,5-tetrayl. Examples of the tetravalent naphthalene ring include naphthalene-1,2,3,4-tetrayl, naphthalene-2,3,6,7-tetrayl and naphthalene-1,4,5,6-tetrayl.

[0162] When the tetravalent linking group L is a tetravalent group formed by bonding an organic group for a linking group, examples thereof include: a C4-20 alkane tetrayl group such as a group in which methylene, methine, methine, and methylene are bonded in sequence (n-butane-1,2,3,4-tetrayl), a group in which ethylene, methine, methine, and ethylene are bonded in sequence (n-hexane-1,3,4,6-tetrayl); a group in which a >C< having an alkyl group is bonded to four of the divalent organic groups for a linking group, for example, a group in which a >C< having a C1-4 alkyl group is bonded to four of the C2-4 alkyl acid C1-4 alkyl ester residues (divalent group); etc.

[0163] The pentavalent organic group for linking groups includes a pentavalent benzene ring, a pentavalent naphthalene ring, etc. Examples of the pentavalent benzene ring include benzene-1,2,3,4,5-pentayl, etc. Examples of the pentavalent naphthalene ring include naphthalene-1,2,3,4,5-pentayl, naphthalene-1,2,3,5,6-pentayl, and naphthalene-1,2,3,6,7-pentayl.

[0164] The hexavalent organic group for the linking group includes a hexavalent benzene ring, a hexavalent naphthalene ring, etc. Examples of the hexavalent naphthalene ring include naphthalene-1,2,3,4,5,6-hexayl and naphthalene-1,2,3,5,6,7-hexayl.

[0165] When the hexavalent linking group L is a hexavalent group formed by bonding an organic group for a linking group, examples thereof include a group formed by bonding three of the divalent organic groups for a linking group in sequence to form >C<, an alkylene group, -O-, an alkylene group, and a group formed by bonding three of the divalent organic groups for a linking group to form >C<, etc. This group may be, for example, a group formed by bonding three of the C2-4 alkyl acid C1-4 alkyl ester residues (divalent groups) in sequence to form >C<, a methylene group, -O-, a methylene group, and a group formed by bonding three of the C2-4 alkyl acid C1-4 alkyl ester residues (divalent groups), etc.

[0166] The divalent, trivalent, tetravalent, pentavalent or hexavalent organic group for the linking group may have a substituent such as a halide, a cyano group, an amino group, a nitro group, etc. as required. As the organic group for the 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, etc. are 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 5,6-dicyanobenzene-1,2,3,4-tetrayl and 3,6-dicyanobenzene-1,2,4,5-tetrayl.

[0167] From the viewpoint of improving the heat resistance of the styrene-based compound, the linking group L is preferably an alkylene group in which a part of the hydrogen atoms can be substituted by a hydroxyl group and / or a thiol group, a cycloalkylene group in which a part of the hydrogen atoms can be substituted by a hydroxyl group and / or a thiol group, an arylene group in which a part of the hydrogen atoms can be substituted by a hydroxyl group and / or a thiol group, -O-, -S-, and a linking group formed by combining these groups (wherein the ether bond and the thioether bond are discontinuous). The number of continuous carbon atoms of the alkylene group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The number of carbon atoms of the cycloalkylene group is preferably 4 or more, more preferably 5 or more, and preferably 10 or less, more preferably 8 or less. The number of carbon atoms of the arylene group is preferably 5 or more, more preferably 6 or more, and preferably 10 or less, more preferably 8 or less.

[0168] As the styrene compound, the styrene compound represented by the following formula (7) is particularly preferred. Such a styrene compound has, for example, a peak with maximum absorption in the wavelength range of 300 nm to 420 nm, can effectively absorb light in the ultraviolet (UVA) to violet region, has excellent stability, and is easy to manufacture. In the following formula (7), R 21a and R 21b Please refer to the above R 21 Description, R 22a and R 22b Please refer to the above R 22 Description, R 23a and R 23b Please refer to the above R 23 Description, X a and X b For the description of , refer to the description of X above.

[0169] [Chemical formula 10]

[0170]

[0171] For details of the styrene compounds represented by formula (6) and formula (7), reference can be made to the description of International Publication No. 2019 / 009093.

[0172] The resin composition preferably further contains at least one selected from a silane coupling agent, a hydrolyzate of a silane coupling agent, and a hydrolysis-condensation product of a silane coupling agent as component (E). When the resin composition contains component (E), the adhesion of the resin layer to the substrate can be improved when the resin composition is applied to a substrate and cured to form a resin layer. The resin layer laminated substrate formed by such a resin composition can be preferably used for an optical filter. Hereinafter, a silane coupling agent, a hydrolyzate of a silane coupling agent, and a hydrolysis-condensation product of a silane coupling agent are sometimes collectively referred to as a "specific silane compound".

[0173] The silane coupling agent preferably has an epoxy-containing group, an amino-containing group, a mercapto-containing group or a polymerizable double bond-containing group, and preferably uses a compound having such a functional group and an alkoxysilyl group. The silane coupling agent may contain only one or more of the above functional groups, and may contain only one or more alkoxysilyl groups.

[0174] When the silane coupling agent contains only one alkoxysilyl group, it is preferred to use an alkoxysilane represented by the following formula (8) as the silane coupling agent. Therefore, it is preferred to use at least one selected from the group consisting of a silane coupling agent represented by the following formula (8), a hydrolyzate thereof, and a hydrolysis-condensate thereof as the component (E).

[0175] S i 31 k R 32 m (OR 33 ) n (OH) 4-k-m-n (8)

[0176] In formula (8), R 31 represents an epoxy-containing group, an amino-containing group, a mercapto-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, a plurality of R 31 They may be the same or different from each other. When m is 2, multiple R 32 They may be the same or different from each other. When n is 2 or more, multiple OR 33 They may be the same or different from each other. 31 , R 32 , OR 33 and OH are groups directly bonded to Si, respectively.

[0177] R 31 The epoxy group-containing group is not particularly limited as long as it is a group containing an epoxy group, and examples thereof include a glycidyloxy group-containing group and a group containing an oxide cycloolefin (alicyclic epoxy group). The glycidyloxy group and the oxide cycloolefin 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 There is only one epoxy group in the 31 Examples of the epoxy-containing group include a glycidyloxy group, a 3-glycidyloxypropyl group, an 8-(glycidyloxy)-n-octyl group, a 3,4-epoxycyclohexyl group, and a 2-(3,4-epoxycyclohexyl)ethyl group.

[0178] R31 The amino group is not particularly limited as long as it is a group having an amino group, and may be a group having a primary amino group, a group having a secondary amino group, a group having a tertiary amino group, or a group having multiple amino groups (e.g., 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 The amino-containing group includes 3-aminopropyl, 3-(2-aminoethyl)aminopropyl, 3-(6-aminohexyl)aminopropyl, 3-(N,N-dimethylamino)propyl, N-phenylaminomethyl, N-phenyl-3-aminopropyl, N-benzyl-3-aminopropyl, N-cyclohexylaminomethyl and the like.

[0179] As R 31 The mercapto group-containing group is not particularly limited as long as it is a group having a mercapto group, and mercaptoalkyl is preferred. The alkyl group in the mercaptoalkyl group may be linear or branched, and the number of carbon atoms in the mercaptoalkyl group is preferably 1 to 12, more preferably 1 to 10, and further preferably 1 to 6. 31 contains only one thiol group. 31 Examples of the mercapto group-containing group include 3-mercaptopropyl, 2-mercaptoethyl, 2-mercaptopropyl, and 6-mercaptohexyl.

[0180] As R 31 The group containing a polymerizable double bond is not particularly limited as long as it is a group having a polymerizable double bond. Examples of the polymerizable double bond group include vinyl, styryl, (meth)acryloyl, etc. 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 group containing a polymerizable double bond include a vinyl group, a 2-propylene group, a styryl group, and a 3-(meth)acryloyloxypropyl group.

[0181] It should be noted that from the viewpoint of improving the adhesion of the resin layer to the substrate, R 31 The epoxy group, amino group, mercapto group or polymerizable double bond group contained is preferably not too far away from the silicon atom, and these groups are preferably bonded to the silicon atom directly or through an alkylene group having 1 to 6 carbon atoms.

[0182] R 32 and R 33 The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. 32 , preferably, methyl, ethyl, n-propyl, and isopropyl are mentioned. 33, preferably, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are mentioned.

[0183] In formula (8), k is preferably 1 or 2, more preferably 1, which makes it easy to improve the adhesion of the resin layer to the substrate. In addition, m is preferably 0 or 1, more preferably 0, and n is preferably 2 or 3.

[0184] In the case where the silane coupling agent contains multiple alkoxysilyl groups, a polymeric multifunctional silane coupling agent can be used as the silane coupling agent. The polymeric multifunctional silane coupling agent has a structure in which a group and a group containing an alkoxysilyl group are bonded to an organic polymer chain, and can contain multiple alkoxysilyl groups in one molecule, and contains multiple epoxy groups, amino groups, mercapto groups, polymerizable double bond groups and other functional groups. It should be noted that polysiloxane is not included in the organic chain of the polymeric multifunctional silane coupling agent. By constituting in this way, the polymeric multifunctional silane coupling agent can form a large number of reaction points with the resin and the substrate, thereby improving the adhesion of the resin layer to the substrate.

[0185] The hydrolyzate of the silane coupling agent used as the component (E) can be obtained by converting the alkoxysilyl group contained in the silane coupling agent into a silanol group by hydrolysis. In addition, the hydrolysis condensate of the silane coupling agent can be obtained by dehydrating and condensing the silanol group contained in the hydrolyzate of the silane coupling agent to form a siloxane bond (-Si-O-Si-). Usually, if the silane coupling agent is hydrolyzed, the hydrolyzate of the silane coupling agent is obtained, and the dehydration condensation reaction of the silanol group contained in the hydrolyzate also occurs, thereby easily obtaining the hydrolysis condensate of the silane coupling agent. The hydrolysis condensate of the silane coupling agent can be a dehydration condensate of the hydrolyzate of the same silane coupling agent, or a dehydration condensate of the hydrolyzate of different silane coupling agents.

[0186] As the component (E), it is preferred to use at least one selected from the group consisting of an epoxy-containing silane coupling agent, a hydrolyzate thereof, and a hydrolysis-condensation product thereof. 31 An epoxy group-containing group is preferred. This makes it easy to improve the adhesion between the resin layer formed by curing the alicyclic epoxy resin and the substrate.

[0187] The resin composition may contain only one (E) component, or may contain two or more. It should be noted that, in the resin composition, as the (E) component, it is preferred to contain at least a hydrolyzate and / or a hydrolysis-condensation product of a silane coupling agent, thereby improving the adhesion of the resin layer to the substrate, especially the adhesion after boiling water as a harsh condition. It is more preferred that the (E) component contains at least a hydrolyzate or a hydrolysis-condensation product of an epoxy-containing silane coupling agent.

[0188] It is more preferred that the hydrolysis condensate of the silane coupling agent is included in the (E) component. As the dehydrated condensate in this case, it is preferred that at least a dimer or trimer of an alkoxysilane (e.g., an alkoxysilane shown in the above formula (8)) is included. For example, when the weight average molecular weight of a specific silane compound used as the (E) component is measured, it is preferably less than the molecular weight of a pentamer (wherein all alkoxy groups become hydroxyl groups), and more preferably less than the molecular weight of a tetramer. As a specific value of the weight average molecular weight, for example, it is preferably more than 300, and preferably less than 1000, more preferably less than 800, and further preferably less than 600.

[0189] The content of (E) component in resin combination, in the solid component 100 mass parts of resin combination, is preferably more than 0.1 mass parts, more preferably more than 0.5 mass parts, more preferably more than 1 mass parts, and, preferably less than 20 mass parts, more preferably less than 10 mass parts, more preferably less than 5 mass parts. If (E) component is included with the content more than 0.1 mass parts in the solid component 100 mass parts of resin combination, then when using resin combination to form resin layer on substrate, it is easy to improve the adhesion of resin layer to substrate. On the other hand, even if excessive (E) component is included in resin combination, the effect of improving the adhesion of resin layer to substrate is not too likely to be further improved, therefore in the solid component 100 mass parts of resin combination, the content of (E) component is preferably less than 20 mass parts. The content of the component (E) based on the alicyclic epoxy resin as the component (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further 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 further preferably 10 parts by mass or less, relative to 100 parts by mass of the alicyclic epoxy resin as the component (A).

[0190] The resin composition may contain a solvent. For example, when the resin composition is a paint-formed resin composition, the resin composition can be easily applied by containing a solvent.

[0191] The solvent may be a solvent that functions to dissolve the components contained in the resin composition, or a solvent that functions 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, etc.); aromatic hydrocarbons such as toluene, xylene, and trimethylbenzene; aliphatic hydrocarbons such as cyclohexane and heptane; ethers such as tetrahydrofuran, dioxane, diethyl ether, and dibutyl ether, etc. These solvents may be used alone or in combination of two or more.

[0192] As the content of the solvent, in 100 parts by mass of the resin composition, for example, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, further preferably 70 parts by mass or more, and, preferably less than 100 parts by mass, more preferably less than 95 parts by mass. By adjusting the content of the solvent within such a range, it is easy to obtain a resin composition with high concentrations of each component.

[0193] The resin composition may contain a surface conditioning agent, whereby, when the resin composition is cured to form a resin layer, defects in appearance such as streaks and depressions on the resin layer can be suppressed. The type of the surface conditioning agent is not particularly limited, and siloxane-based surfactants, acetylene glycol-based surfactants, fluorine-based surfactants, acrylic leveling agents, etc. can be used. As the surface conditioning agent, for example, BYK (registered trademark) series manufactured by BYK-Chemie, KF series manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be used.

[0194] The resin composition can include a dispersant, which can stabilize the dispersibility of the resin composition and suppress re-agglomeration. The type of the dispersion medium is not particularly limited, and the EFKA series of EFKA Additives, BYK (registered trademark) series of BYK-Chemie, Solsperse (registered trademark) series of Lubrizol, DISPARLON (registered trademark) series of Kusunomoto Chemical, AJISPER (registered trademark) series of Ajinomoto Fine-Techno, KP series of Shin-Etsu Chemical, POLYFLOW series of Kyoei Chemical, MEGAFAC (registered trademark) series of DIC, DISPERSANT series of San Nopco, etc. can be used.

[0195] The resin composition may contain various additives such as a plasticizer, a surfactant, a viscosity modifier, a defoaming agent, an antiseptic, a resistivity modifier, a stability enhancer such as polythiol, and an adhesion enhancer as needed.

[0196] The resin composition can be cured to form a cured resin. The resin composition is preferably heated to promote the curing reaction. The heating temperature for curing the resin composition is, for example, preferably 130° C. or more, more preferably 150° C. or more, further preferably 170° C. or more, and preferably 300° C. or less, more preferably 280° C. or less, further preferably 250° C. or less.

[0197] The resin composition can 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, powdery, block-like, particle agglomerate-like, spherical, ellipsoidal, lens-like, cubic, columnar, rod-like, conical, cylindrical, needle-like, fibrous, hollow fiber-like, porous, etc.

[0198] The resin composition can be a resin composition coated by spin coating, solvent casting, roller coating, spray coating, rod coating, dip coating, slit coating, screen printing, flexographic printing, inkjet, etc. In this case, by applying the liquid or pasty resin composition on a substrate (such as a resin plate, film, glass plate, etc.), a film-like resin cured product with a thickness of less than 200 μm and a sheet-like resin cured product with a thickness of more than 200 μm can be obtained. The resin cured product thus obtained can be processed integrally with the substrate.

[0199] The resin composition of the present invention can be preferably used as a resin composition for forming optical filters used in various applications such as optical devices, display devices, mechanical parts, and electrical / electronic components. The resin composition can be preferably used for optical filters such as near-infrared cutoff filters and ultraviolet cutoff filters. For example, the optical filter can be formed by curing the resin composition to form a resin molded body, or by forming a resin layer on a substrate.

[0200] The optical filter preferably comprises a substrate and a resin layer formed from the resin composition of the present invention, and the resin layer is formed on the substrate. Thus, an optical filter in which the substrate and the resin layer are laminated and integrated is obtained. The resin layer can be formed by curing the resin composition of the present invention. The resin layer can be provided on only one side of the substrate or on both sides.

[0201] The thickness of the resin layer is not particularly limited. From the perspective of ensuring the desired light selective transmission performance, it is preferably 0.5 μm or more, and 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 500 μm or less, 200 μm or less, or 50 μm or less. When the coated resin composition is applied to the substrate by spin coating, the thickness of the resin layer can be formed to be thinner. From the perspective of forming a thinner filter, the resin layer is preferably 20 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, further preferably 3 μm or less, and particularly preferably 2 μm or less.

[0202] As the substrate, a transparent substrate such as a resin plate, a resin film, or a glass plate is preferably used. Among them, as the substrate, a glass substrate is preferably used. By providing a resin layer on the glass substrate, a filter having excellent heat resistance can be obtained. The filter thus obtained can be mounted on an electronic component, for example, by reflow soldering, and the miniaturization of the electronic component can be sought. In addition, the glass substrate is not prone to cracking or warping even when exposed to high temperatures, so it is easy to ensure the close adhesion with the resin layer.

[0203] The glass used for the glass substrate may be silicate glass, borosilicate glass, boric acid glass, phosphate glass, or other known 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. 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 exist in the glass. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application.

[0204] The thickness of the substrate is preferably 0.05 mm or more, more preferably 0.1 mm or more, for example, from the perspective of ensuring strength, and is preferably 0.4 mm or less, more preferably 0.3 mm or less, from the perspective of thinning.

[0205] On the resin layer formed by the resin composition of the present invention, a protective layer composed of a resin that is the same as or different from the resin layer can be laminated as a second resin layer. By providing the protective layer, the durability (decomposition resistance) of each component contained in the resin layer can be improved. The protective layer can be provided on only one side of the resin layer, or on both sides.

[0206] The optical filter may have a layer (anti-reflection film) with anti-reflection and anti-glare properties to reduce the reflection of fluorescent lamps, etc., a layer with anti-damage performance, a transparent substrate with other functions, etc. The optical filter may also have an ultraviolet reflection film and a near-infrared reflection film on the resin layer. The ultraviolet reflection film and the near-infrared reflection film are preferably arranged closer to the light incident side than the resin layer. If an ultraviolet reflection film and a near-infrared reflection film are arranged on the optical filter, ultraviolet rays and near-infrared rays can be further cut off from the transmitted light of the optical filter. The ultraviolet reflection film and the near-infrared reflection film may also be a film with ultraviolet reflection function and near-infrared reflection function.

[0207] The ultraviolet reflection film, the near infrared reflection film, and the anti-reflection film (anti-visible light reflection film) can be composed of a dielectric multilayer film formed by alternately stacking a high refractive index material layer and a low refractive index material layer. Therefore, in the case of imparting such a function to the optical filter, the optical filter preferably has a dielectric multilayer film. As a material constituting the high refractive index material layer, a material with a refractive index of 1.7 or more can be used, and a material with a refractive index range of 1.7 to 2.5 is usually selected. As a material constituting the high refractive index material layer, for example, oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide can be listed; nitrides such as silicon nitride; mixtures of the above oxides and nitrides, materials doped with metals such as aluminum and copper, and carbon (for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. As a material constituting the low refractive index material layer, a material with a refractive index of 1.6 or less can be used, and a material with a refractive index range of 1.2 to 1.6 is usually selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium hexafluoroaluminate.

[0208] The optical filter may further include an aluminum vapor-deposited film, a precious metal thin film, a resin film in which metal oxide fine particles having indium oxide as a main component and containing a small amount of tin oxide are dispersed, or the like.

[0209] The thickness of the filter is preferably 1 mm or less, for example. This can fully meet the requirements for miniaturization of imaging elements, for example. The thickness of the filter is more preferably 500 μm or less, further preferably 300 μm or less, further preferably 150 μm or less, and preferably 30 μm or more, further preferably 50 μm or more.

[0210] The optical filter can be used as one of the components of sensors such as image sensors (camera elements), illumination sensors, and proximity sensors. For example, image sensors are used as electronic components that convert the light of the subject into electrical signals and output them, and examples thereof include: CCD (Charge Coupled Device), CMOS (Complementary Metal-Oxide Semiconductor), etc. Image sensors can be used in mobile phone cameras, digital cameras, car cameras, surveillance cameras, display elements (LEDs, etc.), etc. The sensor includes one or more of the above-mentioned filters, and may further have other filters and lenses as needed.

[0211] This application claims the benefit of priority based on Japanese Patent Application No. 2022-118243 filed on Jul. 25, 2022. The entire contents of the specification of Japanese Patent Application No. 2022-118243 filed on Jul. 25, 2022 are incorporated herein by reference.

[0212] Example

[0213] 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 implemented with appropriate modifications within the scope of the above and below. All of these are included in the technical scope of the present invention.

[0214] (1) Synthesis of pigments

[0215] (1-1) Synthesis Example 1: Synthesis of Pigment A

[0216] In a 300 mL four-necked flask, 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 were added, and 4.37 g (0.0606 mol) of isobutylaldehyde was added dropwise over 10 minutes while stirring with a stirring blade under a nitrogen flow (10 mL / min). After the addition was completed, the obtained reaction solution was added to 300 g of water and neutralized with hydrochloric acid. 300 g of ethyl acetate was added thereto, and the organic phase was extracted with a separatory funnel, and magnesium sulfate (anhydrous) was added to the extracted organic phase for dehydration. The solid matter (inorganic component) was separated by filtration from the organic phase, and the solvent was concentrated using an evaporator, and then appropriately subjected to silica gel column chromatography (developing solvent: chloroform), concentrated, and vacuum dried to obtain 1-isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline.

[0217] Next, add 2.8 g (0.012 mol) of 1-isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline and 9.0 g of concentrated hydrochloric acid (hydrochloric acid concentration 36 wt%), and add a solution of 9.1 g of tin chloride dihydrate and 9.1 g of concentrated hydrochloric acid (hydrochloric acid concentration 36 wt%) little by little under nitrogen flow (5 mL / min) while stirring with a magnetic stirrer while paying attention to the heat of reaction. After the addition, stir at room temperature for about 3 hours. Then, add the obtained reaction solution to a beaker containing 100 g of pure water and 100 g of ethyl acetate while stirring. Add potassium hydroxide solution little by little, stir for a while when the pH of the aqueous solution reaches about 10, then extract the organic phase with a separatory funnel, and add magnesium sulfate (anhydrous) to the extracted organic phase for dehydration. The solid matter (inorganic component) was separated by filtration from the organic phase, and the solvent was concentrated using an evaporator, and then appropriately subjected to silica gel column chromatography (developing solvent: chloroform), concentrated, and vacuum dried to obtain 1-isobutyl-7-amino-1,2,3,4-tetrahydroquinoline.

[0218] Next, 2.86 g (0.0143 mol) of 1-isobutyl-7-amino-1,2,3,4-tetrahydroquinoline and 50 g of super dehydrated chloroform were added to a 100 mL three-necked flask, and 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 with a magnetic stirrer under nitrogen flow (5 mL / min), and the mixture was reacted at room temperature for 12 hours. After the reaction was completed, the obtained reaction solution was added to ion exchange water and extracted with ethyl acetate. Magnesium sulfate (anhydrous) was added to the extracted organic phase for dehydration. After filtering and separating the solid matter (inorganic component) from the organic phase, the solvent was concentrated using an evaporator, and then silica gel column chromatography (developing solvent: chloroform) was appropriately used, and concentrated and vacuum dried to obtain 1-isobutyl-7-(N-palmitoylamino)-1,2,3,4-tetrahydroquinoline.

[0219] Next, 1-isobutyl-7-(N-palmitoylamino)-1,2,3,4-tetrahydroquinoline 6.3g (0.0143mol), squaric acid 0.82g (0.0072mmol), 1-butanol 30g, and toluene 30g were added to a 300mL two-necked flask, stirred with a magnetic stirrer under nitrogen flow (10mL / min), and reacted under reflux conditions for 3 hours while removing dissolved water using a Dean-Stark device. After the reaction was completed, it was cooled to room temperature and the precipitate was separated by filtration. The filtered precipitate was washed with methanol, and only the precipitate was filtered again, and the obtained filter cake (solid substance) was purified by column chromatography of alumina (developing solvent: chloroform). The purified product was dried at 60°C for 12 hours with a vacuum dryer to obtain the pigment A (squaric acid cyanine compound) shown in Table 1. The transmission spectrum of pigment A in toluene was measured, and the maximum absorption wavelength was 700nm.

[0220] (1-2) Synthesis Example 2: Synthesis of Pigment B

[0221] In a 200mL four-necked flask, 4.98g (0.039mol) of 4-fluorobenzaldehyde, 3.57g (0.020mol) of ethylene glycol bis (2-mercaptoethyl) ether, 10.86g (0.079mol) of potassium carbonate, and 74g of acetonitrile were added, and the mixture was stirred with a stirring blade under a nitrogen flow (10mL / min) and reacted at 60°C for 12 hours. After the reaction was completed, the insoluble components were filtered and separated by vacuum filtration, and the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200mL four-necked flask, and 11.09g (0.079mol) of isobutyl cyanoacetate, 3.32g (0.039mol) of piperidine, and 68g of methanol were added thereto, and the reaction was carried out under reflux conditions for 4 hours. After the reaction was completed, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain the pigment B (compound having a styrene structure) shown in Table 1. The transmission spectrum of pigment B in toluene was measured, and the maximum absorption wavelength was 364 nm.

[0222] [Table 1]

[0223]

[0224] (2) Preparation of Lewis Acid Catalyst (for comparison)

[0225] According to the synthesis method described in the International Publication No. 1997 / 031924, 255 g of ISOPAR (registered trademark) E solution manufactured by ANDOH PARACHEMIE with a TPB (tri(pentafluorophenyl)borane) content of 7% was prepared. Water was added dropwise to the solution at 60°C, and white crystals precipitated in the middle of the addition. After the reaction solution was cooled to room temperature, the obtained slurry was filtered and washed with n-heptane. After the obtained filter cake was dried under reduced pressure at 60°C, 18.7 g of TPB·water complex (TPB-containing powder) was obtained as white crystals. The moisture content of the TPB-containing powder was 9.2% (Karl Fischer moisture meter), and the TPB content was 90.8%. The dried complex was subjected to 19 F-NMR analysis and gas chromatography analysis showed that no peak other than TPB was detected. Toluene 1.1 g was added to 2.0 g of the obtained TPB-containing powder (1.82 g of pure TPB component, 0.18 g of water), and the mixture was mixed at room temperature for 10 minutes. Then, 2.6 g of a 2 mol / L ammonia·ethanol solution was added, and the mixture was mixed at room temperature for 60 minutes, thereby obtaining a uniform solution of the TPB catalyst as a Lewis acid catalyst.

[0226] (3) Synthesis of compounds containing phenolic hydroxyl groups

[0227] (3-1) Synthesis of Compound A Containing Phenolic Hydroxyl Group

[0228] 4,4'-bis(2,3,4,5,6-pentafluorobenzoyl)diphenyl ether (BPDE) was synthesized according to the method described in Japanese Patent Application Laid-Open No. 2005-41950. 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 were added to a 100 mL flask, and stirred at 60°C for 1 hour under a nitrogen atmosphere. The reaction solution was returned to room temperature, 0.612 g (1.10 mmol) of BPDE was added thereto, and the mixture was heated to 60°C and stirred for 3 hours. After the reaction was completed, the reaction solution was added dropwise to 50 mL of pure water, and the precipitate was recovered. The precipitate was immersed in a 1% acetic acid aqueous solution for 10 hours, filtered and separated, washed with pure water, and dried at 80°C for 24 hours in a reduced pressure dryer to obtain 0.888 g of a phenolic hydroxyl group-containing compound A (molecular weight 974, OH equivalent 487 g / eq) shown in Table 2. The yield was 83%. The structural formula shown in Table 2 is based on the feed ratio of the raw materials.

[0229] (3-2) Synthesis of Compound B Containing Phenolic Hydroxyl Group

[0230] In a 100 mL flask, 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 were added, and stirred at 60°C for 1 hour under a nitrogen atmosphere. The reaction solution was returned to room temperature, 0.979 g (1.75 mmol) of BPDE was added thereto, heated to 60°C and stirred for 3 hours. After the reaction was completed, the reaction solution was added dropwise to 50 mL of pure water to recover the precipitate. The precipitate was immersed in a 1% aqueous solution of acetic acid for 10 hours, filtered and separated, washed with pure water, and dried at 80°C for 24 hours with a reduced pressure dryer to obtain 0.736 g of a phenolic hydroxyl-containing compound B (molecular weight 3212, OH equivalent 1606 g / eq) shown in Table 2. The yield was 52%. The structural formula shown in Table 2 is based on the feed ratio of the raw materials.

[0231] [Table 2]

[0232]

[0233] (4) Preparation of hydrolysis solution of silane coupling agent

[0234] 4.0 g of 3-glycidoxypropyltrimethoxysilane (OFS-6040 manufactured by Dow Toray Co., Ltd.), 5.7 g of 2-propanol, and 0.1 g of distilled water were mixed and uniformly mixed at 25° C. 0.2 g of formic acid was added thereto and mixed for 90 minutes to perform a hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane, thereby preparing a hydrolyzate of 3-glycidoxypropyltrimethoxysilane.

[0235] (5) Preparation of resin composition

[0236] (5-1) Preparation Example 1

[0237] 0.10 g of CELLOXIDE (registered trademark) 2021P (3',4'-epoxycyclohexanecarboxylic acid 3',4'-epoxycyclohexylmethyl ester, epoxy equivalent 126.15 g / eq) manufactured by DAICEL Co., Ltd. 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 ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered with a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0005 g of Curezol (registered trademark) 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Chemical Co., Ltd. as a basic catalyst were mixed in the filtrate to obtain a resin composition 1.

[0238] (5-2) Preparation Example 2

[0239] 0.10 g of EHPE3150 (1,2-epoxy-4-(2-oxirane)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy equivalent 117 g / eq) manufactured by DAICEL Co., Ltd. as an 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 ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered with a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0005 g of Curezol (registered trademark) 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as an alkaline catalyst were mixed in the filtrate to obtain a resin composition 2.

[0240] (5-3) Preparation Example 3

[0241] 0.10 g of EHPE3150 (epoxy equivalent 117 g / eq) manufactured by DAICEL Co., Ltd. and 0.097 g of bisphenol A (OH equivalent 114.14 g / eq) as alicyclic epoxy resin were added to 0.95 g of toluene, heated to 40°C, and ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered with a 0.1 μm filter to obtain a filtrate, and 0.005 g of the pigment B obtained in Synthesis Example 2 and 0.0005 g of Curezol (registered trademark) 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as an alkaline catalyst were mixed in the filtrate to obtain a resin composition 3.

[0242] (5-4) Preparation Example 4

[0243] 0.10 g of EHPE3150 (epoxy equivalent 117 g / eq) manufactured by DAICEL Co., Ltd. as an alicyclic epoxy resin and 0.416 g of a phenolic hydroxyl group-containing compound A (OH equivalent 487 g / eq) were added to 0.95 g of toluene, heated to 40°C, and ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered with a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0005 g of Curezol (registered trademark) 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as an alkaline catalyst were mixed in the filtrate to obtain a resin composition 4.

[0244] (5-5) Preparation Example 5

[0245] 0.10 g of EHPE3150 (epoxy equivalent 117 g / eq) manufactured by DAICEL Co., Ltd. as an alicyclic epoxy resin and 1.373 g of a phenolic hydroxyl group-containing compound B (OH equivalent 1606 g / eq) were added to 0.95 g of toluene, heated to 40°C, and ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered with a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0005 g of Curezol (registered trademark) 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as an alkaline catalyst were mixed in the filtrate to obtain a resin composition 5.

[0246] (5-6) Preparation Example 6

[0247] 0.10 g of CELLOXIDE (registered trademark) 2021P (epoxy equivalent 126.15 g / eq) manufactured by DAICEL Corporation as an alicyclic epoxy resin was added to 0.30 g of toluene, heated to 40°C, and ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0025 g of TPB catalyst as a Lewis acid catalyst were mixed in the filtrate to obtain a resin composition 6.

[0248] (5-7) Preparation Example 7

[0249] 0.10 g of CELLOXIDE (registered trademark) 2021P (epoxy equivalent 126.15 g / eq) manufactured by DAICEL Co., Ltd. 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 ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered with a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0025 g of TPB catalyst as a Lewis acid catalyst were mixed in the filtrate to obtain a resin composition 7.

[0250] (5-8) Preparation Example 8

[0251] 0.10 g of CELLOXIDE (registered trademark) 2021P (epoxy equivalent 126.15 g / eq) manufactured by DAICEL as an alicyclic epoxy resin was added to 0.30 g of toluene, heated to 40°C, and ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0005 g of Curezol (registered trademark) 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as an alkaline catalyst were mixed in the filtrate to obtain a resin composition 8.

[0252] (5-9) Preparation Example 9

[0253] 0.10 g of EHPE3150 (epoxy equivalent 117 g / eq) manufactured by DAICEL Co., Ltd. as an alicyclic epoxy resin was added to 0.30 g of toluene, heated to 40°C, and ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered through a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0005 g of Curezol (registered trademark) 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as an alkaline catalyst were mixed in the filtrate to obtain a resin composition 9.

[0254] (5-10) Preparation Example 10

[0255] 0.10 g of CELLOXIDE (registered trademark) 2021P (epoxy equivalent 126.15 g / eq) manufactured by DAICEL Co., Ltd. and 0.060 g of triethylene glycol (OH equivalent 75.08 g / eq) as a cycloaliphatic epoxy resin were added to 0.50 g of toluene, heated to 40°C, and ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered with a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0005 g of Curezol (registered trademark) 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as an alkaline catalyst were mixed in the filtrate to obtain a resin composition 10.

[0256] (5-11) Preparation Example 11

[0257] 0.10 g of EHPE3150 (epoxy equivalent 117 g / eq) manufactured by DAICEL Co., Ltd. and 0.064 g of triethylene glycol (OH equivalent 75.08 g / eq) as a cycloaliphatic epoxy resin were added to 0.50 g of toluene, heated to 40°C, and ultrasonic waves were applied to dissolve it to obtain a resin solution. The resin solution was filtered with a 0.1 μm filter to obtain a filtrate, and 0.003 g of the pigment A obtained in Synthesis Example 1 and 0.0005 g of Curezol (registered trademark) 2E4MZ manufactured by Shikoku Chemical Co., Ltd. as an alkaline catalyst were mixed in the filtrate to obtain a resin composition 11.

[0258] (6) Fabrication of optical filters

[0259] In resin compositions 1 to 11, 8.3 parts by mass of a hydrolyzed solution of a silane coupling agent and 0.25 parts by mass of BYK-310 (polyether-modified polydimethylsiloxane) manufactured by BYK-Chemie as a surface conditioner were added to 100 parts by mass of alicyclic epoxy resin and mixed uniformly. 1 cc of the mixture was dropped onto a glass substrate (D263Teco manufactured by Schott), and then a spin coater (1H-D7 manufactured by Mikasa) was used to form a film on the glass substrate at 300 revolutions within 0.3 seconds and maintained at this speed for 1 second. The glass substrate on which the resin composition was formed was purged with nitrogen at 50°C for 30 minutes using an inert oven (DN610I manufactured by YAMATO Scientific Co., Ltd.), and then heated to 190°C over 15 minutes, and heated at 190°C for 60 minutes in a nitrogen atmosphere to cure the resin composition formed on the glass substrate to form a resin layer (absorption layer) and prepare an optical filter. The optical filters prepared using resin compositions 1 to 5 were respectively designated as Examples 1 to 5, and the optical filters prepared using resin compositions 6 to 11 were respectively designated as Comparative Examples 1 to 6.

[0260] (7) Evaluation

[0261] (7-1) Measurement of the transmission spectrum of the filter before and after curing

[0262] For each filter, a spectrophotometer (Agilent Technologies, Inc., spectrophotometer 8454) was used to measure the transmission spectrum at a measurement interval of 1 nm, and the transmittance at a wavelength of 200 nm to 1100 nm was obtained. The transmission spectrum of the filter before and after the resin layer was cured was measured. As the spectrum change during curing, the transmittance change before and after curing at the maximum absorption wavelength was evaluated as A within 5%, B for 6% to 50%, and C for 51% or more. As specific examples of transmission spectra, the transmission spectra of the filters prepared in Example 2, Example 3, Example 5, and Comparative Example 4 are shown in FIG. Figure 1 to Figure 4 .

[0263] (7-2) Solvent resistance

[0264] In order to evaluate whether the epoxy resin of the resin layer has been cured, the cured filter was immersed in toluene to observe whether the resin layer dissolved in toluene. The resin layer was evaluated as A if it showed solvent resistance to toluene, and as C if it dissolved in toluene.

[0265] (8) Results

[0266] Table 3 shows the composition of the resin composition used in each example and comparative example, the spectral change during curing, and the evaluation results of solvent resistance. The resin composition used in Examples 1 to 3 contains an alicyclic epoxy resin as component (A), a basic catalyst as component (B), bisphenol A as a phenolic hydroxyl group-containing compound as component (C), and pigment A or pigment B as component (D). Therefore, the optical filter formed by curing the resin composition on a glass substrate has almost no spectral change before and after curing, and shows excellent solvent resistance. The resin compositions of Examples 1 to 5 have suppressed decomposition of the pigment during the thermal curing reaction, and have excellent curability.

[0267] On the other hand, the resin compositions used in Comparative Examples 1 and 2 contained a Lewis acid catalyst instead of the basic catalyst of component (B), but the optical filters produced from the resin compositions had large spectral changes before and after curing, and the absorption characteristics of the pigment were impaired. The resin compositions used in Comparative Examples 3 and 4 did not contain the phenolic hydroxyl group-containing compound of component (C), and the resin compositions used in Comparative Examples 5 and 6 contained triethylene glycol as an alcoholic hydroxyl group-containing compound instead of the phenolic hydroxyl group-containing compound of component (C), but the optical filters produced from these resin compositions had some spectral changes before and after curing, and the curability was insufficient and the solvent resistance was poor.

[0268] An AR film (five layers of TiO2 films and SiO2 films alternately laminated by vapor deposition) was laminated on the resin layer formed on the glass substrate produced in Examples 1 to 5, and as a result, an optical filter having high visible light transmittance and a desired absorption peak due to a pigment was produced. It was found that the optical filter had no change in spectrum, appearance, and adhesion even when kept at high temperature and high humidity such as 85°C and 85%RH for 1000 hours, and had high durability.

[0269] [Table 3]

[0270]

[0271] Industrial Applicability

[0272] The resin composition of the present invention is applied onto a substrate and cured to form a resin layer, and can be used for optical filters useful in applications such as optical devices, display devices, machine parts, and electric / electronic components.

Claims

1. A resin composition, characterized in that The resin composition contains alicyclic epoxy resin, a basic catalyst, a compound containing phenolic hydroxyl group and a pigment.

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

3. The resin composition according to claim 1, wherein The pigment is a carbon oxide compound.

4. The resin composition according to claim 3, wherein The carbon oxide compound is a squarylium compound represented by the following formula (1) and / or a cresone compound represented by the following formula (2), [Chemical formula 1] In formula (1) and formula (2), R 1 ~R 4 Each independently represents a group represented by the following formula (3) or the following formula (4), [Chemical formula 2] In formula (3), Ring P represents an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed 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 With R 13 are optionally linked to each other to form a ring, * represents the bonding site to the four-membered ring in formula (1) or the five-membered ring in formula (2), [Chemical formula 3] In formula (4), R 14 ~R 18 Each independently represents a hydrogen atom, an organic group or a polar functional group, R 14 With R 15 , R 15 With R 16 , R 16 With R 17 , R 17 With R 18 are optionally linked to each other to form a ring, * represents a bonding site to the four-membered ring in formula (1) or the five-membered ring in formula (2).

5. The resin composition according to claim 1, wherein The pigment is a compound having a styrene structure.

6. The resin composition according to claim 5, wherein The compound having a styrene structure is a compound represented by the following formula (6): [Chemical formula 4] In formula (6), R 21 represents a cyano group, an acyl group, a carboxylate group or an amide group, R 22 represents a hydrogen atom, a cyano group, an acyl group, a carboxylate group, an amide group, a hydrocarbon group or a heteroaryl group, In R 21 and R 22 When all R 21 With R 22 are optionally 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. 24 are optionally the same as or different from each other, X represents a sulfur atom or an oxygen atom, a represents an integer greater than or equal to 2, L represents a divalent or higher valent linking group, A plurality of groups bonded to L are optionally the same as or different from each other.

7. The resin composition according to claim 1, wherein The epoxy equivalent of the alicyclic epoxy resin is less than 200 g / eq. 8 . A cured resin product, which is obtained by curing the resin composition according to claim 1 . 9 . An optical filter comprising the cured resin according to claim 8 . 10 . A sensor comprising the optical filter according to claim 9 .

Images