JP6470650B2 - Oxocarbon-based compound-containing resin composition and optical filter including the resin composition - Google Patents

Description

  The present invention relates to an oxocarbon-based compound-containing resin composition having a so-called squarylium skeleton or a croconium skeleton (hereinafter sometimes simply referred to as a resin composition) and an optical filter including the resin composition.

  An oxocarbon compound having a squarylium skeleton or a croconium skeleton in the compound is useful as a dye having absorption in the visible / near infrared region. For example, a cut filter for visible light or infrared light, a near infrared absorption film, security Use as ink etc. is expected.

  An oxocarbon-based compound having a squarylium skeleton or a croconium skeleton is generally synthesized by using squaric acid or croconic acid as a raw material and introducing heterocyclic groups at both ends of the raw material. As the heterocyclic group, a pyrrole ring-containing group, particularly an indole ring-containing group, is well known, and examples of such oxocarbon compounds include the following reports.

  Patent Document 1 discloses a squarylium compound represented by the following formula (claim 1).

(In the formula, groups Ar ¹ and Ar ² each independently represent a substituent of any one of the following formulas (A) to (C), except when both Ar ¹ and Ar ² are represented by formula (A)). )

  Patent Document 2 discloses a squarylium compound represented by the following formula (Formula 17).

  Patent Document 3 discloses a squarylium compound of the following formula together with its absorption wavelength, and discloses that it is used for a near-infrared cut filter.

JP 2014-148567 A US Pat. No. 5,543,086 JP 2014-059550 A

  The indole-based oxocarbon compound disclosed in Patent Document 1 binds an oxocarbon-based compound and a nitrogen-containing ring such as an indole ring via a single methine group (which does not form a ring structure). The contained ring and the squarylium skeleton were conjugated. The oxocarbon compounds disclosed in Patent Documents 2 and 3 are obtained by bonding an oxocarbon compound and a benzene ring without one methine group (not forming a ring structure).

  By the way, although the resin composition containing the squarylium compound disclosed in Patent Documents 1 to 3 sufficiently absorbs light of a red wavelength (610 to 750 nm) that is near the maximum absorption wavelength, it is in the wavelength region of blue light. It turned out that the transmittance | permeability of the light in a certain wavelength 400-450 nm is inadequate. Therefore, it turned out that the color which the light which permeate | transmitted these resin compositions changed. Therefore, in order to prevent the color of the light transmitted through the resin composition from changing as much as possible, it is required to further increase the light transmittance at a wavelength of 400 to 450 nm.

  In addition, the squarylium compounds disclosed in Patent Documents 1 to 3 sometimes have a large shoulder peak on the lower wavelength side than the absorption maximum wavelength when the wavelength absorption spectrum is measured. Therefore, it is also desired to further enhance the spectral performance by eliminating (or reducing) such shoulder peaks.

  Under such circumstances, an object of the present invention is to provide a resin composition having a high average light transmittance at 400 to 450 nm while sufficiently absorbing red wavelength light. In addition, the present invention has been given as a further object to provide a resin composition that preferably has no (or greatly reduced) shoulder peak in the absorption spectrum in the visible / near infrared region.

  As a result of intensive studies to solve the above problems, the present inventors have found that when a nitrogen-containing 5-membered ring is bonded to a squarylium skeleton or a croconium skeleton via a carbon atom, the nitrogen-containing 5-membered ring and the squarylium skeleton are combined. Alternatively, a resin composition having a high average light transmittance at 400 to 450 nm while sufficiently absorbing red wavelength light by using a compound that is molecularly designed so that a methine group that binds to the croconium skeleton has a ring structure As a result, the present invention was completed.

  In addition, the present inventors use a predetermined compound having a molecular design as described above, so that the absorption spectrum in the visible / near infrared region is larger than that of a conventional oxocarbon compound (squarylium compound or croconium compound). It was found that the resin composition has no (or greatly reduced) shoulder peak appearing on the lower wavelength side than the absorption maximum wavelength.

  That is, the resin composition according to the present invention includes an oxocarbon compound represented by the following formula (1) or the following formula (2) and a resin component.

(In formulas (1) and (2), R ^{a1 to} R ^a4 are each independently a structural unit represented by the following formula (3).)

(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 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 Ys are the same. It may be different or different.
Ring B is an optionally substituted aromatic hydrocarbon ring, aromatic heterocyclic ring or condensed ring containing these ring structures.
In addition, * represents the coupling | bond part with the 4-membered ring in Formula (1) or the 5-membered ring in Formula (2). )

  In a preferred embodiment of the oxocarbon compound according to the present invention, the ring B is a benzene ring or a naphthalene ring, and the X is an alkyl group or an aryl group.

  In the resin composition according to the present invention, the resin component includes poly (amide) imide resin, fluorinated aromatic polymer, (meth) acrylic resin, polyamide resin, aramid resin, polysulfone resin, epoxy resin, and polycyclohexane. It is preferably at least one selected from olefin resins.

  The resin composition according to the present invention further comprises at least one solvent selected from ketones, glycol derivatives, amides, esters, pyrrolidones, aromatic hydrocarbons, aliphatic hydrocarbons, and ethers. It is preferable to include. Moreover, it is more preferable that the usage-amount of the said amides is 60 mass% or less in 100 mass% (total quantity containing a solvent) of a resin composition.

  The present invention also includes an optical filter (hereinafter sometimes simply referred to as a filter) characterized by having a resin layer or a resin film formed from the resin composition. Further, an optical filter comprising a support and a resin layer provided on one or both surfaces of the support, wherein the resin layer is formed from the resin composition. Is included. In addition, the filter of the present invention preferably has an average transmittance of 81% or more of spectral rays at a wavelength of 400 to 450 nm of the resin layer or the resin film.

  Furthermore, the present invention also includes a near-infrared cut filter in which the optical filter has a dielectric multilayer film. In addition, the present invention includes an imaging device including at least one of the optical filter and the near-infrared cut filter.

In this specification, the squarylium skeleton refers to a structure in which R ^a1 and R ^a2 are removed from the above formula (1), and the croconium skeleton refers to a structure in which R ^a3 and R ^a4 are removed from the above formula (2). Shall.

  According to the present invention, by using a resin composition containing a predetermined oxocarbon-based compound, the average transmittance of 400 to 450 nm is increased and light having a desired red wavelength can be selectively absorbed. Therefore, since the resin composition of the present invention has high selective permeability, it can be suitably used in optical applications.

  Further, according to the present invention, there is provided a resin composition containing an oxocarbon-based compound having no (or greatly reduced) shoulder peak appearing at a wavelength lower than the absorption maximum wavelength in the absorption spectrum in the visible / near infrared region. As a result, light in the absorption maximum region can be more selectively absorbed, and light in a desired red wavelength region can be efficiently absorbed with good color purity. Therefore, it can be suitably used in optical applications that require extremely high selectivity.

It is the figure which showed the relationship between the wavelength of the resin layer obtained by Example 12 and Comparative Example 3, and the transmittance | permeability. It is the figure which showed the relationship between the wavelength of the resin layer containing the squarylium compound 01, and the resin layer containing the comparison squarylium compound 5, and the transmittance | permeability.

  The resin composition of the present invention is characterized by containing a specific oxocarbon-based compound and a resin component. Since this resin composition is excellent in the light absorption characteristics of the oxocarbon-based compound, the average transmittance of 400 to 450 nm is increased, while the absorbance of red wavelength light is increased and the selective permeability is excellent. From the resin composition of the present invention, a resin layer provided on a resin film, a filter, or the like can be formed. Hereinafter, the resin layer may include a resin film.

1. Oxocarbon-based compound The oxocarbon-based compound used in the present invention is a compound having an oxocarbon skeleton in the chemical structure. Specifically, the following formula (1) having a squarylium skeleton or the following formula (2) having a croconium skeleton. ). Here, R ^{a1 to} R ^a4 in the formula (1) and the formula (2) are each independently a specific structural unit represented by the following formula (3).

  In the formula (3), * represents a binding site to the squarylium skeleton represented by the formula (1) or the croconium skeleton represented by the formula (2). In the oxocarbon-based compound used in the present invention, the squarylium skeleton or It is characterized in that a carbon atom (carbon atom indicated by an arrow in the above formula (3)) bonded to the croconium skeleton forms a hydrocarbon ring (ring A). Due to such structural features, the oxocarbon compound (squarylium compound or croconium compound) used in the present invention has an excellent average light transmittance at 400 to 450 nm. In addition, due to such structural features, the oxocarbon compound (squarylium compound or croconium compound) used in the present invention eliminates the shoulder peak on the lower wavelength side than the absorption maximum wavelength in the absorption spectrum in the visible / near infrared region ( Therefore, light in the absorption maximum wavelength region can be efficiently absorbed with good color purity.

  In formula (3), ring A is an unsaturated hydrocarbon ring having 4 to 9 members. Ring A is a non-bonding compound having at least one double bond between a carbon atom bonded to the squarylium skeleton or the croconium skeleton (in the above formula (3), a carbon atom indicated by an arrow) and a carbon atom constituting the pyrrole ring. It may be a saturated hydrocarbon ring and may have an unsaturated bond (preferably a double bond) in addition to the double bond, but preferably the ring A has one double bond. Ring A is preferably a 5- to 8-membered ring, more preferably a 6- to 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 include cycloalkene structures such as cyclononatetraene. Of these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are preferable.

  In formula (3), 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). 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 constituting the ring A is substituted with Y.

In formula (3), X and Y are organic groups or polar functional groups.
Examples of the organic group as X and Y include, for example, alkyl group, alkoxy group, alkylthiooxy group (alkylthio group), alkyloxycarbonyl group, alkylsulfonyl group, aryl group, aralkyl group, aryloxy group, 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. 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).

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Linear or branched alkyl group such as dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group , Cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like alicyclic alkyl groups; 1-20 are preferable, as for carbon number of an alkyl group, More preferably, it is 1-10, More preferably, it is 1-6, and 3 or more are preferable especially in the case of an alicyclic alkyl group. The alkyl group may have a substituent, and examples of the substituent that the alkyl group has include a halogeno group, a hydroxyl group, a carboxy group, an alkoxy group, a cyano group, a nitro group, an amino group, and a sulfo group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. A tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, an icosyloxy group, and the like. 1-20 are preferable, as for carbon number of an alkoxy group, More preferably, it is 1-10, Most preferably, it is 1-5. The alkyl group in the alkoxy group may be linear or branched.

  Examples of the alkylthio group (alkylthiooxy group) include a methylthiooxy group (methylthio group), an ethylthiooxy group (ethylthio group), a propylthiooxy group (propylthio group), a butylthiooxy group (butylthio group), and pentylthio. Oxy group (pentylthio group), hexylthiooxy group (hexylthio group), heptylthiooxy group (heptylthio group), octylthiooxy group (octylthio group), nonylthiooxy group (nonylthio group), decylthiooxy group (decylthio group) ), Undecylthiooxy group (undecylthio group), dodecylthiooxy group (dodecylthio group), tridecylthiooxy group (tridecylthio group), tetradecylthiooxy group (tetradecylthio group), pentadecylthiooxy group (penta Decylthio group), f Sadecylthiooxy group (hexadecylthio group), heptadecylthiooxy group (heptadecylthio group), octadecylthiooxy group (octadecylthio group), nonadecylthiooxy group (nonadecylthio group), icosylthiooxy group (icosylthio group), etc. Is mentioned. 1-20 are preferable, as for carbon number of an alkylthio group, More preferably, it is 1-10, Most preferably, it is 1-5. The alkyl group in the alkylthio group may be linear or branched.

  Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, and a decyloxycarbonyl group. In addition to unsubstituted alkyloxycarbonyl groups such as octadecyloxycarbonyl group, substituted alkyloxycarbonyl groups such as trifluoromethyloxycarbonyl group can be mentioned. Here, examples of the substituent include a halogeno group. 2-20 are preferable, as for carbon number of an alkyloxycarbonyl group, More preferably, it is 2-10, Most preferably, it is 2-5. The alkyl group in the alkyloxycarbonyl group may be linear or branched.

  Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group, an octylsulfonyl group, and a methoxymethylsulfonyl. Group, a cyanomethylsulfonyl group, a substituted or unsubstituted alkylsulfonyl group of a trifluoromethylsulfonyl group, and the like. 1-20 are preferable, as for carbon number of an alkylsulfonyl group, More preferably, it is 1-10, Most preferably, it is 1-5. The alkyl group in the alkylsulfonyl group may be linear or branched.

  Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, an azulenyl group, a fluorenyl group, a terphenyl group, a quarterphenyl group, a pentarenyl group, a heptaenyl group, and a biphenylenyl group. Group, indacenyl group, acenaphthylenyl group, phenalenyl group and the like. 6-20 are preferable and, as for carbon number of an aryl group, More preferably, it is 6-15. The aryl group may have a substituent, and examples of the substituent of the aryl group include an alkyl group, an alkoxy group, a halogeno group, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, and an aryl group. Examples include oxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like.

  Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylpentyl group. The aralkyl group may have a substituent, and examples of the substituent that the aralkyl group has include an alkyl group, an alkoxy group, a halogeno group, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, and an aryl group. Examples include oxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like. 6-25 are preferable and, as for carbon number of an aralkyl group, 6-15 are more preferable.

  Examples of the aryloxy group include phenyloxy group, biphenyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, pyrenyloxy group, indenyloxy group, azulenyloxy group, fluorenyloxy group, Examples include a phenyloxy group, a quarterphenyloxy group, a pentarenyloxy group, a heptaenyloxy group, a biphenylenyloxy group, an indacenyloxy group, an acenaphthylenyloxy group, and a phenalenyloxy group. 6-25 are preferable and, as for carbon number of an aryloxy group, More preferably, it is 6-15.

  Examples of the arylthiooxy group (arylthio group) include a phenylthiooxy group, a biphenylthiooxy group, a naphthylthiooxy group, an anthrylthiooxy group, a phenanthrylthiooxy group, a pyrenylthiooxy group, and an indenylthio group. Oxy group, azulenylthiooxy group, fluorenylthiooxy group, terphenylthiooxy group, quarterphenylthiooxy group, pentarenylthiooxy group, heptalenylthiooxy group, biphenylenylthiooxy group, indacenylthiooxy group Acenaphthylenylthiooxy group, phenalenylthiooxy group and the like. 6-25 are preferable and, as for carbon number of an arylthiooxy group, 6-15 are more preferable.

  Examples of the aryloxycarbonyl group include phenoxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyl. Oxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxy Substituted or unsubstituted phenyloxycarbonyl groups such as carbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc .; 1-naphthyloxy Carbonyl group, a substituted or unsubstituted naphthyl oxycarbonyl group such as a 2-naphthyloxycarbonyl group; and the like. 6-25 are preferable and, as for carbon number of an aryloxycarbonyl group, More preferably, it is 6-15.

  Examples of the arylsulfonyl group include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and 2-butoxyphenylsulfonyl. Group, 2-fluorophenylsulfonyl group, 3-methylphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 3-fluorophenylsulfonyl Group, 4-methylphenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc. Unsubstituted phenylsulfonyl group; 1-naphthylsulfonyl group, a substituted or unsubstituted naphthylsulfonyl group and a 2-naphthylsulfonyl group; and the like. 6-25 are preferable and, as for carbon number of an arylsulfonyl group, 6-15 are more preferable.

  Examples of the arylsulfinyl group include a phenylsulfinyl group, a 2-chlorophenylsulfinyl group, a 2-methylphenylsulfinyl group, a 2-methoxyphenylsulfinyl group, a 2-butoxyphenylsulfinyl group, a 2-fluorophenylsulfinyl group, and 3-methyl. Phenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-methylphenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyano Substituted or unsubstituted phenylsulfinyl group such as phenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group; 1-naphthylsulfur Iniru group, 2-naphthylsulfinyl substituted or unsubstituted naphthylsulfinyl group such as Le group; and the like. 6-25 are preferable and, as for carbon number of an aryl sulfinyl group, 6-15 are more preferable.

  Examples of the amide group (—NHCOR) include those in which R is a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an araryl group, or a halogenated hydrocarbon group.

Examples of the sulfonamide group (—NHSO ₂ R) include those in which R is a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an araryl group, or a halogenated hydrocarbon group. Can be mentioned.

  Examples of the halogenoalkyl group include monohalogenoalkyl groups such as a fluoromethyl group, a 3-fluoropropyl group, a 3-chloropropyl group, a 6-fluorohexyl group, and a 4-fluorocyclohexyl group; and a dihalogeno group such as a dichloromethyl group. Alkyl group; 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 2,2-bis (trifluoro Methyl) propyl group, alkyl group having a trihalomethyl unit such as 2,2,2-trichloroethyl group; trifluoromethyl group, perfluoroethyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, etc. Perhalogenoalkyl group; and the like. 1-20 are preferable, as for carbon number of a halogenoalkyl group, More preferably, it is 1-10, Most preferably, it is 1-5. The halogen of the halogenoalkyl group is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a fluorine atom.

  Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

  As the organic group or polar functional group as 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 number of carbon atoms of the alkyl group is preferably 1 to 6 if it is a linear or branched alkyl group, more preferably 1 to 4, and 4 to 7 if it is an alicyclic alkyl group. Preferably, it is 5-6. 6-10 are preferable and, as for carbon number of an aryl group, More preferably, it is 6-8. Specifically, preferred examples of the organic group or polar functional group of X include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group.

As the organic group or polar functional group as 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. An alkyl group or a hydroxyl group is preferable. In this case, 1-5 are preferable, as for carbon number of an alkyl group, More preferably, it is 1-3, More preferably, it is 1-2. Specifically, preferred examples of the organic group or polar functional group as Y include a methyl group, an ethyl group, and a hydroxyl group.
When n is 2 or more and a plurality of Y are present, 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, an aromatic heterocycle, or a condensed ring containing these ring structures, which may have a substituent. Examples of the 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 substituents are substituted. preferable. Here, examples of the substituent include the groups described above as the organic group or polar functional group as examples of X and Y, and among them, an alkyl group (particularly preferably a linear or straight chain having 1 to 4 carbon atoms) 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 complex An electron donating group such as a ring group, a hydroxyl group, a thiol group, and a benzothiazole group, a halogeno group (particularly preferably, a fluoro group, a chloro group, a bromo group), a halogenoalkyl group (preferably a 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 A sulfonic acid group), preferably an electron-withdrawing group such as nitro group, particularly a halogeno group. The number of substituents on ring B may be one or two or more (for example, 2 or 3). Moreover, it does not need to have a substituent. When it has a substituent, the number becomes like this. Preferably it is 1-3, More preferably, it is 1-2, Most preferably, it is 1.

  The above formulas (A-1) to (A-14) represent ring B including a part of the pyrrole ring. For example, formula (A-1) is indicated 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 shown.

In addition, R ^a1 and R ^a2 which are specific structural units in the compound (1) having a squarylium skeleton may be the same or different. In view of easy production, R ^a1 and R ^a2 preferably have the same structure. Similarly, R ^a3 and R ^a4 which are specific structural units in the compound (2) having a croconium skeleton may be the same structure or different, and the same structure is a more preferable embodiment.

A particularly preferred oxocarbon-based compound has a squarylium skeleton of the formula (1), and in the structural unit of the formula (3), the ring A is cyclopentene, cyclohexene, cycloheptene, or cyclooctene (most preferably cyclohexene). X is a linear or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxycarbonyl group having 2 to 5 carbon atoms, In this compound, ring B is a benzene ring (A-1), a naphthalene ring (A-2, A-3), or a quinoline ring (A-8, A-13, A-14). In this particularly preferable oxocarbon-based compound, when ring B has a substituent, examples of the substituent include an aryl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 2 carbon atoms. An alkylthio group, a nitro group, a halogenoalkyl group having 1 to 4 carbon atoms (particularly a perfluoroalkyl group), a carboxy group, a halogeno group, a cyano group, and a benzothiazole group are preferred. When this substituent is a halogeno group, it is preferable that 1 to 3 halogeno groups are substituted with ring B. It is preferable that at least one of the substituents is bonded to a carbon atom that is in the para position with respect to a site to which the NH group of the pyrrole ring is bonded in the benzene ring as the ring B. In particular, when an electron-withdrawing group such as a nitro group, a C 1-4 halogenoalkyl group (particularly a perfluoroalkyl group), a carboxy group, a halogeno group, or a cyano group is bonded to the para position, the absorption maximum region Light can be absorbed more selectively.
In addition, when it is desired to obtain a resin composition having high transparency in the visible light region, the substituent in ring B is preferably other than an electron donating group, and more preferably an alkyl group or a carboxylic acid ester group. , A carboxylic acid amide group, a halogeno group, a carboxy group, a nitro group, and a cyano group. These substituents may further have another substituent and may be unsubstituted.
On the other hand, when it is desired to increase the maximum absorption wavelength of the resin composition, the substituent in ring B is preferably an electron donating group, more preferably an alkoxy group, a thioalkoxy group, a dialkylamino group, an amide group. , Phenyl group, naphthyl group, phenoxy group, naphthoxy group, aromatic heterocyclic group, amino group, hydroxyl group, and thiol group. These substituents may further have another substituent and may be unsubstituted.

  The oxocarbon compound used in the present invention, in which the specific structural unit represented by the formula (3) is bonded to the squarylium skeleton represented by the formula (1) or the croconium skeleton represented by the formula (2) There are tautomers. Specifically, when bonded to the squarylium skeleton represented by the formula (1), there is a tautomer represented by (1a) or (1b) 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), there are tautomers represented by (2a), (2b) or (2c) in addition to the compound represented by the following (2). The oxocarbon compound used in the present invention includes not only the compound represented by (1) or (2) but also tautomers corresponding to each compound.

2. Method for Producing Oxocarbon-based Compound The method for producing the oxocarbon-based compound used in the present invention is not particularly limited. For example, the following formula (4):

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

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

Moreover, a squarylium type compound is compoundable by employ | adopting suitably the well-known synthetic | combination method which makes a pyrrole ring containing compound and squaric acid react. For example, a pyrrole ring-containing compound can be synthesized by a synthesis method described in the following paper.
SergueiMiltsov ET AL; 'New Cyanine Dyes: Norindosquarocyanines', Tetrahedron Letters, Volume 40, Issue 21, May 1999, pages 4067-4068

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

  The method for synthesizing the croconium-based compound is not particularly limited, but can be synthesized by appropriately adopting a known synthesis method in which a pyrrole ring-containing compound and croconic acid are reacted. For example, it is compoundable by the method described in Unexamined-Japanese-Patent No. 2002-286931, Unexamined-Japanese-Patent No. 2007-31644, Unexamined-Japanese-Patent No. 2007-31645, and Unexamined-Japanese-Patent No. 2007-169315.

3. Resin Composition The resin composition of the present invention contains the oxocarbon-based compound used in the present invention and a resin component. Furthermore, the resin composition of the present invention can contain a solvent, various additives, and the like, if necessary.

3.1. Oxocarbon-based compound The oxocarbon-based compound contained in the resin composition of the present invention may be a squarylium-based compound, a croconium-based compound, or a mixture of both. Moreover, only 1 type may be sufficient as an oxocarbon type compound, and 2 or more types may be sufficient as it.

  The oxocarbon-based compound functions as a pigment, but the resin composition of the present invention may contain other known pigments together with the oxocarbon-based compound within a range that does not impair the effects of the present invention. it can. Examples of the dye that may be contained in the resin composition of the present invention include squarylium dyes and croconium dyes other than the oxocarbon compounds, and copper (for example, Cu (II)) or zinc (as the central metal ion). For example, cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, cholines, etc.) that may have Zn (II)), cyanine dyes, quaterylene dyes, naphthalocyanine dyes, nickel complexes System dyes, copper ion dyes, diimmonium dyes, subphthalocyanine dyes, xanthene dyes, azo dyes, dipyrromethene dyes, and the like. These other dyes preferably have an absorption maximum wavelength in the wavelength region of 400 to 1100 nm so as not to impair the effects of the present invention. These other dyes may be only one kind or two or more kinds.

  When the resin composition of the present invention also contains other dyes, the content of the other dyes is preferably 60% by weight or less, more preferably with respect to 100% by weight in total of the oxocarbon compound and the other dyes. Is 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 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 compound used in the present invention and the other dye is preferably 0.01% by mass or more, more preferably 100% by mass in the solid content of the resin composition. It is 0.3% by mass or more, more preferably 1% by mass or more. In addition, the upper limit of the total amount of the oxocarbon compound and 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. More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

  The resin composition of the present invention has a structure change of the oxocarbon-based compound, a change in light absorption characteristics due to generation of decomposition products, and a visible light transmittance when oxygen is present during storage of the resin solution, drying of the coating film, and heat curing. There is a possibility that the durability of the resin composition may be reduced due to a decrease in the resistance. For this reason, it is preferable that the oxygen concentration is low when the resin solution is stored or when the coating film is dried or thermoset. The oxygen concentration is preferably 10% by volume or less, more preferably 1% by volume or less, still more preferably 0.1% by volume or less, and most preferably 0.05% by volume or less.

3.2. Resin Component The resin component contained in the resin composition of the present invention is not particularly limited as long as it can sufficiently dissolve or disperse the oxocarbon-based compound, and a known resin can be used. The resin component is not only a resin whose polymerization is completed, but also a resin raw material (including a resin precursor, a raw material of the precursor, a monomer constituting the resin, and the like), and a resin composition is molded. In this case, those which are incorporated into the resin through a polymerization reaction or a crosslinking reaction can also be used. However, depending on the structure of the oxocarbon compound or other dyes, depending on the structure of the other dyes, unreacted substances, reactive terminal functional groups, ions present in the reaction solution obtained by the polymerization reaction Some or all of the structure may be decomposed by a functional group, catalyst, acid / basic group, etc., so in such a case, the polymerization is completed and isolated (if necessary It is desirable to use a purified resin.

  Examples of the resin that can be used as the resin component include poly (amide) imide resins, (meth) acrylic resins, (meth) acrylic urethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, and polyolefin resins (for example, , Polyethylene resin, polypropylene resin), polycycloolefin resin, melamine resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (for example, nylon), aramid resin, polyimide resin, alkyd resin, phenolic resin Resin, polysulfone resin, epoxy resin, polyester resin (for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), etc.), butyral resin, polycarbonate resin, polyether resin, ABS resin (acrylonitrile) Modified butadiene resins such as silyl butadiene styrene resins), AS resins (acrylonitrile-styrene copolymers); (meth) acryl silicone resins, alkylpolysiloxane resins, silicone resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins, etc. Fluorinated aromatic polymer, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), fluorinated polyaryletherketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorine Fluorinated resin such as fluorinated polyethernitrile (FPEN)). These resin components may be only one kind or two or more kinds.

  Among the resins described above, a solvent-soluble resin is preferable as the resin that can be used as the resin component. If the resin component is a solvent-soluble resin, the obtained resin composition can be made into a paint. For example, by forming a film by a spin coat method, a solvent cast method, or the like, a planar molded body (including a film and the like) can be easily formed. It becomes possible to produce. In the present specification, the solvent-soluble resin means a resin that is soluble in an organic solvent. For example, a resin that dissolves 1 part by mass or more with respect to 100 parts by mass of the organic solvent to be used is preferable.

  As the solvent-soluble resin, a thermoplastic resin or a curable resin may be used. From the viewpoint of storage stability of the resin and suppression of transmittance change in the drying step, a thermoplastic resin is preferable, and from the viewpoint of heat resistance, hardness, and solvent resistance of the coating film, a curable resin is preferable. In order to take advantage of the advantages of the thermoplastic resin and the curable resin, a form in which they are mixed and used is also preferable. Moreover, when it is set as the optical filter provided with the below-mentioned antireflection layer, an ultraviolet reflective layer, a near-infrared reflective layer, etc., it is preferable to manufacture a resin layer at high temperature. By doing so, when the anti-reflection layer, ultraviolet reflection layer, near-infrared reflection layer, etc. are laminated on the resin layer by a method such as vapor deposition or sputtering, the denser, higher strength, higher durability, and excellent optical properties are obtained. It can be set as the optical filter which has. In order to produce the resin layer at a high temperature, it is preferable that the resin used in the resin composition of the present invention has high heat resistance, that is, the Tg of the resin used in the resin composition of the present invention is high. Specifically, the Tg of the resin is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 170 ° C. or higher, and most preferably 250 ° C. or higher.

  Examples of the thermoplastic resin used as the solvent-soluble resin include poly (amide) imide resins, fluorinated aromatic polymers, (meth) acrylic resins, polyamide resins, aramid resins, polysulfone resins, and polycycloolefin resins. Examples of the curable resin used as the solvent-soluble resin include epoxy resins, urethane resins, and phenol resins. The solvent-soluble resin is preferably at least one selected from poly (amide) imide resins, fluorinated aromatic polymers, (meth) acrylic resins, polyamide resins, aramid resins, polysulfone resins, polycycloolefin resins, and epoxy resins. More preferably, it is at least one selected from poly (amide) imide resins, fluorinated aromatic polymers, (meth) acrylic resins, polysulfone resins, polycycloolefin resins, and epoxy resins. Hereinafter, these resins will be described in detail.

(I) Thermoplastic resin 3.2.1. Poly (amide) imide resin First, the poly (amide) imide resin referred to in the present specification means a polyimide resin in a narrow sense (which includes an imide bond and does not include an amide bond, and the amide bond referred to here is an amic bond. Means an amide bond that cannot form an imide bond by an acid dehydration reaction) and a polyamide-imide resin (means a resin that contains an amide bond and an imide bond that cannot form an imide bond by an amic acid dehydration reaction) ).

  The imide bond in the polyimide resin is usually a bond chain having an amide bond and a carboxyl group adjacent thereto (in the present invention, this bond chain is also referred to as an amic acid. Usually, carbon adjacent to the carbon atom to which the amide bond is bonded). It is formed by a dehydration reaction between an amide bond and a carboxyl group in a structure in which a carboxyl group is bonded to an atom. When a polyimide resin is produced from a polyamic acid by a dehydration reaction, a slight amount of amic acid can remain in the molecule. Therefore, in the present invention, the term “polyimide resin” includes an imide bond and does not include an amide bond that cannot form an imide bond by a dehydration reaction of an amic acid, but can form an imide bond by a dehydration reaction of an amic acid. It may contain no amide bond or some amount. A polyimide resin in which the imide bond content in the polyimide resin (ratio of the number of imide bonds that can be imidized by the imidation reaction and the total number of imide bonds of 100 mol% with respect to 100 mol%) is 80 mol% or more is preferable. More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more, Most preferably, it is 98 mol% or more.

  The poly (amide) imide resin contains an amide bond and an imide bond that cannot form an imide bond by a dehydration reaction of an amic acid, but includes an amide bond that can form an imide bond by a dehydration reaction of an amic acid. There may be some or some amount. When an amide bond that can form an imide bond by dehydration reaction of amic acid is included, the number of amide bonds (the number of amide bonds that cannot form imide bond by dehydration reaction and the number of amide bonds that can form imide bond by dehydration reaction) The content of the amide bond capable of forming an imide bond by dehydration reaction of the amic acid with respect to 100 mol% of the total amount of the sum and the number of imide bonds is preferably less than 20 mol%. More preferably, it is less than 10 mol%, More preferably, it is less than 5 mol%, Most preferably, it is less than 2 mol%.

  The poly (amide) imide resin preferably has few aromatic rings from the viewpoint of obtaining high transparency. For example, the mass of the aromatic ring in the total mass of 100% of the poly (amide) imide resin is 65% or less. Preferably, it is 45% or less, more preferably 30% or less.

  Examples of the poly (amide) imide resin include the following formula (10):

A compound having a repeating unit represented by the formula (wherein R ^p1 are the same or different and each represents an organic group) is preferable.
As R ^p1 in the above formula (10), a divalent organic group is preferable, and among them, a divalent organic group having 2 to 39 carbon atoms is preferable. The organic group preferably contains one or more hydrocarbon skeletons. The hydrocarbon skeleton is preferably an aliphatic chain hydrocarbon, an aliphatic cyclic hydrocarbon, or an aromatic hydrocarbon. The organic group may have a heterocyclic skeleton.

R ^p1 in the above formula (10) also has two or more kinds selected from the above hydrocarbon skeleton and / or heterocyclic skeleton, which are the same or different, and they are bonded via a carbon-carbon bond or carbon. -The thing containing the skeleton couple | bonded through the coupling group different from a carbon bond is preferable. Examples of the linking group include —O—, —SO ₂ —, —CO—, —Si (CH ₃ ) ₂ —, —C ₂ H ₄ O—, —S— and the like. In addition, each ^Rp1 in the repeating unit represented by the above formula (10) may be the same or different.

The organic group represented by R ^p1 may be directly bonded to a nitrogen atom, and as a bonding group, —O—, —SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -C ₂ H ₄ O-, -S- and the like may be included. In addition, although part or all of the hydrogen atoms in the cyclohexyl ring in Formula (10) may be substituted, those which are unsubstituted (a form in which all are hydrogen atoms) are preferable. The repeating units represented by the above formula (10) may be the same or different, and may be in any form such as block form or random form.

  Preferred examples of the poly (amide) imide resin include the following formula (10-1):

The compound which has a repeating unit represented by these is mentioned.

  The poly (amide) imide resin is a raw material of a poly (amide) imide resin (“poly (amide) imide precursor”) obtained by a reaction between a polyvalent carboxylic acid compound and a polyvalent amine compound and / or a polyvalent isocyanate compound. May be obtained by imidization reaction.

3.2.2. Fluorinated aromatic polymer As the fluorinated aromatic polymer, an aromatic ring having at least one fluorine atom and at least selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond And a polymer composed of a repeating unit containing one bond. Specifically, for example, polyimide, polyether, polyetherimide, polyetherketone, polyether having an aromatic ring having a fluorine atom. Examples include sulfone, polyamide ether, polyamide, polyether nitrile, and polyester. Among these, it is preferable that it is a polymer which has as an essential unit the repeating unit containing the aromatic ring which has an at least 1 or more fluorine atom, and an ether bond, and following formula (11-1) or (11-2) A polyether ketone having a fluorine atom, which contains a repeating unit represented by Among these, fluorinated polyether ketone (FPEK) is particularly preferable. In addition, the repeating unit represented by Formula (11-1) or (11-2) may be the same or different, and may have any form such as a block form or a random form.

In the above formula (11-1), R ^q1 represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. Z represents a divalent chain or a direct bond. x and y are integers of 0 or more, satisfy x + y = 1 to 8, and represent the number of fluorine atoms that are the same or different and are bonded to the aromatic ring. n ¹ represents the degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.

In the formula (11-2), R ^q2 may have a substituent, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkylamino group having 1 to 12 carbon atoms. Represents an alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms. R ^q3 represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. z is the number of fluorine atoms bonded to the aromatic ring and is 1 or 2. n ¹ represents the degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.

In the above formula (11-1), x + y is preferably in the range of 2-8, and more preferably in the range of 4-8. Further, the position at which the ether structure moiety (—O—R ^q1 —O—) is bonded to the aromatic ring is preferably para to Z.

In the above formulas (11-1) and (11-2), R ^q1 and R ^q3 are divalent organic chains. For example, any one represented by the following structural formula group (11-3) Or an organic chain of a combination thereof.

In the structural formula group (11-3), Y ^{1 to} Y ⁴ are the same or different and each represents a hydrogen atom or a substituent, and the substituent may have a halogen atom or a substituent. Represents an alkyl group, an alkoxy group, an alkylamino group, an alkylthio group, an aryl group, an aryloxy group, an arylamino group or an arylthio group.

More preferable specific examples of R ^q1 and R ^q3 include organic chains represented by the following structural formula group (11-4).

  In the above formula (11-1), Z represents a divalent chain or a direct bond. For example, the divalent chain is preferably a chain represented by the following structural formula group (11-5).

  In the structural formula group (11-5), X is a divalent organic chain having 1 to 50 carbon atoms, and examples thereof include the organic chain represented by the structural formula group (11-4) described above. Of these, diphenyl ether chain, bisphenol A chain, bisphenol F chain, and fluorene chain are preferable.

In R ^q2 in the above formula (11-2), the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and an isopentyl group. A group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 2-ethylhexyl group and the like are preferable.

  Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group. , Dodecyloxy group, furfuryloxy group, allyloxy group and the like are preferable.

  As the alkylamino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, propylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group and the like are preferable.

  As the alkylthio group, methylthio group, ethylthio group, propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, iso-propylthio group and the like are preferable.

  As the aryl group, phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, A biphenylyl group, a benzhydryl group, a trityl group, a pyrenyl group, and the like are preferable.

  Examples of the aryloxy group include groups derived from a phenoxy group, a benzyloxy group, hydroxybenzoic acid and esters thereof (for example, methyl ester, ethyl ester, methoxyethyl ester, ethoxyethyl ester, furfuryl ester, and phenyl ester). A naphthoxy group, o-, m- or p-methylphenoxy group, o-, m- or p-phenylphenoxy group, phenylethynylphenoxy group, a group derived from cresotinic acid and esters thereof, and the like are preferable.

  The arylamino group includes an anilino group, o-, m- or p-toluidino group, 1,2- or 1,3-xylidino group, o-, m- or p-methoxyanilino group, anthranilic acid and its Groups derived from esters are preferred.

  The arylthio group is preferably a phenylthio group, a phenylmethanethio group, an o-, m- or p-tolylthio group, a group derived from thiosalicylic acid and esters thereof, and the like.

Of these, R ^q2 is preferably an alkoxy group, an aryloxy group, an arylthio group, or an arylamino group, which may have a substituent. However, R ^q2 may or may not include a double bond or a triple bond.

Examples of the substituent for R ^q2 in the above formula (11-2) include an alkyl group having 1 to 12 carbon atoms as described above; a halogen atom such as fluorine, chlorine, bromine and iodine; a cyano group, a nitro group, and a carboxy ester Groups etc. are preferred. Moreover, hydrogen of these substituents may or may not be halogenated. Among these, preferably, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and a carboxy ester, which may or may not be halogenated. It is a group.

3.2.3. (Meth) acrylic resin (Meth) acrylic resin has a (meth) acrylic acid ester and / or a unit derived from (meth) acrylic acid as an essential constituent unit, and (meth) acrylic acid ester or (meth) You may have the structural unit derived from the derivative | guide_body of acrylic acid. “(Meth) acryl” means “acryl” and / or “methacryl”.

  Examples of the (meth) acrylic acid ester or (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 hydrocarbons such as nyl (alkyl (meth) acrylate, aryl (meth) acrylate, aralkyl (meth) acrylate), dicyclopentanyloxy (meth) acrylate Ether-linked derivatives such as ethyl; chloromethyl (meth) acrylate, (meth) acrylic acid Examples include halogen-introduced derivatives such as 2-chloroethyl; hydroxy group-introduced derivatives; allyl group-containing (meth) acrylic acid esters; vinyl group-containing (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- ( And hydroxyalkylated (meth) acrylic acids such as hydroxymethyl) acrylic acid and 2- (hydroxyethyl) acrylic acid. Among these, methyl methacrylate is preferable from the viewpoints of heat resistance and transparency.
Each of the (meth) acrylic acid ester (unit), (meth) acrylic acid (unit), and derivatives (units) thereof may be only one kind or two or more kinds.

  The hydroxy group-introduced derivatives include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2,3,4,5-tetrahydroxypentyl acrylate; 2- (hydroxymethyl) alkyl acrylate (eg, methyl 2- (hydroxymethyl) acrylate, 2- (hydroxy Methyl) ethyl acrylate, 2- (hydroxymethyl) isopropyl acrylate, 2- (hydroxymethyl) acrylate n-butyl, 2- (hydroxymethyl) acrylate t-butyl, etc.), 2- (hydroxyethyl) acrylic acid 2- (Hydroxy) of alkyl (eg methyl 2- (hydroxyethyl) acrylate) Rokishiarukiru) include alkyl acrylate.

  The allyl group-containing (meth) acrylic acid esters include acrylic acid esters having an allyl group-containing substituent bonded to the α-position, such as allyloxymethyl acrylate esters, 2- (N-allylamino), and the like. Methyl) acrylic esters are preferred. Specifically, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid Allyloxymethyl acrylate esters such as cyclohexyl, α-allyloxymethyl acrylate dicyclopentadienyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyloxymethyl acrylate Methyl 2- (N-allyl N-methylaminomethyl) acrylate, methyl 2- (N-allyl N-ethylaminomethyl) acrylate, methyl 2- (N-allyl Nt-butylaminomethyl) acrylate 2- (N-allyl N-cyclohexyl) Amino) methyl acrylate, 2-(N- allyl-N- phenylamino methyl) methyl acrylate 2-(N- allylamino methyl) acrylic acid esters. Of these, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, and benzyl α-allyloxymethyl acrylate are preferred. Methyl acid (AMA) is preferred.

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

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

  Structural units derived from (meth) acrylic acid monomers in all structural units of (meth) acrylic resins (that is, structural units derived from (meth) acrylic acid ester units, (meth) acrylic acid units and derivatives thereof) 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 constituting the (meth) acrylic resin preferably includes 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 a — (C═O) N— bond or a (C═O) —O— bond. It may be a ring structure that does not contain a 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. More preferred is a lactone ring structure, a glutaric anhydride structure, or a glutarimide structure, and particularly preferred is a lactone ring structure.

  The lactone ring structure is not particularly limited, and may be, for example, any of a 4-membered ring to an 8-membered ring, but is preferably a 5-membered ring or a 6-membered ring because of excellent stability of the ring structure. A 6-membered ring is more preferable. Examples of the lactone ring structure which is a 6-membered ring include the structures disclosed in JP-A No. 2004-168882. The lactone ring structure can be easily introduced. Specifically, the precursor ( (Polymer before lactone cyclization) has a high polymerization yield, the lactone ring content in the cyclization condensation reaction of the precursor can be increased, and a polymer having a methyl methacrylate unit as a constituent unit can be used as a precursor. The structure represented by the following formula (12-1) is particularly preferred for reasons such as.

In the above formula (12-1), 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 (12-1) include carbons such as 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, an ethenyl group, and a propenyl group. In addition to unsaturated aliphatic hydrocarbon groups of 2 to 20 (alkenyl groups, etc.), aromatic hydrocarbon groups of 6 to 20 carbon atoms (aryl groups, etc.) such as phenyl groups, naphthyl groups, etc., these saturated aliphatic hydrocarbons A group in which one or more hydrogen atoms in the group, unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group are 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.

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

Examples of the glutaric anhydride structure or the glutarimide structure include a structure represented by the following formula (12-2) (in the following formula (12-2), when X ^s1 is an oxygen atom, a glutaric anhydride structure: And when X ^s1 is a nitrogen atom, a glutarimide structure is preferred.

In the above formula (12-2), R ^s4 and R ^s5 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 straight-chain 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 in the above formula (12-2) is an oxygen atom is, for example, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid is subjected to dealcoholization cyclocondensation in the molecule. Can be formed.
The glutarimide structure in which X ^s1 in the above formula (12-2) 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, a (meth) acrylic resin having a glutaric anhydride structure or a glutarimide structure in the main chain can be produced, for example, 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 (12-3) (in the following formula (12-3), when X ^s2 is an oxygen atom, maleic anhydride Preferred is an acid structure, and an N-substituted maleimide structure when X ^s2 is a nitrogen atom.

In the above formula (12-3), R ^s7 and R ^s8 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 (12-3) is an oxygen atom can be formed, for example, by subjecting maleic anhydride to polymerization together with (meth) acrylic acid ester and the like.
The N-substituted maleimide structure in which X ^s2 in the above formula (12-3) 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 the main chain is produced, for example, by the method described in JP-A-57-153008 and JP-A-2007-31537. it can.

Among the main chain ring structures in (meth) acrylic resins, the ring structure that does not contain a carbonyl group includes oxygen-containing or nitrogen-containing four-membered rings such as oxetane ring and azetidine ring, tetrahydrofuran rings, and pyrrolidine rings. Alternatively, oxygen-containing or nitrogen-containing 6-membered ring such as nitrogen-containing 5-membered ring, tetrahydropyran ring, piperidine ring and the like can be mentioned.
As an example which has a 5-membered ring or a 6-membered ring structure, the structure shown by following formula (12-4) and the structure shown by following formula (12-5) are mentioned preferably, for example, A 4-membered ring or a 5-membered structure is shown. As an example which has a ring structure, the structure shown by following formula (12-6) and following formula (12-7) is mentioned preferably, for example. The (meth) acrylic resin having a ring structure in the main chain only needs to have one or more of these structures. Usually, the structure of the formula (12-4) and the structure of the formula (12-5) are used. Are often combined, and the structure of formula (12-6) and the structure of formula (12-7) are often combined.

(In the formula, R ^s10 and R ^s11 are the same or different and each represents 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 (12-4) and (12-5), X ¹ and Z ¹ are preferably methylene groups and Y ¹ is an oxygen atom. That is, in the above formula (12-4) and the above formula (12-5), a tetrahydrofuran ring structure or a tetrahydropyran ring structure is preferable. 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 (12-4) and / or the ring structure of the formula (12-5) may be, for example, the allyl group-containing (meth) acrylic acid ester alone or another monomer. It can manufacture by polymerizing together.

(In the formula, R ^s12 and R ^s13 are each a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. X ² and Y ² are the same or different and represent 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 above formulas (12-6) and (12-7), it is preferable that X ² is a methylene group and Y ² is an oxygen atom, an oxetane ring structure or a tetrahydrofuran ring structure. 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 (12-6) and / or the ring structure of the formula (12-7) may be, for example, the vinyl group-containing (meth) acrylic acid ester alone or another monomer. It can manufacture by polymerizing together.

3.2.4. Polysulfone polysulfone resin is typically a divalent aromatic group and (from aromatic compounds, hydrogen atoms bonded to the aromatic ring with two except comprising residues) sulfonyl group - and (-SO ₂₎ A resin having a repeating unit containing an oxygen atom. The polysulfone resin has a repeating unit represented by the following formula (D) (hereinafter referred to as “repeating unit (D)”) or a repeating unit represented by the following formula (E) (from the viewpoint of heat resistance and chemical resistance) In the following, it is preferable to have “repeating unit (E)”, and another repeating unit such as a repeating unit represented by the following formula (F) (hereinafter referred to as “repeating unit (F)”) is 1 You may have more than one seed.
_{^{(D) -Ph 1 -SO 2 -Ph}} 2 -O-
(Ph ¹ and Ph ² each independently represent a phenylene group. The hydrogen atoms in the phenylene group may each independently be substituted with an alkyl group, an aryl group, or a halogen atom.)
_{^{(E) -Ph 3 -SO 2 -Ph}} 4 -O-Ph 5 -R'-Ph 6 -O-
(Ph ³ , Ph ⁴ , Ph ^5, and Ph ⁶ represent a phenylene group. The hydrogen atoms in the phenylene group may each independently be substituted with an alkyl group, an aryl group, or a halogen atom. R ′ Represents an alkylidene group, an oxygen atom or a sulfur atom.)
(F)-(Ph ⁷ ) _n —O—
(Ph ⁷ represents a phenylene group. The hydrogen atoms in the phenylene group may be each independently substituted with an alkyl group, an aryl group or a halogen atom. N represents an integer of 1 to 3. When n is 2 or more, a plurality of Ph ⁷ may be the same as or different from each other.)

The phenylene group represented by any of Ph ^{1 to} Ph ⁷ may be a p-phenylene group, an m-phenylene group, or an o-phenylene group. The p-phenylene group is preferable because the heat resistance and strength of the obtained resin are increased. Examples of the alkyl group which may be substituted for the hydrogen atom in the phenylene group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Examples thereof include a butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Preferably there is. Examples of the aryl group which may substitute a hydrogen atom in the phenylene group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group and 2-naphthyl group. The carbon number is preferably 6-20. Examples of the halogen atom that may substitute a hydrogen atom in the phenylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When the hydrogen atom in the phenylene group is substituted with these groups, the number is preferably 1 or 2 and more preferably 1 for each phenylene group. Examples of the alkylidene group represented by R include a methylene group, an ethylidene group, an isopropylidene group, and a 1-butylidene group, and the number of carbon atoms is preferably 1-5.

  Examples of commercially available aromatic polysulfone resins include Sumika Excel PES3600P manufactured by Sumitomo Chemical Co., Ltd., Sumika Excel PES4100P manufactured by Sumitomo Chemical Co., Ltd. (aromatic polysulfone resin having a repeating unit (D)), and UDEL manufactured by SOLVAY SPECIALTY POLYMERS. ) P-1700 (aromatic polysulfone resin having a repeating unit (E)) and the like. In addition, the terminal group of aromatic polysulfone resin can be suitably selected with the manufacturing method, As an example, -Cl, -OH, -OR (R: alkyl group) is mentioned.

3.2.5. Polycycloolefin resin Polycycloolefin resin refers to a polymer or copolymer containing polycycloolefin as a monomer component constituting the polymer (hereinafter referred to as (co) polymer), and the monomer component is one or two. It may be a (co) polymer comprising only one or more polycycloolefins, or a (co) polymer containing polycycloolefin and other monomers as monomer components. Examples of the other monomer include α-olefins having 2 or more carbon atoms such as ethylene and propylene, and (meth) acrylic acid esters.

  The polycycloolefin resin is preferably a polymer having a cyclic olefin skeleton in the main chain, and among them, a polycycloolefin resin that is a homopolymer or a copolymer is more preferable. Preferred polycycloolefin resins include polycycloolefin resins represented by the following structural formulas (13) and (14) (hereinafter referred to as norbornene resins), polycycloolefin resins represented by the following structural formula (15) (hereinafter referred to as Modified norbornene resin) and polycycloolefin resin represented by the following structural formula (16) (hereinafter referred to as cyclic olefin copolymer resin).

(In Formula (13), m ¹ is an integer of 1 or more, and R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group, and may be the same or different. R ^b1 and R ^{b b2} may be bonded to form a ring.)

(In the formula (14), either m ² or n ² or both are integers of 1 or more. R ^c1 and R ^c2 represent a hydrogen atom or an alkyl group, and may be the same, R ^c1 and R ^c2 may be combined to form a ring.

(In Formula (15), m ³ is an integer of 1 or more, R ^{d1 to} R ^d4 represent a hydrogen atom or an alkyl group, and R ^d5 represents an alkoxycarbonyl group (preferably a methoxycarbonyl group or an ethoxycarbonyl group). R ^{d1 to} R ^d4 may be the same or different from each other, and R ^d1 and R ^d2 may combine to form a ring.

(In the formula (16), m ⁴ and n ⁴ are integers of 1 or more, R ^{e1 to} R ^e4 represent a hydrogen atom or an alkyl group, and R ^e5 represents a hydrogen atom, an alkyl group or an alkoxycarbonyl group (preferably a methoxy group). A carbonyl group or an ethoxycarbonyl group) and R ^{e1 to} R ^e4 may be the same or different from each other, and R ^e1 and R ^e2 may combine to form a ring. )

  Among the polycycloolefin resins, at least one resin selected from the group consisting of norbornene resins, modified norbornene resins, and cyclic olefin copolymer resins is preferable. These polycycloolefin resins can be used singly or in combination of two or more.

  A commercially available product can also be used as the polycycloolefin resin. Examples of commercially available products include ZEONEX (registered trademark) (manufactured by Nippon Zeon Co., Ltd., ring-opening metathesis polymer hydrogenated polymer of norbornene monomer; norbornene resin), ZEONOR (registered trademark) (manufactured by Nippon Zeon, dicyclopentadiene). Copolymer based on ring-opening polymerization of styrene and tetracyclopentadodecene; norbornene resin), ARTON (registered trademark) (manufactured by JSR, cyclic olefin resin containing polar groups starting from dicyclopentadiene and methacrylate ester; modification Norbornene resin), TOPAS (registered trademark) (polyplastics, copolymer of norbornene and ethylene; cyclic olefin copolymer resin), Apel (registered trademark) (manufactured by Mitsui Chemicals, tetracyclododecene and ethylene) Copolymer; cyclic olefin copolymer resin And the like.

  When a soluble polycycloolefin resin is contained in the resin layer composition, the soluble polycycloolefin resin itself may constitute the resin layer, or the soluble polycycloolefin resin is changed by a crosslinking reaction or the like. May constitute a resin layer.

  The content of the soluble polycycloolefin resin in the resin layer composition is preferably 1 to 30% by mass, more preferably 2 to 100% by mass of the resin layer composition (total amount including the solvent). It is 20 mass%, More preferably, it is 3-10 mass%.

(II) Curable resin The curable resin may be a resin that is cured (polymerized) by heat, or may be a resin that is cured (polymerized) by light. The obtained resin layer (cured film) is excellent in heat resistance (heat decomposition resistance and heat coloring property) and chemical resistance.
The curable resin is a resin containing one or more organic compounds having a curable functional group, and the curable functional group is a functional group that undergoes a curing reaction by heat or light (that is, a resin composition). For example, oxirane group (oxirane ring) or epoxy group, oxetane group (oxetane ring), ethylene sulfide group, dioxolane group, trioxolane group, vinyl ether group, vinyl group, Cationic curable groups such as styryl groups; radical curable groups such as acrylic groups, methacrylic groups, and vinyl groups; Therefore, the curable resin preferably contains a compound having a cationic curable group and / or a compound having a radical curable group. Thereby, the time until curing of the curable resin is shortened and productivity is further increased, and the obtained cured product is also more excellent in heat resistance (heat decomposition resistance, heat resistance coloring property). Among them, a resin containing a compound having a cation curable group is more preferable in that the resin shrinkage rate of the resin is low, and thus the resin layer hardly peels off and the shape is easily imparted with a mold or the like. It is.

When using the said curable resin, it is preferable to add a hardening | curing agent. A hardening | curing agent can be used 1 type or in combination of 2 or more types. What is necessary is just to select a hardening | curing agent suitably according to hardening reaction, the kind of curable resin, etc. As a hardening | curing agent, what is normally used may be used, for example, a heat latent cationic curing catalyst, a heat 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 that has a fast curing speed in terms of productivity, and in particular, a thermal latent cationic curing catalyst is used for the purpose of reducing the shrinkage of the cured product. It is more preferable. Moreover, when hardening by active energy ray irradiation, a photoinitiator can be used as a hardening | curing agent. As the photopolymerization initiator, it is preferable to use a photolatent cationic curing catalyst or a photolatent radical curing catalyst, and in order to reduce the shrinkage of the cured product, it is more preferable to use a photolatent cationic curing catalyst. .
The cation curing catalyst is particularly preferably the following general formula (17):

(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 an aromatic ring. A is an integer equal to or greater than 1, b is an integer equal to or greater than 0, and a + b = 3 is satisfied.) And a Lewis base (organic borane). .
When adding a cationic curing catalyst or a radical curing catalyst, the addition amount is 0.01 to 25 parts by mass with respect to 100 parts by mass of the curable resin as an amount of an active ingredient not containing a solvent or the like (in terms of solid content). Is preferred. In addition, when adding the cationic curing catalyst which consists of Lewis acid and Lewis base represented by General formula (17), let the total amount of this Lewis acid and Lewis base be an addition amount.

  In the curing method using a cationic curing catalyst, compared with the case of an addition type curing method such as acid anhydride curing, the resulting cured product is used in optical applications such as heat resistance, chemical stability, and moisture resistance. The required properties are better. In addition, compared with the case of using a conventional cationic curing catalyst such as an antimony sulfonium salt, coloring of the resin composition due to the influence of heat at the time of curing, film formation, and product use is reduced, and resistance to moisture and heat resistance. A cured product excellent in durability such as temperature shock resistance can be obtained.

It does not specifically limit as a hardening method of the said resin composition, For example, various methods, such as thermosetting and photocuring (curing by active energy ray irradiation), can be used suitably. As thermosetting, it is preferable to cure at about 30 to 400 ° C., and as photocuring, it is preferable to cure at 10 to 10,000 mJ / cm ² . From the viewpoint of increasing the curability of the resin, the curing temperature is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, and further preferably 150 ° C. or higher. On the other hand, from the viewpoint of suppressing deterioration of the dye, the curing temperature is preferably less than 300 ° C, more preferably less than 250 ° C, and even more preferably less than 230 ° C. Moreover, it is preferable that it is 1 minute or more from a viewpoint of raising the sclerosis | hardenability of resin, More preferably, it is 10 minutes or more, More preferably, it is 30 minutes or more. On the other hand, from the viewpoint of suppressing the deterioration of the pigment, the curing time is preferably less than 10 hours, more preferably less than 5 hours, and even more preferably less than 2 hours.

3.2.6. Epoxy resin The epoxy resin is not particularly limited, and examples thereof include glycidyl ether epoxy resins obtained by glycidylation of alcohols, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, and the like. . These may be used alone or in combination of two or more.

The epoxy resin is preferably an epoxy resin having an alicyclic epoxy compound skeleton, more preferably an epoxy resin having an epoxycyclohexane skeleton, an epoxy directly to a cyclic aliphatic hydrocarbon or via a hydrocarbon group. It is an epoxy resin to which groups are added. Examples of the epoxy resin having an epoxycyclohexane skeleton and the epoxy resin in which an epoxy group is added directly or via a hydrocarbon group to a cyclic aliphatic hydrocarbon include the following.
Daicel Selcoxide (registered trademark) 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate)
Daicel EHPE3150 (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol)
EHPE3150CE (2,2-bis (hydroxymethyl) -1-butanol and 1,4-epoxy-4- (2-oxiranyl) cyclohexane adduct and 3,4-epoxycyclohexenylmethyl-3,4'-manufactured by Daicel Epoxycyclohexene carboxylate)
Daicel's Celoxide (registered trademark) 3000 (1,2,8,9-diepoxy limonene) Daicel's Celoxide (registered trademark) 2000 (1,2-epoxy-4-vinylcyclohexane)
Of the above, Daicel's Celoxide (registered trademark) 2021P and Daicel's EHPE3150 are more preferred.

3.3. Solvent The resin composition according to the present invention can contain a solvent from the viewpoint of simply performing the coating operation.
Solvents that can be used may be appropriately selected according to the type of resin component and the like. For example, methyl ethyl ketone (2-butanone) (dipole moment: 2.76D), methyl isobutyl ketone (4-methyl-2-pentanone) ) (Dipole moment: 2.56D), ketones such as cyclopentanone and cyclohexanone (dipole moment: 3.01D); PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol mono-n-butyl ether ( Dipole moment: 2.08D), glycol derivatives such as ethylene glycol monoethyl ether (dipole moment: 2.08D), ethylene glycol ethyl ether acetate (for example, ether compounds, ester compounds, ether ester compounds, etc.); N, N-dimethylacetoa Amides such as de (dipole moment: 3.72D); esters such as ethyl acetate, propyl acetate, butyl acetate; N-methyl-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone (dipole) Pyrrolidones such as Moment: 4.08D); aromatic hydrocarbons such as toluene (dipole moment: 0.37D) and xylene; aliphatic hydrocarbons such as cyclohexane and heptane (dipole moment: 0.0D) Ethers such as tetrahydrofuran (dipole moment: 1.70D), dioxane, diethyl ether (dipole moment: 1.12D), dibutyl ether (dipole moment: 1.22D); chlorobenzene, o-dichlorobenzene ( At least selected from halogen-containing aromatic hydrocarbons such as dipole moment: 2.27D) More species may preferably be mentioned. The oxocarbon-based compound has high durability against a solvent having a small dipole moment. Therefore, a solvent having a dipole moment of 4D or less is preferable, a solvent having a dipole moment of 3.5D or less is more preferable, and a solvent having a dipole moment of 3D or less is particularly preferable. Specific examples of such a solvent include, for example, o-dichlorobenzene, cyclopentanone, PGMEA, ethylcyclohexane, xylene, toluene, trimethylbenzene, limonene and the like.

  Usually, the amount of the solvent used is preferably 50% by mass or more, more preferably 70% by mass or more, and 97% by mass or less in 100% by mass of the resin composition (total amount including the solvent). preferable. When the amount of the solvent used is within the above range, a resin composition having a sufficiently high oxocarbon compound concentration can be obtained. In particular, when an amide is used alone or in combination with another solvent as a solvent, the amides may decompose the oxocarbon-based compound. Therefore, the amount of amides used is preferably small and particularly preferable. It is not included. Specifically, the amount of the amide used is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less, in 100% by mass of the resin composition (total amount including the solvent). Particularly preferably 5% by mass or less, and most preferably 0% by mass (that is, not including amides).

3.4. Various additives In the resin composition according to the present invention, an ultraviolet absorber, a plasticizer, a surfactant, a dispersant, a surface tension adjuster, and a viscosity adjuster are included as long as the effects of the present invention are not impaired. Various additives such as an antifoaming agent, a preservative, a specific resistance adjuster, and an adhesion improver may be contained.

4). Molded article, planar molded article The resin composition is useful for producing a molded article, a coating of molded parts, a resin film, or a planar molded article formed into a plate shape. This molded body can be 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, solvent casting. The “planar molded body” includes a film-shaped resin composition molded product of the present invention formed on a support and a support (also referred to as “laminated sheet”). ) Are also included.

  The shape of the molded body or the planar molded body according to the present invention is not particularly limited. If the molded body is a planar molded body, for example, a film having a thickness of less than 200 μm and a plate-shaped object having a thickness of 200 μm or more are used. Can be mentioned.

  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. The spectral light transmittance at the maximum absorption wavelength of the resin layer or resin film is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 5% or less. More preferably 2.5% or less, and most preferably 1% or less. This optical filter preferably includes a support and a film-like resin layer provided on one or both sides of the support, and the resin composition of the present invention is used for the resin layer. Such a filter is, for example, a method of forming a paint resin composition on a support by applying it by spin coating or solvent casting, and drying or curing, or from a resin composition to the support. In addition to the method of forming the formed resin film by thermocompression bonding, it can be produced by a kneading method or the like. Although the film thickness of the resin layer formed with a resin composition is not specifically limited, For example, it is suitable that they are 0.5 micrometer or more and 15 micrometers or less, More preferably, they are 1 micrometer or more and 10 micrometers or less. As the support, a resin plate, a film, a glass substrate or the like can be used, but a glass substrate or a film is preferable. For example, the support film is preferably formed of the above-described resin as a suitable resin component. 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 preferred form. The film thickness of the single-layer resin film (planar molded body) formed by the resin composition is not particularly limited, but is preferably, for example, 30 μm or more and 200 μm or less, 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 an optical device application, a display device application, a mechanical component, and an electric / electronic component.

5. Characteristics in absorption spectrum Since the optical filter contains a specific oxocarbon compound in its resin layer, it has a maximum absorption wavelength (λmax) in the range of 550 to 1200 nm, and has excellent absorption characteristics of red light. Yes. In particular, when a squarylium compound is included as an oxocarbon compound, it preferably has a maximum absorption wavelength at 550 to 1000 nm, more preferably 600 to 900 nm, still more preferably 600 to 800 nm, and most preferably 650 to 750 nm. When a croconium-based compound is included as the compound, it preferably has a maximum absorption wavelength at 700 to 1200 nm, more preferably 750 to 1100 nm. And since the said optical filter contains the specific oxocarbon type compound, in addition to the high light absorption characteristic in the said maximum absorption wavelength, it is characterized by the high average transmittance | permeability of the light in 400-450 nm. Can be mentioned. In order to exhibit sufficient performance as an optical filter, the spectral light transmittance at the maximum absorption wavelength of the optical filter is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. It is particularly preferably 5% or less, more particularly preferably 2.5% or less, and most preferably 1% or less. In the optical filter exhibiting such spectral light transmittance at the maximum absorption wavelength, the average transmittance of spectral light at a wavelength of 400 to 450 nm is, for example, 81% or more (preferably 82% or more, more preferably 83% or more). It is preferable that When such a filter of the present invention is used, it can be said that while the average transmittance of 400 to 450 nm is increased, the absorbance of light having a red wavelength is increased and the film has high selective transmittance. On the other hand, when the average transmittance of spectral rays at a wavelength of 400 to 450 nm is less than 81%, the transmission of blue light is insufficient, and the color of the light transmitted through the filter may be changed. In addition, since the optical filter of the present invention can reduce the angle dependency of transmitted light and reflected light, it is possible to obtain a near-infrared cut filter suitable for visibility correction applications with little change in brightness and hue. In addition, how to obtain the average light transmittance and the maximum absorption wavelength at 400 to 500 nm will be described later.

  The resin composition and filter of the present invention preferably have no shoulder peak (or greatly reduced) in the absorption spectrum in the visible / near infrared region. Thereby, light in the absorption maximum region can be more selectively absorbed.

6). Others An example of the filter of the present invention includes a support and a resin layer provided on one 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 only on one side of the support or on both sides. The underlayer may have either a single layer structure or a multilayer structure.

  The underlayer is preferably formed from a composition containing a silane coupling agent. By including such a silane coupling agent in the composition for the underlayer, there is an effect of improving the adhesion with the support and an effect of suppressing the ingress of moisture into the underlayer by a water repellent action, As a result, a filter excellent in heat resistance and heat and humidity resistance can be obtained. Specifically, peeling or the like can be suppressed during use in a solder reflow process or in a humid heat environment. A silane coupling agent may use only 1 type and may use 2 or more types.

  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 an ordinary method. A liquid medium should just be water, alcohol, etc., and can use 1 type (s) or 2 or more types. 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 solution) is applied on a support and dried by heating is suitable.

  When the support is a glass substrate, the base layer is formed from a composition for a base layer 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 it is formed from the composition containing the silane coupling agent which has an amino group, it is preferable that it is a silane coupling agent which has a primary amino group. When using a composition for an underlayer containing a silane coupling agent having a primary amino group, the adhesiveness to the glass substrate is much higher than when containing a silane coupling agent having an amino group other than the primary amino group. It will be good. The liquid medium is preferably at least one selected from water, ethanol, and isopropyl alcohol. By adding a liquid medium, the alkoxy group is hydrolyzed in the amino group, epoxy group, or mercapto group-containing silane coupling agent to form a silanol group, and this silanol group forms a hydrogen bond with the hydroxyl group on the glass substrate surface. To the surface of the glass substrate. And the adhesiveness of a glass substrate and a base layer improves by producing | generating a strong covalent bond with the glass substrate surface through the dehydration condensation reaction of a silanol group. The catalyst may be any one that acts as a catalyst during the hydrolysis reaction of the amino group, epoxy group, or mercapto group-containing silane coupling agent, and may be either an organic acid or an inorganic acid. It is preferable to use it.

  By adding the silane coupling agent to the resin layer composition instead of the underlayer composition, the adhesiveness of the filter can be improved. In this case, it is preferable that the resin layer is formed from the composition for resin layers which added the silane coupling agent which has an amino group, an epoxy group, or a mercapto group from a viewpoint of an adhesive improvement. When the silane coupling agent is mixed with the oxocarbon-based compound represented by the above formula (1) or (2), the amino group-containing silane coupling agent reacts with the oxocarbon-based compound to cause precipitation of the reaction product. Since there exists a possibility of producing the spectrum change of the composition for resin layers, it is preferable that it is a mercapto group containing silane coupling agent. In addition, when the oxocarbon-based compound and the mercapto group-containing silane coupling agent are mixed and used, the transmittance of 400 to 600 nm may be improved, so that it is a mercapto group-containing silane coupling agent. Is preferred.

  Since the resin composition of the present invention may cause appearance defects such as striations and dents after film formation, additives such as leveling agents (surface conditioning agents) and surfactants are added as necessary. It is preferable to do. As additives, silicone additives, acrylic additives, fluorine additives and the like are effective, but from the viewpoint of adhesiveness of the resin layer and prevention of bleeding out of the additive in the resin layer, the silicone additive or Acrylic additives are preferred. Examples of the additive include BYK (registered trademark) series of BYK Chemie, which is a surface conditioner, and BYK (registered trademark) -306, 330, 337, 354, 355, 378, 392 and the like are preferable. As addition amount, it is preferable that an additive is 0.001-10 mass parts with respect to 100 mass parts of resin, More preferably, it is 0.01-5 mass parts. If the additive amount is excessive, the resin layer after coating may become turbid. If the additive amount is too small, defects in appearance cannot be sufficiently eliminated.

  In addition to the resin layer or resin film formed using the resin composition of the present invention, the optical filter of the present invention is a layer having antireflection properties and / or antiglare properties that reduces reflection of fluorescent lamps, etc. A layer having a scratch-preventing performance and a layer having a function other than the above may be laminated, or a transparent substrate, a glass substrate, a filter, and the like may be laminated.

  The optical filter of the present invention preferably includes an ultraviolet reflecting film that reflects ultraviolet rays and / or a near infrared reflecting film that reflects near infrared rays (hereinafter collectively referred to as “invisible light reflecting film”). Examples of such invisible light reflecting films include an aluminum vapor deposition film, a noble metal thin film, a resin film in which metal oxide fine particles 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 or the like in which material layers are alternately stacked can be used. The invisible light reflecting film may be provided on one side of the resin layer or the support, or may be provided on both sides. When it is provided on one side, it is excellent in production cost and manufacturability, and when it is provided on both sides, it is possible to obtain an ultraviolet cut filter and a near infrared cut filter that have high strength and are less likely to warp. Moreover, when a near-infrared reflective film is laminated | stacked, the near-infrared cut filter which can cut a near-infrared more reliably can be obtained.

  As the invisible light reflecting film, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately stacked is preferably used. As a material constituting 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 constituting 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 Nitrides such as oxides, mixtures of the nitrides and the like, and those doped with metals or carbon such as aluminum or copper (for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. Can be mentioned. As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and aluminum hexafluoride sodium.

  The optical filter of the present invention preferably includes an antireflection film. As the antireflection film, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately stacked is preferably used. As a material constituting 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 constituting 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 Nitrides such as the above, mixtures of the oxides and nitrides, and those doped with 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 a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and aluminum hexafluoride sodium.

The invisible light reflection film and / or the antireflection film is preferably a laminated film in 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, the better the durability of the oxocarbon-based compound. 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 the layers are dense films), and the thickness of at least one layer of the laminated film is increased. (More preferably, the thickness of all layers is increased), and it is also preferable to use both in combination. As a method for producing a dense film, a known technique may be used. For example, the degree of vacuum at the time of vapor deposition is set to a high vacuum, the vapor deposition temperature is increased, or vapor deposition by an ion assist method (IAD) is performed. However, a dense film may be formed using a method other than the above. Specifically, the degree of vacuum is preferably 5 × 10 ⁻² Pa or less, and the 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 becomes equal to or higher than the Tg of the resin used in the resin layer. Therefore, 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 addition, when vapor deposition by the IAD method is performed, if the assist voltage / assist current is too weak, as with the vapor deposition temperature, the vapor deposition film (invisible light reflection film and / or the antireflection film) is dense (a film having a high packing density). If the assist voltage / assist current is too strong, the resin layer may be deteriorated. It is preferable to optimize the various conditions to produce a dense film having a high oxygen-blocking capacity and not to deteriorate the resin layer or to reduce the deterioration.

  By laminating an invisible light reflection film, antireflection film, or other layer having a high oxygen blocking ability on the optical filter of the present invention, the durability of the oxocarbon-based compound of the present invention is drastically improved. An optical filter having excellent optical properties and a near-infrared cut filter can be obtained.

  In the optical filter of the present invention, an invisible light reflection film, an antireflection film, or other layers are laminated as necessary, so that a visible light cut filter, an infrared cut filter, a near infrared cut filter, a security filter, a heat ray blocking / Heat ray absorption filter, band pass filter, (day & night) surveillance camera filter, night vision camera filter, dual band filter, visible light image sensor / infrared sensor filter, neon light / fluorescence light It can be suitably used as a cut filter.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
Hereinafter, “%” indicates “mass%”, and “part” indicates “part by mass”.

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

(Maximum absorption wavelength and transmittance measurement method)
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 a wavelength of 200 to 1100 nm was determined. And the wavelength which becomes an absorption maximum in wavelength 650-750 nm was made into the maximum absorption wavelength. Moreover, the average value of 51 transmittance | permeability measured for every 1 nm of measurement pitches in wavelength 400-450 nm was made into the average transmittance | permeability of 400-450 nm.

(PCT (Pressure Cooker Test) test)
With respect to the test material (resin layer laminated substrate), the resin layer provided in the test material was cut with a cutter (A-300 manufactured by NTT), and 10 crosscut lines were arranged at intervals of 2 mm in each of the vertical and horizontal rows. By providing 81 squares of 4 mm ^2, a sample substrate for evaluation was produced. Next, the sample substrate for evaluation was placed in a high-pressure, high-temperature, high-humidity tank (personal pressure cooker PC-242HS-E (manufactured by Hirayama Seisakusho), operation mode 1) at 120 ° C., 2 atm and 100% humidity for 15 hours or 50 hours. Subsequently, at room temperature, a tape (3M (3M) Scotch (registered trademark) transparent adhesive tape, transparent beautiful color (registered trademark)) was applied so that air would not enter, and left for 10 seconds. Thereafter, the tape was peeled from the substrate within 1 second and evaluated according to the following criteria. Note that the tape was peeled off so that the peeling force was constant in any of the cells.
○: No peeling occurred in one square among the squares of the produced 81 square.
Δ: Peeling occurred in 1 to 9 squares out of the produced 81 squares.
X: Peeling occurred in 10 to 81 squares among the squares of 81 squares produced.

The structural formulas of squarylium compounds 01, 07-11, 13, 15, 17-29 and comparative squarylium compounds 3 and 4 used in the examples are shown below. The squarylium compounds 01, 07-11, 13, 15, 17-29 were prepared by a known synthesis method in which a pyrrole ring-containing compound and squaric acid were reacted, that is, by the synthesis method described in the paper cited in the specification. Is. As the comparative squarylium compound 3, the squarylium compound disclosed in Formula 17 of US Pat. No. 5,543,086 was used.
In addition, about squarylium compound 01, 07-11, 13, 15, 17-29, and comparative squarylium compounds 3 and 4, it analyzed by the said method and confirmed having the structure shown below.

(Preparation of polyimide resin A)
A flask is charged with 5 parts of 1,2,4,5-cyclohexanetetracarboxylic acid (manufactured by Aldrich, purity 95%) and 44 parts of acetic anhydride (manufactured by Wako Pure Chemical Industries), and the reactor is filled with nitrogen gas while stirring. Replaced. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. Thereafter, the mixture was cooled to room temperature with stirring to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain crystals of the desired product (1,2,4,5-cyclohexanetetracarboxylic dianhydride). Subsequently, 4,4′-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 0.89 under a nitrogen stream in a flask equipped with a thermometer, stirrer, nitrogen introducing tube, dropping funnel with side tube, Dean Stark, and cooling tube. And 7.6 parts of N-methyl-2-pyrrolidone as a solvent were dissolved, and then 1 part of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was kept solid at room temperature for 1 hour. Over a period of 2 hours and stirred at room temperature for 2 hours. 2.6 parts of xylene as an azeotropic dehydrating agent was added and reacted at 180 ° C. for 3 hours, and the product water refluxed by Dean Stark was azeotropically separated. Xylene was distilled off while the temperature was raised to 190 ° C., followed by cooling to obtain an N-methyl-2-pyrrolidone solution of polyimide. This N-methyl-2-pyrrolidone solution was further diluted with γ-butyrolactone to obtain a polyimide resin solution having a solid content of 3%. 1 part of this polyimide resin solution was reprecipitated with 50 parts of methanol and separated into solid and liquid. The solid-liquid separated polyimide resin was dissolved in γ-butyrolactone to obtain a polyimide resin solution having a solid content of 3% again, and re-precipitated with 50 parts of methanol in the same manner as described above, followed by solid-liquid separation. The resin obtained by reprecipitation was dried to obtain polyimide resin A. Moreover, it was 297 degreeC when the glass transition temperature (Tg) of the polyimide resin A was measured with the differential scanning calorimeter.

(Synthesis method of acrylic resin B)
In a reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction pipe, 60 parts of methyl α-allyloxymethylacrylate (AMA) and 140 parts of 4-methyl-2-pentanone (methyl isobutyl) as a polymerization solvent Ketone (MIBK) was charged (initial monomer concentration = 30% by mass), and the temperature was raised to 100 ° C. through nitrogen, and then 0.12 part of 1,1′-azobis (cyclohexane-1-carbohydrate) as an initiator. Nitrile (trade name: V-40, manufactured by Wako Pure Chemical Industries, Ltd.) was added to initiate polymerization. As a result of conducting the polymerization reaction for 6 hours, a polymer having a polymerization conversion rate of 97%, an allyl group conversion rate of 96%, and Mw = 21000 was obtained. The 5% mass reduction temperature of this polymer was measured and found to be 360 ° C. The resulting acrylic polymer solution (5 parts) was reprecipitated with 500 parts of methanol and subjected to solid-liquid separation. The solid-liquid separated acrylic resin was dissolved again in MIBK to obtain an acrylic resin solution having a solid content of 10%, and re-precipitated with 500 parts of methanol in the same manner as described above, followed by solid-liquid separation. The resin obtained by reprecipitation was dried to obtain an acrylic resin B. Moreover, it was 70 degreeC when Tg of acrylic resin B was measured with the differential scanning calorimeter.

(Synthesis method of acrylic resin B ′)
In a reaction vessel equipped with a stirring blade, a temperature sensor, a cooling tube, and a gas introduction tube, 21.0 parts of α-allyloxymethyl acrylate (AMA) and 9.0 parts of N-cyclohexylmaleimide as monomers, a polymerization solvent As a starting material, 45.0 parts of ethyl acetate was charged, and stirring and heating were started while flowing nitrogen gas. After confirming that the internal temperature was stabilized 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 operation was performed using tetrahydrofuran as a dilution 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 acrylic resin B ′.
It was 50400 when the weight average molecular weight was measured with the gel permeation chromatography apparatus about obtained acrylic resin B '. Moreover, it was 134 degreeC when Tg was measured with the differential scanning calorimeter.

(Method for synthesizing fluorinated aromatic polymer C)
In a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirrer, 16.74 parts of BPDE (4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether), 10.5 parts of HF (9,9-bis (4-hydroxyphenyl) fluorene), 4.34 parts of potassium carbonate, and 90 parts of DMAc (dimethylacetamide) were charged. The mixture was warmed to 80 ° C. and reacted for 8 hours. After completion of the reaction, the reaction solution was poured into a 1% aqueous acetic acid solution with vigorous stirring with a blender. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated aromatic polymer C (fluorinated polyaryletherketone (FPEK)). The polymer obtained had a Tg of 242 ° C. and a number average molecular weight (Mn) of 70770. In addition, the number average molecular weight in the said synthesis example was measured with the following method. Two gel permeation chromatography (column: TSKgel SuperMultipore HZ-N 4.6 * 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard) were used for measurement.

Example 1
<Preparation and application of resin layer composition solution>
0.6 part of squarylium compound 01 was mixed and dissolved in a resin solution in which 6 parts of polyimide resin A was dissolved in 94 parts of cyclopentanone to prepare a resin layer composition solution. The resin layer composition solution was filtered to remove insolubles and the like, and then a resin layer composition solution was prepared. After 0.6 cc of this resin layer composition solution is dropped on a glass substrate, the spin coater (1H-D7 manufactured by Mikasa Co., Ltd.) is used to make 1000 revolutions over 0.2 seconds and hold at that number of revolutions for 10 seconds. Then, a resin layer was formed so as to be 0 rotation (rpm) over 0.2 seconds. The glass substrate on which the resin layer is formed is initially dried at 100 ° C. for 3 minutes using a precision thermostat (DH611 manufactured by Yamato Scientific Co., Ltd.), and then 30 ° C. at 50 ° C. using an inert oven (DN610I manufactured by Yamato Scientific Co., Ltd.). After substituting with nitrogen for 15 minutes, the temperature was raised to 200 ° C. in about 15 minutes, and additional drying was performed at 200 ° C. for 30 minutes (in a nitrogen atmosphere) to obtain a glass substrate having a resin layer (hereinafter referred to as a resin layer laminated substrate). . When the transmittance of this resin layer laminated substrate was measured, the transmittance at the maximum absorption wavelength (peak top) was 2.5%. The thickness of the resin layer after drying was 1 μm. In addition, the film thickness of the resin layer after drying measured the thickness of the resin layer laminated substrate and the thickness of the glass substrate using the micrometer, and made the difference of both the film thickness of the resin layer after drying. The composition of the resin layer laminated substrate, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 1 below.

(Examples 2 to 11 and Comparative Examples 1 and 2)
A resin layer laminated substrate was obtained in the same manner as in Example 1, except that the amount of resin, the type / amount of solvent, and the type / amount of pigment were changed as shown in Table 1. In Examples 2 to 11 and Comparative Examples 1 and 2, resin layer composition solutions were prepared and applied so that the transmittance at the maximum absorption wavelength was 2.5%. The composition of the resin layer laminated substrate, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 1 below.

(Examples 12-16, Comparative Examples 3-7)
A resin layer laminated substrate was obtained in the same manner as in Example 1 except that the type and amount of the resin, the type and amount of the solvent, and the type and amount of the pigment were changed as shown in Table 2. However, Example 16 and Comparative Example 7 were heated without initial drying at 100 ° C. for 3 minutes after coating. In Examples 12 to 16 and Comparative Examples 3 to 7, resin layer composition solutions were prepared and applied so that the transmittance at the maximum absorption wavelength was 2.5%. As a resin, polycycloolefin resin P (ARTON (registered trademark) (modified norbornene-based resin) manufactured by JSR)), acrylic resin B, polysulfone resin (SOLVY SPECIALTY POLYMERS UDEL (registered trademark) P-1700), and the above A fluorinated aromatic polymer C and an epoxy resin (EHPE 3150 manufactured by Daicel Corporation, Celoxide (registered trademark) 2021P manufactured by Daicel Corporation) were used. Moreover, cyclopentanone, o-dichlorobenzene, and PGMEA (2-acetoxy-1-methoxypropane) were used as a solvent. The cationic curing catalyst D added in Example 16 and Comparative Example 7 will be described later. The composition of the resin layer laminated substrate, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 2 below.

Preparation Example 1 (Synthesis of TPB-containing powder)
According to the synthesis method described in International Publication No. 1997/031924, 255 g of Isopar (registered trademark) E solution manufactured by Ando Parachemy Co., Ltd. having a TPB (tris (pentafluorophenyl) borane) content of 7% was prepared. Water was added dropwise to this solution at 60 ° C. White crystals precipitated from the middle of 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 at 60 ° C. under reduced pressure, and 18.7 g of TPB / water complex (TPB-containing powder B) as white crystals was obtained. This complex had a water content of 9.2% (Karl Fischer moisture meter) and a TPB content of 90.8%. ¹⁹ F-NMR analysis and GC analysis were performed on the complex after drying, 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 D)
1.1 g of γ-butyrolactone was added to 2 g of TPB-containing powder B obtained in Preparation Example 1 (TPB pure content: 1.816 g (3.547 mmol), water: 0.184 g (10.211 mmol)), Mix for 10 minutes at room temperature. Thereafter, 2.6 g of a 2 mol / L ammonia / ethanol solution was added and mixed for 60 minutes at room temperature to obtain a uniform solution of the cationic curing catalyst D (TPB catalyst). This was designated as cationic curing catalyst D.

(Example 17)
Polyimide resin A was dissolved in N, N-dimethylacetamide, a film was formed using a solvent casting method, and a film was prepared so that the thickness after drying was 100 μm. The drying was sufficiently performed at 250 ° C. under nitrogen, and the residual solvent was 1.5%. The same resin composition as in Example 1 was used on both sides of this polyimide film, and both sides were applied so that the maximum absorption wavelength (peak top) transmittance was 2.5%. The obtained absorption film is obtained by applying a resin composition containing a pigment to a film to be a substrate (support).

(Comparative Example 8)
In the same manner as in Example 17, a polyimide film was obtained, and then the same resin composition as in Comparative Example 1 was used, and double-sided coating was performed in the same manner as in Example 17 to obtain an absorption film.

(Example 18)
The polycycloolefin resin P was dissolved in o-dichlorobenzene, and the squarylium compound 01 was further dissolved. This resin solution was filtered and applied to a glass substrate using a solvent casting method so that the thickness after drying was 50 μm and the transmittance at the maximum absorption wavelength (peak top) was 2.5%. After being partially dried, it was peeled off from the glass substrate. The peeled film was further dried under nitrogen at 150 ° C. for 30 minutes. The obtained absorption film is not a film coated on a support, but a film having absorption in a single layer.

(Comparative Example 9)
An absorbent film was obtained in the same manner as in Example 18 except that the comparative squarylium compound 3 was used.

(Examples 19 to 30)
In Example 1, the resin layer laminated substrate was obtained like Example 1 except having changed the quantity of resin, the quantity of solvent, and the kind and quantity of the pigment | dye as shown in Table 4. In Examples 19 to 30, resin layer composition solutions were prepared and applied so that the transmittance at the maximum absorption wavelength was 2.5%. The composition of the resin layer laminated substrate, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 4 below.

(Example 31)
(Underlayer composition (undercoat solution))
<Preparation of undercoat solution>
Silane coupling agent (Shin-Etsu Silicone KBM-903 (3-aminopropyltrimethoxysilane)) 1.52 parts, ethanol 2 parts, water 0.455 parts, and formic acid aqueous solution 0.26 parts mixed and dissolved Liquid S was produced. Next, 1 part of the mixed solution S was diluted and dissolved with 99 parts of ethanol, and the undercoat solution No. 1 was produced.

<Application of undercoat solution>
1 cc of the undercoat solution was dropped on a glass substrate (D263 Teco, manufactured by SCHOTT, 60 mm × 60 mm × 0.3 mm), and then 2200 rotations (rpm) using a spin coater (1H-D7 manufactured by Mikasa Co., Ltd.) over 3 seconds. ) And held at that number of rotations for 20 seconds, and then a base layer was formed so as to achieve 0 rotations (rpm) over 3 seconds. The glass substrate after forming the underlayer was dried at 100 ° C. for 10 minutes using a precision thermostat (DH611 manufactured by Yamato Kagaku Co., Ltd.) to obtain a glass substrate provided with the underlayer (hereinafter referred to as an underlayer laminated substrate). .

<Preparation and application of resin layer composition solution>
In Example 1, instead of hanging the resin layer composition solution on the glass substrate, the resin layer composition solution was hung on the underlayer of the underlayer laminated substrate (the surface directly in contact with the underlayer). Obtained a resin layer laminated substrate in the same manner as in Example 1. In Example 31, a resin layer composition solution was prepared and applied so that the transmittance at the maximum absorption wavelength was 2.5%. The composition of the resin layer laminated substrate, the results of the PCT test, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 5 below.

(Examples 32-36)
A resin layer laminated substrate was obtained in the same manner as in Example 31 except that the type and amount of the dye were changed as shown in Table 5 in Example 31. In Examples 32-36, a resin layer composition solution was prepared and applied so that the transmittance at the maximum absorption wavelength was 2.5%. The composition of the resin layer laminated substrate, the results of the PCT test, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 5 below.

(Examples 37 to 39, 42, 43)
A resin layer laminated substrate was obtained in the same manner as in Example 31 except that the type and amount of resin, the type and amount of solvent, and the type and amount of pigment were changed as shown in Table 6. In Examples 37 to 39, 42, and 43, resin layer composition solutions were prepared and applied so that the transmittance at the maximum absorption wavelength was 2.5%. As the resin, polycycloolefin resin P (ARTON (registered trademark) (modified norbornene resin) manufactured by JSR), polycycloolefin resin Q (TOPAS (registered trademark) (polyolefin copolymer resin) manufactured by Polyplastics)) Was used. Moreover, o-dichlorobenzene and xylene were used as a solvent. The composition of the resin layer laminated substrate, the results of the PCT test, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 6 below.

(Examples 40 and 41)
A resin layer laminated substrate was obtained in the same manner as in Example 1 except that the type and amount of the resin, the type and amount of the solvent, and the type and amount of the pigment were changed as shown in Table 6. In Examples 40 and 41, resin layer composition solutions were prepared and applied so that the transmittance at the maximum absorption wavelength was 2.5%. As the resin, the polycycloolefin resin P and the polycycloolefin resin Q were used. Moreover, o-dichlorobenzene and xylene were used as a solvent. The composition of the resin layer laminated substrate, the results of the PCT test, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 6 below.

(Examples 44 to 47)
In Example 1, except that the type / amount of resin was changed to 15 parts of acrylic resin B ′, the type / amount of solvent was changed to 85 parts of cyclopentanone, and the type / amount of dye was changed as shown in Table 7. Obtained a resin layer laminated substrate in the same manner as in Example 1. In Examples 44 to 47, resin layer composition solutions were prepared and applied so that the transmittance at the maximum absorption wavelength was 2.5%. The composition of the resin layer laminated substrate, the average transmittance of 400 to 450 nm, and the results of the maximum absorption wavelength are summarized in Table 7 below.

(Example 48, Comparative Example 10)
A resin layer laminated substrate was obtained in the same manner as in Example 1 except that the type and amount of resin, the type and amount of solvent, and the type and amount of pigment were changed as shown in Table 8. In Example 48 and Comparative Example 10, a resin layer composition solution was prepared and applied so that the transmittance at the maximum absorption wavelength was 12%. The average transmittance of 400 to 450 nm and the results of the maximum absorption wavelength are summarized in Table 8 below.

(Examples 49 to 54)
In Example 31, the resin type / amount, the solvent type / amount, the pigment type / amount were changed as shown in Table 9, and the curing agent and additives were added. Thus, resin layer laminated substrates of Examples 49 to 52 were obtained. Further, in Example 16, the type / amount of resin, the type / amount of solvent, the type / amount of curing agent, the type / amount of pigment were changed as shown in Table 9, and the additives were added, Resin layer laminated substrates of Examples 53 to 54 were obtained in the same manner as Example 16. In Examples 49 to 54, resin layer composition solutions were prepared and applied so that the transmittance at the maximum absorption wavelength was 0.5%. The results of the average transmittance of 400 to 450 nm and the maximum absorption wavelength are summarized in Table 9 below. In Examples 53-54, Toray Dow Corning Z-6062 (3-mercaptopropyltrimethoxysilane) was used as a silane coupling agent. In Examples 49 to 54, BYK (registered trademark) -306 (silicone additive) manufactured by BYK Chemie was used as an additive, and the curing agent was prepared by the above-described cationic curing catalyst D or the following adjustment method. Cationic curing catalyst E was used.

Preparation Example 3 (Preparation of cationic curing catalyst E)
In Preparation Example 2, a uniform solution of a cation curing catalyst (TPB catalyst) was prepared in the same manner as Preparation Example 2 except that γ-butyrolactone was changed to toluene. This was designated as cationic curing catalyst E.

FIG. 1 is a graph showing the relationship between the wavelength and the transmittance in the resin layer of Example 12 and the resin layer of Comparative Example 3. From FIG. 1, in the resin layer of Comparative Example 3 containing the comparative squarylium compound 3, the transmittance at the absorption maximum wavelength is 2.5%, but the average transmittance at 400 to 450 nm is only about 76%. However, in the resin layer of Example 12 containing squarylium compound 01, the transmittance at the absorption maximum wavelength is 2.5%, while the average transmittance at 400 to 450 nm is about 84%. Therefore, it can be seen that the resin composition containing squarylium compound 01 has higher selective permeability than the resin layer containing comparative squarylium compound 3.
Also, from FIG. 1, a large shoulder peak is observed on the shorter wavelength side than the absorption maximum wavelength in the resin layer of Comparative Example 3 including the comparative squarylium compound 3, but the same shoulder is observed in the resin layer of Example 12 including the squarylium compound 01. It can be seen that the peak almost disappears and a smooth absorption waveform is obtained. Therefore, the resin layer containing squarylium compound 01 can more selectively absorb light in the absorption maximum region than the resin layer containing comparative squarylium compound 3.

FIG. 2 shows the relationship between wavelength and absorbance in the resin layer containing the squarylium compound 01 in the polycycloolefin resin P and the resin layer containing the squarylium compound of the following formula (18) (hereinafter referred to as comparative squarylium compound 5). FIG. 2 that the resin layer containing the squarylium compound 01 is excellent in selective permeability as in FIG.
As in FIG. 1, in the resin layer containing the comparative squarylium compound 5 in the polycycloolefin resin P as shown in FIG. 1, a large shoulder peak is observed on the shorter wavelength side than the absorption maximum wavelength, but the resin containing the squarylium compound 01 It can be seen that the same shoulder peak almost disappears in the layer, and a smooth absorption waveform is obtained. Therefore, the resin layer containing the squarylium compound 01 can more selectively absorb light in the absorption maximum region than the resin layer containing the comparative squarylium compound 5.

A near-infrared cut filter was prepared by laminating an antireflection film on one side of the optical filter obtained in Examples 1 to 54 and a near-infrared reflection film on the other side. A near-infrared reflective film and an antireflective film were produced by alternately depositing silica layers and titanium oxide layers by the IAD method. In addition, the vapor deposition temperature at the time of vapor-depositing a silica layer and a titanium oxide layer was made to become below Tg of each resin.
Near-infrared cut filters produced using the optical filters obtained in Examples 1 to 54 all showed good transmittance characteristics and almost no angle dependency of transmitted light. As a representative example, the near-infrared cut filter obtained by depositing the antireflection film and the near-infrared reflection film on the optical filter of Example 12 has transmittance at each wavelength when light is incident at an incident angle of 0 ° and light at an incident angle of 30 °. Table 10 shows the measurement results of the transmittance at each wavelength when light is incident. The wavelength at which the transmittance is 50% when light is incident at an incident angle of 0 ° is 631 nm, and the wavelength at which the transmittance is 50% when light is incident at an incident angle of 30 ° is 629 nm. Regardless of the incident angle of light, the wavelength at which the transmittance was 50% was almost the same.
Moreover, with respect to the near-infrared cut filter produced using the optical filter obtained in Examples 1-54, ultraviolet resistance, wet heat resistance, water resistance, weather resistance, impact resistance, and heat resistance evaluation were performed. However, it was found that none of the near-infrared cut filters showed very excellent durability with no deterioration of the pigment.

  The resin composition of the present invention has a higher average light transmittance at a wavelength of 400 to 450 nm and eliminates a shoulder peak near the absorption maximum wavelength, compared to a case where a filter using a conventional oxocarbon compound is used. (Or greatly reduced), it is possible to efficiently absorb light in a desired near-infrared region with good color purity. Furthermore, even if the addition amount of the oxocarbon-based compound is increased, it is difficult to reduce the transmittance of visible light, so that the absorption characteristics can be easily controlled. In addition, by combining the resin composition or filter of the present invention with another filter such as a near-infrared cut filter, light in a high-wavelength region such as a red wavelength or near-infrared light is cut, and visible light having a low wavelength is cut. In addition, it is possible to produce a filter that can be sufficiently transmitted. Therefore, optical filters for semiconductor light-receiving elements that have the function of absorbing and cutting near infrared rays and some visible light; near infrared absorbing films and near infrared absorbing plates that block heat rays for energy saving; security inks and invisible barcode inks Information display materials as materials; Materials for solar cells using visible light and near-infrared light; Specific wavelength absorption filters for plasma display panels (PDPs) and CCDs; Photothermal conversion materials for laser welding; Can be used for a photofixing method using light that hardly causes the generation of toner (electrostatic charge developing toner for flash fixing method);

Claims (13)

A resin composition comprising an oxocarbon compound represented by the following formula (1) or the following formula (2) and a resin component.
(In formulas (1) and (2), R ^{a1 to} R ^a4 are each independently a structural unit represented by the following formula (3).)
(In formula (3),
Ring A is a 4-9 membered unsaturated hydrocarbon ring.
X and Y are each independently an alkyl group, alkoxy group, alkylthiooxy group, alkyloxycarbonyl group, alkylsulfonyl group, aryl group, aralkyl group, aryloxy group, arylthiooxy group, aryloxycarbonyl group, arylsulfonyl A group, an arylsulfinyl group, an amide group, a sulfonamide group, a carboxy group, a benzothiazole group, a halogenoalkyl group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, an amino group, or a sulfo group .
n is an integer of 0 to 6 and 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 Ys are the same. It may be different or different.
Ring B is an optionally substituted aromatic hydrocarbon ring, aromatic heterocyclic ring or condensed ring containing these ring structures.
In addition, * represents the coupling | bond part with the 4-membered ring in Formula (1) or the 5-membered ring in Formula (2). )   The resin composition according to claim 1, wherein the ring B is a benzene ring or a naphthalene ring.   The resin composition according to claim 1, wherein X is an alkyl group or an aryl group. Furthermore, at least one selected from ketones, glycol derivatives, amides, esters, pyrrolidones, aromatic hydrocarbons, aliphatic hydrocarbons and ethers (however, ethers do not include glycol derivatives) The resin composition of any one of Claims 1-3 containing these solvents.   The resin composition according to claim 4, wherein the amount of the amide used is 60% by mass or less in 100% by mass of the resin composition. The resin component is a poly (amide) imide resin , a (meth) acrylic resin, a polyamide resin , a fluorinated aromatic polymer (however, the fluorinated aromatic polymer does not include a polyamide resin), a polysulfone resin, an epoxy resin, The resin composition according to claim 1, wherein the resin composition is at least one selected from polycycloolefin resins and polycycloolefin resins.   An optical filter comprising a resin layer formed from the resin composition according to claim 1.   It is an optical filter provided with the support body and the resin layer provided in the single side | surface or both surfaces of the said support body, Comprising: The said resin layer is from the resin composition as described in any one of Claims 1-6. An optical filter formed.   The optical filter according to claim 7 or 8, wherein the resin layer has an average transmittance of 81% or more of spectral rays at a wavelength of 400 to 450 nm.   An optical filter comprising a resin film formed from the resin composition according to claim 1.   The optical filter according to claim 10, wherein the resin film has an average transmittance of 81% or more of spectral rays at a wavelength of 400 to 450 nm.   The near-infrared cut filter, wherein the optical filter according to any one of claims 7 to 11 has a dielectric multilayer film.   An image pickup device comprising at least one of the optical filter according to any one of claims 7 to 11 and the near-infrared cut filter according to claim 12.