Resin composition and optical filter

Abstract

To provide a resin composition which allows for forming a resin layer that offers superior adhesion with phosphoric acid glass or fluorophosphate glass.SOLUTION: A resin composition for directly forming a resin layer on a phosphoric acid glass or fluorophosphate glass is provided, the resin composition containing (A) a resin, (B) a compound containing an M-O-C bond (M represents Ti, Zr, or Al), and (C) an epoxy compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition and an optical filter having a resin layer obtained by curing the resin composition.

Background Art

[0002] In imaging devices such as cameras for mobile phones, digital cameras, in-vehicle cameras, video cameras, and display elements (such as LEDs), an imaging element that converts the light of a subject into an electrical signal or the like and outputs it is usually used. Such an imaging element includes, for example, a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) and a lens, and in order to improve performance, an optical filter such as a near-infrared cut filter for removing optical noise (such as ghost and flare) that hinders image processing may be provided.

[0003]

[0004] ​As an optical filter using a blue glass as a substrate, Patent Document 2 discloses an optical filter in which a bonding layer having a single-layer structure containing an M-O-Si bond (where M is at least one selected from Ti, Zr, and Al) is provided on a phosphoric acid-based glass or a fluorophosphoric acid-based glass substrate, and a resin layer is provided on this bonding layer. Patent Document 2 also discloses an optical filter in which a resin layer containing an M-O-Si bond (where M is at least one selected from Ti, Zr, and Al) is provided on a phosphoric acid-based glass or a fluorophosphoric acid-based glass substrate. However, there are no examples of actually preparing a resin composition for forming a resin layer containing an M-O-Si bond (where M is at least one selected from Ti, Zr, and Al), nor are there examples of producing an optical filter by coating the resin composition on a phosphoric acid-based glass or a fluorophosphoric acid-based glass substrate to form a resin layer. In the examples of Patent Document 2, only an example of preparing a coating film-forming liquid for forming a bonding layer is shown. In this example, a titanium alkoxide or the like is reacted with tetraethyl orthosilicate to form a compound having a Ti-O-Si bond, and the titanium alkoxide or the like is formulated so that the entire amount reacts with tetraethyl orthosilicate. Further, the compound having a Ti-O-Si bond is reacted with water to convert the entire amount of the alkoxy group into a hydroxy group, thereby preparing a coating film-forming liquid. Therefore, it is considered that no titanium alkoxide or the like remains in the coating film-forming liquid.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition capable of forming a resin layer having excellent adhesion to a phosphoric acid-based or phosphoric acid-based glass. The present invention also provides an optical filter and an imaging device having a resin layer formed from the resin composition.

Means for Solving the Problems

[0007] The resin composition, optical filter, and imaging device of the present invention that have solved the above problems are as follows. [1] A resin composition for directly forming a resin layer on a phosphoric acid-based or phosphoric acid-based glass, comprising (A) a resin, (B) a compound containing an M-O-C bond (where M represents Ti, Zr, or Al), and (C) an epoxy compound. [2] The resin composition according to [1], wherein the epoxy compound as the component (C) has a partial structure represented by the following formula (1).

Chemical formula

Effect of the Invention

[0008] By using the resin composition of the present invention, a resin layer excellent in adhesion to a phosphoric acid-based or fluophosphoric acid-based glass can be formed, and particularly excellent in adhesion after boiling in water under severe conditions. The optical filter of the present invention is excellent in adhesion between a phosphoric acid-based or fluophosphoric acid-based glass substrate and a resin layer.

Embodiment for Carrying Out the Invention

[0009] The resin composition of the present invention is a resin composition for directly forming a resin layer on a phosphoric acid-based or fluophosphoric acid-based glass, and contains (A) a resin, (B) a compound containing an M-O-C bond (where M represents Ti, Zr or Al), and (C) an epoxy compound. By using the resin composition of the present invention, a resin layer excellent in adhesion to a phosphoric acid-based or fluophosphoric acid-based glass can be formed, and the resin layer formed on the phosphoric acid-based or fluophosphoric acid-based glass is excellent in adhesion after boiling in water under severe conditions.

[0010] In the present invention, the phosphoric acid-based or fluophosphoric acid-based glass is used as a base material for forming a resin layer. The phosphoric acid-based glass and the fluophosphoric acid-based glass have a network structure in which phosphorus atoms and oxygen atoms are connected, which forms the main skeleton of the glass, and the fluophosphoric acid-based glass further contains fluorine atoms. In addition to these atoms, the phosphoric acid-based glass and the fluophosphoric acid-based glass may contain atoms such as sodium, calcium, magnesium, barium, strontium, lithium, potassium, cesium, aluminum, iron, silver, copper, cobalt, nickel, lead, and zinc, and these may be contained in ionic form. The phosphoric acid-based or fluophosphoric acid-based glass preferably contains copper atoms, whereby the glass exhibits a blue color and has an absorption band in the near-infrared region around 800 nm. The copper atoms may be contained in ionic form.

[0011] A known phosphoric acid-based glass can be used. The composition of the phosphoric acid-based glass (composition in terms of oxides) is not particularly limited. For example, the P2O5 content is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, still more preferably 20 to 50% by mass, the Al2O3 content is preferably 0 to 40% by mass, more preferably 0.1 to 25% by mass, still more preferably 0.2 to 10% by mass, and M 2 O (where M 2 represents at least one selected from Ca, Ba, Mg, Sr, and Zn) content is preferably 0 to 40% by mass, more preferably 1 to 30% by mass, still more preferably 2 to 20% by mass, the CuO content is preferably 0 to 30% by mass, more preferably 0.5 to 20% by mass, still more preferably 1 to 15% by mass.

[0012] A known metaphosphoric acid-based glass can be used. The composition of the metaphosphoric acid-based glass (composition in terms of oxides) is not particularly limited. For example, the P2O5 content is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, still more preferably 20 to 50% by mass, the Al2O3 content is preferably 0 to 40% by mass, more preferably 0.1 to 25% by mass, still more preferably 0.2 to 10% by mass, and M 2 O (where M 2 represents at least one selected from Ca, Ba, Mg, Sr, and Zn) content is preferably 0 to 40% by mass, more preferably 1 to 30% by mass, still more preferably 2 to 20% by mass, the CuO content is preferably 0 to 30% by mass, more preferably 0.5 to 20% by mass, still more preferably 1 to 15% by mass. Also, in the metaphosphoric acid-based glass, the molar ratio F / (F + O) of the fluorine atom content to the total content of fluorine atoms and oxygen atoms is preferably 0.05 to 0.95, more preferably 0.10 to 0.90, still more preferably 0.20 to 0.80.

[0013] In soda-lime glass and borosilicate glass widely used as transparent glass, a network structure in which silicon atoms and oxygen atoms are connected forms the main skeleton of the glass, and Si-OH bonds exist on the glass surface. Therefore, for example, by blending a silane coupling agent into a resin, the silane coupling agent can react with the Si-OH bonds to enhance the adhesion between the resin and the glass. On the other hand, in phosphate glass and fluorophosphate glass, since P=O bonds exist instead of Si-OH bonds on the glass surface, it is difficult to enhance the adhesion between the resin and the glass as in the case of soda-lime glass and borosilicate glass even when a silane coupling agent is blended into the resin.

[0014] Therefore, in the resin composition of the present invention, together with (A) a resin, (B) a compound containing an M-O-C bond (where M represents Ti, Zr or Al) and (C) an epoxy compound are contained. By using a resin composition containing the compound containing an M-O-C bond as the component (B) and the epoxy compound as the component (C) and coating this on a phosphate-based or fluorophosphate-based glass to directly form a resin layer on the phosphate-based or fluorophosphate-based glass, the adhesion between the resin and the glass can be enhanced, and the adhesion between the resin and the glass can be enhanced even after boiling in water, which is a severe condition.

[0015] As the resin of component (A), known resins can be used, and for example, it is preferable to use a resin with high transparency. Examples of the resin of component (A) include (meth)acrylic resins, (meth)acrylic urethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins (e.g., polyethylene resins, polypropylene resins), cycloolefin resins, melamine resins, urethane resins, styrene resins, polyvinyl acetate, polyamide resins (e.g., nylon), aramid resins, polyimide resins, polyamideimide resins, alkyd resins, phenolic resins, epoxy resins, polyester resins (e.g., polybutylene terephthalate (PBT), polyethylene terephthalate (PET), etc.), butyral resins, polycarbonate resins, polyether resins, polysulfone resins, ABS resins (acrylonitrile-butadiene-styrene resins), AS resins (acrylonitrile-styrene copolymers), silicone resins, modified silicone resins (e.g., (meth)acrylic silicone resins, alkyl polysiloxane resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins, etc.), fluorine-based resins (e.g., fluorinated aromatic polymers, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), fluorinated polyaryl ether ketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorinated polyether nitrile (FPEN), etc.). Among these, from the viewpoints of excellent transparency and heat resistance, (meth)acrylic resins, cycloolefin resins, polyimide resins, polyamideimide resins, polyester resins, polyarylate resins, polyamide resins, polycarbonate resins, epoxy resins, polysulfone resins, and fluorinated aromatic polymers are preferable.

[0016] (Meta)acrylic resins are polymers having repeating units derived from (meta)acrylic acid or its derivatives. For example, resins having repeating units derived from (meta)acrylic acid esters such as poly(meth)acrylate resins are preferably used. (Meta)acrylic resins preferably have a ring structure in the main chain. Examples include carbonyl group-containing ring structures such as lactone ring structures, glutaric anhydride structures, glutarimide structures, maleic anhydride structures, and maleimide ring structures; and carbonyl group-free ring structures such as oxetane ring structures, azetidine ring structures, tetrahydrofuran ring structures, pyrrolidine ring structures, tetrahydropyran ring structures, and piperidine ring structures. The carbonyl group-containing ring structures also include structures containing carbonyl group derivative groups such as imide groups. As the (meta)acrylic resin having a carbonyl group-containing ring structure, those described in, for example, JP-A-2004-168882, JP-A-2008-179677, WO 2005 / 54311, JP-A-2007-31537, etc. can be used.

[0017] Cycloolefin resins are polymers obtained by polymerizing cycloolefins as at least a part of the monomer components, and are not particularly limited as long as they have an alicyclic structure in a part of the main chain. As the cycloolefin resins, for example, Topas (registered trademark) manufactured by Polyplastics Co., Ltd., Apel (registered trademark) manufactured by Mitsui Chemicals, Inc., Zeonex (registered trademark) and Zeonor (registered trademark) manufactured by Nippon Zeon Co., Ltd., Arton (registered trademark) manufactured by JSR Corporation, etc. can be used.

[0018] A polyimide resin is a polymer containing an imide bond in the repeating unit of the main chain. For example, it can be produced by polymerizing a tetracarboxylic dianhydride and a diamine to obtain a polyamic acid, and then dehydrating and cyclizing (imidizing) it. As the polyimide resin, it is preferable to use an aromatic polyimide in which aromatic rings are linked by imide bonds. As the polyimide resin, for example, Kapton (registered trademark) manufactured by DuPont, Aurum (registered trademark) manufactured by Mitsui Chemicals, Meldin (registered trademark) manufactured by Saint-Gobain, TPS (registered trademark) TI3000 series manufactured by Toray Plastics Seiko Co., Ltd., etc. can be used.

[0019] A polyamideimide resin is a polymer containing an amide bond and an imide bond in the repeating unit of the main chain. As the polyamideimide resin, for example, Torlon (registered trademark) manufactured by Solvay Advanced Polymers, Birolmax (registered trademark) manufactured by Toyobo Co., Ltd., TPS (registered trademark) TI5000 series manufactured by Toray Plastics Seiko Co., Ltd., etc. can be used.

[0020] A polyester resin is a polymer containing an ester bond in the repeating unit of the main chain. For example, it can be obtained by polycondensing a polyvalent carboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. For example, the OKP series manufactured by Osaka Gas Chemical Co., Ltd., the TRN series manufactured by Teijin Limited, Teonex (registered trademark), Laitite (registered trademark) manufactured by DuPont, Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation, Novaduran (registered trademark) manufactured by Mitsubishi Engineering-Plastics Corporation, Lumirror (registered trademark) manufactured by Toray Industries, Inc., Trecon (registered trademark), etc. can be used.

[0021] The polyarylate resin is a polymer obtained by polycondensing a divalent phenol compound and a dibasic acid (for example, an aromatic dicarboxylic acid such as phthalic acid), and has a repeating unit containing an aromatic ring and an ester bond in the repeating unit of the main chain. As the polyarylate resin, for example, Victrex (registered trademark) manufactured by Kuraray Co., Ltd., U Polymer (registered trademark) manufactured by Unitika Ltd., etc. can be used.

[0022] The polyamide resin is a polymer containing an amide bond in the repeating unit of the main chain, and can be obtained, for example, by polycondensing a diamine and a dicarboxylic acid. The polyamide resin may have an aliphatic skeleton in the main chain, and for such an amide resin, for example, nylon can be used. The polyamide resin may have an aromatic skeleton, and an aramid resin is known as such a polyamide resin. The aramid resin is preferably used because of its excellent heat resistance and strong mechanical strength. For example, Twaron (registered trademark), Conex (registered trademark) manufactured by Teijin Limited, Kevlar (registered trademark), Nomex (registered trademark) manufactured by DuPont, etc. can be used.

[0023] The polycarbonate resin is a polymer containing a carbonate group (-O-(C=O)-O-) in the repeating unit of the main chain. As the polycarbonate resin, Panlite (registered trademark) manufactured by Teijin Limited, Upitzer (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Inc., Iupilon (registered trademark), Novarex (registered trademark), Zanter (registered trademark) manufactured by Mitsubishi Engineering-Plastics Corporation, SD Polycar (registered trademark) manufactured by Sumika Styron Polycarbonate Co., Ltd., etc. can be used.

[0024] Epoxy resins can be cured by crosslinking epoxy compounds (prepolymers) in the presence of a curing agent or a curing catalyst. Examples of epoxy compounds include aromatic epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, hydrogenated epoxy compounds, etc. For example, fluorene epoxy (Ogsol (registered trademark) PG-100) manufactured by Osaka Gas Chemical Co., Ltd., bisphenol A type epoxy compound (JER (registered trademark) 828EL) and hydrogenated bisphenol A type epoxy compound (JER (registered trademark) YX8000) manufactured by Mitsubishi Chemical Corporation, alicyclic liquid epoxy compounds (Celoxide (registered trademark) 2021P, EHPE-3150) manufactured by Daicel Corporation, etc. can be used.

[0025] Polysulfone resins are polymers having repeating units containing an aromatic ring, a sulfonyl group (-SO2-), and an oxygen atom. For polysulfone resins, for example, Sumika Excel (registered trademark) PES3600P and PES4100P manufactured by Sumitomo Chemical Co., Ltd., UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers, etc. can be used.

[0026] Fluorinated aromatic polymers are polymers having repeating units containing an aromatic ring having one or more fluorine atoms and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. Among these, it is preferably a polymer essentially containing a repeating unit containing an aromatic ring having one or more fluorine atoms and an ether bond. As the fluorinated aromatic polymer, for example, those described in JP-A-2008-181121 can be used.

[0027] The resin preferably has high transparency, which makes it easier to suitably apply the resin composition to optical applications. For the resin, for example, the total light transmittance at a thickness of 0.1 mm is preferably 75% or more, more preferably 80% or more, and even more preferably 85% or more. The upper limit of the total light transmittance of the resin is not particularly limited, and the total light transmittance may be 100% or less, for example, it may be 95% or less. The total light transmittance is measured based on JIS K 7105.

[0028] The glass transition temperature (Tg) of the resin is not particularly limited, but it is preferably relatively high, whereby the heat resistance of the resin layer formed from the resin composition can be enhanced. The glass transition temperature of the resin is, for example, preferably 110 °C or higher, more preferably 120 °C or higher, and even more preferably 130 °C or higher. The upper limit of the glass transition temperature of the resin is not particularly limited, but from the viewpoint of enhancing the moldability of the resin composition, it is preferably 380 °C or lower, for example.

[0029] The content of the component (A) in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less in 100% by mass of the solid content of the resin composition. Note that the solid content of the resin composition means the amount of the resin composition excluding the solvent when the resin composition contains a solvent.

[0030] (B) The compound containing an M-O-C bond is not particularly limited as long as it is a compound having a structure in which a metal atom M selected from Ti, Zr, and Al is connected to a carbon atom via an oxygen atom in one molecule. The compound containing an M-O-C bond has higher reactivity than, for example, a silane coupling agent or its condensate, and acts on the P=O bond or P-O-P bond present on the surface of a phosphoric acid-based or metaphosphoric acid-based glass, and is considered to form, for example, P-O-M. Therefore, by including a compound containing an M-O-C bond in the resin composition, the adhesion between the resin layer formed from the resin composition and the phosphoric acid-based or metaphosphoric acid-based glass can be enhanced. The resin composition may contain only one kind of the compound containing an M-O-C bond as the component (B), or may contain two or more kinds. For example, two or more kinds selected from a compound containing a Ti-O-C bond, a compound containing a Zr-O-C bond, and a compound containing an Al-O-C bond may be contained in the resin composition.

[0031] In a compound containing an M-O-C bond, the Ti atom, Zr atom, or Al atom may be connected to an oxygen atom by a covalent bond or a coordination bond. Therefore, the bond between M and O may be a covalent bond or a coordination bond. Examples of compounds containing an M-O-C bond in which the bond between M and O is a covalent bond include compounds in which an alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc. are bonded to a Ti atom, Zr atom, or Al atom. Examples of compounds containing an M-O-C bond in which the bond between M and O is a coordination bond include compounds in which an enolate, oxalate, etc. are bonded (coordinated) to a Ti atom, Zr atom, or Al atom. A compound containing an M-O-C bond may have a plurality of M-O bonds, and a part of the M-O bonds may be covalent bonds and the other part may be coordination bonds.

[0032] In a compound containing an M-O-C bond, when an alkoxy group is bonded to a Ti atom, Zr atom, or Al atom, the number of carbon atoms in the alkyl group contained in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 8, and even more preferably 3 to 8. The alkyl group is preferably linear or branched. Examples of the alkyl group contained in the alkoxy group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, etc.

[0033] In a compound containing an M-O-C bond, when an aryloxy group is bonded to a Ti atom, Zr atom, or Al atom, the number of carbon atoms in the aryl group contained in the aryloxy group is preferably 6 to 20, more preferably 6 to 12. Examples of the aryl group contained in the aryloxy group include phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl group, etc.

[0034] In a compound containing an M-O-C bond, when an aralkyloxy group is bonded to a Ti atom, a Zr atom or an Al atom, the number of carbon atoms of the aralkyl group contained in the aralkyloxy group is preferably 7 to 25, more preferably 7 to 15. Examples of the aralkyl group contained in the aralkyloxy group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a naphthylmethyl group and the like.

[0035] In a compound containing an M-O-C bond, when an acyloxy group is bonded to a Ti atom, a Zr atom or an Al atom, examples of the acyloxy group include those represented by the formula: R a1 -CO-O-, where R a1 is an alkyl group, an aryl group, or an aralkyl group. For the alkyl group, aryl group, and aralkyl group of R a1 , reference is made to the descriptions of the alkyl group contained in the above alkoxy group, the aryl group contained in the aryloxy group, and the aralkyl group contained in the aralkyloxy group. The number of carbon atoms of the alkyl group of R a1 is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 8, and even more preferably 1 to 4.

[0036] In a compound containing an M-O-C bond, when an enolate is bonded (coordinated) to a Ti atom, a Zr atom or an Al atom, examples of the enolate include those represented by the following formula (2), where R 11 and R 12 are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and R 13 is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or -CO-R 14 , and R 14 is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.

[0037]

Chemical formula

[0038] In the above formula (2), R11 ~R 14 The alkoxy group of ~R refers to the description of the above alkoxy group. R 11 ~R 14 For the alkyl group, aryl group, and aralkyl group of ~R, the descriptions of the alkyl group included in the above alkoxy group, the aryl group included in the aryloxy group, and the aralkyl group included in the aralkyloxy group are referred to. R 11 ~R 14 The carbon number of the alkyl group and alkoxy group of ~R is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 8, and even more preferably 1 to 4. R 11 R is preferably an alkyl group, alkoxy group, aryl group or aralkyl group, more preferably an alkyl group or aryl group. R 12 R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. R 13 R is preferably an alkyl group, aryl group, aralkyl group or -CO-R 14 is preferably an alkyl group or -CO-R 14 is more preferably. R 13 R is -CO-R 14 is particularly preferred. In this case, the enolate of the above formula (2) is represented by the following formula (2A). R 14 R is preferably an alkyl group, alkoxy group, aryl group or aralkyl group, more preferably an alkyl group or aryl group.

[0039]

Chemical formula

[0040] Compounds containing M-O-C bonds may have only one metal atom M of Ti, Zr or Al in one molecule, or may have two or more. In the latter case, it is preferable that two or more metal atoms M are bonded via oxygen atoms to form an M-O-M bond. Also, it is preferable that each metal atom M forms an M-O-C bond. Such a compound can be obtained, for example, by hydrolyzing and dehydrating condensing a metal alkoxide, and the compound can be regarded as a condensate of the metal alkoxide. Compounds containing M-O-C bonds may have two or three kinds of metal atoms M.

[0041] Compounds containing M-O-C bonds only need to contain one or more M-O-C bonds in one molecule. It is more preferable that two or more M-O-C bonds are contained, and even more preferable that three or more M-O-C bonds are contained. When two or more M-O-C bonds are contained in one molecule, the plurality of groups forming the M-O-C bonds may be the same or different from each other. Compounds containing M-O-C bonds may have an organic group that does not form an M-O-C bond bonded to a Ti atom, Zr atom or Al atom, and examples of such an organic group include an alkyl group, an aryl group, and an aralkyl group. It is particularly preferable that all of the groups bonded to the Ti atom, Zr atom or Al atom form M-O-C bonds.

[0042] The compound having an M-O-C bond is preferably a metal alkoxide or a metal enolate. Therefore, in the compound having an M-O-C bond, an alkoxy group and / or an enolate is preferably bonded to a Ti atom, a Zr atom or an Al atom. Examples of such compounds include tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-tert-butoxytitanium, titanium tetra-2-ethylhexyloxide, tetrastearyl titanium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-tert-butoxyzirconium, octoxytri-decoxyzirconium, triisopropoxyaluminum, tri-tert-butoxyaluminum, titanium tetraacetylacetonate, titanium diisopropoxide bis(acetylacetonate), a phosphate ester titanium complex, titanium octylene glycolate, and the like.

[0043] In the compound containing an M-O-C bond, the ratio of the number of alkoxy groups and enolates bonded to a Ti atom, a Zr atom or an Al atom is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more, based on 100% of the total number of bonds of the Ti atom, the Zr atom or the Al atom. The ratio is preferably even higher, and may be 60% or more, 70% or more, 80% or 90% or more.

[0044] It is preferable that all of the groups bonded to the Ti atom, Zr atom or Al atom are alkoxy groups or enolates in the metal alkoxide or metal enolate. For example, among compounds having a Ti—O—C bond, titanium tetraalkoxide, titanium tetraenolate, titanium alkoxide tris enolate, titanium dialkoxide bis enolate, and titanium trialkoxide enolate are preferable; among compounds having a Zr—O—C bond, zirconium tetraalkoxide, zirconium tetraenolate, zirconium alkoxide tris enolate, zirconium dialkoxide bis enolate, and zirconium trialkoxide enolate are preferable; and among compounds having an Al—O—C bond, aluminum trialkoxide, aluminum tris enolate, aluminum alkoxide bis enolate, and aluminum dialkoxide enolate are preferable.

[0045] In the condensate of the metal alkoxide, it is preferable that all of the groups bonded to the Ti atom, Zr atom or Al atom are alkoxy groups or enolates, except for the M—O—M (where M represents Ti, Zr or Al) bond.

[0046] The compound containing an M—O—C bond may react with the resin to form a bond. For example, when the resin has an ester bond, the compound containing an M—O—C bond can react with the ester bond contained in the resin. In the resin having an ester bond, the ester bond can be cleaved by the reaction with the compound containing an M—O—C bond, and the compound containing an M—O—C bond can be bonded to a part of the resin from which it has been cleaved via an —O—M (where M represents Ti, Zr or Al) bond. Such a reaction can be advanced, for example, by heating the resin composition. The resin having an ester bond may have an ester bond in the main chain or may have an ester bond in the side chain. Examples of the resin having an ester bond in the main chain include polyester resins and polyarylate resins, and examples of the resin having an ester bond in the side chain include poly(meth)acrylate resins.

[0047] The content of component (B) in the resin composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less, based on 100% by mass of the solid content of the resin composition. The compounding amount of component (B) with respect to 100 parts by mass of the resin of component (A) is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less. By blending the compound containing the M-O-C bond of component (B) with the resin of component (A) in this way, it becomes easy to enhance the adhesion between the resin layer formed from the resin composition and the phosphoric acid-based or metaphosphoric acid-based glass. 100 parts by mass of the resin of component (A) corresponds to 100 parts by mass of the solid content of the resin of component (A).

[0048] In 100% by mass of the solid content of the resin composition, the content of the metal atom M of component (B) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 3.0% by mass or less, more preferably 2.0% by mass or less, still more preferably 1.5% by mass or less.

[0049] (C) The epoxy compound is not particularly limited as long as it is a compound having an oxirane ring in one molecule. The epoxy compound of component (C) is considered to act on the metal atom M of the compound containing the M-O-C bond of component (B) by the hydroxyl group or -O generated by the ring-opening reaction of the oxirane ring, and form a bond with the metal atom M. Thereby, the adhesion between the resin layer formed from the resin composition and the phosphoric acid-based or metaphosphoric acid-based glass can be further enhanced, and the adhesion can be enhanced even after boiling in water, which is a severe condition. The reaction between the epoxy compound and the compound containing the M-O-C bond can be advanced, for example, by heating the resin composition. The resin composition may contain only one kind of the epoxy compound of component (C), or may contain two or more kinds. - It is considered to act on the metal atom M of the compound containing the M-O-C bond of component (B) and form a bond with the metal atom M. Thereby, the adhesion between the resin layer formed from the resin composition and the phosphoric acid-based or metaphosphoric acid-based glass can be further enhanced, and the adhesion can be enhanced even after boiling in water, which is a severe condition. The reaction between the epoxy compound and the compound containing the M-O-C bond can be advanced, for example, by heating the resin composition. The resin composition may contain only one kind of the epoxy compound of component (C), or may contain two or more kinds.

[0050] The epoxy compound may contain an oxirane ring in the form of a glycidyl group, or the oxirane ring and an aliphatic hydrocarbon ring may exist in a form that shares carbon atoms, such as cycloalkene oxide.

[0051] The epoxy compound may have only one oxirane ring in one molecule, or may have two or more oxirane rings. In addition, the epoxy compound is preferably a polyfunctional epoxy compound having two or more oxirane rings in one molecule, whereby the adhesion between the resin layer formed from the resin composition and the phosphoric acid-based or metaphosphoric acid-based glass can be further enhanced. The epoxy compound may have three or more oxirane rings in one molecule. The upper limit of the number of oxirane rings possessed by the epoxy compound is not particularly limited, and may be, for example, 10 or less, 8 or less, or 6 or less.

[0052] The epoxy compound preferably has a monovalent or divalent or higher hydrocarbon group, and the hydrocarbon group preferably contains an aliphatic hydrocarbon group and / or an aromatic hydrocarbon group. Thereby, the solubility of the epoxy compound in the resin can be increased. The aliphatic hydrocarbon group is preferably linear or branched, and preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms. Note that the aliphatic hydrocarbon group does not contain the ethylene group contained in the oxirane ring.

[0053] The molecular weight of the epoxy compound is preferably, for example, 100 or more, more preferably 130 or more, even more preferably 160 or more, and even more preferably 180 or more. Thereby, the residual property in the resin composition of the epoxy compound can be enhanced. For example, after coating the resin composition on phosphoric acid-based or metaphosphoric acid-based glass and then heating, the bonding between the epoxy compound of component (C) and the compound containing the M-O-C bond of component (B) can be promoted. At this time, by increasing the molecular weight of the epoxy compound, the epoxy compound becomes less likely to volatilize from the resin composition when the resin composition is heated. Thereby, the adhesion between the resin layer formed from the resin composition and the phosphoric acid-based or metaphosphoric acid-based glass can be further enhanced. On the other hand, the upper limit of the molecular weight of the epoxy compound is preferably, for example, 1000 or less, more preferably 800 or less, and even more preferably 600 or less. Thereby, the solubility of the epoxy compound in the resin can be enhanced.

[0054] The epoxy compound preferably contains an oxirane ring in the form of a glycidyl group. Therefore, the epoxy compound preferably has a partial structure represented by the following formula (1).

[0055]

Chemical formula

[0056] The partial structure represented by formula (1) is preferably a partial structure represented by the following formula (1A) or formula (1B). In the following formula (1A), X represents an oxygen atom, a sulfur atom or NH.

[0057]

Chemical formula

[0058] The epoxy compound preferably has a group represented by the above formula (1A) and / or formula (1B) bonded to a monovalent or divalent or higher hydrocarbon group, and the hydrocarbon group is preferably composed of an aliphatic hydrocarbon group and / or an aromatic hydrocarbon group. When the hydrocarbon group is composed only of an aliphatic hydrocarbon group, the number of carbon atoms of the aliphatic hydrocarbon group is preferably 2 or more, more preferably 3 or more.

[0059] The epoxy compound of component (C) may have an alkoxysilyl group or an alkylsilyl group. In this case, the epoxy compound having an alkoxysilyl group or an alkylsilyl group may react with the compound having an M - O - C bond of component (B) to form M - O - Si, but it is preferable that the compound having an M - O - C bond of component (B) is not completely consumed. Therefore, in the resin composition, the ratio of the number of M - O - Si bonds to the total number of bonds of Ti atoms, Zr atoms or Al atoms of the compound having an M - O - C bond of component (B) is preferably 90% or less, more preferably 70% or less, and even more preferably 50% or less with respect to 100% of the total number of bonds. The compound having an M - O - C bond of component (B) preferably does not react as much as possible with the epoxy compound having an alkoxysilyl group or an alkylsilyl group. From this viewpoint, the ratio is more preferably 30% or less, 20% or less, 10% or less, 5% or less, or 1% or less.

[0060] The content of component (C) in the resin composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less in 100% by mass of the solid content of the resin composition. The blending amount of component (C) with respect to 100 parts by mass of the resin of component (A) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 0.8 part by mass or more, and preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

[0061] In the resin composition, the molar equivalent of the epoxy group of component (C) to the metal atom M of component (B), that is, the molar amount of the epoxy group of component (C) per 1 mol of the metal atom M of component (B) is preferably 0.5 mol / mol or more, more preferably 1 mol / mol or more, and even more preferably 1.5 mol / mol or more. The upper limit of the molar equivalent of the epoxy group of component (C) to the metal atom M of component (B) is not particularly limited, and may be, for example, 40 mol / mol or less.

[0062] The resin composition may contain a dye as component (D). The dye contained in the resin composition may be a dye that absorbs visible light, a dye that absorbs near-infrared light with a longer wavelength than visible light, or a dye that absorbs ultraviolet light with a shorter wavelength than visible light. The dye preferably has an absorption maximum in the range of 200 nm to 1100 nm in wavelength. If the resin composition contains a dye, it can be suitably applied to an optical filter having light selective transmittance by coating it on a phosphoric acid-based or borophosphoric acid-based glass to form a resin layer on the phosphoric acid-based or borophosphoric acid-based glass.

[0063] When the dye of component (D) is a visible light absorbing dye, the dye may have an absorption maximum in the visible light region (for example, in the range of more than 420 nm and less than 680 nm in wavelength). For example, it is preferably one having an absorption maximum in the range of 500 nm or more and less than 680 nm in wavelength with high visual sensitivity. The resin composition containing a visible light absorbing dye can be suitably used for the production of optical filters such as color filters and blue light reducing filters.

[0064] When the dye of component (D) is a near-infrared absorbing dye, the dye preferably has an absorption maximum in the range of, for example, 680 nm or more and 1100 nm or less in wavelength. The resin composition containing a near-infrared absorbing dye can be suitably used for the production of an optical filter that suppresses the transmission of light in the near-infrared region and preferentially transmits light in the visible light region. It can also be used for the production of a near-infrared cut filter that cuts light in the red to near-infrared region.

[0065] The near-infrared absorbing dye has a peak with an absorption maximum in the range of 680 nm or more and 1100 nm or less in the absorption spectrum in the range of 200 nm or more and 1100 nm or less, and it is preferable that the absorption maximum of the absorption peak takes the maximum value in the range of 200 nm or more and 1100 nm or less. The absorption maximum wavelength is more preferably 685 nm or more, even more preferably 690 nm or more, also more preferably 1000 nm or less, even more preferably 900 nm or less, and even more preferably 800 nm or less.

[0066] When the dye of the (D) component is an ultraviolet absorbing dye, the dye preferably has an absorption maximum in the range of 200 nm or more and 420 nm or less, for example. The resin composition containing the ultraviolet absorbing dye can be suitably used for the production of an optical filter that suppresses the transmission of light in the purple to ultraviolet region and preferentially transmits light in the visible light region. It can also be used for the production of an ultraviolet cut filter that cuts light in the ultraviolet region. Furthermore, even when the resin composition is exposed to ultraviolet light during storage or during the production and processing (for example, vapor deposition and mounting) of the optical filter, the resin component and other components contained in the resin composition can be protected from the ultraviolet light, and the deterioration of these components can be suppressed.

[0067] The ultraviolet absorbing dye has a peak with an absorption maximum in the range of 200 nm or more and 420 nm or less in the absorption spectrum in the range of 200 nm or more and 1100 nm or less, and it is preferable that the absorption maximum of the absorption peak takes the maximum value in the range of 200 nm or more and 1100 nm or less. The absorption maximum wavelength is more preferably 250 nm or more, even more preferably 300 nm or more, and also more preferably 400 nm or less.

[0068] The dye of the (D) component is not particularly limited, and it 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).

[0069] Examples of the near-infrared absorbing dye and the visible light absorbing dye include squarylium dyes, croconium dyes, and cyclic tetrapyrrole dyes (such as porphyrins, chlorins, phthalocyanines, naphthalocyanines, corins, etc.) which may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as the central metal ion, cyanine dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethane dyes, quaterrylene dyes, diimonium dyes, perylene dyes, quinacridone dyes, oxazine dyes, dipyrromethene dyes, nickel complex dyes, copper ion dyes, etc. These dyes may be used alone or in combination of two or more.

[0070] Examples of the ultraviolet absorbing dye include known compounds known as ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazinone compounds, methine compounds (e.g., cyanoacrylate compounds and merocyanine compounds), benzoxazole compounds, triazine compounds, etc. The ultraviolet absorbing dye may be used alone or in combination of two or more.

[0071] When the resin composition contains the dye as the component (D), the content of the component (D) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, based on 100% by mass of the solid content of the resin composition. The blending amount of the component (D) with respect to 100 parts by mass of the resin as the component (A) is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, still more preferably 1.5 part by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less.

[0072] The resin composition preferably contains a near-infrared absorbing dye and / or an ultraviolet absorbing dye as the dye of component (D). Thereby, the resin layer obtained by curing the resin composition suppresses the transmission of light in the near-infrared region and / or the ultraviolet region and preferentially transmits light in the visible light region, and can be suitably applied to optical filters such as near-infrared cut filters and ultraviolet cut filters.

[0073] As the dye of component (D), for example, an oxocarbon-based compound can be preferably used. The oxocarbon-based compound is not particularly limited as long as it is a compound containing a carbon oxide as a basic skeleton, but a squarylium compound or a croconium compound, which is widely known as a compound having an absorption wavelength in the red to near-infrared region and a relatively high light transmittance in the visible light region, is preferable. If the resin composition contains such an oxocarbon-based compound, by forming a resin layer on a phosphoric acid-based or fluorophosphoric acid-based glass substrate, it can be applied to an optical filter that cuts light in the red to near-infrared region.

[0074] The oxocarbon-based compound contained in the resin composition may be a squarylium compound, a croconium compound, or both. The oxocarbon-based compound contained in the resin composition may be only one kind or two or more kinds.

[0075] As the squarylium compound, a compound having a squarylium skeleton represented by the following formula (3) is specifically shown, and as the croconium compound, a compound having a croconium skeleton represented by the following formula (4) is specifically shown. In the following formulas (3) and (4), R 21 ~R 24 each independently represents an organic group.

[0076]

Chemical formula

[0077] As the oxocarbon-based compound, in the above formulas (3) and (4), R 21 ~R 24 is each independently preferably a group represented by the following formula (5) or the following formula (6). A squarylium compound or a croconium compound having a group represented by the following formula (5) has a broad absorption peak in the red to near-infrared region and can cut light in a relatively wide wavelength range. On the other hand, a squarylium compound or a croconium compound having a group represented by the following formula (6) has a sharp absorption peak in the red to near-infrared region, so it is possible to selectively cut light in the wavelength range corresponding to this absorption peak.

[0078]

Chemical formula

[0079] In formula (5), 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 31 ~R 33 each independently represents a hydrogen atom, an organic group, or a polar functional group, and R 32 and R 33 may be linked to each other to form a ring. In formula (6), R 34 ~R 38 each independently represents a hydrogen atom, an organic group, or a polar functional group, and R 34 and R 35 , R 35 and R 36 , R 36 and R 37 , R 37 and R 38 may each be linked to each other to form a ring. * represents the bonding site with the 4-membered ring in formula (3) or the 5-membered ring in formula (4).

[0080] There may be compounds in resonance relationship in squarylium compounds and croconium compounds, but the squarylium compounds represented by the above formula (3) and the croconium compounds represented by the above formula (4) also include these compounds in resonance relationship.

[0081] In the above formula (3), the groups bonded to one side and the other side of the squarylium skeleton may be the same as or different from each other. In the above formula (4), the groups bonded to one side and the other side of the croconium skeleton may be the same as or different from each other. When the groups bonded to one side and the other side of the squarylium skeleton or the croconium skeleton are the same, an improvement in the durability of the squarylium compound or the croconium compound against heat and light can be expected. When the groups bonded to one side and the other side of the squarylium skeleton or the croconium skeleton are different from each other, the association and aggregation of the squarylium compounds or the croconium compounds are suppressed, and an improvement in the solubility in solvents and resins can be expected.

[0082] R 31 ~R 38 Examples of the organic groups of R 31 ~R 38 include alkyl groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, alkylsulfonyl groups, alkylsulfinyl groups, aryl groups, aralkyl groups, aryloxy groups, arylthio groups, aryloxycarbonyl groups, arylsulfonyl groups, arylsulfinyl groups, heteroaryl groups, amino groups, amide groups, sulfonamide groups, carboxy groups (carboxylic acid groups), cyano groups, and the like. Examples of the polar functional groups of R

[0083] R 31 ~R 38Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl; and cyclic (alicyclic) alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. The alkyl group may have a substituent, and examples of such a substituent include aryl group, heteroaryl group, halogeno group, hydroxyl group, carboxy group, alkoxy group, cyano group, nitro group, amino group, and sulfo group. Examples of the alkyl group having a halogeno group include monohalogenoalkyl group, dihalogenoalkyl group, alkyl group having a trihalomethyl unit, and perhalogenoalkyl group. The halogeno group is preferably a fluoro group, chloro group, or bromo group, and particularly preferably a fluoro group. The number of carbon atoms of the alkyl group (excluding the carbon atoms of the substituent) is preferably 1 to 20. Specifically, for a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. For a cyclic alkyl group, the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8.

[0084] R 31 ~R 38 Specific examples of the alkyl group included in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group, and alkylsulfinyl group of R~R are as described above for the alkyl group.

[0085] R 31 ~R 38Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group and the like. The aryl group may have a substituent. Examples of the substituent of the aryl group include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group and the like. The number of carbon atoms of the aryl group (the number of carbon atoms excluding substituents) is preferably 6 to 20, more preferably 6 to 12.

[0086] R 31 ~R 38 Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a naphthylmethyl group and the like. The aralkyl group may have a substituent. Examples of the substituent of the aralkyl group include an alkyl group, an alkoxy group, a halogeno group, a halogenoalkyl group, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group and the like. The number of carbon atoms of the aralkyl group (the number of carbon atoms excluding substituents) is preferably 7 to 25, more preferably 7 to 15.

[0087] R 31 ~R 38 Specific examples of the aryl group contained in the aryloxy group, arylthio group, aryloxycarbonyl group, arylsulfonyl group and arylsulfinyl group may be referred to the description of the above aryl group.

[0088] R 31 ~R 38Examples of the heteroaryl group include, for example, a thienyl group, a thiopyranyl group, an isothiochromenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrralidinyl group, a pyrimidinyl group, a pyridazinyl group, a thiazolyl group, an isothiazolyl group, a furanyl group, a pyranyl group, and the like. The heteroaryl group may have a substituent, and examples of the substituent of the heteroaryl group include an alkyl group, an alkoxy group, an aryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, an amino group, a nitro group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and the like. The number of carbon atoms of the heteroaryl group (the number of carbon atoms excluding the substituent) is preferably 2 to 20, more preferably 3 to 15.

[0089] R 31 ~R 38 Examples of the amino group of R a2 R a3 are represented by the formula: -NR a2 R a3 wherein R a2 and R a3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group can be referred to the descriptions of these groups above. Examples of the alkenyl group and alkynyl group include groups in which a part of the carbon-carbon single bond of the alkyl group exemplified above is replaced by a double bond or a triple bond. R a2 and R a3 may be linked to each other to form a ring.

[0090] R 31 ~R 38 Examples of the amide group of R a4 are represented by the formula: -NH-C(=O)-R a4 wherein R a4 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group can be referred to the descriptions of these groups above.

[0091] R 31 ~R 38 Examples of the sulfonamide group of ~R include the formula: -NH-SO2-R a5 represented by, and R a5 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group can be found in the descriptions of these groups above.

[0092] R 31 ~R 38 Examples of the halogeno group of ~R include a fluoro group, a chloro group, a bromo group, an iodo group, and the like.

[0093] R 32 ~R 38 Examples of each ring structure formed from ~R include a hydrocarbon ring and a heterocyclic ring. These ring structures may or may not have aromaticity, but are preferably a non-aromatic hydrocarbon ring or a non-aromatic heterocyclic ring. Examples of the non-aromatic hydrocarbon ring include cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane; cycloalkenes such as cyclopentene, cyclohexene, cyclohexadiene (e.g., 1,3-cyclohexadiene), cycloheptene, and cycloheptadiene. Examples of the non-aromatic heterocyclic ring include rings in which one or more of the carbon atoms constituting the ring of the non-aromatic hydrocarbon ring described above are replaced by at least one atom selected from N (nitrogen atom), S (sulfur atom), and O (oxygen atom). Examples of the non-aromatic heterocyclic ring include a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a tetrahydropyran ring, a tetrahydrothiopyran ring, a morpholine ring, a hexamethyleneimine ring, a hexamethylene oxide ring, a hexamethylene sulfide ring, and a heptamethyleneimine ring.

[0094] In formula (5), when R 31 ~R 33 are independent groups, R 31 ~R 33is preferably independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, or an aralkyl group, more preferably a hydrogen atom, an alkyl group, or an aryl group. R 31 ~R 33 Examples of the alkyl group and the aryl group of R

[0095] In formula (5), R 32 and R 33 The ring structure formed by the linkage is preferably a 4- to 9-membered unsaturated hydrocarbon ring, and among them, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are more preferable. If the group of formula (5) is configured in this way, the shoulder peak of the absorption waveform in the red to near-infrared region is reduced, and the absorption peak becomes sharp.

[0096] Examples of the aromatic hydrocarbon ring of ring P in formula (5) include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, a cyclotetradecaheptaene ring, and the like. The aromatic hydrocarbon ring may have only one ring structure, or may be a structure in which two or more ring structures are condensed. The aromatic heterocyclic ring of ring P contains one or more atoms selected from N (nitrogen atom), O (oxygen atom), and S (sulfur atom) in the ring structure and has aromaticity. For example, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a purine ring, a pteridine ring, and the like can be mentioned. The aromatic heterocyclic ring may have only one ring structure, or may be a structure in which two or more ring structures are condensed. The condensed ring containing these ring structures of ring P has a structure in which an aromatic hydrocarbon ring and an aromatic heterocyclic ring are condensed. For example, an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, a benzopyran ring, an acridine ring, a xanthene ring, a carbazole ring, and the like can be mentioned. By appropriately setting the π-conjugated system of ring P, the absorption wavelength in the red to near-infrared region can be easily adjusted.

[0097] 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 thereof is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1. Ring P may not have a substituent.

[0098] For details of the squarylium compound and croconium compound having the group represented by formula (5), reference is made to, for example, the description in JP-A-2016-74649.

[0099] In formula (6), when R 34 ~R 38 are independent groups, R 34 ~R 38 are each independently preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, an amide group, or a hydroxyl group. R 34 ~R 38By appropriately selecting, it becomes possible to control the absorption maximum wavelength of the squarylium compound or the croconium compound to a desired value. Among them, from the viewpoints of the stability and ease of production of the squarylium compound and the croconium compound, R 34 ~R 38 are each independently preferably a hydrogen atom, an alkyl group, or an amide group. In this case, the alkyl group is preferably linear or branched, and the number of carbon atoms thereof is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3.

[0100] The group represented by formula (6) preferably forms a ring by the connection of R 35 and R 36 , and further, R 36 and R 37 may form a ring by connection. In this case, at least R 34 and R 38 are independent groups. If the group of formula (6) is configured in this way, the absorption peak in the red to near-infrared region becomes sharp. Note that the ring structure formed from R 35 and R 36 and the ring structure formed from R 36 and R 37 preferably have 5 or more ring members, more preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0101] In the group represented by formula (6), R 36 is an amino group, or an amino group R 36 forms a ring by connecting with R 35 , or further forms a ring by connecting with R 37 as well. It is preferable that an amino group R 36 is R 35 or R 37The number of ring members of the ring formed by linking is preferably 5 or more, more preferably 6 or more, also preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. In this case, the absorption maximum wavelength shifts to the long wavelength side (for example, 685 nm or more), increasing the transmittance of light in the red region and making the color tone of the transmitted light closer to the actual one. Also, from the same viewpoint, R 34 or R 38 is preferably an amide group.

[0102] In the squarylium compound and croconium compound having the group represented by formula (6), the benzene rings on both sides of the squarylium skeleton or croconium skeleton may be linked by a linking group. Examples of such compounds include the squarylium compounds disclosed in JP-A-2015-176046.

[0103] As the dye of the component (D), it is also preferable to use a compound having a styrene structure represented by the following formula (7) (hereinafter referred to as "styrene compound"). The styrene compound represented by the following formula (7) functions as an ultraviolet absorbing dye, forms an absorption wavelength region in the range of 350 nm to 395 nm, and can form a sharp boundary between the absorption wavelength region and the transmission wavelength region on the long wavelength side of the absorption wavelength region. Therefore, if the resin composition contains such a styrene compound, it can be suitably applied to an optical filter or the like that cuts light in the purple to ultraviolet region by forming a resin layer on a phosphate-based or fluophosphate-based glass substrate.

[0104] [Chemical formula]

[0105] In the above formula (7), R 41 represents a cyano group, an acyl group, a carboxylic acid ester group or an amide group, R 42 represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or a heteroaryl group, and R 41 and R 42When both are an acyl group, a carboxylic acid ester group or an amide group, R 41 and R 42 may be linked to each other to form a ring, R 43 represents a hydrogen atom or an alkyl group, R 44 represents a hydrogen atom, an organic group or a polar functional group, and a plurality of R 44 may be the same as or different from each other, Y represents a sulfur atom or an oxygen atom, L represents a hydrogen atom or a divalent or higher linking group, a represents an integer of 1 or more, and when a is 2 or more, a plurality of groups bonded to L may be the same as or different from each other. In formula (7), R 41 (or R 42 ) may be in the cis position or the trans position with respect to R 43 .

[0106] R 41 and R 42 Examples of the acyl group (alkanoyl group) include a methanoyl group, an ethanoyl group, a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a tridecanoyl group, a tetradecanoyl group, a pentadecanoyl group, a hexadecanoyl group, a heptadecanoyl group, an octadecanoyl group, a nonadecanoyl group, an eicosanoyl group and the like. In the acyl group, a part of the hydrogen atoms may be substituted with an aryl group, an alkoxy group, a halogeno group, a hydroxyl group or the like. The alkyl group in the acyl group may be linear or branched. The number of carbon atoms of the acyl group (the number of carbon atoms excluding substituents) is preferably 2 to 21, more preferably 2 to 11, and still more preferably 2 to 6.

[0107] R 41 and R 42 Examples of the carboxylic acid ester group include those represented by the formula: -C(=O)-O-R b1 , where R b1 is an alkyl group, an aryl group or an aralkyl group. Specific examples of the alkyl group, aryl group and aralkyl group can be referred to the descriptions of these groups of R 31 to R 38 above.

[0108] R 41 and R 42 Examples of the amide group include the formula: -C(=O)-NR b2 R b3 represented by, where R b2 is a hydrogen atom or an alkyl group, and R b3 is an alkyl group, an acyl group, an aryl group or an aralkyl group. Specific examples of the alkyl group, aryl group and aralkyl group of R b2 and R b3 are as described for these groups of the above R 31 ~R 38 and are referred to, and specific examples of the acyl group of R b3 are as described for the acyl group of the above R 41 and R 42 and are referred to.

[0109] R 41 and R 42 are both acyl groups and are linked to each other to form a ring. Examples of the group formed from R 41 and R 42 include the formula: -C(=O)-R b4 -C(=O)-. R 41 and R 42 are both carboxylic acid ester groups and are linked to each other to form a ring. Examples of the group formed from R 41 and R 42 include the formula: -C(=O)-O-R b5 -O-C(=O)-. R 41 and R 42 are both amide groups and are linked to each other to form a ring. Examples of the group formed from R 41 and R 42 include the formula: -C(=O)-NR b6 -R b7 -NR b8 -C(=O)-. In these formulas, R b4 、R b5 and R b7 each independently represent a linear or branched alkylene group, and R b6 and R b8Each independently represents a hydrogen atom or a hydrocarbon group, and the carbon atoms of the carbonyl groups at both ends of the structures shown in these formulas are bonded to the carbon atoms of the ethylene double bond of formula (7). R b4 , R b5 and R b7 The alkylene groups of may have some hydrogen atoms substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, etc. R b4 , R b5 and R b7 The number of carbon atoms of the alkylene groups of (excluding the carbon atoms of the substituents) is preferably 2 to 10, more preferably 3 to 8. R b6 and R b8 As the hydrocarbon group of, an alkyl group, an aryl group or an aralkyl group is preferably exemplified, and specific examples of these groups are the above R 31 ~R 38 Refer to the descriptions of the alkyl group, aryl group and aralkyl group of.

[0110] R 42 As the hydrocarbon group of, an aliphatic hydrocarbon group, an aromatic hydrocarbon group (aryl group) can be mentioned. The aliphatic hydrocarbon group may be either saturated or unsaturated, and may be linear, branched or cyclic. Specific examples of the aliphatic saturated hydrocarbon group are the above R 31 ~R 38 Refer to the description of the alkyl group of, and specific examples of the aliphatic unsaturated hydrocarbon group are those in which a part of the carbon-carbon single bond of the alkyl group of R 31 ~R 38 is replaced by a double bond or a triple bond. Specific examples of the aromatic hydrocarbon group (aryl group) are the above R 31 ~R 38 Refer to the description of the aryl group of.

[0111] R 42 Specific examples of the heteroaryl group of are the above R 31 ~R 38Reference is made to the description of the heteroaryl group. The heteroaryl group is preferably bonded to the carbon atom of the ethylene double bond of formula (7) through a carbon atom, more preferably bonded to the carbon atom of the ethylene double bond of formula (7) through a carbon atom adjacent to the heteroatom, which facilitates the synthesis of the styrene compound.

[0112] R in formula (7) 43 represents a hydrogen atom or an alkyl group. Specific examples of the alkyl group are the same as those of R 31 ~R 38 in the description of the alkyl group. The alkyl group of R 43 is preferably C1-C3, more preferably C1-C2. As R 43 a hydrogen atom is particularly preferred.

[0113] R in formula (7) 44 For the details of the organic group and the polar functional group of R 31 ~R 38 reference is made to the description of the organic group and the polar functional group. R 44 is preferably one or more selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group, and an arylthio group, more preferably a hydrogen atom or an alkyl group. The carbon number of the alkyl group is preferably 1-4, more preferably 1-3. Among them, for the four Rs 44 bonded to the benzene ring of formula (7), it is preferably that 2 or more are hydrogen atoms, more preferably 3 or more are hydrogen atoms, and particularly preferably all 4 are hydrogen atoms.

[0114] In formula (7), Y represents a sulfur atom or an oxygen atom. Y may be bonded to the ethylene structural part containing R 41 ~R 43 at the ortho position, meta position, or para position. From the viewpoint of the ease of producing the styrene compound, Y is preferably bonded to the ethylene structural part at the para position. Also, Y is preferably a sulfur atom.

[0115] In formula (7), when L is a divalent or higher linking group, examples of the linking group include divalent linking groups such as an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, -SO2-, -NH-; trivalent linking groups such as a methine group (-CH<) and -N< which may be substituted with an alkyl group; tetravalent linking groups such as >C<; and linking groups formed by combining these. The alkylene group may be linear, branched, or cyclic. Further, the alkylene group and the arylene group may have a hydroxyl group and / or a thiol group.

[0116] From the viewpoint of enhancing the heat resistance of the styrene-based compound, a is preferably an integer of 2 or more, and L preferably represents a divalent or higher linking group. Further, the linking group L is preferably an alkylene group in which a part of the hydrogen atoms may be replaced by a hydroxyl group and / or a thiol group, an arylene group in which a part of the hydrogen atoms may be replaced by a hydroxyl group and / or a thiol group, -O-, -S-, and a linking group formed by combining these groups (however, ether bonds and thioether bonds are not continuous). The number of carbon atoms (continuous carbon atoms) of the linear or branched alkylene group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. In the case of a cyclic alkylene group, the number of carbon atoms is preferably 4 or more, more preferably 5 or more, preferably 10 or less, and more preferably 8 or less. The number of carbon atoms of the arylene group is preferably 5 or more, more preferably 6 or more, preferably 10 or less, and more preferably 8 or less.

[0117] As the styrene-based compound, the styrene-based compound represented by the following formula (7A) is particularly preferably shown. Such a styrene-based compound has, for example, a peak having an absorption maximum in the range of wavelengths of 300 nm to 420 nm, can effectively absorb light in the ultraviolet (UVA) to purple region, has excellent stability, and is easy to manufacture. In the following formula (7A), R 41a and R 41b are described with reference to the description of R 41 above, and the description of R 42a and R 42b is described with reference to the description of R 42 above, and R43a and R 43b is described in the above R 43 is described and Y a and Y b is described in the above Y description is referred to.

[0118]

Chemical formula

[0119] For the details of the styrene-based compound represented by Formula (7) or Formula (7A), the description in International Publication No. 2019 / 009093 is referred to.

[0120] The resin composition may contain a solvent. For example, when the resin composition is a resin composition made into a paint, containing a solvent facilitates the coating of the resin composition.

[0121] The solvent may function to dissolve each component contained in the resin composition or may function as a dispersion medium. Examples of the solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycol derivatives such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol ethyl ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); 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; and the like. These solvents may be used alone or in combination of two or more.

[0122] The solvent content is preferably, for example, 30% by mass or more, more preferably 45% by mass or more, still more preferably 60% by mass or more, and preferably less than 100% by mass, more preferably 95% by mass or less, based on 100% by mass of the resin composition. By adjusting the solvent content within such a range, the coatability of the resin composition can be enhanced.

[0123] The resin composition preferably contains little water. Thereby, hydrolysis of the compound containing the M - O - C bond of component (B) in the resin composition is suppressed, and it becomes easier to exist stably. The water content in the resin composition is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, based on 100% by mass of the resin composition. Also, the water content in the resin composition is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1 part by mass or less, relative to 100 parts by mass of the solid content of the resin composition. It is particularly preferable that the resin composition does not contain water. The water content in the resin composition can be analyzed by the Karl Fischer method (volumetric titration method).

[0124] In the resin composition, the molar ratio (H2O / M) of the water content to the content of Ti atoms, Zr atoms or Al atoms is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less. As described above, the epoxy compound of component (C) may have an alkoxysilyl group or an alkylsilyl group, but in the resin composition, the molar ratio (H2O / (M + Si)) of the water content to the total content of Ti atoms, Zr atoms or Al atoms and Si atoms is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less.

[0125] From the viewpoint of suppressing the hydrolysis of the compound containing the M-O-C bond of component (B) and enhancing the storage stability of the resin composition, the resin composition may contain an alcohol compound as component (E). Even when the resin composition contains the alcohol compound of component (E), by containing the compound containing the M-O-C bond of component (B) and the epoxy compound of component (C), a resin layer excellent in adhesion to a phosphoric acid-based or pyrophosphoric acid-based glass can be formed.

[0126] The alcohol compound is not particularly limited as long as it has at least one alcoholic hydroxyl group, and is preferably a polyhydric alcohol compound having two or more alcoholic hydroxyl groups. The upper limit of the number of alcoholic hydroxyl groups possessed by the alcohol compound is not particularly limited, and may be 10 or less, 8 or less, 6 or less, or 4 or less.

[0127] The alcohol compound is preferably a compound in which an alcoholic hydroxyl group is bonded to an aliphatic hydrocarbon chain. The number of carbon atoms of the alcohol compound is preferably 4 or more, more preferably 5 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. By using such an alcohol compound, it becomes easy to ensure solubility or compatibility with the resin, and the storage stability of the resin composition can be enhanced.

[0128] When the resin composition contains the alcohol compound of component (E), the content of component (E) in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, based on 100% by mass of the solid content of the resin composition. The blending amount of component (E) with respect to 100 parts by mass of the resin of component (A) is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, even more preferably 0.5 part by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less.

[0129] In the resin composition, the molar equivalent of the alcoholic hydroxyl group of component (E) to the metal atom M of component (B), that is, the molar amount of the alcoholic hydroxyl group of component (E) per 1 mol of the metal atom M of component (B) is preferably 1 mol / mol or more, more preferably 2 mol / mol or more, still more preferably 3 mol / mol or more, and preferably 100 mol / mol or less, more preferably 80 mol / mol or less, still more preferably 50 mol / mol or less.

[0130] The resin composition may contain a surface conditioner, whereby when the resin composition is cured to form a resin layer, it is possible to suppress the occurrence of appearance defects such as striations and dents in the resin layer. The type of the surface conditioner is not particularly limited, and a siloxane-based surfactant, an acetylene glycol-based surfactant, a fluorine-based surfactant, an acrylic leveling agent, etc. can be used. As the surface conditioner, for example, BYK (registered trademark) series manufactured by BYK Chemie GmbH, KF series manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be used.

[0131] The resin composition may contain a dispersant, whereby the dispersibility of the resin composition can be stabilized and re-aggregation can be suppressed. The type of the dispersant is not particularly limited, and EFKA series manufactured by Efka Additives, BYK (registered trademark) series manufactured by BYK Chemie GmbH, Solsperse (registered trademark) series manufactured by Lubrizol Japan Ltd., Disparon (registered trademark) series manufactured by Namboku Kasei Co., Ltd., Ajisper (registered trademark) series manufactured by Ajinomoto Fine-Techno Co., Inc., KP series manufactured by Shin-Etsu Chemical Co., Ltd., Polyflow series manufactured by Kyoeisha Chemical Co., Ltd., Megafac (registered trademark) series manufactured by DIC Corporation, Disper Aid series manufactured by San Nopco Ltd., etc. can be used.

[0132] The resin composition may contain various additives such as a plasticizer, a surfactant, a viscosity modifier, an antifoaming agent, a preservative, a specific resistance modifier, a stability improver such as a polyvalent mercaptan, and an adhesion improver, as required.

[0133] The resin composition may contain a reaction product of (A) a resin and (B) a compound containing an MOC bond. The resin composition may also contain a reaction product of (B) a compound containing an MOC bond and (C) an epoxy compound.

[0134] The resin composition can be prepared by blending (A) a resin, (B) a compound containing an MOC bond, and (C) an epoxy compound. The resin composition may further comprise (D) at least one selected from the group consisting of a near-infrared absorbing dye, an ultraviolet absorbing dye, and a visible light absorbing dye. For details of the method for preparing the resin composition, see the resin composition preparation step described below.

[0135] The resin composition can be cured to a cured product by curing. The resin composition can be cured, for example, by injection molding, extrusion molding, vacuum molding, compression molding, blow molding, etc. In this case, the resin composition may be molded after being heated to, for example, about 150°C to 350°C to melt. The shape of the molded product is not particularly limited, and examples thereof include plate-like, sheet-like, granular, powdery, lumpy, particle aggregate-like, spherical, elliptical, lenticular, cubic, columnar, rod-like, conical, cylindrical, needle-like, fibrous, hollow fiber-like, and porous shapes.

[0136] The resin composition may be prepared as a paint so that it can be applied by spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, slit coating, screen printing, flexographic printing, inkjet printing, etc. In this case, a film-like cured product having a thickness of 200 μm or less or a sheet-like product having a thickness of more than 200 μm can be obtained by applying a liquid or paste-like resin composition onto a substrate.

[0137] The resin composition in the form of a coating can form a resin layer laminated substrate by coating it on a substrate to form a resin layer. As the substrate, a resin plate, a resin film, a glass plate, etc. can be used. Examples of the glass used for the substrate include silicate glass, borosilicate glass, boric acid glass, etc. However, considering the characteristics of the resin composition of the present invention, it is preferable to use a substrate composed of a phosphoric acid-based or fluophosphoric acid-based glass. If the resin composition of the present invention is used, even when the resin composition is coated on a phosphoric acid-based or fluophosphoric acid-based glass substrate and a resin layer is directly formed on the glass substrate, the adhesion between the resin and the glass substrate can be enhanced. The present invention can also provide a resin laminated substrate having a phosphoric acid-based or fluophosphoric acid-based glass substrate and a resin layer directly formed on the substrate and obtained by curing the resin composition of the present invention.

[0138] In the resin laminated substrate formed as described above, the phosphoric acid-based or fluophosphoric acid-based glass substrate and the resin layer are laminated and integrated, and the adhesion between the phosphoric acid-based or fluophosphoric acid-based glass substrate and the resin layer is enhanced. The resin layer may be provided on only one side of the substrate or on both sides.

[0139] The resin laminated substrate can be applied to filters used in various applications such as opto-device applications, display device applications, mechanical parts, electrical and electronic parts, etc. Therefore, the resin composition and the resin laminated substrate of the present invention can be used for optical filter applications such as near-infrared cut filters and light-selective transmission filters.

[0140] The thickness of the resin layer of the optical filter is not particularly limited, but from the viewpoint of ensuring desired light selective transmission performance, for example, 0.5 μm or more is preferable, and 1 μm or more is more preferable. As the upper limit of the thickness of the resin layer, for example, it may be 1 mm or less, 500 μm or less, 200 μm or less, or 50 μm or less. When the resin composition in the form of a coating is applied onto a substrate by the spin coating method, the thickness of the resin layer can be made even thinner. From the viewpoint of forming a thinner optical filter, the resin layer is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 2 μm or less.

[0141] The thickness of the substrate is, for example, preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoint of ensuring strength, and preferably 0.4 mm or less, more preferably 0.3 mm or less, from the viewpoint of thinning.

[0142] The resin laminated substrate or the optical filter is preferably manufactured by the following method. That is, the method for manufacturing the resin laminated substrate or the optical filter of the present invention includes a step of obtaining a resin composition by blending (A) a resin, (B) a compound containing an M-O-C bond, and (C) an epoxy compound (resin composition preparation step), a step of applying the resin composition onto a phosphoric acid-based or fluorophosphoric acid-based glass substrate to form a coating film of the resin composition (coating step), and a step of heating the coating film to form a resin layer obtained by curing the resin composition on the phosphoric acid-based or fluorophosphoric acid-based glass substrate (resin layer forming step).

[0143] In the resin composition preparation step, a resin composition is obtained by blending (A) a resin, (B) a compound containing an M-O-C bond, and (C) an epoxy compound. For details of the resin as component (A), the compound containing an M-O-C bond as component (B), and the epoxy compound as component (C), reference is made to the above description. In the resin composition preparation step, the resin as component (A) and the compound containing an M-O-C bond as component (B) may react to form a reaction product of component (A) and component (B). Also, the compound containing an M-O-C bond as component (B) and the epoxy compound as component (C) may react to form a reaction product of component (B) and component (C).

[0144] In the resin composition preparation step, it is preferable to blend components (A), (B), and (C) and stir them. The stirring time at this time is preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 3 hours or more. The upper limit of the stirring time is not particularly limited and may be, for example, 48 hours or less, 24 hours or less, or 16 hours or less.

[0145] In the resin composition preparation step, at least one selected from the group consisting of (D) a near-infrared absorbing dye, an ultraviolet absorbing dye, and a visible light absorbing dye may be further blended. For details of the dye as component (D), reference is made to the above description. If the resin composition contains a dye, it can be suitably used for an optical filter having light selective permeability for a resin laminated substrate.

[0146] In the resin composition preparation step, an (E) alcohol compound may be further blended. For details of the alcohol compound as component (E), reference is made to the above description.

[0147] In the resin composition preparation step, it is preferable to further blend a solvent. This makes it easier to uniformly coat the resin composition on a substrate in the subsequent coating step. In the resin composition preparation step, various additives such as a plasticizer, a surfactant, a viscosity modifier, an antifoaming agent, a preservative, a specific resistance modifier, a stability improver such as a polyvalent mercaptan, and an adhesion improver may be blended.

[0148] In the resin composition preparation step, it is preferable that an M-O-C bond of component (B) is present in the resin composition obtained. Therefore, in the resin composition preparation step, it is preferable to suppress the reaction of the compound containing the M-O-C bond of component (B). From such a viewpoint, it is preferable to carry out the blending of each component or the stirring after blending in the resin composition preparation step at 60°C or lower, more preferably 50°C or lower, and even more preferably 40°C or lower. On the other hand, from the viewpoint of easy uniform mixing of each component, it is preferable to carry out the blending of each component or the stirring after blending in the resin composition preparation step at 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher.

[0149] In order to make an M-O-C bond of component (B) present in the resin composition obtained in the resin composition preparation step, in the resin composition preparation step, it is preferable not to blend water or to keep the blending amount of water low. For example, the blending amount of water in the resin composition preparation step is preferably 3 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.5 part by mass or less, even more preferably 0.3 part by mass or less, and particularly preferably 0.1 part by mass or less with respect to a total of 100 parts by mass of the resin of component (A) and the solvent (excluding water). Also, with respect to 100 parts by mass of the resin of component (A), the blending amount of water in the resin composition preparation step is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and even more preferably 0.5 part by mass or less. The molar ratio (H2O / M) of the blending amount of water to the blending amount of the Ti atom, Zr atom, or Al atom of component (B) is preferably 50 or less, more preferably 20 or less, even more preferably 10 or less, and even more preferably 5 or less. When the epoxy compound of component (C) has an alkoxysilyl group or an alkylsilyl group, the molar ratio (H2O / (M + Si)) of the blending amount of water to the total blending amount of the Ti atom, Zr atom, or Al atom of component (B) and the Si atom of component (C) is preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and even more preferably 2 or less.

[0150] In the coating process, the resin composition is coated on a phosphoric acid-based or metaphosphoric acid-based glass substrate to form a coating film of the resin composition. In the coating process, for example, the resin composition can be coated on a phosphoric acid-based or metaphosphoric acid-based glass substrate by a spin coating method, a solvent casting method, a roll coating method, a spray coating method, a bar coating method, a dip coating method, a slit coating method, a screen printing method, a flexographic printing method, an inkjet method, etc., to form a coating film of the resin composition. From the viewpoint of easily forming a thin and uniform coating film, it is preferable to adopt the spin coating method in the coating process.

[0151] In the resin layer forming process, the coating film formed on the phosphoric acid-based or metaphosphoric acid-based glass substrate is heated to form a resin layer in which the resin composition is cured on the substrate. In the resin layer forming process, it is preferable to heat the coating film in a state where the M-O-C bond of the component (B) exists in the resin composition. By heating the coating film of the resin composition, the resin composition is cured to form a resin layer, and the M-O-C bond of the component (B) reacts or acts with the P=O bond or P-O-P bond present on the surface of the phosphoric acid-based or metaphosphoric acid-based glass, and the adhesion between the resin layer and the phosphoric acid-based or metaphosphoric acid-based glass can be enhanced.

[0152] The heating temperature in the resin layer forming process is preferably 100 °C or higher, more preferably 120 °C or higher, further preferably 140 °C or higher, and preferably 380 °C or lower, more preferably 300 °C or lower, and further preferably 260 °C or lower. The heating time in the resin layer forming process may be set to a time sufficient for the resin composition to be cured to form a resin layer, and may be appropriately set, for example, between 10 minutes and 180 minutes. The heating atmosphere in the resin layer forming process is not particularly limited, but it is preferably carried out in an inert atmosphere such as nitrogen or argon.

[0153] The optical filter may have, as the second resin layer, a protective layer made of the same or different resin as the above resin layer. By providing the protective layer, the durability (decomposition resistance) of each component contained in the resin layer can be enhanced. The protective layer is preferably provided on the side of the resin layer opposite to the substrate.

[0154] The optical filter may have a layer (antireflection film) having antireflection properties and antiglare properties for reducing reflections from fluorescent lamps and the like, a layer having scratch prevention performance, a transparent substrate having other functions, and the like. The optical filter may have an ultraviolet reflection film or a near-infrared reflection film on the resin layer. The ultraviolet reflection film and the near-infrared reflection film are preferably provided on the light incident side rather than the resin layer. If an ultraviolet reflection film or a near-infrared reflection film is provided on the optical filter, ultraviolet rays and near-infrared rays can be more effectively cut from the transmitted light of the optical filter. The ultraviolet reflection film and the near-infrared reflection film may have a single ultraviolet reflection function and near-infrared reflection function.

[0155] An ultraviolet reflection film, a near-infrared reflection film, and an antireflection film (visible light antireflection film) can be composed of a dielectric film. The dielectric film is usually configured as a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated, but it may also be composed of only one of the high refractive index material layer and the low refractive index material layer. As the material for forming the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 or more and 2.5 or less is preferably selected. The refractive index range is more preferably 1.8 or more, and even more preferably 2.0 or more. Examples of the material for forming the high refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; nitrides such as silicon nitride; mixtures of the above oxides and nitrides, and those doped with metals such as aluminum and copper or carbon (for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. As the material for forming the low refractive index material layer, a material having a refractive index of less than 1.7 can be used, and a material having a refractive index range of 1.2 to 1.6 is preferably selected, and a material having a refractive index range of 1.3 to 1.5 is more preferably selected. Examples of the material for forming the low refractive index material layer include silicon oxide (silica, SiOx (x = 1 to 2)), alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoroaluminate, etc. Among these, the high refractive index material layer is preferably composed of titanium oxide, and the low refractive index material layer is preferably composed of silicon oxide.

[0156] The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably adjusted to the range of 0.1λ to 0.5λ of the wavelength λ (nm) of the light to be blocked, and more preferably adjusted to the range of 0.2λ to 0.3λ. By forming the dielectric film in this way, light in a desired wavelength range can be selectively reflected, and a near-infrared reflection film, an ultraviolet reflection film, an antireflection film (visible light antireflection film), etc. can be formed by the dielectric film. The ultraviolet reflection film and the near-infrared reflection film may have both an ultraviolet reflection function and a near-infrared reflection function.

[0157] The number of dielectric layers is not particularly limited as long as it is one or more, but from the viewpoint of exhibiting desired optical performance as a near-infrared reflection film, ultraviolet reflection film, antireflection film, etc., it is preferably, for example, 2 to 80 layers. The number of dielectric layers may be 5 or more, 10 or more, or 20 or more, and may also be 70 or less or 60 or less. The thickness of the dielectric film is not particularly limited and may be, for example, in the range of 0.01 μm to 10 μm. However, from the viewpoint of sufficiently cutting off the incidence of light in a desired wavelength range, 0.02 μm or more is preferable, 0.03 μm or more is more preferable, and from the viewpoint of thinning, 5 μm or less is preferable, and 3 μm or less is more preferable.

[0158] The optical filter may have an aluminum vapor deposition film, a noble metal thin film, a resin film in which metal oxide fine particles mainly composed of indium oxide and containing a small amount of tin oxide are dispersed, and the like.

[0159] The thickness of the optical filter is preferably, for example, 1 mm or less. Thereby, for example, it is possible to sufficiently meet the demand for miniaturization of the imaging device. The thickness of the optical filter is more preferably 500 μm or less, even more preferably 300 μm or less, even more preferably 150 μm or less, and preferably 30 μm or more, and more preferably 50 μm or more.

[0160] The optical filter of the present invention is particularly suitable for imaging device applications. The present invention includes an imaging device having the optical filter. The imaging device, also referred to as a solid-state imaging device or an image sensor chip, is an electronic component that converts the light of a subject into an electrical signal and outputs it as an electrical signal. The imaging device usually has a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor), and may have a lens. The imaging device is used, for example, in a camera for mobile phones, a digital camera, an in-vehicle camera, a surveillance camera, a display element (such as an LED), etc. The imaging device includes one or more of the optical filters of the present invention and may further have other members as necessary.

Examples

[0161] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and it is also possible to appropriately modify and implement it within the range that conforms to the gist of the foregoing and following descriptions, and all of them are included in the technical scope of the present invention.

[0162] (1) Synthesis of Compounds (1-1) Synthesis of Near-Infrared Absorbing Dye A According to the method described in Examples 1-18 of JP-A-2016-74649, the near-infrared absorbing dye A (squarylium compound) shown in Table 1 was synthesized. When the transmission spectrum of near-infrared absorbing dye A in toluene was measured, the absorption maximum wavelength was 737 nm.

[0163] (1-2) Synthesis of Near-Infrared Absorbing Dye B According to Synthesis Example 2 described in the examples of JP-A-2020-132699, the near-infrared absorbing dye B shown in Table 1 was synthesized.

[0164] (1-3) Synthesis of Ultraviolet Absorbing Dye A According to Synthesis Example 12 described in the examples of JP-A-2018-14707, the ultraviolet absorbing dye A shown in Table 1 was synthesized.

[0165]

Table 1

[0166] (2) Preparation of Resin Composition (2-1) Preparation Example 1: Preparation of Resin Composition 1 In a 2 L reaction vessel equipped with a stirring blade, 10.0 g (0.044 mol) of 2,2'-bis(4-hydroxyphenyl)propane, 3.6 g (0.090 mol) of sodium hydroxide, and 300 g of ion-exchanged water were charged and dissolved. Then, 0.89 g (0.009 mol) of triethylamine was added thereto and dissolved. A solution prepared by dissolving 3.6 g (0.021 mol) of terephthaloyl dichloride and 3.6 g (0.021 mol) of isophthaloyl dichloride in 500 g of methylene chloride was placed in a dropping funnel, and this was attached to the reaction vessel. While maintaining the solution in the reaction vessel at 20 °C, it was stirred, and the methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Further, a solution prepared by dissolving 0.71 g (0.005 mol) of benzoyl chloride in 10 g of methylene chloride was added thereto, and the mixture was stirred for 60 minutes. An aqueous acetic acid solution was added to the obtained reaction solution for neutralization to adjust the pH of the aqueous phase to 7, and then the oil phase and the aqueous phase were separated using a separating funnel. The obtained oil phase was added dropwise to methanol with stirring to reprecipitate the polymer, and the precipitate was collected by filtration and dried in an oven at 80 °C to obtain 1.5 g of a white solid polyarylate resin (PAR resin). The weight-average molecular weight (Mw) of the obtained polyarylate resin was 33,780, and the number-average molecular weight (Mn) was 8,130. The weight-average molecular weight and the number-average molecular weight of the polyarylate resin are values in terms of polystyrene determined by gel permeation chromatography measurement.

[0167] 79 parts by mass of the polyarylate resin obtained above was added to a mixed solvent of 280 parts by mass of toluene and 523 parts by mass of o-xylene. Further, 7.6 parts by mass of near-infrared absorbing dye A, 2.6 parts by mass of near-infrared absorbing dye B, and 11 parts by mass of ultraviolet absorbing dye A were added thereto, and the mixture was stirred at 40 °C for 1 hour. Next, 0.30 part by mass of BYK-310 (polyether-modified polydimethylsiloxane) manufactured by BYK-Chemie was added thereto as a surface conditioner to obtain a base resin composition. Separately, 20 parts by mass of a polyarylate resin, 75 parts by mass of toluene, and 5.2 parts by mass of Ti compound 1 (tetrakis(2-ethylhexyl) orthotitanate, manufactured by Tokyo Chemical Industry Co., Ltd.) shown in Table 2 as a compound having an M-O-C bond were blended and stirred at 25 °C for 12 hours to obtain a resin solution of Ti compound 1. The resin solution of Ti compound 1 thus obtained was added to the base resin composition, and further 7.0 parts by mass of EP compound 1 (4,4'-methylenebis(N,N-diglycidylaniline), manufactured by Sumitomo Chemical Co., Ltd., Sumiepoxy (registered trademark) ELM-434) shown in Table 2 as an epoxy compound was added and stirred at 25 °C overnight (for 12 hours or more). This was filtered through a filter with a pore size of 0.1 μm (GL Sciences Inc., non-aqueous 13N) to remove foreign matters, and resin composition 1 was obtained.

[0168] (2-2) Preparation Example 2: Preparation of Resin Composition 2 In Preparation Example 1, resin composition 2 was obtained in the same manner as in Preparation Example 1, except that 5.0 parts by mass of EP compound 2 (4-(2,3-epoxypropan-1-yloxy)-N,N-bis(2,3-epoxypropan-1-yl)-2-methylaniline, manufactured by Sumitomo Chemical Co., Ltd., Sumiepoxy (registered trademark) ELM-100) shown in Table 2 was added as the epoxy compound instead of EP compound 1.

[0169] (2-3) Preparation Example 3: Preparation of Resin Composition 3 In Preparation Example 1, resin composition 3 was obtained in the same manner as in Preparation Example 1, except that 4.0 parts by mass of EP compound 3 (1,4-butanediol diglycidyl ether, manufactured by Tokyo Chemical Industry Co., Ltd.) shown in Table 2 was added as the epoxy compound instead of EP compound 1.

[0170] (2-4) Preparation Example 4: Preparation of Resin Composition 4 As the epoxy compound, 4.0 parts by mass of EP Compound 4 (3-glycidoxypropyltrimethoxysilane, manufactured by Dow Corning Toray Co., Ltd., OFS-6040) shown in Table 2, 5.2 parts by mass of 2-propanol, and 0.55 parts by mass of distilled water were blended and uniformly mixed at 25°C. Then, 0.25 parts by mass of formic acid was added and mixed for 90 minutes to allow the hydrolysis reaction to proceed, obtaining a hydrolyzed solution of EP Compound 4. The resin composition 4 was obtained in the same manner as in Preparation Example 1, except that the hydrolyzed solution of EP Compound 4 thus obtained was used instead of EP Compound 1 in Preparation Example 1.

[0171] (2-5) Preparation Example 5: Preparation of Resin Composition 5 The resin composition 5 was obtained in the same manner as in Preparation Example 1, except that 2.6 parts by mass of Ti Compound 1 was used in Preparation Example 1.

[0172] (2-6) Preparation Example 6: Preparation of Resin Composition 6 In Preparation Example 1, as the compound having an M-O-C bond, 2.6 parts by mass of Ti Compound 2 (titanium tetraisopropoxide, manufactured by Fujifilm Wako Pure Chemical Corporation) shown in Table 2 was used instead of Ti Compound 1 to obtain a resin solution of Ti Compound 2. The resin composition 6 was obtained in the same manner as in Preparation Example 1, except that this was added to the base resin composition instead of the resin solution of Ti Compound 1.

[0173] (2-7) Preparation Example 7: Preparation of Resin Composition 7 In Preparation Example 1, as the compound having an M-O-C bond, 2.6 parts by mass of Ti Compound 3 (tetrakis(2,4-pentanedionato)titanium, manufactured by Tokyo Chemical Industry Co., Ltd.) shown in Table 2 was used instead of Ti Compound 1 to obtain a resin solution of Ti Compound 3. The resin composition 7 was obtained in the same manner as in Preparation Example 1, except that this was added to the base resin composition instead of the resin solution of Ti Compound 1.

[0174] (2-8) Preparation Example 8: Preparation of Resin Composition 8 In Preparation Example 1, as the compound having an M-O-C bond, 2.6 parts by mass of Ti Compound 4 shown in Table 2 (bis(2,4-pentanedionato)bis(2-propanolato)titanium, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of Ti Compound 1 to obtain a resin solution of Ti Compound 4, and Resin Composition 8 was obtained in the same manner as in Preparation Example 1 except that this was added to the base resin composition instead of the resin solution of Ti Compound 1.

[0175] (2-9) Preparation Example 9: Preparation of Resin Composition 9 In Preparation Example 4, Resin Composition 9 was obtained in the same manner as in Preparation Example 4 except that 16.8 parts by mass of Additive 1 (2-ethyl-1,3-hexanediol, manufactured by Tokyo Chemical Industry Co., Ltd.) was further added to the resin solution of Ti Compound 1.

[0176] (2-10) Preparation Example 10: Preparation of Resin Composition 10 20 parts by mass of polyarylate resin, 61.3 parts by mass of toluene, 1.9 parts by mass of Al Compound 1 shown in Table 2 (aluminum triisopropoxide, manufactured by Fujifilm Wako Pure Chemical Corporation) as the compound having an M-O-C bond, and 16.8 parts by mass of Additive 1 were blended and stirred at 25°C for 12 hours to obtain a resin solution of Al Compound 1. Resin Composition 10 was obtained in the same manner as in Preparation Example 1 except that the resin solution of Al Compound 1 thus obtained was added to the base resin composition instead of the resin solution of Ti Compound 1 in Preparation Example 1.

[0177] (2-11) Preparation Example 11: Preparation of Resin Composition 11 20 parts by mass of polyarylate resin, 59.7 parts by mass of toluene, 3.5 parts by mass of Zr Compound 1 shown in Table 2 (zirconium tetrabutoxide, manufactured by Tokyo Chemical Industry Co., Ltd.) as the compound having an M-O-C bond, and 16.8 parts by mass of Additive 1 were blended and stirred at 25°C for 12 hours to obtain a resin solution of Zr Compound 1. Resin Composition 11 was obtained in the same manner as in Preparation Example 1 except that the resin solution of Zr Compound 1 thus obtained was added to the base resin composition instead of the resin solution of Ti Compound 1 in Preparation Example 1.

[0178] (2-12) Preparation Example 12: Preparation of Resin Composition 12 A resin composition 12 was obtained in the same manner as in Preparation Example 11, except that 2.6 parts by mass of Zr compound 1, 5.3 parts by mass of EP compound 1, and 12.6 parts by mass of Additive 1 were used.

[0179] (2-13) Preparation Example 13: Preparation of Resin Composition 13 A resin composition 13 was obtained in the same manner as in Preparation Example 11, except that 1.8 parts by mass of Zr compound 1, 3.5 parts by mass of EP compound 1, and 8.4 parts by mass of Additive 1 were used.

[0180] (2-14) Preparation Example 14: Preparation of Resin Composition 14 A resin composition 14 was obtained in the same manner as in Preparation Example 11, except that 0.7 parts by mass of Zr compound 1, 1.3 parts by mass of EP compound 1, and 3.6 parts by mass of Additive 1 were used.

[0181] (2-15) Preparation Example 15: Preparation of Resin Composition 15 A resin composition 15 was obtained in the same manner as in Preparation Example 11, except that 7.0 parts by mass of Zr compound 1, 14.0 parts by mass of EP compound 1, and 6.7 parts by mass of Additive 1 were used.

[0182] (2-16) Preparation Example 16: Preparation of Resin Composition 16 20 parts by mass of polyarylate resin, 75.6 parts by mass of toluene, 2.6 parts by mass of Ti compound 1 and 1.8 parts by mass of Zr compound 1 shown in Table 2 as a compound having an M-O-C bond were blended and stirred at 25 ° C for 12 hours to obtain a resin solution of Ti compound 1 and Zr compound 1. A resin composition 16 was obtained in the same manner as in Preparation Example 1, except that the resin solution of Ti compound 1 and Zr compound 1 thus obtained was added to the base resin composition instead of the resin solution of Ti compound 1.

[0183] (2-17) Preparation Example 17: Preparation of Resin Composition 17 In Preparation Example 16, a resin composition 17 was obtained in the same manner as in Preparation Example 16, except that 5.2 parts by mass of Ti Compound 1, 3.5 parts by mass of Zr Compound 1, and further 16.8 parts by mass of Additive 1 were used to obtain a resin solution of Ti Compound 1 and Zr Compound 1.

[0184] (2-18) Preparation Example 18: Preparation of Resin Composition 18 20 parts by mass of a polyarylate resin, 65 parts by mass of toluene, 5.2 parts by mass of Ti Compound 1 and 3.5 parts by mass of Zr Compound 1 shown in Table 2 as a compound having an M-O-C bond were blended and stirred at 25°C for 12 hours to obtain a resin solution of Ti Compound 1 and Zr Compound 1. A resin composition 18 was obtained in the same manner as in Preparation Example 4, except that the resin solution of Ti Compound 1 and Zr Compound 1 thus obtained was added to the base resin composition instead of the resin solution of Ti Compound 1 in Preparation Example 4.

[0185] (2-19) Preparation Example 19: Preparation of Resin Composition 19 In Preparation Example 18, a resin composition 19 was obtained in the same manner as in Preparation Example 18, except that 2.6 parts by mass of Ti Compound 1 and 1.8 parts by mass of Zr Compound 1 were used to obtain a resin solution of Ti Compound 1 and Zr Compound 1.

[0186] (2-20) Preparation Example 20: Preparation of Resin Composition 20 77.3 parts by mass of EHPE3150 (an adduct of 1,2-epoxy-4-(2-oxiranyl)cyclohexane with 2,2-bis(hydroxymethyl)-1-butanol) manufactured by Daicel Corporation and 75.0 parts by mass of bisphenol A were added to 734.4 parts by mass of toluene. Further, 6.8 parts by mass of near-infrared absorbing dye A, 2.3 parts by mass of near-infrared absorbing dye B, and 3.9 parts by mass of ultraviolet absorbing dye A were added thereto, and the mixture was stirred at 40°C for 1 hour to obtain a base resin composition. Separately, 30 parts by mass of EHPE3150, 3.5 parts by mass of Zr compound 1, and 16.8 parts by mass of additive 1 were added to 49.7 parts by mass of toluene, and the mixture was stirred at 25°C for 12 hours to obtain a resin solution of Zr compound 1 and additive 1. The resin solution of Zr compound 1 and additive 1 thus obtained was added to the base resin composition, and further 7.0 parts by mass of EP compound 1 and 0.4 parts by mass of Curezol (registered trademark) 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Kasei Co., Ltd. as a curing catalyst were added and stirred, and this was filtered through a filter with a pore size of 0.1 μm (manufactured by GL Sciences Inc., non-aqueous 13N) to remove foreign matters, thereby obtaining resin composition 20.

[0187] (2-21) Preparation Example 21: Preparation of Resin Composition 21 Resin composition 21 was obtained in the same manner as in Preparation Example 11, except that the base resin composition was prepared without adding near-infrared absorbing dye A, near-infrared absorbing dye B, and ultraviolet absorbing dye A.

[0188] (2-22) Preparation Example 22: Preparation of Resin Composition 22 Resin composition 22 was obtained in the same manner as in Preparation Example 1, except that Ti compound 1 and EP compound 1 were not added.

[0189] (2-23) Preparation Example 23: Preparation of Resin Composition 23 Resin composition 23 was obtained in the same manner as in Preparation Example 1, except that EP compound 1 was not added.

[0190] (2-24) Preparation Example 24: Preparation of Resin Composition 24 In Preparation Example 23, a resin composition 24 was obtained in the same manner as in Preparation Example 23, except that 1.0 part by mass of Additive 2 (ethyl acetoacetate, manufactured by Tokyo Chemical Industry Co., Ltd.) was further added.

[0191] (2-25) Preparation Example 25: Preparation of Resin Composition 25 In Preparation Example 23, a resin composition 25 was obtained in the same manner as in Preparation Example 23, except that 2.0 parts by mass of Additive 3 (diphenyl phosphate, manufactured by Tokyo Chemical Industry Co., Ltd.) was further added.

[0192]

Table 2

[0193] (3) Fabrication of Resin Layer-Laminated Substrate After dropping 2 cc of the resin composition onto a phthalic acid-based glass substrate (manufactured by HOYA, CD700), the resin composition was formed into a film on the glass substrate using a spin coater (manufactured by Mikasa, 1H-D7). The glass substrate on which the resin composition was formed was dried at 190°C for 60 minutes in a nitrogen atmosphere using an inert oven (manufactured by Yamato Scientific Co., Ltd., DN610I) to form a resin layer on the glass substrate, thereby fabricating a resin layer-laminated substrate. The thickness of the resin layer formed on the glass substrate was 2 μm. The thickness of the resin layer was determined by measuring the thickness of the glass substrate on which the resin layer was formed and the thickness of the glass substrate alone with a micrometer and calculating the difference between the two.

[0194] (4) Adhesion Evaluation of Resin Layer-Laminated Substrate (4-1) Peel Resistance Test after Boiling in Water A cut was made in the resin layer of each resin layer-laminated substrate obtained above using a cutter (manufactured by NT Corp., A-300), and six cross-cut lines were provided at 2 mm intervals in the vertical and horizontal rows, respectively, to obtain 4 mm 2Twenty-five squares were prepared to fabricate a sample substrate for evaluation. Next, the sample substrate was placed in boiling ultrapure water and boiled for 2 hours. After boiling, the sample substrate was taped (Scotch (registered trademark) transparent adhesive tape, manufactured by 3M) at room temperature to prevent air from entering and left for 5 seconds. Then, the tape was peeled off from the sample substrate within 1 second and evaluated according to the following criteria. The tape was peeled off so that the peel strength was constant in each square. A: The peelability test was conducted twice, and no peeling or chipping occurred in any square. B: The peelability test was conducted twice, and in one of the tests, peeling or chipping occurred in 1 to 5 squares. C: The peelability test was conducted twice, and in both tests, peeling or chipping occurred in 1 to 5 squares. D: The peelability test was conducted twice, and in both tests, peeling or chipping occurred in all squares.

[0195]

Table 3

[0196]

Table 4

[0197] (4-2) Test Results The results of the peel resistance test after boiling water are shown in Tables 3 and 4. Resin compositions 1 to 21 all contained a resin, a compound having an M-O-C bond, and an epoxy compound. Therefore, for the resin laminated substrates obtained by coating resin compositions 1 to 21 on a phosphoric acid-based glass to form a resin layer, the evaluation results of the peel resistance test after boiling water were "A" or "B", indicating high peel resistance. On the other hand, resin composition 22 did not contain a compound having an M-O-C bond and an epoxy compound, and resin compositions 23 to 25 did not contain an epoxy compound. Therefore, for the resin laminated substrates obtained by coating resin compositions 22 to 25 on a phosphoric acid-based glass to form a resin layer, the evaluation results of the peel resistance test after boiling water were "D", indicating poor peel resistance.

Industrial Applicability

[0198] The resin composition of the present invention can be used for optical filters and the like useful for applications such as optical devices, display devices, mechanical parts, electrical and electronic parts, etc. by coating on a substrate to form a resin layer.

Claims

1. A resin composition for directly forming a resin layer on a phosphoric acid-based or fluophosphoric acid-based glass, comprising: (A) a resin, (B) a compound containing an M-O-C bond (where M represents Ti, Zr, or Al), and (C) an epoxy compound. The resin composition is characterized by containing these components.

2. The resin composition according to Claim 1, wherein the epoxy compound as component (C) has a partial structure represented by the following formula (1). 【Chemical Formula 1】

3. The resin composition according to Claim 1, wherein the epoxy compound as component (C) is a polyfunctional epoxy compound having two or more oxirane rings in one molecule.

4. The resin composition according to Claim 1, wherein the molecular weight of the epoxy compound as component (C) is 1000 or less.

5. The resin composition according to Claim 1, wherein the compound having an M-O-C bond as component (B) is a metal alkoxide or a metal enolate.

6. The resin composition according to Claim 1, further containing at least one selected from the group consisting of (D) a near-infrared absorbing dye, an ultraviolet absorbing dye, and a visible light absorbing dye.

7. An optical filter having a phosphoric acid-based or fluophosphoric acid-based glass substrate and a resin layer directly formed on the substrate and obtained by curing the resin composition according to any one of Claims 1 to 6.

8. The optical filter according to Claim 7, further having a dielectric film.

9. An image sensor having the optical filter according to Claim 7.

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