JP6723762B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition containing a mercapto group-containing compound, a resin, a curing catalyst, and an oxocarbon-based compound, and an optical filter and an imaging device obtained by forming a layer of the resin composition on a support. ..

BACKGROUND ART In recent years, in various fields such as optical devices such as display elements and image pickup elements, members and materials having a laminated structure in which various layers are formed on a support made of glass or the like (multilayer or (Also referred to as a laminate) has been widely used. Examples of the layer formed on the support include an ITO (indium-tin complex oxide) transparent conductive layer used for a touch panel, an infrared (IR) cut layer for reducing optical noise in an image sensor, and light on the substrate surface. And an antireflection (AR) layer for reducing the reflection of the above.

The image pickup device is also called a solid-state image pickup device or an image sensor chip, and is an electronic component that converts the light of a subject into an electric signal and outputs the electric signal, such as a camera for a mobile phone, a digital camera, a vehicle-mounted camera, or a surveillance camera. It is used in cameras, display devices (LEDs, etc.), etc. Such an image pickup device usually comprises a detection device (sensor) such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal-Oxide Semiconductor) and a lens. Therefore, there is an increasing demand for reduction of optical noise that hinders image processing and the like.

The reduction of optical noise in an image sensor is conventionally achieved by providing an absorbing glass in which a component having a light absorbing function or a reflecting function for reducing optical noise is kneaded into glass, or a resin filter having the same function in a resin component. Has been done. However, although the absorbing glass is very excellent in heat resistance, cracks and chippings easily occur and the workability is not sufficient. On the other hand, the resin filter can suppress the occurrence of cracks and chippings and is excellent in workability, but on the other hand, it has insufficient heat resistance as compared with glass, and warpage due to linear expansion cannot be denied. Therefore, in recent years, development of an optical filter having a laminated structure in which a layer having a light absorbing function and a reflecting function is formed on a support such as glass has been under development.

An oxocarbon-based compound having a squarylium skeleton or a croconium skeleton is conventionally used as a dye having absorption in the visible/near infrared region for a resin composition forming a layer having a light absorbing function or a reflecting function. Has been. For example, Patent Documents 1 and 2 describe optical filters in which a resin layer containing a squarylium compound is formed on a glass substrate.

JP, 2014-63144, A JP, 2014-126642, A

As described above, in recent years, development of a laminated body in which an IR cut layer or the like is formed on a support has been progressing, and a laminating material for obtaining the laminated body has been studied.

By the way, when forming a layer such as an IR cut layer on a support, a method of vapor deposition at high temperature is desired from the viewpoint of forming a dense layer. Therefore, high heat resistance is required for the material of the layer (lamination material) formed on the support.
Further, for example, image pickup devices such as digital camera modules are becoming smaller in size because they are mounted on mobile phones and the like, and cost reductions are also required. Therefore, as image pickup lenses, resin lenses have been used instead of conventional inorganic glass. Hiring is progressing. In the mounting process of such members, the solder reflow method is mainly used to realize cost reduction. Therefore, the material of the layer formed on the surface of the lens or the like is required to have heat resistance such that the cured product (molded product) thereof can withstand the reflow process.

As described above, Patent Document 1 and Patent Document 2 propose an optical filter in which a resin layer containing a squarylium compound is formed on a glass substrate. However, even when these optical filters are used, it is possible to sufficiently absorb light in the red wavelength (especially near the wavelength of 700 nm) and increase the transmittance of light in the visible light region (especially near the wavelength of 500 nm). That is, it is hard to say that these optical filters have high selective transmission.

The present invention has been made in view of the above circumstances, a resin composition having high selective permeability as a material for forming a layer on a support, and a layer made of the resin composition on a support. It is an object of the present invention to provide an optical filter having high selective transmission obtained by forming. Another object of the present invention is to provide an image pickup device using such an optical filter.

As a result of intensive studies to solve the above-mentioned problems, the present inventors used a curing catalyst and a mercapto group-containing compound in combination to sufficiently absorb light of a red wavelength (particularly near 700 nm). At the same time, it has been found that it is possible to increase the light transmittance in the visible light region (particularly near the wavelength of 500 nm).

That is, the resin composition according to the present invention is characterized by containing a mercapto group-containing compound, a resin, a curing catalyst, and an oxocarbon compound.

The resin preferably contains an oxirane ring-containing compound.

The curing catalyst preferably contains a cationic curing catalyst. Further, it is preferable that the resin composition further contains a siloxane-based surfactant.

The present invention is an optical filter including a support and a resin layer provided on at least one surface of the support, and the resin layer also includes an optical filter formed from the resin composition. Further, the present invention is an optical filter in which an underlayer is provided between the support and the resin layer, wherein the underlayer is an optical layer formed from a composition for an underlayer containing a silane coupling agent. It also includes a filter. In addition, the present invention also includes an image pickup device including the optical filter.

According to the present invention, by using a resin composition containing a mercapto group-containing compound, a resin, a curing catalyst, and an oxocarbon-based compound, it is possible to increase the light transmittance in the visible light region (particularly near the wavelength of 500 nm). In addition, it is possible to selectively absorb light having a desired red wavelength (especially near a wavelength of 700 nm). Therefore, since the resin composition of the present invention has high selective permeability, the optical filter having the resin composition of the present invention laminated thereon can be suitably used in optical applications.

The resin composition of the present invention is characterized by containing a mercapto group-containing compound, a resin, a curing catalyst, and an oxocarbon compound. Furthermore, the resin composition of the present invention may contain a surface modifier, a solvent, various additives, and the like, if necessary. Since this resin composition has excellent light absorption characteristics of the oxocarbon-based compound, it has a high transmittance in the visible light region (especially near the wavelength of 500 nm), while absorbing light in the red wavelength (especially near the wavelength of 700 nm). The rate is high and the selective permeability is excellent.

<Oxocarbon compound>
It is considered that the oxocarbon-based compound is slightly decomposed by heating to generate a coloring component having absorption in the visible light region. The oxocarbon-based compound preferably contains at least one of a squarylium-based compound and a croconium-based compound.

The structure of the squarylium compound is not particularly limited, and examples thereof include compounds represented by the following formula (1).

(In the formula (1), at least one of R ^a1 and R ^a2 represents a heterocyclic ring which may have a substituent or an aromatic ring which may have a substituent.)

The structure of the croconium compound is not particularly limited, and examples thereof include compounds represented by the following formula (2).

(In the formula (2), at least one of R ^a3 and R ^a4 represents a heterocyclic ring which may have a substituent or an aromatic ring which may have a substituent.)

Examples of the heterocycle include aromatic heterocycle and alicyclic heterocycle.
As the aromatic heterocycle, for example, a 5-membered or 6-membered monocyclic aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and a condensed 2- to 3-membered ring Examples thereof include condensed aromatic heterocycles which are cyclic or tricyclic and contain at least one atom selected from nitrogen atom, oxygen atom and sulfur atom, and more specifically, pyridine ring, pyrazine ring, pyrimidine ring, Pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, thiophene ring, furan ring, thiazole ring, oxazole ring , Indole ring, isoindole ring, indazole ring, benzimidazole ring, benztriazole ring, benzothiazole ring, benzoxazole ring, purine ring, carbazole ring and the like.

Further, as the alicyclic heterocycle, for example, a 5-membered or 6-membered monocyclic alicyclic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, a 3- to 8-membered ring And condensed bicyclic or tricyclic condensed ring alicyclic heterocycles containing at least one atom selected from nitrogen atom, oxygen atom and sulfur atom, and more specifically, pyrrolidine ring and piperidine. Ring, piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, homopiperazine ring, tetrahydropyridine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydrofuran ring, tetrahydropyran ring, dihydrobenzofuran ring, tetrahydrocarbazole ring, etc. ..

Examples of the aromatic ring include those having 6 to 14 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, and an anthracene ring.

The heterocyclic or aromatic ring substituents are the same or different and are 1 to 5 substituents, for example, a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an alkyloxycarbonyl group, an amide group, a sulfonamide group, an alkyl group. Group, aralkyl group, cyano group, halogen atom, -R'=R"-Ar (R' and R" are the same and represent N or CH, and Ar is a hydroxyl group, a carboxyl group, a nitro group or an alkoxy group. , An alkyl group which may be substituted with a halogen group, a cyano group and an aryl group which may be substituted with a substituent selected from the group consisting of halogen atoms). Examples of the substituent of the alkyl group or the alkoxy group include the same or different 1 to 3 substituents such as a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an aryl group and a halogen atom.

Of these, a 5-membered or 6-membered heterocyclic ring which may have a substituent or a 5-membered or 6-membered aromatic ring which may have a substituent is preferable.

The oxocarbon-based compound preferably contains at least one of a squarylium-based compound having the structure of the above formula (1) and a croconium-based compound having the structure of the above formula (2), and has the structure of the above formula (1). It is more preferable to contain a squarylium compound, and it is further preferable to consist of a squarylium compound having the structure of the above formula (1).

<Squarylium compound (squarylium dye)>
As the squarylium compound, it is particularly preferable that R ^a1 and R ^a2 in the above formula (1) are each independently a specific structural unit represented by the following formula (3).

(In formula (3), ring A is a 4- to 9-membered unsaturated hydrocarbon ring.
X and Y are each independently an organic group or a polar functional group.
n is an integer of 0 to 6 and is m or less (where m is a value obtained by subtracting 3 from the number of members of ring A), and when n is 2 or more, a plurality of Y are the same. May be different or different.
Ring B is an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle, or a condensed ring containing these ring structures.
Note that * represents a binding site with the 4-membered ring in the formula (1). )

In the formula (3), * represents a binding site with the squarylium skeleton represented by the formula (1), and a carbon atom (a carbon atom indicated by an arrow in the above formula (3)) bonded to the squarylium skeleton is a hydrocarbon. It is characterized in that it forms a ring (ring A).

In formula (3), ring A is an unsaturated hydrocarbon ring having 4 to 9 members. Ring A is an unsaturated hydrocarbon having at least one double bond between the carbon atom (the carbon atom indicated by the arrow in the above formula (3) indicated by an arrow in the above formula (3)) bonded to the squarylium skeleton and the carbon atom constituting the pyrrole ring. It may be a ring and may have an unsaturated bond (preferably a double bond) in addition to the double bond, but the ring A preferably has one double bond. Ring A is preferably a 5- to 8-membered ring, more preferably a 6- to 8-membered ring, and even more preferably an 8-membered ring.

Examples of the structure of ring A include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononene, cyclononadiene, cyclononatriene, Examples thereof include cycloalkene structures such as cyclononatetraene. Of these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are preferable.

In the formula (3), n is an integer of 0 to 6 and is m or less (however, m is a value obtained by subtracting 3 from the number of members of the ring A). n is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and still more preferably an integer of 0 to 2. When n is 1 or more, the hydrogen atom bonded to the carbon atom forming the ring A is substituted with Y.

In the formula (3), X and Y are organic groups or polar functional groups. Examples of the organic group as X and Y include an alkyl group, an alkoxy group, an alkylthiooxy group (alkylthio group), an alkyloxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, and arylthiooxy. group (an arylthio group), an aryloxycarbonyl group, an arylsulfonyl group, an arylsulfinyl group, an amide group (-NHCOR), a sulfonamido group (-NHSO ₂ R), a carboxy group (carboxylic acid group), benzothiazole group, halogenoalkyl Group, cyano group and the like. In addition, examples of the polar functional group include a halogeno group, a hydroxyl group, a nitro group, an amino group, and a sulfo group (sulfonic acid group).

As the organic group or the polar functional group which is an example of X, among the above, an alkyl group, an alkyloxycarbonyl group and an aryl group are preferable, and an alkyl group or an aryl group is more preferable. In this case, the carbon number of the alkyl group is preferably 1 to 6 in the case of a linear or branched alkyl group, more preferably 1 to 4, and 4 to 7 in the case of an alicyclic alkyl group. It is preferably 5-6. The aryl group preferably has 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms. Specifically, as the organic group or the polar functional group which is an example of X, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and the like are preferable.

As the organic group or polar functional group which is an example of Y, among the above, an alkyl group, an alkoxy group, a halogeno group, a phenyl group, an alkoxycarbonyl group (ester group), an amide group, a sulfonamide group and a hydroxyl group are preferable, and It is preferably an alkyl group or a hydroxyl group. In this case, the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 to 2 carbon atoms. Specifically, as the organic group or polar functional group which is an example of Y, a methyl group, an ethyl group, a hydroxyl group and the like are preferably mentioned.
When n is 2 or more and there are a plurality of Ys, each Y may be the same or different. When n is 2 or more, a plurality of Ys may be bonded to different carbon atoms, or two Ys may be bonded to one carbon atom.

In formula (3), ring B is an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle, or a condensed ring containing these ring structures. Examples of ring B include rings having the structures of the following formulas (A-1) to (A-14), and rings in which one or more hydrogen atoms of these rings are substituted with an arbitrary substituent. Among these, a benzene ring (A-1), a naphthalene ring (A-2, A-3), a quinoline ring (A-8, A-13, A-14) or a ring in which the above substituent is substituted is preferable. Examples of the substituent include the organic groups as examples of X and Y or the groups described above as the polar functional group. Among them, an alkyl group (particularly preferably a straight chain having 1 to 4 carbon atoms or A branched alkyl group), an aryl group, an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms), an alkylthio group (particularly preferably 1 to 2 carbon atoms), an amino group, an amide group, a sulfonamide group, an aromatic hetero group. Electron-donating groups such as ring groups, hydroxyl groups, thiol groups, and benzothiazole groups, halogeno groups (particularly preferably fluoro groups, chloro groups, bromo groups), halogenoalkyl groups (preferably perhalogenoalkyl having 1 to 3 carbon atoms). Group), cyano group, alkoxycarbonyl group (ester group), carboxy group (carboxylic acid group), carboxylic acid ester group, carboxylic acid amide group, sulfo group (sulfonic acid group), nitro group and the like are preferable. Especially, an electron-withdrawing group is preferable, and a halogeno group is most preferable. The number of substituents on ring B may be one or two or more (eg, 2 or 3). Moreover, it does not need to have a substituent. When it has a substituent, the number thereof is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

The above formulas (A-1) to (A-14) represent the ring B including a part of the pyrrole ring, and the formula (A-1) is shown by an arrow a in the figure below. The carbon atom at the β-position of the pyrrole ring and the carbon atom at the α-position of the pyrrole ring indicated by the arrow b in the figure below are included.

The specific structural units R ^a1 and R ^a2 in the compound (1) having a squarylium skeleton may have the same structure or different structures. It is preferable that R ^a1 and R ^a2 have the same structure because they can be easily produced.

A particularly preferred squarylium compound has a squarylium skeleton of formula (1), and in the structural unit of formula (3), ring A is cyclohexene, cycloheptene, or cyclooctene, and X is an alkyl group having 1 to 4 carbon atoms. And a ring B is a benzene ring (A-1) or a naphthalene ring (A-2, A-3). In this particularly preferred squarylium compound, when ring B has a substituent, the substituent is preferably an alkyl group, a trihalogenomethyl group, a phenyl group, an alkoxy group, a cyano group, a carboxyl group or a halogeno group.

<Croconium compound (croconium dye)>
As the croconium compound, it is more preferable that R ^a3 and R ^a4 in the above formula (2) are each independently a structural unit represented by the following formula (3). R ^a3 and R ^a4 may be the same or different.

(In formula (3),
Ring A is a 4-9 membered unsaturated hydrocarbon ring.
X and Y are each independently an organic group or a polar functional group.
n is an integer of 0 to 6 and is m or less (where m is a value obtained by subtracting 3 from the number of members of ring A), and when n is 2 or more, a plurality of Y are the same. May be different or different.
Ring B is an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle, or a condensed ring containing these ring structures.
In addition, * represents a binding site to the 5-membered ring in the formula (2). )

<Tautomer of oxocarbon compound, content, etc.>
The specific structural unit represented by the above formula (3) is bonded to the squarylium skeleton represented by the formula (1) or the croconium skeleton represented by the formula (2). Tautomers exist. Specifically, when bound to the squarylium skeleton represented by the formula (1), a tautomer represented by (1a) or (1b) exists in addition to the compound represented by the following (1). On the other hand, when bound to the croconium skeleton represented by the formula (2), in addition to the compound represented by the following (2), the tautomer represented by (2a), (2b) or (2c) exists. The oxocarbon-based compound of the present invention includes not only the compound represented by (1) or (2) but also tautomers corresponding to each.

Although the oxocarbon-based compound functions as a dye, the resin composition of the present invention may contain other known dyes together with the oxocarbon-based compound of the present invention within a range that does not impair the effects of the present invention. be able to. Examples of the dye that may be contained in the resin composition of the present invention include, for example, squarylium dyes and croconium dyes other than the oxocarbon compound of the present invention, copper (for example, Cu(II)) as a central metal ion, Cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, cholines, etc.) that may have zinc (eg, Zn(II)), cyanine dyes, quaterrylene dyes, naphthalocyanine dyes, Examples thereof include nickel complex dyes, copper ion dyes, diimmonium dyes, subphthalocyanine dyes, xanthene dyes, azo dyes, and dipyrromethene dyes. These other dyes preferably have an absorption maximum wavelength in the wavelength range of 400 to 1100 nm so as not to impair the effects of the present invention. These other dyes may be used alone or in combination of two or more.

When the resin composition of the present invention also contains another dye, the content of the other dye is preferably 60% by mass or less in the total 100% by mass of the oxocarbon compound of the present invention and the other dye, It is preferably 40% by mass or less, more preferably 20% by mass or less, and particularly preferably substantially free from other dyes.

The content of the oxocarbon-based compound of the present invention in the resin composition is preferably such that the total amount with the other dyes (total dye amount) falls within a predetermined range. Specifically, the total amount of the oxocarbon-based compound of the present invention and the other dye is preferably 0.01% by mass or more, more preferably 0.1% by mass based on 100% by mass of the solid content of the resin composition. It is 3% by mass or more, and more preferably 1% by mass or more. In addition, the upper limit of the total amount of the oxocarbon compound and the other dye used in the present invention is 25% by mass or less in 100% by mass of the solid content of the resin composition in order to facilitate uniform film formation. The amount is preferably 20% by mass or less, more preferably 15% by mass or less.

The resin composition of the present invention, when oxygen is present during storage of the resin solution, drying of the coating film, and thermosetting, changes in structure of the oxocarbon-based compound, changes in absorption characteristics due to generation of decomposition products, and visible light transmittance. For example, the durability of the resin composition may be deteriorated due to such a decrease. Therefore, it is preferable that the oxygen concentration is low during the storage of the resin solution or the drying/thermosetting process of the coating film, and specifically, the oxygen concentration is preferably 10% by volume or less. The oxygen concentration in normal air is about 20% by volume, but by storing or using it in an atmosphere of 10% by volume or less, deterioration of physical properties of the oxocarbon-based compound due to light or heat can be further suppressed. The oxygen concentration is more preferably 3% by volume or less, further preferably 1% by volume or less, particularly preferably 0.5% by volume or less, and most preferably 0.3% by volume or less. The oxygen concentration can be measured with an oxygen concentration meter (for example, Cosmo Detector (registered trademark) XPO-318 manufactured by New Cosmos Electric Co., Ltd.).

The means for adjusting the oxygen concentration to the above range is not particularly limited, but for example, it is preferable to replace oxygen in the system with an inert gas and perform the curing in an inert gas atmosphere. The inert gas is not particularly limited, and examples thereof include nitrogen and rare gases such as helium, neon, and argon. Of these, argon and nitrogen are preferable, and nitrogen is particularly preferable. Further, any atmosphere under reduced pressure, normal pressure, or increased pressure may be used.

<Method for producing oxocarbon compound>
The method for producing the oxocarbon-based compound according to the present invention is not particularly limited, and for example, the following formula (4):

(In the formula (4), the ring A, the ring B, X, Y and n are the same as those in the formula (3)) is used as an intermediate raw material, and this is reacted with squaric acid or croconic acid. Can be manufactured by.

The pyrrole ring-containing compound used as the intermediate raw material can be synthesized by appropriately adopting a known synthesis method. For example, a pyrrole ring-containing compound can be synthesized by the synthetic method described in the following papers.
SAJJADIFAR ET AL:'New 3H-Indole Synthesis by Fischer's Method.Part I.' Molecules 2010, no. 15, April 2010, pages 2491-2498

Further, the squarylium compound can be synthesized by appropriately adopting a known synthesis method of reacting a pyrrole ring-containing compound with squaric acid. For example, a pyrrole ring-containing compound can be synthesized by the synthetic method described in the following papers.
Serguei Miltsov ET AL;'New Cyanine Dyes: Norindosquarocyanines', Tetrahedron Letters, Volume 40, Issue 21, May 1999, pages 4067-4068

The obtained squarylium compound can be appropriately purified, if necessary, by known purification means such as filtration, silica gel column chromatography, alumina column chromatography, sublimation purification, recrystallization, crystallization and the like.

The method for synthesizing the croconium-based compound is not particularly limited, but the croconium-based compound can be synthesized by appropriately adopting a known synthetic method of reacting a pyrrole ring-containing compound with croconic acid. For example, it can be synthesized by the method described in JP-A-2002-286931, JP-A-2007-31644, JP-A-2007-31645, and JP-A-2007-169315.

[resin]
The resin composition of the present invention contains a resin. The resin preferably contains one or more organic compounds having a curable functional group. The curable functional group refers to a functional group that undergoes a curing reaction by heat or light (that is, a group that causes a curing reaction of the resin composition), for example, an oxirane group (oxirane ring), an oxetane group (oxetane ring). , Cation curable groups such as ethylene sulfide group, dioxolane group, trioxolane group, vinyl ether group and styryl group; radical curable groups such as acryl group, methacryl group and vinyl group; and the like. Therefore, the resin preferably contains a compound having a cation-curable group and/or a compound having a radical-curable group. As a result, the time until curing is shortened and the productivity is further improved, and the cured product obtained is also superior in heat resistance (heat decomposition resistance, heat coloring resistance). Above all, it is more preferable to include a compound having a cationically curable group in that the curing shrinkage rate is low and thus it is easy to impart a shape with a mold or the like. In this specification, a resin layer formed by using the above resin composition on a support, and a resin molded body and a single-layer resin film formed from the resin composition are collectively referred to as a cured product. .. The content of the compound having a cation-curable group is preferably 30% by mass or more in 100% by mass of the total amount of the resin. It is more preferably 50% by mass or more, and further preferably 80% by mass or more.

(Cationically curable group)
Among the compounds having a cation-curable group, it is preferable to include an oxirane ring-containing compound having one or more oxirane rings in the molecule (hereinafter, also simply referred to as an oxirane compound). The content of the oxirane compound is preferably 30% by mass or more in 100% by mass of the total amount of the resin. It is more preferably 50% by mass or more, and further preferably 80% by mass or more.

The oxirane compound is a compound (cation-curable compound) that has a cation-curable group called an oxirane ring and is cured (polymerized) by heat or light. When the resin composition contains an oxirane compound, the shrinkage of the cured product can be sufficiently reduced, the time until curing is shortened, and the productivity is increased. It is excellent in (heat decomposition resistance and heat discoloration resistance) and chemical resistance.

In the present specification, compounds that are cured (polymerized) by heat or light are collectively referred to as "curable compound" or "resin component", and among them, curable compounds having a cationically curable group are collectively referred to as "cationically curable". Compound.
A group containing an oxirane ring, which is a three-membered ether, is called an "epoxy group". The "epoxy group" is, in addition to an epoxy group in a narrow sense, a group in which an oxirane ring is bonded to carbon like a glycidyl group, a group containing an ether bond or an ester bond like a glycidyl ether group and a glycidyl ester group, An epoxy cyclohexane ring etc. shall be included.

The oxirane compound is preferably one or more selected from the group consisting of alicyclic epoxy compounds, hydrogenated epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds. When these oxirane compounds are used, coloring of the oxirane compound itself does not easily occur during curing, and coloring and deterioration due to light do not occur easily, that is, transparency, low coloring property, and light resistance are excellent. Therefore, when a resin composition containing these oxirane compounds is used, it is possible to obtain a cured product and a laminate which are free from coloration and have excellent light resistance with high productivity. More preferably, it is an alicyclic epoxy compound.

The alicyclic epoxy compound is a compound having an alicyclic epoxy group. The alicyclic epoxy compound is preferably a compound obtained by ring-opening polymerization of an epoxy ring of an epoxy compound with alcohol. Specific examples thereof include an alcohol vinylcyclohexene diepoxide adduct, an alcohol 3,4-epoxycyclohexanecarboxylic acid-3′,4′-epoxycyclohexylmethyl adduct, an alcohol adipate bis3,4-epoxycyclohexylmethyl. Adduct, dicyclopentadiene diepoxide adduct of alcohol, ε-caprolactone-modified bis(3,4-epoxycyclohexylmethyl)-4,5-epoxycyclohexane-1,2-dicarboxylic acid adduct of alcohol, ε-of alcohol Caprolactone-modified tetra(3,4-epoxycyclohexylmethyl)butane-tetracarboxylic acid adduct, alcohol dipentene dioxide adduct, alcohol 1,4-cyclooctadiene diepoxide adduct, alcohol bis(2,3- Examples thereof include epoxycyclopentyl) ether adducts, and these can be used alone or in combination of two or more. Among the alicyclic epoxy compounds, an adduct of vinylcyclohexene diepoxide of alcohol is preferable, a vinylcyclohexene diepoxide adduct of 2,2-bis(hydroxymethyl)-1-butanol is more preferable, and particularly preferably the following formula ( It is a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol represented by 5).

（上記式中、ｐ¹、ｐ²、ｐ³は同一又は異なって、１〜３０の整数である。）

(In the above formula, p ¹ , p ² , and p ³ are the same or different and are integers of 1 to 30.)

The alicyclic epoxy compound can be produced by a known method, and a commercially available product can also be used. Examples of commercially available products include Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, EHPE3150 (above, manufactured by Daicel) and the like. Among them, 1 of 2,2-bis(hydroxymethyl)-1-butanol is used. , 2-epoxy-4-(2-oxiranyl)cyclohexane adduct, EHPE3150 (weight average molecular weight: 2400) is preferable.

The content of the alicyclic epoxy compound in the oxirane compound is preferably 50% by mass or more in 100% by mass of the total amount of the oxirane compound. It is more preferably 60% by mass or more, and further preferably 70% by mass or more.

The hydrogenated epoxy compound is preferably a compound having a glycidyl ether group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound is preferable. Such hydrogenated epoxy compound is preferably a complete or partial hydrogenated product of an aromatic epoxy compound, more preferably a hydrogenated product of an aromatic glycidyl ether compound, and further preferably an aromatic polyfunctional compound. It is a hydrogenated product of a glycidyl ether compound. Specifically, hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds and the like are preferable. More preferred are hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds.

The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule. Preferable examples of the aromatic epoxy compound include epoxy compounds having an aromatic ring conjugated system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, and an anthracene ring. Above all, a compound having a bisphenol skeleton and/or a fluorene skeleton is preferable in order to realize a lower water absorption and a higher refractive index. More preferably, it is a compound having a fluorene skeleton, which makes it possible to remarkably increase the refractive index and further improve the releasability. Further, in the aromatic epoxy compound, a compound in which the epoxy group is a glycidyl group is preferable, and among them, a compound in which the glycidyl ether group is a glycidyl ether group (also referred to as an aromatic glycidyl ether compound) is more preferable. It is also preferable to use a brominated compound of an aromatic epoxy compound because a higher refractive index can be achieved, but since the Abbe number increases a little, it is preferable to use it appropriately according to the application.

Preferable examples of the aromatic epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a fluorene type epoxy compound, and an aromatic epoxy compound having a bromo substituent. Of these, bisphenol A type epoxy compounds and fluorene type epoxy compounds are preferable.

Examples of the aromatic glycidyl ether compound include epibis type glycidyl ether type epoxy resin and high molecular weight epibis type glycidyl ether type epoxy resin.

Preferable examples of the above-mentioned epibis type glycidyl ether type epoxy resin include those obtained by a condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol with epihalohydrin.

As the high molecular weight epibis type glycidyl ether type epoxy resin, for example, the epibis type glycidyl ether type epoxy resin is further subjected to an addition reaction with bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol. Preferred are those obtained by.

The aliphatic epoxy compound is a compound having an aliphatic epoxy group. Of these, aliphatic glycidyl ether type epoxy resins are preferable.

Examples of the aliphatic glycidyl ether type epoxy resin include polyhydroxy compounds (ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG600), propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol. , Polypropylene glycol (PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimers, pentaerythritol and its multimers, glucose, fructose, lactose, maltose and other mono/polysaccharides, etc.) and epihalohydrin Those obtained by the condensation reaction with are suitable examples. Of these, an aliphatic glycidyl ether type epoxy resin having a propylene glycol skeleton, an alkylene skeleton, and an oxyalkylene skeleton in the central skeleton is more preferable.

The oxirane compound preferably contains an oxirane compound having a weight average molecular weight of 2000 or more. The content of the oxirane compound having a weight average molecular weight of 2000 or more is preferably 10 to 100 mass% in the total 100 mass% of the oxirane compounds contained in the resin composition. As a result, the above resin composition becomes more excellent in film formability when the resin layer is formed on the support. As described above, a form in which the oxirane compound contains 10 to 100% by mass of the compound having a weight average molecular weight of 2000 or more in 100% by mass of the whole oxirane compound is one of the preferable forms of the present invention. The amount is more preferably 30 to 100% by mass, further preferably 50 to 100% by mass, and particularly preferably 70 to 100% by mass.

In the oxirane compound having a weight average molecular weight of 2000 or more, the weight average molecular weight is preferably 2200 or more. It is more preferably 2400 or more. The weight average molecular weight is preferably 1,000,000 or less from the viewpoints of film-forming property and keeping the glass transition temperature of the cured product high. It is more preferably 100,000 or less, still more preferably 10,000 or less.

In the present specification, the weight average molecular weight can be determined by GPC (gel permeation chromatography) measurement under the following conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GEL G5000HXL (both manufactured by Tosoh Corporation) are connected in series and used. Eluent: tetrahydrofuran (THF)
Standard substance for calibration curve: polystyrene (manufactured by Tosoh Corporation)
Measurement method: The object to be measured is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using the product filtered through a filter as a measurement sample.

(Radical curable group)
Among the compounds having a radical curable group, a (meth)acrylic resin containing a (meth)acrylic group is preferable. In addition, "(meth)acryl" shall mean "acryl" and/or "methacryl." The content of the (meth)acrylic resin is preferably 30% by mass or more in 100% by mass of the total amount of the resins. It is more preferably 50% by mass or more, and further preferably 80% by mass or more.

The (meth)acrylic resin has a unit derived from (meth)acrylic acid ester and/or (meth)acrylic acid as an essential constituent unit, and is derived from a (meth)acrylic acid ester or a derivative of (meth)acrylic acid. It may have a structural unit that

Examples of the (meth)acrylic acid ester or the (meth)acrylic acid ester derivative include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate. , T-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopenta (meth)acrylate Esters of (meth)acrylic acid and hydroxy hydrocarbon such as nyl (alkyl (meth)acrylate, aryl (meth)acrylate, aralkyl (meth)acrylate, etc.), dicyclopentanyloxy (meth)acrylate Ether bond introduction derivative such as ethyl; halogen introduction derivative such as chloromethyl (meth)acrylate and 2-chloroethyl (meth)acrylate; hydroxy introduction derivative; allyl group-containing (meth)acrylate ester; vinyl group containing ( Examples thereof include (meth)acrylic acid esters.

Examples of the (meth)acrylic acid or (meth)acrylic acid derivative include (meth)acrylic acids such as acrylic acid and methacrylic acid; alkylated (meth)acrylic acids such as methyl methacrylate and crotonic acid; 2-( Examples thereof include hydroxyalkylated (meth)acrylic acids such as hydroxymethyl)acrylic acid and 2-(hydroxyethyl)acrylic acid. Of these, methyl methacrylate is particularly preferable from the viewpoint of heat resistance and transparency.
Each of the (meth)acrylic acid ester (unit), the (meth)acrylic acid (unit) and the derivative (unit) thereof may have only one type, or may have two or more types.

The hydroxy group-introduced derivative includes 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth)acrylate, and (meth). Hydroxyalkyl (meth)acrylates such as 2,3,4,5-tetrahydroxypentyl acrylate; alkyl 2-(hydroxymethyl)acrylate (eg, methyl 2-(hydroxymethyl)acrylate, 2-(hydroxy) Methyl)ethyl acrylate, 2-(hydroxymethyl)isopropyl acrylate, n-butyl 2-(hydroxymethyl)acrylate, t-butyl 2-(hydroxymethyl)acrylate, etc.), 2-(hydroxyethyl)acrylic acid Included are alkyl 2-(hydroxyalkyl)acrylates such as alkyl (eg, methyl 2-(hydroxyethyl)acrylate).

The allyl group-containing (meth)acrylic acid esters include acrylic acid esters having an allyl group-containing substituent bonded to the α-position, and examples thereof include allyloxymethyl acrylic acid esters and 2-(N-allylamino). Methyl)acrylic acid esters are preferred. Specifically, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate Allyloxymethyl acrylic acid esters such as cyclohexyl, α-allyloxymethyl acrylate dicyclopentadienyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl adamantyl acrylate, α-allyloxymethyl acrylate benzyl Methyl 2-(N-allyl N-methylaminomethyl)acrylate, methyl 2-(N-allyl N-ethylaminomethyl)acrylate, methyl 2-(N-allyl Nt-butylaminomethyl)acrylate Preferred are 2-(N-allylaminomethyl)acrylic acid esters such as methyl 2-(N-allyl N-cyclohexylaminomethyl)acrylate and methyl 2-(N-allyl N-phenylaminomethyl)acrylate. is there. Among these, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, and benzyl α-allyloxymethyl acrylate are preferable, and α-allyloxymethyl acrylate is particularly preferable. Methyl acid (AMA) is preferred.

The vinyl group-containing (meth)acrylic acid esters include acrylic acid esters in which a vinyl group-containing substituent is bonded to the α-position, and examples thereof include vinyloxymethyl acrylic acid esters and 2-(N-vinylamino). Methyl)acrylic acid esters are preferred. Specifically, methyl α-vinyloxymethyl acrylate, ethyl α-vinyloxymethyl acrylate, butyl α-vinyloxymethyl acrylate, t-butyl α-vinyloxymethyl acrylate, α-vinyloxymethyl acrylate Vinyloxymethyl acrylic acid such as cyclohexyl, dicyclopentadienyl α-vinyloxymethyl acrylate, isobornyl α-vinyloxymethyl acrylate, adamantyl α-vinyloxymethyl acrylate, and benzyl α-vinyloxymethyl acrylate Esters; N-methyl-N-vinyl-2-(methoxycarbonyl)allylamine, N-ethyl-N-vinyl-2-(methoxycarbonyl)allylamine, Nt-butyl-N-vinyl-2-(methoxycarbonyl) ) N-methyl-N-vinyl-2-(methoxy) such as allylamine, N-cyclohexyl-N-vinyl-2-(methoxycarbonyl)allylamine and N-phenyl-N-vinyl-2-(methoxycarbonyl)allylamine Carbonyl) allylamines; methyl 2-(N-vinyl N-methylaminomethyl)acrylate, methyl 2-(N-vinyl N-ethylaminomethyl)acrylate, 2-(N-vinyl Nt-butylaminomethyl) ) Methyl acrylate, methyl 2-(N-vinyl N-cyclohexylaminomethyl)acrylate, methyl 2-(N-vinyl N-phenylaminomethyl)acrylate, and the like 2-(N-vinylaminomethyl)acrylic acid ester Classes are preferred. Of these, methyl α-vinyloxymethyl acrylate, ethyl α-vinyloxymethyl acrylate, cyclohexyl α-vinyloxymethyl acrylate, and benzyl α-vinyloxymethyl acrylate are preferable, and α-vinyloxymethyl acrylate is particularly preferable. Methyl acid is preferred.

The (meth)acrylic resin may have another structural unit introduced by copolymerizing the above-mentioned (meth)acrylic acid monomer with another monomer. The glass transition temperature of the (meth)acrylic resin can be increased by copolymerizing the (meth)acrylic acid-based monomer with another monomer. The glass transition temperature of the (meth)acrylic resin is preferably 110°C or higher, more preferably 120°C or higher. Other monomers include, for example, styrene, vinyltoluene, α-methylstyrene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, acrylonitrile, methacrylonitrile, methallyl alcohol, allyl alcohol, N-cyclohexylmaleimide, N-. A single monomer having a polymerizable double bond such as phenylmaleimide, ethylene, propylene, 4-methyl-1-pentene, vinyl acetate, 2-hydroxymethyl-1-butene, methyl vinyl ketone, N-vinylpyrrolidone, and N-vinylcarbazole. Examples include a polymer. These other monomers (units) may have only one type, or may have two or more types.

A structural unit derived from a (meth)acrylic acid-based monomer in all structural units of a (meth)acrylic resin (that is, a structural unit derived from a (meth)acrylic acid ester unit, a (meth)acrylic acid unit and derivatives thereof). The total proportion of is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. There is no particular upper limit, and most preferably 100% by mass.

The main chain forming the (meth)acrylic resin preferably contains a ring structure. The main chain ring structure in the (meth)acrylic resin is not particularly limited, and is a ring structure using a carbonyl group-containing bond such as -(C=O)N- bond or (C=O)-O- bond. Or a ring structure containing no carbonyl group. Examples of the ring structure containing a carbonyl group include a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, a maleic anhydride structure, and an N-substituted maleimide structure. A lactone ring structure, a glutaric anhydride structure, or a glutarimide structure is more preferable, and a lactone ring structure is particularly preferable.

The lactone ring structure is not particularly limited and may be, for example, a 4-membered ring to an 8-membered ring, but is preferably a 5-membered ring or a 6-membered ring because the stability of the ring structure is excellent. A 6-membered ring is more preferred. Examples of the lactone ring structure that is a 6-membered ring include the structure disclosed in JP-A-2004-168882, but the introduction of the lactone ring structure is easy, specifically, the precursor ( Polymerization yield of (polymer before lactone cyclization) is high, lactone ring content in the cyclization condensation reaction of the precursor can be increased, and a polymer having a methyl methacrylate unit as a constitutional unit can be used as the precursor The structure represented by the following formula (6-1) is particularly preferable for the reasons described above.

In the above formula (6-1), R ^s1 , R ^s2 and R ^s3 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, and the organic group may contain an oxygen atom. ..
Examples of the organic group in the formula (6-1) include a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms (such as an alkyl group) such as a methyl group, an ethyl group and a propyl group, a carbon such as an ethenyl group and a propenyl group. In addition to unsaturated aliphatic hydrocarbon groups having 2 to 20 carbon atoms (alkenyl groups, etc.), aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl groups, naphthyl groups (aryl groups, etc.), and saturated aliphatic hydrocarbons thereof. A group in which one or more hydrogen atoms in a group, unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group is substituted with at least one group selected from a hydroxy group, a carboxyl group, an ether group and an ester group, etc. Can be mentioned.

The lactone ring structure is formed by polymerizing (preferably copolymerizing) a (meth)acrylic acid-based monomer A having a hydroxy group and a (meth)acrylic acid-based monomer B, or a hydroxy group and an ester group in the molecular chain. It can be formed by introducing a carboxyl group and then causing dealcoholization or dehydration cyclocondensation between the hydroxy group and the ester group or the carboxyl group. As a polymerization component, a (meth)acrylic acid-based monomer A having a hydroxy group is essential, and the (meth)acrylic acid-based monomer B includes the monomer A. The monomer B may or may not match the monomer A. When the monomer B coincides with the monomer A, the monomer A is homopolymerized.
Specifically, the (meth)acrylic polymer having a lactone ring structure in the main chain can be prepared by, for example, the method described in JP-A-2006-96960, JP-A-2006-171464, or JP-A-2007-63541. Can be manufactured.

Examples of the glutaric anhydride structure or the glutaric imide structure include a structure represented by the following formula (6-2) (in the formula (6-2) below, when X ^s1 is an oxygen atom, a glutaric anhydride structure). And has a glutarimide structure when X ^s1 is a nitrogen atom).

R ^s4 and R ^s5 in the above formula (6-2) are each independently a hydrogen atom or a methyl group, and X ^s1 is an oxygen atom or a nitrogen atom. When X ^s1 is an oxygen atom, R ^s6 does not exist, and when X ^s1 is a nitrogen atom, R ^s6 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group). , Butyl group, pentyl group, hexyl group), cyclopentyl group, cyclohexyl group or phenyl group.

The glutaric anhydride structure in which X ^s1 is an oxygen atom in the above formula (6-2) is, for example, a dealcoholization cyclocondensation of a copolymer of (meth)acrylic acid ester and (meth)acrylic acid in the molecule. It can be formed by
The glutarimide structure in which X ^s1 in the above formula (6-2) is a nitrogen atom can be formed, for example, by imidizing a (meth)acrylic acid ester polymer with an imidizing agent such as methylamine.
Specifically, the (meth)acrylic resin having a glutaric anhydride structure or a glutarimide structure in the main chain can be produced by the method described in WO2007/26659 and WO2005/108438.

Examples of the maleic anhydride structure or the N-substituted maleimide structure include a structure represented by the following formula (6-3) (in the formula (6-3), when X ^s2 is an oxygen atom, maleic anhydride is used. Acid structure, and when X ^s2 is a nitrogen atom, it becomes an N-substituted maleimide structure).

R ^s7 and R ^s8 in the above formula (6-3) are each independently a hydrogen atom or a methyl group, and X ^s2 is an oxygen atom or a nitrogen atom. When X ^s2 is an oxygen atom, R ^s9 does not exist, and when X ^s2 is a nitrogen atom, R ^s9 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group). , Butyl group, pentyl group, hexyl group), cyclopentyl group, cyclohexyl group, benzyl group or phenyl group.

The maleic anhydride structure in which X ^s2 in the above formula (6-3) is an oxygen atom can be formed, for example, by subjecting maleic anhydride to polymerization with a (meth)acrylic acid ester or the like.
The N-substituted maleimide structure in which X ^s2 in the above formula (6-3) is a nitrogen atom can be formed, for example, by subjecting an N-substituted maleimide such as N-phenylmaleimide to polymerization together with a (meth)acrylic acid ester or the like. ..
Specifically, a (meth)acrylic resin having a maleic anhydride structure or an N-substituted maleimide structure in its main chain is produced, for example, by the method described in JP-A-57-153008 and 2007-31537. it can.

Further, among the main chain ring structures in the (meth)acrylic resin, as the ring structure not containing a carbonyl group, an oxygen-containing one such as an oxetane ring or an azetidine ring or a nitrogen-containing four-membered ring, a tetrahydrofuran ring, a pyrrolidine ring or the like is included. Alternatively, an oxygen-containing or nitrogen-containing six-membered ring such as a nitrogen-containing five-membered ring, a tetrahydropyran ring, or a piperidine ring can be used.
As an example having a five-membered ring or a six-membered ring structure, for example, a structure represented by the following formula (6-4) or a structure represented by the following formula (6-5) is preferably exemplified, and a four-membered ring or a five-membered ring Preferred examples of the ring structure include structures represented by the following formula (6-6) and the following formula (6-7). The (meth)acrylic resin having a ring structure in the main chain may have one or more of each of these structures, but usually, the structure of formula (6-4) and the structure of formula (6-5) In many cases, the structure of formula (6-6) and the structure of formula (6-7) are combined.

(In the formula, R ^s10 and R ^s11 are the same or different and each is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. X ¹ , Y ¹ and Z ¹ are The same or different, a methylene group, an oxygen atom or an imino group, provided that at least one of X ¹ , Y ¹ and Z ¹ is an oxygen atom or an imino group.)

In the structures represented by the above formulas (6-4) and (6-5), it is preferable that X ¹ and Z ¹ are methylene groups, and Y ¹ is an oxygen atom. That is, in the above formula (6-4) and the above formula (6-5), a tetrahydrofuran ring structure or a tetrahydropyran ring structure is preferable. Further, R ^s10 and R ^s11 are preferably a hydrocarbon group having 1 to 5 carbon atoms, particularly a methyl group.

The resin having the ring structure of the formula (6-4) and/or the ring structure of the formula (6-5) is, for example, the allyl group-containing (meth)acrylic acid ester alone or in another monomer. It can be produced by polymerizing with.

(In the formula, R ^s12 and R ^s13 are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom. X ² and Y ² are the same or different and are a methylene group, An oxygen atom or an imino group, provided that at least one of X ² and Y ² is an oxygen atom or an imino group.)

In the structures represented by the formulas (6-6) and (6-7), it is preferable that X ² is a methylene group, and Y ² is an oxetane ring structure or an tetrahydrofuran ring structure in which Y ² is an oxygen atom. Further, R ^s12 and R ^s13 are preferably a hydrocarbon group having 1 to 5 carbon atoms, particularly a methyl group.

The resin having the ring structure of the formula (6-6) and/or the ring structure of the formula (6-7) is, for example, the vinyl group-containing (meth)acrylic acid ester alone or in another monomer. It can be produced by polymerizing with.

[Curing catalyst]
The resin composition further contains a curing catalyst. The curing catalyst may be used alone or in combination of two or more.

The curing catalyst may be appropriately selected depending on the curing reaction and the type of the curable compound (curable resin). The curing catalyst may be a commonly used one, for example, in the case of performing thermal curing, a thermal latent cationic curing catalyst, a thermal latent radical curing catalyst, an acid anhydride catalyst, a phenol catalyst, an amine catalyst, etc. Can be mentioned. Among them, it is preferable to use a thermal latent cationic curing catalyst or a thermal latent radical curing catalyst, which has a high curing rate in terms of productivity, and a thermal latent cationic curing catalyst is particularly used for the purpose of reducing the shrinkage amount of the cured product. Is more preferable. Further, when curing is performed by irradiation with active energy rays, a photopolymerization initiator can be used as a curing catalyst. As the photopolymerization initiator, it is preferable to use a photolatent cation curing catalyst or a photolatent radical curing catalyst, and it is particularly preferable to use a photolatent cation curing catalyst for the purpose of reducing the shrinkage amount of the cured product. ..
Thus, the cationic curing catalyst is particularly preferable as the curing catalyst. In the present specification, a catalyst that promotes a cation curing reaction, such as a thermal latent cation curing catalyst or a photolatent cation curing catalyst, is also referred to as a “cation curing catalyst”. The cation curing catalyst is a catalyst that accelerates the cation curing reaction, and functions differently from the curing accelerator in the acid anhydride curing reaction, for example.

Above all, it is preferable to use at least a thermal latent cationic curing catalyst. Of the above curing catalysts, the thermal latent cationic curing catalyst is different from acid anhydrides, amines, phenolic resins and the like which are generally used as curing catalysts, even if contained in the resin composition, the resin composition It does not cause a viscosity increase or gelation with time at room temperature, and as a function of the heat-latent cation curing catalyst, it can sufficiently accelerate the curing reaction and exhibit an excellent effect, and is superior in handling property. It is also possible to provide a one-component resin composition.

In addition, the use of a heat-latent cation curing catalyst dramatically improves the moisture resistance of the cured product formed from the resulting resin composition, maintaining the excellent optical properties of the resin composition even in harsh operating environments. However, it can be preferably used for various purposes. Usually, when water having a low refractive index is contained in a resin composition or a cured product thereof, it causes turbidity. However, when a heat-latent cation curing catalyst is used, excellent moisture resistance can be exhibited, and thus such turbidity is generated. Will be suppressed. By improving the moisture resistance, moisture absorption in the resin composition is suppressed, and oxygen radical generation due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed, so that yellowing of the cured product or strength reduction does not occur for a long time. It can exhibit excellent heat resistance.

As the thermal latent cation curing catalyst, for example, a compound represented by (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^+m (AX _n ) ^-m is suitable. In the formula, Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and a halogen element. R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents an organic group. a, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z. The cation (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^+m represents an onium salt. A represents a metal element or a metalloid element which is a central atom of the halide complex, and is composed of B, P, As, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn and Co. At least one selected from the group. X represents a halogen element. m is the net charge of the halide complex ion. n is the number of halogen elements in the halide complex ion.

Specific examples of the anion (AX _n ) ^{-m in} the compound represented by (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^+m (AX _n ) ^-m include tetrafluoroborate (BF ₄ ^-), hexafluorophosphate (PF ₆ ^-), hexafluoroantimonate (SbF ₆ ^-), hexafluoroarsenate (AsF ₆ ^-), hexachloroantimonate (SbCl ₆ ^-), and the like. An anion represented by the general formula AX _n (OH) ⁻ can also be used. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, trinitrobenzenesulfone ion. An acid ion etc. are mentioned.

Examples of the photolatent cation curing catalyst include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, p-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)] Phenyl] sulfide bishexafluoroantimonate, (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe-hexafluorophosphate, diallyliodonium hexafluoroantimonate and the like can be mentioned.

Examples of the photolatent radical curing catalyst include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, benzyldimethylketal, and the like. 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, 1,1-dichloroacetophenone, etc. Acetophenones; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3′,4,4′-tetra(t-butylperoxylcarbonyl)benzophenone, 2,4,6-Trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium Examples thereof include benzophenones such as chlorides; acylphosphine oxides; and the like.

When a cation curing catalyst or a radical curing catalyst is used as the curing catalyst, the blending amount thereof means the amount of the active ingredient containing no solvent and the like (means the solid content equivalent. The Lewis acid represented by the general formula (7) described later). And a Lewis base, the total amount of the Lewis acid and the Lewis base is 100% by mass of the total amount of the cation-curable compound and the total amount of the radical-curable compound. It is preferable that the content is 0.01 to 10 parts by mass. As a result, the curing rate can be further increased, the productivity can be further improved, and the risk of coloration during curing, heating, use, etc. can be further suppressed. Further, for example, when a cured product or a laminate obtained by using the above resin composition is reflow-mounted, heat resistance of 200° C. or higher is required, and therefore 10 parts by mass or less from the viewpoint of colorlessness and transparency. Is preferred. It is more preferably 0.1 part by mass or more, further preferably 0.2 part by mass or more, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less.

Examples of the acid anhydride-based, phenol-based or amine-based curing catalysts usually used include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrophthalic anhydride. it can.

The cationic curing catalyst preferably contains a boron compound, more preferably an aromatic fluorine compound. Particularly preferably, the cationic curing catalyst is the following general formula (7):

(In the formula, R is the same or different and represents a hydrocarbon group which may have a substituent. x is an integer of 1 to 5 and is the same or different and is a fluorine atom bonded to the aromatic ring. A is an integer of 1 or more, b is an integer of 0 or more, and satisfies a+b=3, which is a form composed of a Lewis acid (organic borane) and a Lewis base. ..

As a result, cationic curing can be adopted as the curing method, so that the resulting cured product will have better heat resistance, chemical stability, and moisture resistance than the case where addition type curing such as acid anhydride curing is adopted. It is more excellent in properties required for optical applications such as properties. Further, as compared with the case of using a conventional cationic curing catalyst such as an antimony-based sulfonium salt, coloring of the resin composition due to the influence of heat during curing, film formation, and product use is reduced, and the heat and humidity resistance is improved. A cured product excellent in durability such as temperature shock resistance can be obtained.
The presence/absence and degree of coloring of the cured product based on the catalyst used can usually be confirmed from the change in transmittance at 400 nm. That is, by measuring the transmittance of the cured product at 400 nm, it is possible to evaluate the presence/absence and degree of coloring of the cured product.

R in the general formula (7) is the same or different and represents a hydrocarbon group which may have a substituent. The hydrocarbon group is not particularly limited, but is preferably a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group or an alkenyl group. The alkyl group, aryl group, or alkenyl group may be an unsubstituted group or a group in which one or more hydrogen atoms are replaced with another organic group or a halogen atom. In this case, the other organic group includes an alkyl group (when the hydrocarbon group represented by R is an alkyl group, the substituted hydrocarbon group as a whole corresponds to an unsubstituted alkyl group), Examples thereof include an aryl group, an alkenyl group, an alkoxy group and a hydroxyl group.

X in the general formula (7) is an integer of 1 to 5, which is the same or different and represents the number of fluorine atoms bonded to the aromatic ring. The bonding position of the fluorine atom in the aromatic ring is not particularly limited. x is preferably 2 to 5, more preferably 3 to 5, and most preferably 5.
Further, a is an integer of 1 or more, b is an integer of 0 or more, and satisfies a+b=3. That is, the Lewis acid has at least one aromatic ring bonded to a fluorine atom bonded to a boron atom. The value of a is more preferably 2 or more, particularly preferably 3, that is, a form in which three aromatic rings to which fluorine atoms are bonded are bonded to boron atoms.

Specific examples of the Lewis acid include tris(pentafluorophenyl)borane (referred to as “TPB”), bis(pentafluorophenyl)phenylborane, pentafluorophenyl-diphenylborane, tris(4-fluorophenyl)borane. Etc. are preferred. Among these, TPB is more preferable because it can improve the heat resistance, wet heat resistance, temperature shock resistance and the like of the cured product. Among the cationic curing catalysts, those containing TPB as a Lewis acid are also referred to as "TPB-based catalysts".

The Lewis base is not limited as long as it can be coordinated with the Lewis acid, that is, as long as it can form a coordinate bond with the boron atom of the Lewis acid, and a commonly used Lewis base is used. However, compounds having atoms with unshared electron pairs are preferred. Specifically, a compound having a nitrogen atom, a phosphorus atom or a sulfur atom is suitable. In this case, the Lewis base forms a coordination bond by donating the unshared electron pair possessed by the nitrogen atom, the phosphorus atom or the sulfur atom to the boron atom of the Lewis acid. Further, the Lewis base is more preferably a compound having a nitrogen atom or a phosphorus atom.

Preferred examples of the compound having a nitrogen atom include amines (monoamine, polyamine), ammonia and the like. More preferred are amines having a hindered amine structure, low-boiling amines and ammonia, and even more preferred are polyamines having a hindered amine structure and ammonia. When a polyamine having a hindered amine structure is used as the Lewis base, it is possible to prevent oxidation of the cured product due to the radical scavenging effect, and the resulting cured product becomes more excellent in heat resistance (moisture heat resistance). On the other hand, when ammonia or an amine having a low boiling point is used as the Lewis base, the obtained cured product has low water absorption and excellent UV irradiation resistance. Volatilization of ammonia or low-boiling point amine in the curing step reduces the salt structure derived from ammonia or low-boiling point amine in the final molded product (cured product), thus reducing the water absorption of the cured product. It is supposed to be possible. Ammonia is particularly preferable because it is excellent in the above effects.

Here, as will be described later, in the present invention, it is preferable to include a nitrogen-containing compound having a boiling point of 120° C. or lower, and therefore it is also preferable to use a nitrogen-containing compound having a boiling point of 120° C. or lower as the Lewis base. That is, it is also suitable that the nitrogen-containing compound having a boiling point of 120° C. or less is contained in the resin composition as a part of forming the above-mentioned cationic curing catalyst.

As the amine having a hindered amine structure, a nitrogen atom forming a coordinate bond with a boron atom constitutes a secondary or tertiary amine from the viewpoint of storage stability of the resin composition and curability during molding. Is more preferable, and it is more preferable that the polyamine is a diamine or more. As the amine having a hindered amine structure, specifically, 2,2,6,6-tetramethylpiperidine, N-methyl-2,2,6,6-tetramethylpiperidine; TINUVIN (registered trademark) 770, TINUVIN( (Registered trademark) 765, TINUVIN (registered trademark) 144, TINUVIN (registered trademark) 123, TINUVIN (registered trademark) 744, CHIMASSORB (registered trademark) 2020FDL (above, manufactured by BASF); ADK STAB (registered trademark) LA52, ADK STAB (registered trademark) Trademark) LA57 (above, manufactured by ADEKA) and the like. Among them, TINUVIN (registered trademark) 770, TINUVIN (registered trademark) 765, ADK STAB (registered trademark) LA52, and ADK STAB (registered trademark) LA57 having two or more hindered amine structures in one molecule are preferable.

As the low-boiling amine, it is preferable to use an amine having a boiling point of 120° C. or lower, more preferably 80° C. or lower, further preferably 50° C. or lower, further preferably 30° C. or lower, and particularly preferably Is 5° C. or lower. Specifically, primary amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and ethylenediamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, methylethylamine and piperidine; And tertiary amines such as trimethylamine and triethylamine; and the like.

Phosphines are preferable as the compound having a phosphorus atom. Specific examples include triphenylphosphine, trimethylphosphine, tritoluylphosphine, methyldiphenylphosphine, 1,2-bis(diphenylphosphino)ethane and diphenylphosphine.

The compounds having a sulfur atom are preferably thiols and sulfides. Specific examples of the thiols include methylthiol, ethylthiol, propylthiol, hexylthiol, decanethiol, phenylthiol and the like. Specific examples of sulfides include diphenyl sulfide, dimethyl sulfide, diethyl sulfide, methylphenyl sulfide, methoxymethylphenyl sulfide, and the like.

In the cation curing catalyst composed of the Lewis acid and the Lewis base represented by the general formula (7), the mixing ratio of the Lewis acid and the Lewis base does not necessarily have to be the stoichiometric ratio. That is, either one of the Lewis acid and the Lewis base (converted to the basic point amount) may be contained in excess of the theoretical amount (equivalent amount). Specifically, the mixing ratio of the Lewis acid and the Lewis base in the cation curing catalyst is such that the number of atoms at the Lewis base point is n(b) relative to the number of atoms at the Lewis acid point of boron (n(a)). Even if the ratio (n(b)/n(a)) is not 1 (stoichiometric ratio), it acts as a cation curing catalyst. Here, the ratio n(b)/n(a) in the cation curing catalyst affects the storage stability of the resin composition and the cation curing characteristics (curing speed, curing degree of the cured product, etc.).
When the Lewis base has two Lewis base points in the molecule, such as diamines, when the mixing molar ratio of the Lewis base to the cation curing catalyst is 0.5, the ratio n (B)/n(a)=1 (stoichiometric ratio). In this way, the ratio n(b)/n(a) is calculated.

In the above cationic curing catalyst, from the viewpoint of storage stability of the resin composition containing it, if the Lewis acid is present in an excessively large amount relative to the Lewis base, the storage stability may not be sufficient, so the storage stability In order to obtain a more excellent resin composition, the ratio n(b)/n(a) is preferably 0.5 or more. For the same reason, it is more preferably 0.8 or more, further preferably 0.9 or more, particularly preferably 0.95 or more, and most preferably 0.99 or more.
On the other hand, from the viewpoint of cation curing properties, if the Lewis base is excessively excessive, the low temperature curability of the cured product may not be sufficient, and therefore n(b)/ It is preferable that n(a) is 100 or less. For the same reason, it is more preferably 20 or less, further preferably 10 or less, particularly preferably 5 or less.

As the above ratio n(b)/n(a), the Lewis base is made of a compound having a nitrogen atom, a sulfur atom or a phosphorus atom, and has a structure in which 2 or more carbon atoms are substituted (a structure in which 2 or more carbon atoms are substituted). , Means a structure in which two or more organic groups are bonded to these atoms via carbon atoms), the acid dissociation constant is high and the steric hindrance is large from the viewpoint of cation curing characteristics. n(b)/n(a) is preferably 2 or less. It is more preferably 1.5 or less, still more preferably 1.2 or less. For structures such as hindered amines, this range is preferred.
Further, when the Lewis base is a nitrogen-containing compound having a boiling point of 120° C. or lower (especially ammonia or a low-boiling amine having a small steric hindrance), particularly ammonia, the ratio n(b)/n(a) Is preferably greater than 1. It is more preferably 1.001 or more, still more preferably 1.01 or more, particularly preferably 1.1 or more, and most preferably 1.5 or more.

The existence form of the Lewis acid and the Lewis base constituting the above-mentioned cationic curing catalyst is not particularly limited, but it is preferable that the Lewis base exists in a state in which the Lewis base has an electronic interaction with the Lewis acid. More preferably, at least part of the Lewis base is coordinated to the Lewis acid, and even more preferably, at least an equivalent amount of the Lewis base to the Lewis acid present is coordinated to the Lewis acid. It is a form. When the abundance ratio of the Lewis base to the Lewis acid is equivalent or less than the equivalent, that is, when the ratio n(b)/n(a) is 1 or less, almost all of the Lewis base present is coordinated with the Lewis acid. The preferred form is On the other hand, in the form in which the Lewis base is contained in excess (more than the equivalent amount), it is preferable that the Lewis base is coordinated with the Lewis acid in the equivalent amount, and the excess Lewis base is present near the complex.

Specific examples of the cation curing catalyst composed of a Lewis acid and a Lewis base represented by the general formula (7) include TPB/monoalkylamine complex, TPB/dialkylamine complex, TPB/trialkylamine complex and the like. TPB alkylamine complex, organic borane/amine complex such as TPB/hindered amine complex; organic borane/ammonia complex such as TPB/NH ₃ complex; TPB/triarylphosphine complex, TPB/diarylphosphine complex, TPB/monoarylphosphine complex, etc. Organic borane/phosphine complex; organic borane/thiol complex such as TPB/alkyl thiol complex; organic borane/sulfide complex such as TPB/diaryl sulfide complex and TPB/dialkyl sulfide complex. Among them, TPB/alkylamine complex, TPB/hindered amine complex, TPB/NH ₃ complex, and TPB/phosphine complex are preferable.

In the resin composition, the content of the cation curing catalyst means the amount of the active ingredient containing no solvent or the like (means the solid content equivalent. The cation composed of the Lewis acid and the Lewis base represented by the general formula (7). When a curing catalyst is used, the total amount of the Lewis acid and Lewis base is 0.01 to 10 parts by mass in 100 parts by mass of the total amount of the cationically curable compound contained in the resin composition. Is preferred. As a result, the curing rate can be further increased, the productivity can be further improved, and the risk of coloration during curing, heating, use, etc. can be further suppressed. In addition, for example, when reflow mounting a laminate obtained using the above resin composition, heat resistance of 200° C. or higher is required, so from the viewpoint of colorlessness and transparency, the amount should be 10 parts by mass or less. Is preferred. More preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, particularly preferably 0.2 parts by mass or more, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, It is particularly preferably 2 parts by mass or less.

[Mercapto group-containing compound]
The resin composition of the present invention contains a mercapto group-containing compound. When a resin composition in which an oxocarbon-based compound and a curing catalyst are combined is used, it is difficult to produce a cured product having a resin composition with sufficiently high selective permeability. However, the oxocarbon-based compound and the curing catalyst are combined. By including a mercapto group-containing compound in the resin composition, a cured product having sufficiently high selective permeability can be obtained, and further the adhesiveness (particularly the adhesiveness to a glass substrate) can be improved. .. Further, it is considered that the generation of the coloring component having absorption in the visible light region is suppressed by containing the mercapto group-containing compound in the resin composition.

Examples of the mercapto group-containing compound include compounds represented by the following formula.
HS-R-Si(OR') _n (R") _3-n
R is an alkyl group, preferably an alkyl group having 1 to 3 carbon atoms. R'is an alkyl group, an acetyl group, or a methoxyalkyl group, preferably a methyl group or an ethyl group, and more preferably a methyl group. R″ is an alkyl group, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. n is 1 or more and 3 or less, preferably 3.

The mercapto group-containing compound is preferably a mercapto group-containing compound containing at least one —O—C(═O)(CH ₂ ) ₂ —SH group, and more preferably three or more —O—C(= O)(CH ₂ ) ₂ -SH group-containing mercapto group-containing compound, more preferably mercapto group-containing compound containing 3 —O—C(═O)(CH ₂ ) ₂ —SH groups. Examples of the mercapto group-containing compound include 3-mercaptopropyltrimethoxysilane, pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, and dipentaerythritol hexa. Kiss (3-mercaptopropionate), p-mercaptophenol, octanethiol, 3-mercaptopropionic acid, 3-mercapto-1,2-propanediol, 2-mercaptoethanol, pentaerythritol tetrakis (3-mercaptobutyrate) , Trimethylolpropane tris(3-mercaptopropionate), 2-ethylhexyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and the like. Among them, pentaerythritol tetrakis (3-mercaptopropionate). Nate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, and dipentaerythritol hexakis(3-mercaptopropionate).

A mercapto group-containing silane coupling agent may be used as the mercapto group-containing compound. By containing a mercapto group-containing silane coupling agent in the resin composition, it has the effect of improving the adhesion to the glass substrate and the effect of suppressing the infiltration of water into the resin composition by the water repellent effect, As a result, it is possible to obtain a near infrared ray cut filter having excellent heat resistance and wet heat resistance. Specifically, it is possible to suppress peeling and the like in the solder reflow process and use in a wet heat environment.
In addition, when a resin composition containing an oxocarbon compound and a curing catalyst is used, visible light may be absorbed. However, by containing a silane coupling agent having a mercapto group, Can prevent absorption.

As the mercapto group-containing silane coupling agent, those in which a mercapto group and an organic group are directly bonded to a silicon atom and a partial hydrolysis-condensation product thereof are generally used. By using the silane coupling agent, it is possible to further improve the moist heat resistance.

That is, as the mercapto group-containing silane coupling agent, a mercapto group-containing silane coupling agent having an alkoxy group is preferable. As the mercapto group-containing silane coupling agent, a mercapto group-containing silane coupling agent having a methoxy group is more preferable. In addition, the mercapto group-containing silane coupling agent is preferably linear (preferably linear without a ring structure).

Examples of the mercapto group-containing silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like, and among them, 3-mercaptopropyltrimethoxy. Silane is preferable because it is easily available, has high compatibility in the resin composition, and exhibits high adhesion to the glass substrate. Examples of commercially available products include KBM-802 (3-mercaptopropylmethyldimethoxysilane) manufactured by Shin-Etsu Silicone, KBM-803 (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Silicone, and Z-6062 manufactured by Toray Dow Corning. (3-mercaptopropyltrimethoxysilane), DYNASYLAN (registered trademark) MTMO (3-mercaptopropyltriethoxysilane) manufactured by Evonik Degussa, and the like can be mentioned. The mercapto group-containing silane coupling agent may be used alone or in combination of two or more kinds.

As the silane coupling agent, a silane coupling agent other than the mercapto group-containing silane coupling agent may be used. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysisilane, γ- (2,3-epoxycyclohexyl)propyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and the like can be mentioned.

The content of the mercapto group-containing silane coupling agent in the total amount of 100% by mass of the silane coupling agent is preferably 50 to 100% by mass. It is more preferably 70 to 100% by mass, further preferably 90 to 100% by mass, and particularly preferably 100% by mass.

The blending ratio of the mercapto group-containing silane coupling agent is preferably 0.1 part by mass or more and 25 parts by mass or less, more preferably 2 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the oxirane ring-containing compound. Parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less, particularly preferably 7 parts by mass or more and 18 parts by mass or less, and most preferably 10 parts by mass or more and 15 parts by mass or less. By setting the mixing ratio of the mercapto group-containing silane coupling agent within the above range, heat resistance, adhesion, and light selective transmission filter performance can be enhanced.

The content of the mercapto group-containing silane coupling agent in the resin composition is preferably 0.00001 to 20% by mass, more preferably 0.00001 to 10% by mass in 100% by mass of the resin composition (solid content). 0.00005 to 5 mass% is particularly preferable.

[Surface conditioner]
The resin composition according to the present invention may contain a surface modifier. By including the surface modifier in the resin composition according to the present invention, it is possible to suppress appearance defects such as striations and dents after the cured product is produced. The surface conditioner is not particularly limited, and examples thereof include a siloxane-based surfactant, an acetylene glycol-based surfactant, a fluorine-based surfactant, an acrylic leveling agent, and the like. A siloxane-based surfactant or an acrylic leveling agent. Is preferred, and a siloxane-based surfactant is more preferred.

The siloxane-based surfactant is a surfactant having a siloxane bond (-Si-O-Si-), and includes, for example, polyether-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, Examples thereof include aralkyl-modified polydimethylsiloxane, and from the viewpoint of dispersibility of the oxocarbon-based compound in the resin composition, polyether-modified polydimethylsiloxane is preferably contained. Further, the polyether-modified polydimethylsiloxane preferably contains a polyether chain composed of alkylene oxide (more preferably ethylene oxide and/or propylene oxide).

The polyether-modified polydimethylsiloxane is more preferably a polyether-modified polydimethylsiloxane represented by the following formula (8).

(In the formula, R ⁴ is a hydrogen atom or a methyl group. R ⁵ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms. m is an integer of 1 to 30 and n is 1 Is an integer of 30 to 30. X is an integer of 1 to 50. Y is an integer of 1 to 50.)

The polyether-modified polydimethylsiloxane can be produced by a known method, and a commercially available product can also be used. Examples of commercially available products include BYK-306, BYK-307, BYK-330, BYK-331, BYK-337, BYK-344 (above, manufactured by Big Chemie), KF-618, KF-351, KF-352, KF-353, KF-6011, KF-6015 (above, Shin-Etsu Chemical Co., Ltd. make) etc. are mentioned.

Examples of the acetylene glycol-based surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol and 3,3. 5-dimethyl-1-hexyn-3-ol and the like can be mentioned.

Examples of the fluorine-based surfactant include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide compound. And so on.

Examples of the acrylic leveling agent include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl. Acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, a polymer obtained by polymerizing alone, Alternatively, there may be mentioned a copolymer obtained by copolymerizing two or more kinds. Further, the acrylic leveling agent is preferably a polymer having only an ester formed from (meth)acrylic acid and alcohol as a constituent monomer. By including an acrylic leveling agent in the resin composition, the leveling property of a cured product or a laminate obtained using the resin composition can be improved.

The acrylic leveling agent can be produced by a known method, and a commercially available product can also be used. Examples of commercially available products include BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-381, BYK-392 (above, manufactured by BYK Chemie).

[Various additives]
In the resin composition according to the present invention, in addition to the above-mentioned essential components and suitable contained components, a curing accelerator, a reactive diluent, an unsaturated bond, if necessary, within a range that does not impair the effects of the present invention. -Free saturated compounds, pigments, dyes, antioxidants, ultraviolet absorbers, IR-cutting agents, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers Agents, organic fillers, adhesion improvers other than coupling agents, heat stabilizers, antibacterial/antifungal agents, flame retardants, matting agents, defoamers, leveling agents, wetting/dispersing agents, anti-settling agents, increasing agents Even if it contains a sticky agent/anti-sagging agent, anti-color separation agent, emulsifier, anti-slip/scratch agent, anti-skin agent, desiccant, antifouling agent, antistatic agent, conductive agent (electrostatic aid), etc. Good.
Since the resin composition contains an inorganic filler, it is possible to reduce the coefficient of linear expansion, and it is possible to suppress thermal expansion in the solder reflow step, the inorganic oxide vapor deposition step, and the like. .. As the inorganic filler, from the viewpoint of not impairing the transparency, those containing nanoparticles are preferable, and those containing silica, titanium oxide, zinc oxide, and zirconia oxide having a particle diameter of 40 nm or less are preferable. For example, MEK-ST manufactured by Nissan Chemical Industries, Ltd. is preferably used. In the above resin composition, the number of foreign matters having a particle diameter of 10 μm or more contained in 1 cm ^{3 of} the resin composition is preferably 1000 or less, more preferably 100 or less, and further preferably 10 or less. The foreign matter contained in the resin composition can be removed by performing filtration when the resin composition is prepared.

[solvent]
The resin composition according to the present invention may contain a solvent from the viewpoint of easily performing the coating operation.
The solvent that can be used may be appropriately selected according to the type of resin component, etc., but in the present invention, a solvent having a dipole moment of 4D (Debye) or less is preferable. When a solvent having a dipole moment of 4D or less is used in combination with an oxocarbon-based compound, deterioration of physical properties of the oxocarbon-based compound due to light or heat is sufficiently suppressed, and stable storage or use is possible. The dipole moment of the solvent is preferably 3.5D or less, more preferably 3D or less, particularly preferably 1.5D or less, and most preferably 1D or less. The lower limit of the dipole moment is not particularly limited and is preferably 0D or more.

Examples of the solvent having a dipole moment of 4D or less include the following compounds and the like, and one or more of these can be used.
Methyl ethyl ketone (also called 2-butanone) (dipole moment: 2.76D), methyl isobutyl ketone (also called 4-methyl-2-pentanone) (dipole moment: 2.56D), cyclopentanone (dipole moment: 3.3D), ketones such as cyclohexanone (dipole moment: 3.01D);
PGMEA (also referred to as 2-acetoxy-1-methoxypropane or propylene glycol monomethyl ether acetate) (dipole moment: 1.8D), ethylene glycol mono-n-butyl ether (dipole moment: 2.08D), ethylene glycol monoethyl Ethers (dipole moment: 2.08D), glycol derivatives such as ethylene glycol ethyl ether acetate (eg, ether compounds, ester compounds, ether ester compounds, etc.);
Ethers such as tetrahydrofuran (dipole moment: 1.70D), dioxane (dipole moment: 3.0D), diethyl ether (dipole moment: 1.12D), dibutyl ether (dipole moment: 1.22D);
Esters such as ethyl acetate, propyl acetate, butyl acetate;
Alcohols such as methyl cellosolve (also called 2-methoxyethanol) (dipole moment: 2.1D);
Amides such as N,N-dimethylacetamide (dipole moment: 3.72D);
Aromatic hydrocarbons such as toluene (dipole moment: 0.37D) and xylene (dipole moment: 1D or less);
Aliphatic hydrocarbons such as cyclohexane, ethylcyclohexane (dipole moment: 0D), heptane (dipole moment: 0.0D), limonene (dipole moment: 1D or less);
Halogen-containing aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene (dipole moment: 2.27D);

Among these, ketones containing a ring structure (also called cyclic ketone); ethers containing a ring structure (also called cyclic ether); alcohols having a chain structure (also called chain alcohol); chains among glycol derivatives Preferred are acetates having a chain structure (also referred to as chain acetate); aromatic hydrocarbons; aliphatic hydrocarbons. Thus, a form in which the solvent is at least one selected from the group consisting of cyclic ketones, cyclic ethers, chain alcohols, chain acetates, aromatic hydrocarbons and aliphatic hydrocarbons is also preferable in the present invention. It is one of the forms. As the solvent, it is preferable to use at least one of a cyclic ketone and aromatic hydrocarbons, it is more preferable to use cyclopentanone as the cyclic ketone, and it is preferable to use toluene as the aromatic hydrocarbons. More preferable.

The solvent having a dipole moment of 4D or less preferably has a boiling point of 90°C or more. For example, when the composition further contains a resin, by containing at least the solvent having the boiling point, volatilization during coating or the like can be sufficiently suppressed, and occurrence of unevenness or the like can be suppressed. The boiling point is more preferably 100°C or higher, still more preferably 110°C or higher. The upper limit is not particularly limited, but is preferably 250° C. or lower.

In the present invention, in addition to the solvent having a dipole moment of 4D or less, one or more other solvents may be contained, but from the viewpoint of further enhancing the effect of the present invention, the total amount of the solvent (dipole moment is 4D or more is 4D). It is preferable to use 50% by mass or more of a solvent having a dipole moment of 4D or less in 100% by mass of the total amount of the following solvents and other solvents. It is more preferably 70% by mass or more, and further preferably 90% by mass or more.

Other solvents are not particularly limited, but the water content in 100% by mass of the total amount of the solvent used in the present invention is preferably 3% by mass or less.

In the above-mentioned composition, the content of the solvent is not particularly limited, but for example, the total amount of the solvent (the total amount of the solvent having a dipole moment of 4D or less and the other solvent) relative to 100 parts by mass of the total resin (solid content). Is preferably 10 to 4000 parts by mass. The amount is more preferably 300 to 3000 parts by mass, and further preferably 500 to 2000 parts by mass.

In particular, when amides are used alone or in combination with another solvent as a solvent, the amides may decompose the oxocarbon-based compound, and therefore the amount of the amides used is preferably small, and particularly preferable. Is that it does not contain amides. Specifically, the amount of the amides used is preferably 60% by mass or less, more preferably 40% by mass or less, and further preferably 20% by mass or less in 100% by mass of the resin composition (total amount including the solvent). And particularly preferably 5% by mass or less, and most preferably 0% by mass (that is, containing no amides).

[Molded product, planar molded product]
The resin composition is useful for producing a molded product, a coating for molded parts, a resin film, or a planar molded product molded into a plate shape. This molded product is obtained by molding the resin composition of the present invention into a predetermined shape by a known method such as injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or solvent casting method. The "planar molded product" includes a film-shaped resin composition molded product of the present invention formed on a support and a support integrated with each other.

A particularly preferable molded body is a planar molded body, and more preferably an optical filter. The optical filter of the present invention preferably has a resin layer or a resin film formed from the resin composition of the present invention. This optical filter preferably comprises a support and a resin layer provided on at least one side of the support, and the resin composition of the present invention is used for this resin layer. Such a filter is formed, for example, by applying a resin composition made into a coating on a support by a spin coating method or a solvent casting method, and drying or curing the resin composition, or a resin composition for a support. In addition to the method of forming the formed resin film by thermocompression bonding, it can be manufactured by a kneading method or the like. The film thickness of the resin layer formed of the resin composition is not particularly limited, but is preferably 0.5 μm or more and 15 μm or less, and more preferably 1 μm or more and 10 μm or less. A substrate such as a resin plate, a film or a glass substrate can be used as the support, but a glass substrate or a film is preferable, and a glass substrate is more preferable. The support film is preferably formed of, for example, the resin described above as a suitable resin component. Further, as a form other than the above, a single-layer resin film (planar molded body) formed from the resin composition of the present invention is also a preferable form. The film thickness of the single-layer resin film (planar molded body) formed of the resin composition is not particularly limited, but is preferably 30 μm or more and 200 μm or less, and more preferably 50 μm or more and 150 μm or less. is there. Such a filter can be preferably used in various applications such as optical device applications, display device applications, mechanical parts, electric/electronic parts, and the like. Further, it may be used as an image pickup device including one or more of the above optical filters.

Since the optical filter contains a specific oxocarbon-based compound, it has high light absorption characteristics in the red wavelength (wavelength near 700 nm) and high transmittance in the visible light region (wavelength near 500 nm). Is one of its features. In order to exhibit sufficient performance as an optical filter, the transmittance of spectral rays at a wavelength of 700 nm is, for example, 12.5% or less (preferably 10% or less, more preferably 8% or less, and further preferably 7% or less. ) Is preferable. Further, it is preferable that the spectral light transmittance at a wavelength of 500 nm is, for example, 87.5% or more (preferably 88% or more, more preferably 88.5% or more, still more preferably 89% or more). When such a filter of the present invention is used, the transmittance of light in the visible light region is increased, while the absorptance of light of red wavelength is increased, and it can be said that the filter has high selective transmittance. On the other hand, when the transmittance of the spectral ray at the wavelength of 500 nm is less than 87.5%, the transmission of bluish light is insufficient, and the tint of the light transmitted through the filter may change. Further, since the optical filter of the present invention can reduce the angle dependence of transmitted light and reflected light, it is possible to obtain a near-infrared cut filter suitable for use in visibility correction in which changes in brightness and hue are small. The method of measuring the transmittance will be described later.

Further, from the viewpoint of increasing the transmittance of light in the visible light region, the transmittance (λ ₁ ) of a spectral ray at a wavelength of 500 nm of the optical filter made of the resin composition P containing the mercapto group-containing compound, and the mercapto group-containing compound The difference between the transmittance (λ ₂ ) of the spectral ray at a wavelength of 500 nm of the optical filter made of the resin composition Q having the same structure as that of the resin composition P (λ ₁ −λ ₂ (hereinafter, Δ wavelength of 500 nm)) is, for example, 0.6% or more (preferably 1% or more, more preferably 1.3% or more, still more preferably 1.5% or more).

[Other]
One example of the filter of the present invention includes a support and a resin layer provided on one side or both sides of the support, but a base layer may be provided between the support and the resin layer. Good. The underlayer may be provided on only one side of the support or on both sides. The underlayer may have either a single-layer structure or a multi-layer structure.

The underlayer is preferably formed from a composition containing a silane coupling agent, more preferably an epoxy group-containing silane coupling agent. By containing such a silane coupling agent in the composition for the underlayer, it has the effect of improving the adhesion to the support and the effect of suppressing the infiltration of water into the underlayer by the water repellent action, As a result, a filter having excellent heat resistance and moist heat resistance can be obtained. Specifically, it is possible to suppress peeling and the like in the solder reflow process and use in a wet heat environment. As the silane coupling agent, only one kind may be used, or two or more kinds may be used.

Examples of the epoxy group-containing silane coupling agent include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxy. Examples thereof include silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane.

The epoxy group-containing silane coupling agent can be produced by a known method, and a commercially available product can also be used. Examples of commercially available products include KBM-303 (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane), KBM-402 (3-glycidoxypropylmethyldimethoxysilane), and KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. (3-glycidoxypropyltrimethoxysilane), KBE-402 (3-glycidoxypropylmethyldiethoxysilane), KBE-403 (3-glycidoxypropyltriethoxysilane) and the like.

The method for preparing the composition for the underlayer is not particularly limited, and it can be obtained by adding a liquid medium and a catalyst to the silane coupling agent and mixing them by a usual method. The liquid medium may be water, alcohol or the like, and one kind or two or more kinds can be used. Further, the catalyst may be either an organic acid or an inorganic acid.

As a method for forming the underlayer, a known method can be used, but a method in which the underlayer composition (undercoat liquid) is applied on a support and dried by heating is preferable.

When the support is a glass substrate, the base layer is formed from a base layer composition containing a silane coupling agent having an amino group, an epoxy group, or a mercapto group, from the viewpoint of improving adhesiveness. It is preferable. When formed from a composition containing a silane coupling agent having an amino group, it is preferably a silane coupling agent having a primary amino group. When the composition for the underlayer containing the silane coupling agent having a primary amino group is used, the adhesiveness to the glass substrate is much higher than that in the case where the silane coupling agent having an amino group other than the primary amino group is contained. Will be good. The liquid medium is preferably at least one selected from water, ethanol and isopropyl alcohol. By adding the liquid medium, the alkoxy group is hydrolyzed in the amino group, the epoxy group, or the mercapto group-containing silane coupling agent to generate a silanol group, and the silanol group forms a hydrogen bond with the hydroxyl group on the glass substrate surface. Through the glass substrate surface. Then, by forming a strong covalent bond with the surface of the glass substrate through the dehydration condensation reaction of the silanol group, the adhesion between the glass substrate and the underlayer is improved. The catalyst may be any one that acts as a catalyst during the hydrolysis reaction of the amino group, the epoxy group, or the mercapto group-containing silane coupling agent, and may be either an organic acid or an inorganic acid. It is preferably used.

The optical filter of the present invention, in addition to the resin layer or the resin film formed using the resin composition of the present invention, a layer having antireflection and/or antiglare property for reducing the reflection of a fluorescent lamp or the like, A layer having a scratch prevention property and a layer having a function other than the above may be laminated, and a transparent substrate, a glass substrate, a filter and the like may be laminated.

The optical filter of the present invention preferably comprises an ultraviolet ray reflecting film that reflects ultraviolet rays and/or a near infrared ray reflecting film that reflects near infrared rays (hereinafter collectively referred to as "invisible light reflecting film"). Such an invisible light reflection film includes an aluminum vapor deposition film, a noble metal thin film, a resin film in which fine particles of metal oxide containing indium oxide as a main component and a small amount of tin oxide are dispersed, a high refractive index material layer and a low refractive index. A dielectric multilayer film in which material layers are alternately laminated can be used. The invisible light reflection film may be provided on one surface of the resin layer or the support, or may be provided on both surfaces. When provided on one side, it is possible to obtain an ultraviolet cut filter or a near infrared cut filter which is excellent in production cost and easiness of production, and when provided on both sides, has high strength and is resistant to warping. In addition, when the near-infrared reflective film is laminated, a near-infrared cut filter that can surely cut near-infrared rays can be obtained.

As the invisible light reflection film, it is preferable to use a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated. As the material 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 to 2.5 is usually selected. Examples of the material 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; silicon nitride. And the like; a mixture of the oxides and the nitrides, or a mixture thereof containing a metal such as aluminum or copper or carbon (eg, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. Can be mentioned. As the material forming the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected. Examples of the material forming the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoroaluminate and the like.

The optical filter of the present invention preferably comprises an antireflection film. As the antireflection film, it is preferable to use a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated. As the material 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 to 2.5 is usually selected. Examples of the material 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; silicon nitride. And the like; a mixture of the oxides and the nitrides, or a mixture thereof containing a metal such as aluminum or copper or carbon; for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), etc. Can be mentioned. As the material forming the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected. Examples of the material forming the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The invisible light reflection film and/or the antireflection film is preferably a laminated film from which oxygen does not permeate (can block oxygen) from the air layer (outside air side) to the resin layer. As described above, the lower the oxygen concentration is, the more the durability of the oxocarbon compound is improved. Therefore, it is preferable to stack an invisible light reflection film or an antireflection film having a high oxygen blocking ability. In order to increase the oxygen blocking ability, it is preferable that at least one layer of the laminated film is a dense film (more preferably, all layers are dense films), and at least one layer of the laminated film is thickened. It is preferable to increase the thickness of all layers, and it is also preferable to use both in combination. As a method for forming a dense film, a known technique may be used, and examples thereof include a high degree of vacuum during vapor deposition, a high vapor deposition temperature, and vapor deposition by an ion assist method (IAD). However, a dense film may be formed by using a method other than the above. Specifically, the degree of vacuum is preferably 5×10 ^-2 Pa or less for vapor deposition, and the vapor deposition temperature is preferably 80°C or higher and 300°C or lower. In vapor deposition by the IAD method, it is preferable that the assist acceleration voltage is 500 V or more and 1200 V or less and the assist acceleration current is 500 mA or more and 1200 mA or less. If the vapor deposition temperature is too high, the temperature of the resin layer will be equal to or higher than the Tg of the resin used in the resin layer, so the resin layer may be deteriorated by vapor deposition. If the vapor deposition temperature is too low, the vapor deposition film (invisible light The reflection film and/or the antireflection film may not be a dense film. In the case of performing the vapor deposition by the IAD method, if the assist voltage and the assist current are too weak like the vapor deposition temperature, the vapor deposition film (the invisible light reflection film and/or the antireflection film) is a dense film (a film having a high packing density). ) May not occur, and if the assist voltage/assist current is too strong, the resin layer may be deteriorated. By optimizing various conditions, it is preferable to produce a dense film having a high oxygen blocking ability, and not to deteriorate the resin layer or to reduce the deterioration.

By stacking an invisible light reflection film having a high oxygen blocking ability, an antireflection film, or another layer on the optical filter of the present invention, the durability of the oxocarbon-based compound of the present invention is dramatically improved, and the durability is improved. It is possible to obtain an optical filter and a near-infrared cut filter having excellent optical characteristics.

The optical filter of the present invention, a visible light cut filter, an infrared cut filter, a near infrared cut filter, a security filter, a heat ray shield, by stacking an invisible light reflection film, an antireflection film, or other layers as necessary. Heat ray absorption filter, bandpass filter, (day & night) surveillance camera filter, night vision camera filter, dual band filter, visible light image sensor/infrared sensor filter, neon light, fluorescent light, etc. It can be suitably used as a cut filter.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples, and may be appropriately modified within a range compatible with the gist of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.
Below, "%" shall mean "mass %" and "part" shall mean "mass part."

(Chemical structure analysis method)
About 1 mg of the obtained compound was applied on a glass rod to be adhered, and ionized by a direct ionization unit (DART) (“DART-OS” manufactured by Shimadzu Corporation, heater temperature 500° C.), and a mass spectrometer (manufactured by Shimadzu Corporation). The MS spectrum of the obtained compound was measured by "LCMS-2020" manufactured by M/Z=50-2000, positive and negative simultaneous scanning.

(Measurement method of transmittance)
Using a spectrophotometer (UV-1800 manufactured by Shimadzu Corporation), the absorption spectrum (transmission spectrum) of the resin layer laminated substrate was measured at a measurement pitch of 1 nm, and the light transmittance at the wavelengths of 430 nm, 500 nm and 700 nm was measured. I asked.

[Method for producing squarylium compound A]
The structural formulas of the squarylium compounds A to D used in the examples are shown below. The squarylium compound described below is produced by a known synthetic method of reacting a pyrrole ring-containing compound with squaric acid, that is, a synthetic method described in the articles cited in the specification. The squarylium compounds A to D described below were analyzed by the above method, and were confirmed to have the structures shown below.

[Method for producing cationic curing catalyst F]
Preparation Example 1 (Synthesis of TPB-containing powder E)
In accordance with the synthetic method described in WO 1997/031924, 255 g of Isopar (registered trademark) E solution manufactured by Ando Parachemy Co. having a TPB (tris(pentafluorophenyl)borane) content of 7% was prepared. Water was added dropwise to this solution at 60°C. White crystals precipitated during the dropping. After cooling the reaction solution to room temperature, the resulting slurry was suction filtered and washed with n-heptane. The obtained cake was dried under reduced pressure at 60° C., and 18.7 g of TPB/water complex (TPB-containing powder E) that was a white crystal was obtained. This complex had a water content of 9.2% (Karl Fischer water content meter) and a TPB content of 90.8%. The dried complex was subjected to ¹⁹ F-NMR analysis and GC analysis, but no peaks other than TPB were detected.
The measurement results of ¹⁹ F-NMR are shown below.
¹⁹ F-NMR (CDCl ³ ) ppm (standard substance: CFCl ³ 0 ppm)
δ=−135.6 (6F,m)
δ=-156.5 (3F, dd)
δ=-163.5 (6F, d)

Preparation Example 2 (Preparation of cationic curing catalyst F)
1.1 g of toluene was added to 2 g of the TPB-containing powder E obtained in Preparation Example 1 (TPB pure content: 1.816 g (3.547 mmol), water: 0.184 g (10.211 mmol)), and at room temperature Mix for 10 minutes. Thereafter, 2.6 g of a 2 mol/L ammonia/ethanol solution was added and mixed at room temperature for 60 minutes to obtain a uniform solution of a cation curing catalyst (TPB catalyst). This was used as a cation curing catalyst F.

(Example 1-1)
(Composition for underlayer (undercoat liquid))
<Preparation of undercoat liquid>
As a silane monomer, Toray Dow Corning Z-6040 (3-glycidoxypropyltrimethoxysilane) 40 parts, Wako Pure Chemical Industries, Ltd. 2-propanol 45 parts, Wako Pure Chemical Industries, Ltd. 98% formic acid 5 And 10 parts of deionized water were uniformly mixed at 40°C. Then, the foreign matter was filtered with a 0.45 μm filter (GL Science Co., Ltd., non-aqueous 13N) to obtain an undercoat liquid.

<Application of undercoat liquid>
After dropping 1 cc of the undercoat liquid on a glass substrate (D263Teco manufactured by SCHOTT, 60 mm×60 mm×0.3 mm), 2200 rotations (rpm) for 3 seconds using a spin coater (1H-D7 manufactured by Mikasa Co., Ltd.) ), the rotation speed was maintained for 20 seconds, and then the underlayer was formed so as to be 0 rotation (rpm) over 3 seconds. The glass substrate after forming the underlayer was dried at 100° C. for 10 minutes by using a precision thermostat (DH611 manufactured by Yamato Scientific Co., Ltd.) to obtain a glass substrate having an underlayer (hereinafter referred to as underlayer laminated substrate). ..

<Preparation of Composition Solution for Resin Layer>
Containing 100 parts of EHPE3150 (alicyclic epoxy resin) manufactured by Daicel as a resin, 250 parts of toluene manufactured by Wako Pure Chemical Industries, Ltd. as a solvent, 12 parts of the above squarylium compound A (absorption maximum wavelength 730 nm) as an oxocarbon compound, containing a mercapto group Toray Dow Corning's Z-6062 (3-mercaptopropyltrimethoxysilane) 10 parts as a compound, and BYK-306 (polyether modified polydimethylsiloxane) 0.3 part BYK-Chemie as a surface conditioner at 80°C. Mixed evenly. Thereafter, the temperature is lowered to 40° C., 2.5 parts of the above cationic curing catalyst F as a curing catalyst is uniformly mixed, and foreign matter is filtered through a 0.45 μm filter (GL Science Co., non-aqueous 13N) to form a resin layer composition. A product solution was obtained.

<Production of resin layer laminated substrate>
After dropping 1 cc of the resin layer composition solution on the base layer, a spin coater (1H-D7 manufactured by Mikasa Co., Ltd.) was used to make 1000 revolutions over 0.5 seconds and hold at that revolution for 20 seconds. Then, the resin layer was formed so that the rotation speed would be 0 rpm for 3 seconds. The glass substrate on which the resin layer was formed was replaced with nitrogen using an inert oven (DN610I manufactured by Yamato Scientific Co., Ltd.) at 50° C. for 30 minutes, heated to 150° C. in about 15 minutes, and dried at 150° C. for 1 hour ( Under a nitrogen atmosphere) to obtain a glass substrate provided with a resin layer (hereinafter referred to as a resin layer laminated substrate). The film thickness of the resin layer after drying was 2 μm. The film thickness of the resin layer after drying was determined by measuring the thickness of the resin layer laminated substrate and the thickness of the glass substrate using a micrometer, and the difference between the two was taken as the film thickness of the resin layer after drying. The constitution of the resin layer laminated substrate and the transmittance at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 1 below.

(Example 1-2)
A resin layer-laminated substrate having no underlayer was prepared in the same manner as in Example 1-1, except that the resin layer composition solution was dropped on the glass substrate instead of the underlayer-laminated substrate in an amount of 1 cc. The constitution of the resin layer laminated substrate and the transmittance at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 1 below.

(Example 1-3)
A resin layer laminated substrate having no underlayer was produced in the same manner as in Example 1-2, except that the temperature rising temperature was changed from 150°C to 130°C. The constitution of the resin layer laminated substrate and the transmittance at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 1 below.

(Comparative Example 1-1)
Resin layer-laminated substrate was prepared in the same manner as in Example 1-1, except that the resin layer composition solution prepared without containing Toray Dow Corning Z-6062 (3-mercaptopropyltrimethoxysilane) was used. Was produced. The constitution of the resin layer laminated substrate and the transmittance at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 1 below.

(Comparative Example 1-2)
A resin layer laminated substrate was produced in the same manner as in Comparative Example 1-1, except that the temperature rising temperature was changed from 150°C to 130°C. The constitution of the resin layer laminated substrate and the transmittance at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 1 below.

(Examples 2-1 to 8 and Comparative examples 2-1 to 2)
A resin layer-laminated substrate was produced in the same manner as in Example 1-1, except that the mercapto group-containing compound was changed to those shown in Table 2 below. The constitution of the resin layer laminated substrate and the transmittances at the wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 2 below. In addition, for Examples 2-1 to 9, the Δ wavelength of 500 nm calculated as λ ₂ as the transmittance at the wavelength of 500 nm of Comparative Example 1-1 is also shown in Table 2 below. The abbreviations in Table 2 are as follows.
PEMP: Pentaerythritol tetrakis (3-mercaptopropionate) manufactured by SC Organic Chemical Co., Ltd.
TEMPIC: SC Organic Chemical Co., Ltd. tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate DPMP: SC Organic Chemical Co., Ltd. dipentaerythritol hexakis (3-mercaptopropionate)

Regarding p-mercaptophenol, octanethiol, 3-mercaptopropionic acid, 3-mercapto-1,2-propanediol, 2-mercaptoethanol, dimethyldisulfide, and dimethylsulfoxide described in Table 2, those manufactured by Wako Pure Chemical Industries, Ltd. I used one.

(Comparative Examples 3-1 to 3)
A resin layer laminated substrate was produced in the same manner as in Comparative Example 1-1, except that the squarylium compound was changed to any of the above squarylium compounds B to D. The constitution of the resin layer laminated substrate and the transmittances at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 3 below.

(Examples 3-1 to 3)
A resin layer laminated substrate was produced in the same manner as in Example 1-1, except that the squarylium compound was changed to any of the above squarylium compounds B to D. The constitution of the resin layer laminated substrate and the transmittances at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 3 below. The Δ wavelength of 500 nm is also shown in Table 3 below.

(Example 4-1)
A resin layer-laminated substrate was produced in the same manner as in Example 1-1, except that the resin layer composition solution described below was used.

<Method of synthesizing acrylic resin G>
In a reaction vessel equipped with a stirring blade, a temperature sensor, a cooling pipe, and a gas introduction pipe, 21.0 parts of α-allyloxymethylmethyl acrylate (AMA) as a monomer and 9.0 parts of N-cyclohexylmaleimide, a polymerization solvent As a solvent, 45.0 parts of ethyl acetate was charged, and the mixture was stirred while flowing nitrogen gas, and the temperature started to be raised. After confirming that the internal temperature was stable at 70° C., 0.03 part of an azo radical polymerization initiator (ABN-V manufactured by Nippon Finechem Co., Ltd.) was added to initiate polymerization. The reaction was continued for 3.5 hours while adjusting the internal temperature to 69°C to 71°C, and then cooled to room temperature. Reprecipitation was performed using tetrahydrofuran as a diluting solvent and n-hexane as a poor solvent, and the precipitate was separated by suction filtration. The precipitate was dried under reduced pressure at 80° C. for 2 hours using a vacuum dryer to obtain an acrylic resin G.

<Preparation of Composition Solution for Resin Layer>
A resin solution in which 100 parts of acrylic resin G was dissolved in 400 parts of cyclopentanone was mixed and dissolved with 4 parts of squarylium compound A and 10 parts of PEMP to prepare a resin layer composition solution.

The constitution of the resin layer laminated substrate and the transmittance at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 4 below. Further, the Δ wavelength of 500 nm calculated as λ ₂ as the transmittance at a wavelength of 500 nm in Comparative Example 4-1 described later is also shown in Table 4 below.

(Comparative Example 4-1)
A resin layer-laminated substrate was produced in the same manner as in Example 4-1 except that the resin layer composition solution produced without containing SC organic chemical PEMP was used. The constitution of the resin layer laminated substrate and the transmittance at wavelengths of 430 nm, 500 nm and 700 nm are summarized in Table 4 below.

Claims (7)

A resin containing a mercapto group-containing compound, a resin containing at least one of a cation-curable group and a radical-curable group, a curing catalyst for promoting a curing reaction, and a squarylium compound represented by the following formula (1). Composition.

(In the formula (1), R ^{a1 and} R ^a2 are each independently a structural unit represented by the following formula (3).)

(In formula (3), ring A is a 4- to 9-membered unsaturated hydrocarbon ring.
X and Y are each independently an organic group or a polar functional group.
n is an integer of 0 to 6 and is m or less (however, m is a value obtained by subtracting 3 from the number of members of ring A), and when n is 2 or more, a plurality of Ys are the same. May be different or different.
Ring B is an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle, or a condensed ring containing these ring structures.
Note that * represents a binding site with the 4-membered ring in the formula (1). ) The resin composition according to claim 1 , wherein the resin contains an oxirane ring-containing compound. The curing catalyst, the resin composition according to claim 1 or 2 comprising a cationic curing catalyst. The resin composition further resin composition according to any one of claims 1 to 3, which contains the siloxane-based surfactant. A support, an optical filter with at least one surface resin provided on layer of the support, the resin layer is formed from a resin composition according to any one of claims 1-4 An optical filter characterized in that The optical filter according to claim 5 , wherein an underlayer is provided between the support and the resin layer, wherein the underlayer is formed of a composition for an underlayer containing a silane coupling agent. filter. Imaging element which comprises an optical filter according to claim 5 or 6.