KR20160041786A - Oxo carbon-based compounds, a resin composition comprising the same, and a filter containing the resin composition - Google Patents

Abstract

A purpose of the present invention is to provide a novel oxo carbon-based compound which is free of shoulder peaks or has drastically reduced shoulder peaks in absorption spectrums of visible and near infrared areas. An oxo carbon-based compound according to the present invention is characterized in that it is represented by chemical formula (1) or chemical formula (2). In chemical formula (1) and chemical formula (2), each of R^a1 to R^a4 independently is a structural unit represented by chemical formula (3). In chemical formula (3), the ring A is an unsaturated hydrocarbon ring of 4 to 9 atoms; each of X and Y independently is a functional group; n is an integer of 0 to 6, and further is m or lower (Provided that m is a value obtained by subtracting 3 from the number of atoms composing the ring A), and plural Ys may be identical to or different from each other if n is 2 or higher; the ring B is an aromatic hydrocarbon ring that may have substituents, an aromatic heterocyclic ring that may have substituents, or a fused ring comprising the ring structures, the fused ring that may have substituents; and * represents a part that is bonded with a four atom ring in chemical formula (1) or a five atom ring in chemical formula (2).

Description

FIELD OF THE INVENTION [0001] The present invention relates to an oxocarbon-based compound, a resin composition containing the same, and a filter containing the resin composition.

The present invention relates to a novel oxocarbon compound having a so-called squarylium skeleton or a crochanium skeleton, a resin composition containing the same (hereinafter, simply referred to as a resin composition), and a filter containing the resin composition .

The oxocarbon compound having a squarylium skeleton or a chromanium skeleton in a compound is useful as a coloring matter having absorption in the visible and near infrared regions, and for example, a cut filter of visible light or infrared light, a near infrared absorbing film, And the like are expected.

An oxocarbon compound having a squarylium skeleton or a crochanium skeleton is generally synthesized by using squalic acid or croconic acid as a raw material and introducing a heterocyclic group 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. Examples of such oxocarbon-based compounds include indole-based squarylium compounds and indole-based chloronium compounds.

Patent Document 1 discloses a squarylium compound represented by the following formula (claim 2).

[Chemical Formula 1]

Patent Document 2 discloses a squarylium compound represented by the following formula (Example 14).

(2)

Patent Document 2 also discloses a chromium compound represented by the following formula (Example 17).

(3)

Patent Document 3 discloses a squarylium compound represented by the following formula (claim 1).

[Chemical Formula 4]

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

[Chemical Formula 5]

Patent Document 4 discloses a squarylium compound represented by the following formula (Formula 17).

[Chemical Formula 6]

Patent Document 5 discloses that a squarylium compound of the following formula is shown together with its absorption wavelength and is used for a near infrared ray cut filter.

(7)

Non-Patent Document 1 discloses a squarylium compound represented by the following formula (Compound 3a-g).

[Chemical Formula 8]

Non-patent document 2 discloses a chromium compound represented by the following formula (compound 3a-g).

[Chemical Formula 9]

Japanese Laid-Open Patent Publication No. 2008-308602 Japanese Unexamined Patent Application Publication No. 6-25165 Japanese Patent Application Laid-Open No. 2014-148567 U.S. Patent No. 5,543,086 Japanese Laid-Open Patent Publication No. 2014-059550

 Tetrahedron Letters, 1999, vol. 40, 4067-4068  Tetrahedron Letters, 2002, vol 43, 8391-8393

As described above, the indole-based squarylium compounds or the indol-based chrononium compounds disclosed in Patent Documents 1 to 3 and Non-Patent Documents 1 and 2 can be obtained by reacting a squarylium skeleton or a croconium skeleton with a nitrogen- Carbazole ring) via a methine group (which does not form a ring structure), thereby conjugating the nitrogen-containing ring with the squarylium skeleton or the crochanium skeleton. The oxocarbon-based compounds disclosed in Patent Documents 4 and 5 were obtained by bonding an oxocarbon-based compound and a benzene ring without interposing one (not forming a ring structure) methine group.

Further, all the squarylium compounds or the chromium compounds disclosed in Patent Document 1, Non-Patent Document 1 and Non-Patent Document 2 have a large shoulder peak on the lower wavelength side than the absorption maximum wavelength when the wavelength absorption spectrum is measured (See FIGS. 1 to 3 of Patent Document 1, FIG. 1 of Non-Patent Document 1, and FIG. 1 of Non Patent Document 2). Therefore, it is required to eliminate (or reduce) such shoulder peaks and further increase spectral performance. Although the results of measurement of the wavelength absorption spectrum are not disclosed in Patent Document 2, the squarylium compound and the croconium compound described in Patent Document 2 also have a structure in which the nitrogen-containing ring (dihydrocarbazole ring) is a squarylium skeleton or a And the compound disclosed in Patent Document 1, Non-Patent Document 1 and Non-Patent Document 2 in that a methine group that does not form a ring structure is bonded when bound to a crochanan skeleton. In view of the applicant's results, The ability is presumed to be bad.

The resin composition containing squarylium compounds disclosed in Patent Documents 3 to 5 sufficiently absorbs light having a red wavelength (610 to 750 nm) near the maximum absorption wavelength, but absorbs light having a wavelength of 400 to 400 nm, It was found that the transmittance of light at 450 nm was insufficient. As a result, it was found that the light transmitted through these resin compositions was changed in color taste. Therefore, in order to prevent the color tone of the light transmitted through the resin composition from changing as much as possible, it is required to further increase the transmittance of light at a wavelength of 400 to 450 nm.

Further, the squarylium compounds disclosed in Patent Documents 3 to 5 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 increase the spectral performance by eliminating (or reducing) such a shoulder peak.

Under such circumstances, the present invention relates to an oxocarbon compound in which a nitrogen-containing five-membered ring (pyrrole ring) -containing group is bonded to a squarylium skeleton or a crochanium skeleton, wherein the carbon atom bonded to the squarylium skeleton or the crochanium skeleton is a hydrocarbon ring , Thereby providing a novel oxocarbon-based compound as a problem. It is another object of the present invention to provide a resin composition having a high average transmittance of light at 400 to 450 nm while sufficiently absorbing light of a red wavelength. It is another object of the present invention to provide a novel oxocarbon compound and a resin composition containing the same which are free from (or significantly reduced) shoulder peaks in the absorption spectrum of the visible / near infrared region I did it.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, it has been found that when a nitrogen-containing five-membered ring is bonded to a squarylium skeleton or a crochanium skeleton via a carbon atom, It is possible to obtain a novel oxocarbon compound which has not previously been known by designing the molecule so that the methine group bonding to the skeleton or the crochanium skeleton becomes a ring structure and that the compound and the resin composition using the compound can be produced by using a conventional oxo It is found that there is no (or significantly reduced) a shoulder peak appearing on the lower wavelength side than the absorption maximum wavelength in the absorption spectrum of the visible / near infrared region as compared with the carbon-based compound (squarylium compound or the chromium compound) Thereby completing the invention. Further, the inventors of the present invention have found that a resin composition having a high average transmittance of light at 400 to 450 nm, while sufficiently absorbing light of a red wavelength, is obtained by using a compound designed as described above.

That is, the oxocarbon compound related to the present invention is characterized by being represented by the following formula (1) or (2).

[Chemical formula 10]

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

(11)

(In the formula (3)

Ring A is an unsaturated hydrocarbon ring of 4-9 atoms.

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 (provided that m is a value obtained by subtracting 3 from the number of constituent atoms of the ring A). When n is 2 or more, a plurality of Ys may be the same or different.

Ring B is an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures, which may have a substituent.

And * represents a bonding site of a 4-membered ring in formula (1) or a 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, Y is an alkyl group or a hydroxyl group, and X is an alkyl group or an aryl group.

The present invention also includes the oxocarbon compound of the present invention and the resin composition containing the resin component.

The resin composition according to the present invention preferably further contains at least one solvent selected from ketones, glycol derivatives, amides, esters, pyrrolidones, aromatic hydrocarbons, aliphatic hydrocarbons and ethers , And particularly, the amount of the amide to be used is preferably 60 mass% or less in 100 mass% of the resin composition. In the resin composition according to the present invention, the resin component may be at least one selected from the group consisting of a poly (amide) imide resin, a fluorinated aromatic polymer, a (meth) acrylic resin, a polyamide resin, an aramid resin, a polysulfone resin, And at least one kind selected from cycloolefin resins.

The present invention also includes a molded article and a surface formed article comprising the resin composition of the present invention.

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

The present invention also includes a near-infrared cut filter characterized in that the optical filter has a dielectric multilayer film. In addition, the present invention also includes an image pickup device including at least one of the optical filter and the near-infrared ray cut filter.

In the present specification, the squarylium skeleton refers to a structure obtained by removing R ^a1 and R ^a2 from the formula (1), and the crochanium skeleton refers to a structure obtained by removing R ^a3 and R ^a4 from the formula (2) do.

According to the present invention, a novel oxocarbon-based compound having no (or significantly reduced) shoulder peak appearing on the lower wavelength side than the absorption maximum wavelength in the absorption spectrum of the visible / near infrared region can be obtained. Such an oxocarbon compound, a resin composition containing the same, and a molded product thereof can absorb light in the maximum absorption region more efficiently, and can efficiently absorb light in a desired red wavelength region with high color purity. Therefore, it can be preferably used in optical applications requiring high transmittance with high selectivity.

Further, according to the present invention, the resin composition containing a predetermined oxocarbon compound can increase the average transmittance of 400 to 450 nm, and can selectively absorb light having a desired red wavelength. Therefore, the resin composition of the present invention has high selective permeability, and thus can be preferably used in optical applications.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing MS spectra (positive and negative modes) of a squarylium compound 01 obtained in Example 1-1. FIG.
Fig. 2 is a schematic diagram for explaining the area ratio X in the absorption spectrum. Fig.
Fig. 3 is a view showing corrected absorption spectra of the squarylium compounds obtained in Example 1-1, Comparative Example 1-1 and Comparative Example 1-2. Fig.
4 is a diagram showing the absorption spectrum of the resin composition obtained in Example 2-1, Comparative Example 2-1 and Comparative Example 2-2, corrected.
5 is a graph showing the relationship between the wavelength and the transmittance of the resin layer obtained in Examples 3-12 and 3-3.
Fig. 6 is a graph showing the relationship between the wavelength and the transmittance of a resin layer containing a squarylium compound 01 and a resin layer containing a comparative squarylium compound 5. Fig.

1. Oxocarbon compound

The novel oxocarbon compound according to the present invention is a compound having an oxocarbon skeleton in its chemical structure and specifically represented by the following formula (1) having a squarylium skeleton or the following formula (2) having a chromium skeleton. Here, R ^a1 to R ^a4 in the formulas (1) and (2) each independently represent a specific structural unit represented by the following formula (3).

[Chemical Formula 12]

[Chemical Formula 13]

In the formula (3), * represents a bonding site of the squarylium skeleton represented by the formula (1) or the crochanium skeleton represented by the formula (2), and in the present invention, the bonding to the squarylium skeleton or the croconium skeleton (The carbon atom indicated by an arrow in the formula (3)) forming a hydrocarbon ring (ring A). According to such structural features, the oxocarbon compound (squarylium compound or croconium compound) of the present invention has an excellent average transmittance of light at 400 to 450 nm. In addition, since the oxocarbon compound of the present invention can eliminate (or significantly reduce) the shoulder peak of the lower wavelength side in the absorption spectrum of the visible / near infrared region, the light of the absorption maximum wavelength region can be obtained Color purity can be efficiently absorbed.

In the formula (3), the ring A is an unsaturated hydrocarbon ring having 4 to 9 constituent atoms. The ring A is preferably an unsaturated (meth) acrylate having at least one double bond between a carbon atom which bonds to a squarylium skeleton or a crochanium skeleton (carbon atom shown by an arrow in the formula (3)) and a carbon atom constituting the pyrrole ring (Preferably a double bond) in addition to the double bond, but the double bond of the ring A is preferably one. Ring A is preferably a 5- to 8-membered ring, more preferably a 6- to 8-membered ring.

As the structure of the ring A, there can be mentioned, for example, a structure of cyclopentene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene , Cycloalkene structures such as cyclononene, cyclononadiene, cyclononatriene, and cyclononetetraene. Among them, cycloalkane monoene such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene is preferable.

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

In the formula (3), X and Y are an organic group or a polar functional group.

Examples of organic groups which are examples of X and Y include alkyl groups, alkoxy groups, alkylthioxy groups (alkylthio groups), alkyloxycarbonyl groups, alkylsulfonyl groups, aryl groups, aralkyl groups, aryloxy groups, arylthioxy groups (-NHCOR), a sulfonamide group (-NHSO ₂ R), a carboxy group (carboxylic acid group), a benzothiazole group, a halogenoalkyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an arylsulfonyl group, an arylsulfinyl group, And cyano group. 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, , A linear or branched alkyl group such as a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, An alicyclic alkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group; and the like. The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 6, and particularly preferably 3 or more in the case of an alicyclic alkyl group. The alkyl group may have a substituent. Examples of the substituent of the alkyl group include a halogeno group, a hydroxyl group, a carboxyl group, an alkoxy group, a cyano group, a nitro group, an amino group and a sulfo group.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, Dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, icosyloxy group and the like. The carbon number of the alkoxy group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group in the alkoxy group may be linear or branched.

Examples of the alkylthio group (alkylthiooxy group) include methylthioxy group (methylthio group), ethylthioxy group (ethylthio group), propylthioxy group (propylthio group), butylthioxy group (Butylthio group), pentylthioxy group (pentylthio group), hexylthioxy group (hexylthio group), heptylthioxy group (heptylthio group), octylthioxy group (Decylthio group), undecylthio group (nonylthio group), dodecylthio group (dodecylthio group), tridecylthio group (tridecylthio group), decylthio group (Pentadecylthio group), hexadecylthio group (hexadecylthio group), heptadecylthio group (heptadecylthio group), octadecylthio group (pentadecylthio group), pentadecylthio group (Octadecylthio group), nonadecylthio group (nonadecylthio group), eicosylthio group (eicosylthio group), and the like. have. The alkylthio group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. The alkyl group in the alkylthio group may be linear or branched.

Examples of the alkyloxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, , And substituted alkyloxycarbonyl groups such as a trifluoromethyloxycarbonyl group. Examples of the substituent include a halogeno group and the like. The number of carbon atoms of the alkyloxycarbonyl group is preferably 2 to 20, more preferably 2 to 10, and particularly preferably 2 to 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, , A substituted or unsubstituted alkylsulfonyl group of a methoxymethylsulfonyl group, a cyanomethylsulfonyl group, and a trifluoromethylsulfonyl group. The carbon number of the alkylsulfonyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 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 biphenylenyl group, an indacenyl group, an acenaphthylenyl group, and a phenalenyl group. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15. The aryl group may have a substituent and examples of the substituent of the aryl group include an alkyl group, alkoxy group, halogeno group, cyano group, nitro group, thiocyanate group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, A sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

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 of the aralkyl group include alkyl groups, alkoxy groups, halogeno groups, cyano groups, nitro groups, thiocyanate groups, acyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, A sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The carbon number of the aralkyl group is preferably 6 to 25, more preferably 6 to 15.

Examples of the aryloxy group include phenyloxy, biphenyloxy, naphthyloxy, anthryloxy, phenanthryloxy, pyrrolyloxy, indenyloxy, , A terphenyloxy group, a tetraphenyloxy group, a pentalenyloxy group, a heptarenyloxy group, a biphenylenyloxy group, an indacenyloxy group, an acenaphthylenyloxy group, and a phenalenyloxy group. The carbon number of the aryloxy group is preferably 6 to 25, more preferably 6 to 15.

Examples of the arylthioxy group (arylthio group) include a phenylthio group, a biphenylthio group, a naphthylthio group, an anthrylthio group, a phenanthrylthio group, a pyrenylthio group , An indenyl thio group, an azulenyl thio group, a fluorenyl thio group, a terphenyl thio group, a quaterphenyl thio group, a pentenyl thio group, a heptalenyl thio group, a biphenylenyl thio group An acenaphthylthio group, an phenanthryl group, an oxy group, an indanecylthio group, an acenaphthylenylthio group, a phenalenylthio group and the like. The carbon number of the arylthioxy group is preferably 6 to 25, more preferably 6 to 15.

Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 4-dimethylaminophenyloxycarbonyl group, a 4-diethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group, A 4-fluorophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 3-chlorophenyloxycarbonyl group, - a substituted or unsubstituted phenyloxycarbonyl group such as a cyanophenyloxycarbonyl group and a 4-methoxyphenyloxycarbonyl group; a substituted or unsubstituted naphthyloxycarbonyl group such as a 1-naphthyloxycarbonyl group and a 2-naphthyloxycarbonyl group; And the like. The carbon number of the aryloxycarbonyl group is preferably 6 to 25, more preferably 6 to 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, A 2-fluorophenylsulfonyl group, a 3-chlorophenylsulfonyl group, a 3-trifluoromethylphenylsulfonyl group, a 3-cyanophenylsulfonyl group, a 3-nitrophenylsulfone group, Substitution of a phenyl group, a 3-fluorophenylsulfonyl group, a 4-methylphenylsulfonyl group, a 4-fluorophenylsulfonyl group, a 4-cyanophenylsulfonyl group, a 4-methoxyphenylsulfonyl group or a 4-dimethylaminophenylsulfonyl group Or an unsubstituted phenylsulfonyl group; a substituted or unsubstituted naphthylsulfonyl group such as a 1-naphthylsulfonyl group and a 2-naphthylsulfonyl group; and the like. The arylsulfonyl group preferably has 6 to 25 carbon atoms, and more preferably 6 to 15 carbon atoms.

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 , 3-methylphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-methylphenylsulfinyl group, Substituted or unsubstituted phenylsulfinyl groups such as a 1-naphthylsulfinyl group, a 4-cyanophenylsulfinyl group, a 4-methoxyphenylsulfinyl group and a 4-dimethylaminophenylsulfinyl group; A substituted or unsubstituted naphthylsulfinyl group, and the like. The arylsulfinyl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms.

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

Examples of the halogenoalkyl group include a monohalogenoalkyl group such as a fluoromethyl group, a 3-fluoropropyl group, a 3-chloropropyl group, a 6-fluorohexyl group and a 4-fluorocyclohexyl group; Dihalo-perfluoro-n-propyl group, 1,1-dihydro-perfluoro-n-butyl group such as 1,1-dihydro-perfluoroethyl group, An alkyl group having a trihalomethyl unit such as a 2,2-bis (trifluoromethyl) propyl group and a 2,2,2-trichloroethyl group, a trifluoromethyl group, a perfluoroethyl group, a perfluoro- n-pentyl group, and perfluoro-n-hexyl group; and the like. The number of carbon atoms of the halogenoalkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 5. As the halogen of the halogenoalkyl group, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom is particularly preferable.

Examples of the nitrogen-containing group include a fluoro group, a chloro group, a bromo group, and an iodo group.

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 as the organic group or the polar functional group which is a group of X. In this case, the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 4, in the case of a linear or branched alkyl group, and is preferably 4 to 7 in terms of an alicyclic alkyl group, more preferably 5 ~ 6. The carbon number of the aryl group is preferably from 6 to 10, more preferably from 6 to 8. Specifically, examples of the organic group or the polar functional group which is an example 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.

Y is preferably an alkyl group, an alkoxy group, a halogeno group, a phenyl group, an alkoxycarbonyl group (ester group), an amide group, a sulfonamide group or a hydroxyl group, more preferably an alkyl group or a hydroxyl group to be. In this case, the number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2. Specifically, as the organic group or the polar functional group which is an example of Y, a methyl group, an ethyl group, a hydroxyl group and the like are preferably exemplified.

When n is 2 or more and a plurality of Y exist, each Y may be the same or different. When n is 2 or more, a plurality of Y's may be bonded to different carbon atoms, or two Y's may be bonded to one carbon atom.

In the formula (3), the ring B is an aromatic hydrocarbon ring, aromatic heterocyclic ring or condensed ring containing these ring structures which may have a substituent. Examples of the ring B include a ring having a structure represented by the following formulas (A-1) to (A-14), and a ring in which at least one of the hydrogen atoms of these rings is substituted with an arbitrary substituent. Among them, a benzene ring (A-1), a naphthalene ring (A-2, A-3), a quinoline ring (A-8, A-13 and A-14) . Examples of the substituent include the above-mentioned groups as organic groups or polar functional groups which are examples of X and Y, and among them, an alkyl group (particularly preferably a linear or branched alkyl group having 1 to 4 carbon atoms), an aryl group, An alkoxy group (preferably having 1 to 4 carbon atoms), an alkylthio group (particularly preferably having 1 to 2 carbon atoms), an amino group, an amide group, a sulfonamide group, an aromatic heterocyclic group, a hydroxyl group, (Particularly preferably a fluoro group, a chloro group, a bromo group), a halogenoalkyl group (preferably a perhalogenoalkyl group having 1 to 3 carbon atoms), a cyano group, an alkoxy group An electron withdrawing group such as a carbonyl group (ester group), a carboxy group (carboxylic acid group), a carboxylic acid ester group, a carboxylic acid amide group, a sulfo group (sulfonic acid group), or a nitro group is preferable, And a halogeno group is most preferable. The number of substituents in ring B may be one or two or more (for example, 2 or 3). And may have no substituent. When having a substituent, the number thereof is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

[Chemical Formula 14]

(A-1) to (A-14) represent the ring B including a part of the pyrrole ring. For example, the formula (A- The carbon atom at the? -Position of the ring and the carbon atom at the? -Position of the pyrrole ring shown by the arrow in b in the figure below.

[Chemical Formula 15]

The specific structural units R ^a1 and R ^a2 in the compound (1) having a squarylium skeleton may have the same structure or different from each other. It is preferable that R ^a1 and R ^a2 have the same structure in terms of ease of production. Similarly, R ^a3 and R ^{a4, which} are specific structural units in the compound (2) having a crochaninium skeleton, may be the same or different and are more preferably the same structure.

A particularly preferable oxocarbon compound is a compound having a squarylium skeleton of the formula (1) and having a structure A in which the ring A is a cyclopentene, cyclohexene, cycloheptene, or cyclooctene 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, And the ring B is a benzene ring (A-1), a naphthalene ring (A-2, A-3), a quinoline ring (A-8, A-13, A-14). In the particularly preferable oxocarbon compound, when the 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, an alkylthio group having 1 to 2 carbon atoms, a nitro group , A halogenoalkyl group having 1 to 4 carbon atoms (particularly perfluoroalkyl group), a carboxy group, a halogeno group, a cyano group, and a benzothiazole group are preferable. When this substituent is a halogeno group, it is preferable that 1 to 3 halogeno groups are substituted with a ring B. It is preferable that at least one of the substituents is bonded to a carbon atom which is in a para position with respect to a site to which the NH group of the pyrrole ring in the benzene ring of the ring B is bonded. Particularly, when an electron-withdrawing group such as a nitro group, a halogenoalkyl group having 1 to 4 carbon atoms (in particular, perfluoroalkyl group), a carboxy group, a halogeno group or a cyano group is bonded to this para position, .

When it is desired to obtain a resin composition having high transparency in the visible light region, the substituent in the ring B is preferably an electron-donating group, more preferably an alkyl group, a carboxylic acid ester group, A carboxyl group, a nitro group, and a cyano group. These substituents may further have other substituents or may be unsubstituted.

On the other hand, when it is desired to increase the maximum absorption wavelength of the resin composition, the substituent in the ring B is preferably an electron-donating group, more preferably an alkoxy group, a thioalkoxy group, a dialkylamino group, A phenyl group, a naphthyl group, a phenoxy group, a naphthoxy group, an aromatic heterocyclic group, an amino group, a hydroxyl group and a thiol group. These substituents may further have other substituents or may be unsubstituted.

The oxocarbon compound of the present invention in which the specific structural unit represented by the formula (3) as described above is bonded to the squarylium skeleton represented by the formula (1) or the crochanium skeleton represented by the formula (2) Lt; / RTI > Specifically, when bound 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 formula (1). On the other hand, in the case of binding to the crochanan skeleton represented by the formula (2), there is a tautomer represented by (2a), (2b) or (2c) in addition to the compound represented by the following formula (2). The oxocarbon compound of the present invention includes not only compounds represented by (1) or (2) but also tautomers corresponding thereto.

[Chemical Formula 16]

[Chemical Formula 17]

2. Manufacturing method of oxocarbon compound

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

[Chemical Formula 18]

(Wherein, in formula (4), ring A, ring B, X, Y and n are the same as in formula (3)) is used as an intermediate raw material and reacted with squaric acid or croconic acid can do.

The pyrrole ring-containing compound used as an intermediate raw material can be synthesized by appropriately employing a known synthetic method. For example, when ring A is cyclohexene, ring B is benzene ring and n = 0 (i.e., 4a-substituted-2,3,4,4a-tetrahydro-1H-carbazole), phenylhydrazine hydrochloride and Can be synthesized by the reaction of 2-substituted cyclohexanone, and the substituent which becomes X can be introduced at the 2-position of cyclohexanone. Further, when the compound is modified with a substituent group of Y at the 3-position, 4-position, 5-position and 6-position of cyclohexanone, the compound can be arranged as a compound wherein n is 1 or more and the ring A is Y. In addition, the structure of the ring B can be arranged by changing the phenylhydrazine hydrochloride to another aromatic hydrazine hydrochloride, and the number of constituent atoms of the ring A is preferably 2-substituted cyclohexanone as the other 2-substituted cyclohexanone Alcanon. ≪ / RTI >

The pyrrole ring-containing compound used as the intermediate material can be synthesized, for example, by the synthesis method described in the following articles.

SAJJADIFAR ET AL: 'New 3H-Indole Synthesis by Fischer's Method. Part I. ' Molecules 2010, no. 15, April 2010, pages 2491-2498

The amount of the pyrrole ring-containing compound to be used in the reaction of the squalic acid or the croconic acid with the pyrrole ring-containing compound is preferably at least 1 mol, more preferably at least 1.5 mol per mol of the squalic acid or the croconic acid , More preferably not less than 2 times mol, and not more than 5 times mol, more preferably not more than 4 times mol, still more preferably not more than 3 times mol.

The reaction of the squaric acid or croconic acid with the pyrrole ring-containing compound is preferably carried out in the presence of a solvent. Examples of the solvent that can be used include chlorinated hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene, Ethers such as tetrahydrofuran, dioxane, cyclopentyl methyl ether, diisopropyl ether and diethyl ether, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol, ethanol, ; Amides such as dimethylformamide and dimethylacetamide; and the like. These solvents may be used alone, or two or more solvents may be used in combination.

The amount of the solvent used (total) is preferably not less than 1 time, more preferably not less than 5 times, more preferably not less than 10 times the mass of squalic acid or croconic acid, It is 100 times mass or less.

In the reaction of squalic acid or croconic acid with a compound containing a pyrrole ring, the reaction temperature may be suitably set, for example, 80 DEG C or higher, more preferably 100 DEG C or higher and 170 DEG C or lower, More preferably not higher than 140 占 폚. This reaction may be carried out in a reflux state in particular. The reaction time is not particularly limited. For example, the reaction time is preferably 0.5 hour or more, more preferably 1 hour or more, and 24 hours or less, and more preferably 12 hours or less. The atmosphere during the reaction is preferably an inert gas (nitrogen, argon, etc.) atmosphere.

The squarylium-based compound can be synthesized by appropriately employing a known synthetic method for reacting the pyrrole ring-containing compound with squaric acid. For example, the pyrrole ring-containing compound can be synthesized by the synthesis method described in the following articles.

Serguei Miltsov ET AL; 'New Cyanine Dyes: Norindosquarocyanines', Tetrahedron Letters, Volume 40, Issue 21, May 1999, pages 4067-4068

The method for synthesizing the above-mentioned chromium compound is not particularly limited, but can be synthesized by appropriately employing a known synthetic method for reacting the pyrrole ring-containing compound with croconic acid. For example, it can be synthesized by the method described in Japanese Patent Application Laid-Open Nos. 2002-286931, 2007-31644, 2007-31645, and 2007-169315.

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

The chemical structure of the oxocarbon compound obtained by the above reaction can be analyzed by a known method such as mass spectrometry, single crystal X-ray structure analysis, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy.

3. Resin composition

The resin composition of the present invention contains the above oxocarbon compound of the present invention and a resin component. The resin composition of the present invention may contain a solvent, various additives, and the like, if necessary. This resin composition has an excellent light absorption property of the oxocarbon compound, so that the average transmittance at 400 to 450 nm is increased, while the absorption rate of light at a red wavelength is increased, and the selectivity is excellent. A resin layer or the like to be formed on a resin film, a filter or the like can be formed from the resin composition of the present invention. Hereinafter, the resin layer may include a resin film.

3.1. Oxocarbon compound

The oxocarbon compound of the present invention contained in the resin composition of the present invention may be a squarylium compound, a chromium compound, or a mixture of both. The oxocarbon-based compound may be one kind or two or more kinds.

The oxocarbon-based compound functions as a coloring matter. However, the resin composition of the present invention may contain other coloring matters known together with the oxocarbon-based compound of the present invention within a range not hindering the effect of the present invention. Examples of the dye which may be contained in the resin composition of the present invention include a squarylium-based dye or a chromium-based dye other than the oxocarbon-based compound of the present invention, copper (for example, Cu (II) (Porphyrins, chlorines, phthalocyanines, cholines, etc.), which may have zinc (for example, Zn (II) Based dye, a nickel complex-based dye, a copper ion-based dye, a diimmonium-based dye, a subphthalocyanine-based dye, a zotensin-based dye, an azo-based dye and a dipyramethene-based dye. These other pigments preferably have an absorption maximum wavelength in a wavelength range of 400 to 1100 nm so as not to hinder the effect of the present invention. These other pigments may be of only one kind or two or more kinds.

When the resin composition of the present invention also contains other pigments, the content of the other pigments is preferably 60% by mass or less, more preferably 40% by mass or less, more preferably 40% by mass or less based on the total 100% by mass of the oxo carbon- By mass or less, more preferably 20% by mass or less, and particularly preferably substantially free from other pigments.

The content of the oxocarbon-based compound of the present invention in the resin composition is preferably such that the total amount (total amount of small amounts of the coloring matters) with the other coloring matters is within a predetermined range. Specifically, the total amount of the oxocarbon-based compound and other pigments of the present invention is preferably 0.01 mass% or more, more preferably 0.3 mass% or more, and still more preferably 1 mass% or more, in the solid content of 100 mass% %. The upper limit of the total amount of the oxo-carbon-based compound and other pigments used in the present invention is preferably 25% by mass or less, more preferably 20% by mass or less, in 100% by mass of the solid content of the resin composition, By mass or less, more preferably 15% by mass or less.

The resin composition of the present invention is a resin composition which, when oxygen is present at the time of storage of the resin solution or during drying or thermal curing of the coating film, changes the structure of the oxocarbon compound, changes in the absorption characteristics due to generation of decomposed products, There is a fear that the durability of the resin composition is deteriorated by reason. Therefore, it is preferable that the oxygen concentration is low during the storage of the resin solution, the drying process of the coating film, and the heat curing process. Specifically, the oxygen concentration is preferably 10 vol% or less. The oxygen concentration in the air is usually about 20% by volume, but the property deterioration of the oxocarbon compound due to light or heat can be further suppressed by storing or using it in an atmosphere of 10% by volume or less. The oxygen concentration is more preferably 3 vol% or less, further preferably 1 vol% or less, particularly preferably 0.5 vol% or less, and most preferably 0.3 vol% or less. The oxygen concentration can be measured with an oxygen concentration meter (for example, Cosmo Tektor (registered trademark) XPO-318 manufactured by Shin Cosmos Co., Ltd.).

The means for bringing the oxygen concentration to the above-mentioned range is not particularly limited. For example, it is preferable that oxygen in the system is replaced with an inert gas and curing is performed in an inert gas atmosphere. The inert gas is not particularly limited, and examples thereof include rare gases such as helium, neon and argon in addition to nitrogen. Of these, argon and nitrogen are preferable, and nitrogen is particularly preferable. The atmosphere may be any of reduced pressure, normal pressure, and pressure.

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 oxo carbon compound, and known resins can be used. As the resin component, not only a resin in which polymerization is completed but also a resin raw material (including a precursor of a resin, a raw material of the precursor, a monomer constituting the resin, etc.), a polymerization reaction or a cross- May be used. However, when the structure of the oxocarbon compound of the present invention or another coloring matter is used, depending on the structure of the other coloring matter, the amount of unreacted material, reactive end functional group, ionic group, catalyst, In some cases, it is preferable to use a resin which has been completely polymerized and which is isolated (purified as necessary), in such a case that part or all of its structure may be decomposed by an acid or a basic group.

Examples of the resin that can be used as the resin component include a resin such as a poly (amide) imide resin, a (meth) acrylic resin, a (meth) acrylurethane resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, 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, (E.g., polybutylene terephthalate (PBT), polyethylene terephthalate (PET), etc.), butyral resins, polycarbonate-based resins, (Acrylonitrile-butadiene styrene resin), AS resin (acrylonitrile-styrene copolymer), (meth) acrylic resin, Modified silicone resin such as fluorinated aromatic polymer, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluorine resin (PFA), fluorine-containing silicone resin, ), Fluorinated resins such as fluorinated polyaryl ether ketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamide acid (FPAA) and fluorinated polyether nitrile (FPEN). These resin components may be either one kind alone, or two or more kinds.

Among the resins usable as the resin component, among them, a solvent-soluble resin is preferable. When the resin component is a solvent-soluble resin, the obtained resin composition can be made into a coating material, and it is possible to easily produce a planar molded product (including a film or the like) by, for example, spin coating or solvent casting . In the present specification, the solvent-soluble resin means a resin soluble in an organic solvent, and for example, a resin dissolving at least 1 part by mass based on 100 parts by mass of the organic solvent used is preferable.

As the solvent-soluble resin, a thermoplastic resin may be used, or a curable resin may be used. From the viewpoints of the storage stability of the resin and the suppression of the transmittance change in the drying step, a thermoplastic resin is preferred, and a curable resin is preferable from the viewpoints of heat resistance, hardness and solvent resistance of the coating film. In order to take advantage of the advantages of the thermoplastic resin and the curable resin, a form in which a mixture is used is also preferable. In the case of using an optical filter having an antireflection layer, an ultraviolet reflection layer, a near-infrared reflection layer and the like to be described later, it is preferable to manufacture the resin layer at a high temperature. Thus, when an antireflection layer, an ultraviolet reflection layer, a near-infrared reflection layer, or the like is laminated on the resin layer by vapor deposition, sputtering or the like, an optical filter having more compact, high strength, high durability and excellent optical characteristics can be obtained. In order to produce the resin layer at a high temperature, it is preferable that the resin used for the resin composition of the present invention has high heat resistance, that is, the resin used for the resin composition of the present invention has a high Tg. Specifically, the Tg of the resin is preferably 100 ° C or higher, more preferably 130 ° C or higher, even 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 resin, fluorinated aromatic polymer, (meth) acrylic resin, polyamide resin, aramid resin, polysulfone resin, polycycloolefin resin, Examples of the curable resin that can be used as the solvent-soluble resin include an epoxy-based resin, a urethane-based resin, and a phenol-based resin. The solvent-soluble resin is preferably at least one selected from a poly (amide) imide resin, a fluorinated aromatic polymer, a (meth) acrylic resin, a polyamide resin, an aramid resin, a polysulfone resin, a polycycloolefin resin, , More preferably at least one kind selected from a poly (amide) imide resin, a fluorinated aromatic polymer, a (meth) acrylic resin, a polyamide resin, an aramid resin, a polycycloolefin resin and an epoxy resin, Is at least one member selected from a poly (amide) imide resin, a fluorinated aromatic polymer, a (meth) acrylic resin, a polysulfone resin, a polycycloolefin resin and an epoxy resin, (Meth) acrylic resin, a polycycloolefin resin, and an epoxy resin. Hereinafter, the poly (amide) imide resin, the fluorinated aromatic polymer, the (meth) acrylic resin, the polysulfone resin, the polycycloolefin resin, and the epoxy resin will be described in detail.

(I) Thermoplastic resin

3.2.1. The poly (amide) imide resin

First, the poly (amide) imide resin referred to in the present specification is a polyimide resin having a narrower structure (including an imide bond and not containing an amide bond), and the amide bond referred to herein means a dehydration reaction of an amic acid And a polyamideimide resin (a resin containing an amide bond and an imide bond which can not form an imide bond by dehydration reaction of an amic acid, is referred to as " amide bond "Quot;).

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, the bond chain is also referred to as an amic acid). Usually, Is a structure in which a carboxyl group is bonded to an adjacent carbon atom) and a dehydration reaction of a carboxyl group with an amide bond. When the polyimide resin is produced from the polyamic acid by dehydration reaction, a small amount of the amic acid may remain in the molecule. Therefore, in the present invention, the term " polyimide resin " does not include an amide bond which contains an imide bond and can not form an imide bond by the dehydration reaction of an amic acid. However, May not contain an amide bond capable of forming an imide bond or may contain a slight amount. Polyimide having an imide bond content in the polyimide resin (ratio of the number of imide bonds per 100 mol% of the total amount of amide bonds and imide bonds imidizable by the imidization reaction) is 80 mol% Resins are preferred. , More preferably not less than 90 mol%, still more preferably not less than 95 mol%, particularly preferably not less than 98 mol%.

The poly (amide) imide resin contains an amide bond and an imide bond which can not form an imide bond by the dehydration reaction of an amic acid. However, the poly (amide) imide resin can form an imide bond by dehydration reaction of an amic acid As for the amide bond, it may or may not contain a little amount. In the case of containing an amide bond capable of forming an imide bond by dehydration reaction of amic acid, an amide bond number (an amide bond number which can not form an imide bond by a dehydration reaction and an imide bond by a dehydration reaction The content of the amide bond capable of forming an imide bond by the dehydration reaction of amic acid with respect to the total amount of 100 mol% of the imide bond is preferably less than 20 mol% Do. , More preferably less than 10 mol%, even more preferably less than 5 mol%, particularly preferably less than 2 mol%.

The poly (amide) imide resin is preferable because it can obtain high transparency. For example, the mass of the aromatic ring in 100% of the total mass of the poly (amide) imide resin is 65 Or less, more preferably 45% or less, further preferably 30% or less.

As the poly (amide) imide resin, for example, the following formula (10):

[Chemical Formula 19]

( ^Wherein R < ^{p1 >} is the same or different and represents an organic group) is preferable.

As R ^p1 in the formula (10), a divalent organic group is preferable, and among them, a divalent organic group having 2 to 39 carbon atoms is preferable. It is preferable that the organic group contains one or more kinds of hydrocarbon skeletons. The hydrocarbon skeleton is preferably an aliphatic chain-like hydrocarbon, an aliphatic cyclic hydrocarbon, or an aromatic hydrocarbon. The organic group may have a heterocyclic skeleton.

The R ^p1 in the formula (10) also preferably has at least two of the same or different selected from the above-mentioned hydrocarbon skeleton and / or heterocyclic skeleton, and they have a carbon-carbon bond or a carbon- It is preferable that the carbon-carbon bond includes a bonded skeleton via a bonding group different from the carbon-carbon bond. Examples of the bonding group include -O-, -SO ₂ -, -CO-, -Si (CH ₃ ) ₂ -, -C ₂ H ₄ O-, -S- and the like. Each R ^p1 in the repeating unit represented by the formula (10) may be the same or different.

The organic group represented by the R ^p1, and may be directly bonded to the nitrogen atom, as coupler _{-O-, -SO 2 -, -CO-,} -CH 2 -, -C (CH 3) 2 -, -Si (CH 3 ) ₂ -, -C ₂ H ₄ O-, -S-, and the like. In addition, some or all of the hydrogen atoms in the cyclohexyl ring in the formula (10) may be substituted, but are preferably unsubstituted (all are hydrogen atoms). The repeating unit represented by the formula (10) may be the same or different, and may be any of a block form, a random form, and the like.

Preferable examples of the poly (amide) imide resin include, for example, the following formula (10-1):

[Chemical Formula 20]

, And the like.

The poly (amide) imide resin is a raw material (a "poly (amide) imide precursor") of a poly (amide) imide resin obtained by reacting a polycarboxylic acid compound with a polyvalent amine compound and / or a polyvalent isocyanate compound May also be referred to as an imidization reaction.

3.2.2. Fluorinated aromatic polymer

As the fluorinated aromatic polymer, a polymer composed of an aromatic ring having at least one fluorine atom and a repeating unit containing at least one bond selected from the group of ether bond, ketone bond, sulfone bond, amide bond, imide bond and ester bond Specific examples thereof include polyimides having an aromatic ring having a fluorine atom, polyether, polyetherimide, polyetherketone, polyether sulfone, polyamide ether, polyamide, polyether nitrile , Polyester, and the like. Among these, a polymer having an aromatic ring having at least one fluorine atom and a repeating unit containing an ether bond as an essential unit is preferable, and a polymer having a repeating unit represented by the following formula (11-1) or (11-2) And more preferably a polyether ketone having a fluorine atom. Of these, fluorinated polyether ketone (FPEK) is particularly preferred. The repeating unit represented by the formula (11-1) or (11-2) may be the same or different, and may be any of a block form, a random form, and the like.

[Chemical Formula 21]

In the formula (11-1), R ^q1 represents a divalent organic chain having an aromatic ring of 1 to 150 carbon atoms. Z represents a divalent chain or direct bond. x and y are integers of 0 or more, and represent the number of fluorine atoms that satisfy x + y = 1 to 8 and are the same or different and are bonded to an aromatic ring. n ¹ represents a degree of polymerization, preferably in the range of 2 to 5,000, more preferably in the range of 5 to 500.

In formula (11-2), R ^q2 represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylamino group having 1 to 12 carbon atoms, 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 of 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 a degree of polymerization, preferably in the range of 2 to 5,000, more preferably in the range of 5 to 500.

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

3.2.3. (Meth) acrylic resin

The (meth) acrylic resin has a unit derived from a (meth) acrylate ester and / or a (meth) acrylic acid as essential constituent units and has a constituent unit derived from a (meth) acrylic acid ester or a derivative of (meth) acrylic acid do. The term "(meth) acryl" means "acrylic" 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, n-butyl (meth) acrylic acid such as n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl Ester derivatives of hydrocarbon such as alkyl (meth) acrylate, aryl (meth) acrylate, aralkyl (meth) acrylate and the like, ether bond-introducing derivatives such as dicyclopentanyl (meth) acrylate, chloromethyl (Meth) acrylate; halogen-introduced derivatives such as 2-chloroethyl acrylate; hydroxyl group-introduced derivatives; allyl group-containing (meth) acrylate esters; vinyl group-containing (meth) acrylate esters.

Examples of the (meth) acrylic acid or (meth) acrylic acid derivatives include alkyl (meth) acrylates such as (meth) acrylic acid such as acrylic acid and methacrylic acid, methyl methacrylate and crotonic acid, Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, and 2- (hydroxyethyl) acrylic acid. Of these, methyl methacrylate is particularly preferable from the viewpoint of heat resistance and transparency.

(Meth) acrylic acid ester (unit), (meth) acrylic acid (unit) and derivatives thereof (unit) may be either one kind or two or more kinds.

Examples of the hydroxyl-group-containing derivatives include (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2,3,4,5,6- (Meth) acrylic acid hydroxyalkyls such as 2,3,4,5-tetrahydroxypentyl acrylate; alkyl 2- (hydroxymethyl) acrylates such as methyl 2- (hydroxymethyl) (Hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, n-butyl (2- (hydroxymethyl) acrylate, Ethyl) acrylic acid alkyl (for example, 2- (hydroxyethyl) acrylate, etc.) alkyl 2- (hydroxyalkyl) acrylate.

Examples of the allyl group-containing (meth) acrylate esters include acrylate esters to which an allyl group-containing substituent is bonded at the α-position, and examples thereof include allyloxymethylacrylic acid esters, 2- (N-allylaminomethyl) Is preferred. Specific examples include methyl α-allyloxymethylacrylate, ethyl α-allyloxymethylacrylate, butyl α-allyloxymethylacrylate, t-butyl α-allyloxymethylacrylate, cyclohexyl α-allyloxymethylacrylate, Allyloxymethylacrylic acid esters such as dicyclopentadienyl oxymethyl acrylate, isobornyl α-allyloxymethylacrylate, adamantyl α-allyloxymethylacrylate and benzyl α-allyloxymethylacrylate; (N-allyl N-ethylaminomethyl) acrylate, methyl 2- (N-allyl N-ethylaminomethyl) acrylate, 2- 2- (N-allylaminomethyl) acrylic acid esters such as methyl N- (aminomethyl) acrylate and methyl 2- (N-allyl N-phenylaminomethyl) acrylate are preferable. Of these, methyl α-allyloxymethylacrylate, ethyl α-allyloxymethylacrylate, cyclohexyl α-allyloxymethylacrylate and benzyl α-allyloxymethylacrylate are preferable, and among them, methyl α-allyloxymethylacrylate AMA) is preferred.

Examples of the vinyl group-containing (meth) acrylate esters include acrylate esters to which a vinyl group-containing substituent is bonded at the α-position, and examples thereof include vinyloxymethylacrylic acid esters, 2- (N-vinylaminomethyl) Is preferred. Specific examples thereof include methyl α-vinyloxymethylacrylate, ethyl α-vinyloxymethylacrylate, butyl α-vinyloxymethylacrylate, t-butyl α-vinyloxymethylacrylate, cyclohexyl α-vinyloxymethylacrylate, α-vinyl Vinyloxymethylacrylic acid esters such as isobornyl alpha -vinyloxymethyl acrylate, adamantyl alpha -vinyloxymethylacrylate, and benzyl alpha -vinyloxymethylacrylate; N-methyl-N N-vinyl-2- (methoxycarbonyl) allylamine, N-ethyl-N-vinyl-2- (methoxycarbonyl) allylamine, Nt- Methyl-N-vinyl-N-vinylcarbamate such as N-cyclohexyl-N-vinyl-2- (methoxycarbonyl) allylamine, N-phenyl- 2- (methoxycarbonyl) allylamines, methyl 2- (N-vinyl N-ethylaminomethyl) acrylate, 2- (N-vinyl Nt-butyl Amino (N-vinylaminomethyl) acrylic acid esters such as methyl (meth) acrylate, methyl 2- (N-vinyl N-cyclohexylaminomethyl) desirable. Among these, methyl α-vinyloxymethylacrylate, ethyl α-vinyloxymethylacrylate, cyclohexyl α-vinyloxymethylacrylate and benzyl α-vinyloxymethylacrylate are preferable, and methyl α-vinyloxymethylacrylate is particularly preferable Do.

The (meth) acrylic resin may have other constituent units introduced by copolymerizing the above-mentioned (meth) acrylic acid-based monomer with another monomer. By copolymerizing (meth) acrylic acid-based monomer with another monomer, the glass transition temperature of the (meth) acrylic-based resin can be increased. The glass transition temperature of the (meth) acrylic resin is preferably 110 ° C or higher, more preferably 120 ° C or higher. Examples of other monomers include styrene, vinyltoluene,? -Methylstyrene,? -Hydroxymethylstyrene,? -Hydroxyethylstyrene, acrylonitrile, methacrylonitrile, methallyl alcohol, allyl alcohol, N- Cyclohexylmaleimide, N-phenylmaleimide, ethylene, propylene, 4-methyl-1-pentene, vinyl acetate, 2-hydroxymethyl-1-butene, methylvinylketone, N- vinylpyrrolidone, And monomers having a polymerizable double bond such as carbazole. These other monomers (units) may have only one kind or two or more kinds thereof.

(Meth) acrylic acid ester units, (meth) acrylic acid units and constituent units derived from these (meth) acrylic acid monomers) in the total constituent units of the (meth) acrylic resin The ratio is preferably 50% by mass or more, more preferably 60% by mass or more, furthermore preferably 70% by mass or more. The upper limit is not particularly limited, and most preferably 100% by mass.

It is preferable that the main chain constituting the (meth) acrylic resin contains a ring structure. The main chain ring structure in the (meth) acrylic resin is not particularly limited and may be a cyclic structure using a carbonyl group-containing bond such as - (C═O) N-bond or (C═O) -O- bond, Or a ring structure not containing a carbonyl group. Examples of the ring structure containing a carbonyl group include a lactone ring structure, an anhydroglutaric acid structure, a glutarimide structure, a maleic anhydride structure, and an N-substituted maleimide structure. More preferably, it is a lactone ring structure, an anhydroglutaric acid structure, or a glutarimide structure, and particularly preferably a lactone ring structure.

The maleic anhydride structure or the N-substituted maleimide structure includes, for example, a structure represented by the following formula (12-1) (in the formula (12-1) below, when X ^s2 is an oxygen atom, Acid structure, and when X ^s2 is a nitrogen atom, it becomes an N-substituted maleimide structure).

(27)

R ^s7 and R ^s8 in the formula (12-1) are, independently from each other, 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 represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms (methyl, ethyl, propyl, butyl, Hexyl group), cyclopentyl group, cyclohexyl group, benzyl group or phenyl group.

The maleic anhydride structure in which X ^s2 in the formula (12-1) is an oxygen atom can be formed, for example, by polymerizing maleic anhydride together with (meth) acrylic acid ester or the like.

The N-substituted maleimide structure in which X ^s2 in the formula (12-1) is a nitrogen atom can be obtained by, for example, polymerizing an N-substituted maleimide such as N-phenylmaleimide together with a (meth) .

Specifically, a (meth) acrylic resin having a maleic anhydride structure or an N-substituted maleimide structure in the main chain is disclosed, for example, in JP-A-57-153008 and JP-A-2007-31537 Can be prepared by the method described.

Of the main chain ring structures in the (meth) acrylic resin, examples of the ring structure not containing a carbonyl group include oxygen-containing or nitrogen-containing quaternary rings such as oxetane ring and azetidine ring, tetrahydrofuran ring, pyrrolidine An oxygen-containing or nitrogen-containing six-membered ring such as an oxygen or nitrogen-containing five-membered ring, a tetrahydropyran ring, a piperidine ring and the like.

An example having a 5-atomic ring or a 6-atomic ring structure is preferably a structure represented by the following formula (12-2) or a structure represented by the following formula (12-3) As an example having a ring structure, for example, a structure represented by the following formula (12-4) or the following formula (12-5) is preferably exemplified. The (meth) acrylic resin having a cyclic structure in the main chain may have at least one of these structures, but usually has a structure in which the structure of the formula (12-2) is combined with the structure of the formula (12-3) (12-4) and (12-5) are combined in many cases.

(28)

(Wherein R ^s10 and R ^s11 are the same or different and each is a hydrocarbon group of 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, 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 formulas (12-2) and (12-3), it is preferable that X ¹ and Z ¹ are methylene groups and Y ¹ is an oxygen atom. That is, in the formulas (12-2) and (12-3), a tetrahydrofuran ring structure or a tetrahydropyran ring structure is preferable. It is preferable that R ^s10 and R ^s11 are hydrocarbon groups of 1 to 5 carbon atoms, especially methyl.

The resin having the cyclic structure of the formula (12-2) and / or the cyclic structure of the formula (12-3) can be obtained, for example, by reacting the allyl group-containing (meth) acrylic acid esters, alone or in combination with other monomers Followed by polymerization.

[Chemical Formula 29]

(Wherein R ^s12 and R ^s13 are each a hydrocarbon group of 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 each represents a methylene group, Wherein at least one of X ² and Y ² is an oxygen atom or an imino group.

In the structures represented by the formulas (12-4) and (12-5), an oxetane ring structure in which X ² is a methylene group and Y ² is an oxygen atom or a tetrahydrofuran ring structure is preferable. It is preferable that R ^s12 and R ^s13 are a hydrocarbon group having 1 to 5 carbon atoms, particularly a methyl group.

The resin having the cyclic structure of the formula (12-4) and / or the cyclic structure of the formula (12-5) can be obtained, for example, by reacting the vinyl group- containing (meth) Followed by polymerization.

3.2.4. Polysulfone resin

Typically, a polysulfone resin is a resin obtained by reacting a bivalent aromatic group (a residue obtained by removing two hydrogen atoms bonded to the aromatic ring from an aromatic compound), a repeating unit containing a sulfonyl group (-SO ₂ -) and an oxygen atom . The polysulfone resin is preferably a repeating unit represented by the following formula (D) (hereinafter referred to as a "repeating unit (D)") or a repeating unit represented by the following formula (E) (Hereinafter referred to as "repeating unit (E)"), and may have one or more other repeating units such as a repeating unit represented by the following formula (F) (hereinafter referred to as "repeating unit (F)") .

(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 be independently 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 be independently substituted with an alkyl group, an aryl group or a halogen atom. An oxygen atom or a sulfur atom.)

(F) - (Ph ⁷ ) _n -O-

(Ph ⁷ is represents a phenylene group. Hydrogen atoms which groups the phenylene group is, independently, an alkyl group, is optionally substituted aryl group, or a halogen atom. N is an integer of 1 ~ 3. N is 2 or more , The plural Ph ⁷ present may be the same or different from each other.)

The phenylene group represented by any one of Ph ¹ to Ph ⁷ may be a p-phenylene group, an m-phenylene group or an o-phenylene group, but since the resulting resin has high heat resistance and strength, desirable. Examples of the alkyl group which may be substituted on the hydrogen atom in the phenylene group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Pentyl group, n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group and n-decyl group. The carbon number thereof is preferably 1 to 10. Examples of the aryl group which may be substituted for the 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, Is preferably 6 to 20. Examples of the halogen atom which may be substituted for the hydrogen atom in the phenylene group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. When the hydrogen atoms in the phenylene group are substituted by these groups, the number of the phenylene groups is preferably 1 or 2, and more preferably 1, for each of the phenylene groups. Examples of the alkylidene group represented by R include a methylene group, an ethylidene group, an isopropylidene group, and a 1-butyrylidene group, and the number of carbon atoms thereof is preferably 1 to 5.

Examples of commercial products of aromatic polysulfone resins include Sumica Excel PES3600P manufactured by Sumitomo Chemical Co., Ltd., Sumika Excel PES4100P (aromatic polysulfone resin having repeating unit (D) manufactured by Sumitomo Chemical Co., Ltd.), UDEL (registered trademark) P manufactured by SOLVAY SPECIALTY POLYMERS -1700 (an aromatic polysulfone resin having a repeating unit (E)). The terminal group of the aromatic polysulfone resin can be appropriately selected according to the production method, and examples thereof include -Cl, -OH and -OR (R: alkyl group).

3.2.5. Polycycloolefin Resin

The polycycloolefin resin refers to a polymer or copolymer (hereinafter referred to as a (co) polymer) containing a polycycloolefin as a monomer component constituting the polymer. The polycycloolefin resin refers to a resin in which a monomer component is composed of only one kind or two or more kinds of polycycloolefins (Co) polymer, or a (co) polymer containing a polycycloolefin and other monomers as monomer components. Examples of the other monomer include? -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 its main chain, and among these, a homopolymer or a polycycloolefin resin as a copolymer is more preferable. Preferred examples of the polycycloolefin resin include polycycloolefin resins represented by the following structural formulas (13) and (14) (hereinafter referred to as norbornene resin), polycycloolefin resins represented by the following structural formula (15) (Hereinafter referred to as " cyclic olefin copolymer resin ") and a polycycloolefin resin represented by the following structural formula (16) (hereinafter referred to as cyclic olefin copolymer resin).

(30)

(In the 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, and R ^b1 and R ^b2 , .

(31)

(Formula 14 of the, m ² and n ² is either is, or are both an integer of 1 or more. R ^c1 and R ^c2 represents a hydrogen atom or an alkyl group, and may be respectively identical or different. R ^c1 and R ^c2 may combine with each other to form a ring.)

(32)

(Formula (15) and of the, m ³ is an integer equal to or greater than 1, R ^d1 ~ R ^d4 represents a hydrogen atom or an alkyl group, 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, and R ^d1 and R ^d2 may be combined to form a ring.)

(33)

(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, an alkoxycarbonyl group (preferably a methoxycarbonyl group or And R ^e1 to R ^e4 may be the same or different, and R ^e1 and R ^e2 may be combined to form a ring.)

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

As the polycycloolefin resin, commercially available products may be used. Examples of commercially available products include ZEONEX (registered trademark) (ring-opening metathesis polymer hydrogenated polymer of norbornene monomer, norbornene resin manufactured by Nippon Zeon Co., Ltd.), ZEONOR (registered trademark) (manufactured by Nippon Zeon Co., A copolymer based on ring-opening polymerization of pentadiene and tetracyclopentadodecene, a norbornene resin), ARTON (registered trademark) (manufactured by JSR Corporation, containing a polar group having dicyclopentadiene and methacrylic acid ester as raw materials) (A copolymer of norbornene and ethylene; a copolymer of a cyclic olefin copolymer), APEL (registered trademark) (manufactured by Mitsui Chemicals, Inc., A copolymer of tetracyclododecene and ethylene, and a cyclic olefin-based copolymer resin).

When the composition for a resin layer contains a soluble polycycloolefin resin, the soluble polycycloolefin resin itself may constitute a resin layer, and the resin layer in which the soluble polycycloolefin resin is changed by a crosslinking reaction or the like may be constituted.

The content of the usable polycycloolefin resin in the composition for the resin layer is preferably 1 to 30% by mass, more preferably 2 to 30% by mass based on 100% by mass of the composition for a resin layer (total amount including the solvent) 20% by mass, and more preferably 3% by mass to 10% by 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 (thermal decomposition resistance and heat resistance coloring property) and chemical resistance.

The curable resin is a resin containing at least one organic compound having a curable functional group, and the curable functional group is a functional group which reacts with heat or light (that is, a group which causes a curing reaction of the resin composition For example, an oxetane group (oxetane ring), an ethylene sulfide group, a dioxolane group, a trioxoranane group, a vinyl ether group, a vinyl group, Styryl groups and the like, and radical-curable groups such as an acryl group, a methacryl group and a vinyl group. Therefore, it is preferable that the curable resin contains a compound having a cationically curable group and / or a compound having a radical curable group. As a result, the time required for curing of the curable resin is shortened and the productivity is further increased, and the resulting cured product is also excellent in heat resistance (heat resistance decomposability and heat resistance coloring property). Among them, it is more preferable to use a resin containing a compound having a cationically curable group from the viewpoint that peeling of the resin layer is less likely to occur due to a low curing shrinkage ratio of the resin,

When the curable resin is used, it is preferable to add a curing agent. The curing agent may be used alone or in combination of two or more. The curing agent may be appropriately selected depending on the curing reaction or the kind of the curable resin. The curing agent is not particularly limited as long as it is commonly used, and examples thereof include a thermal latent cationic curing catalyst, a thermal latent radical curing catalyst, an acid anhydride catalyst, a phenol catalyst, and an amine catalyst. Among them, it is preferable to use a thermal latent cationic curing catalyst or a thermal latent radical curing catalyst having a high curing rate in terms of productivity. In order to reduce the shrinkage of a cured product, a thermal latent cationic curing catalyst It is more preferable to use it. In the case of curing by irradiation with active energy rays, a photo polymerization initiator can be used as a curing agent. As the photopolymerization initiator, it is preferable to use a photothermic cationic curing catalyst or a photocatalytic radical curing catalyst. It is more preferable to use a photocatalytic cationic curing catalyst for the purpose of reducing the shrinkage of a cured product .

As the cationic curing catalyst, particularly preferred is a compound represented by the following formula (17):

(34)

(Wherein R is the same or different and represents a hydrocarbon group which may have a substituent, x represents an integer of 1 to 5, which is the same or different and represents the number of fluorine atoms bonded to the aromatic ring. B is an integer of 0 or more and satisfies a + b = 3), and a Lewis base.

When the cationic curing catalyst or the radical curing catalyst is added, the addition amount thereof is preferably 0.01 to 25 parts by mass based on 100 parts by mass of the curable resin, as an effective component amount (in terms of solid content) containing no solvent or the like. When a cationic curing catalyst comprising a Lewis acid represented by the formula (17) and a Lewis base is added, the total amount of the Lewis acid and the Lewis base is added.

In the curing method using the cationic curing catalyst, the cured product obtained is superior in properties required for optical applications such as heat resistance, chemical stability, moisture resistance, etc., as compared with the addition curing method such as acid anhydride curing . Further, as compared with the case of using a conventional cationic curing catalyst such as an antimony-based sulfonium salt, the coloring of the resin composition due to the influence of heat at the time of curing, film formation and product use is reduced, A cured product having excellent durability such as impact resistance can be obtained.

The curing method of the resin composition is not particularly limited and various methods such as heat curing and photo curing (curing by irradiation with active energy ray) can be preferably used. As the thermosetting, it is preferable to cure at about 30 to 400 DEG C, and as the photo-curing, it is preferable to cure at 10 to 10000 mJ / cm < 2 >. The curing temperature is preferably 100 占 폚 or higher, more preferably 130 占 폚 or higher, even more preferably 150 占 폚 or higher, from the viewpoint of raising the curability of the resin. On the other hand, from the viewpoint of suppressing deterioration of the coloring matter, the curing temperature is preferably lower than 300 캜, more preferably lower than 250 캜, still more preferably lower than 230 캜. The curing time is preferably 1 minute or more, more preferably 10 minutes or more, and still more preferably 30 minutes or more, from the viewpoint of raising the curability of the resin. On the other hand, the curing time is preferably less than 10 hours, more preferably less than 5 hours, and still more preferably less than 2 hours from the viewpoint of suppressing deterioration of the coloring matter.

3.2.6. Epoxy resin

Examples of the epoxy resin include, but are not particularly limited to, glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, And the like. These may be used alone, or two or more kinds may be used.

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 resin having an epoxy group added directly or via a hydrocarbon group to the cyclic aliphatic hydrocarbon Based resin. Examples of the epoxy resin to which an epoxy group is added directly or via a hydrocarbon group to an epoxy resin or cyclic aliphatic hydrocarbon having an epoxy cyclohexane skeleton include the following.

(Manufactured by Daicel Chemical Industries, Ltd.), Celllockside 2021P (3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate)

(1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol)

(2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and 3,4-epoxycyclohexenylmethyl-3 , 4'-epoxycyclohexene carboxylate)

Celloxide (registered trademark) 3000 (1,2,8,9-diepoxy limonene) manufactured by Dai-

Manufactured by Dai-ichi Kogyo Seiyaku (registered trademark) 2000 (1,2-epoxy-4-vinylcyclohexane)

Above all, Celloxide (registered trademark) 2021P manufactured by Daicel Chemical Industries, Ltd. and EHPE 3150 manufactured by Daicel Corporation are more preferable.

3.3. menstruum

The resin composition according to the present invention may contain a solvent from the viewpoint of easily carrying out the coating operation.

The solvent that can be used may be appropriately selected depending on the kind of the resin component and the like. In the present invention, a solvent having a dipole moment of 4D (Debye) or less is preferable. When a solvent having a dipole moment of 4D or less is used in combination with the oxocarbon compound, deterioration of physical properties of the oxocarbon compound due to light or heat is sufficiently suppressed and can be stably stored or used. The dipole moment of the solvent is preferably 3.5 D or less, more preferably 3 D or less. Thus, it is particularly preferable that the solvent has a dipole moment of 3 D or less. The lower limit of the dipole moment is not particularly limited and is preferably 0 D or more.

As the solvent having the above-mentioned dipole moment of 4 D or less, for example, the following compounds and the like can be mentioned, and one or more of these solvents can be used.

(Dipole moments: 2.76 D), methyl isobutyl ketone (also called 4-methyl-2-pentanone) (dipole moment: 2.56 D), cyclopentanone (dipole moment: 3.3 D), and cyclohexanone (dipole moment: 3.01 D);

(Dipole moment of 1.8 D), ethylene glycol mono-n-butyl ether (dipole moment of 2.08 D), ethylene glycol monoethyl ether (ethylene glycol monoethyl ether) Ether (dipole moment: 2.08 D), glycol derivatives such as ethylene glycol ethyl ether acetate (for example, ether compounds, ester compounds, ether ester compounds and the like);

Ethers such as tetrahydrofuran (dipole moment 1.70 D), dioxane (dipole moment 3.0 D), diethyl ether (dipole moment 1.12 D) and dibutyl ether (dipole moment 1.22 D);

Esters such as ethyl acetate, propyl acetate and butyl acetate;

Methylcellosolve (also referred to as 2-methoxyethanol) (dipole moment: 2.1 D);

N, N-dimethylacetamide (dipole moment: 3.72 D);

Pyrrolidone such as N-methyl-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone (dipole moment: 4.08 D));

Aromatic hydrocarbons such as toluene (dipole moment: 0.37 D) and xylene (dipole moment: 1 D or less);

Aliphatic hydrocarbons such as cyclohexane, ethylcyclohexane (dipole moment 0D), heptane (dipole moment 0.0D) and limonene (dipole moment 1D or less);

Chlorobenzene, and o-dichlorobenzene (dipole moment: 2.27 D);

Of these, ketones (referred to as cyclic ketones) having a cyclic structure, ethers (also referred to as cyclic ethers) having a cyclic structure, alcohols having a cyclic structure (also referred to as chain alcohols) Acetates (also referred to as chain type acetates) having a chain structure, aromatic hydrocarbons, and aliphatic hydrocarbons are preferred. Thus, the solvent is at least one selected from the group consisting of cyclic ketones, cyclic ethers, chained alcohols, chain acetates, aromatic hydrocarbons and aliphatic hydrocarbons, which is also one of the preferred embodiments of the present invention.

The solvent having a dipole moment of 4 D or less preferably has a boiling point of 90 캜 or higher. For example, when the composition further contains a resin, it is possible to sufficiently inhibit volatilization at the time of coating or the like and to suppress occurrence of unevenness or the like by containing at least the solvent having the boiling point. The boiling point is more preferably 100 DEG C or more, still more preferably 110 DEG C or more, particularly preferably 120 DEG C or more, and most preferably 130 DEG C or more. The upper limit is not particularly limited, but is preferably 250 DEG C or lower, for example.

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

The other solvent is not particularly limited, but the water content in 100 mass% of the total solvent used in the present invention is preferably 3 mass% or less.

The content of the solvent in the composition is not particularly limited. For example, when the composition contains a solvent, the total amount of the solvent (the solvent having a dipole moment of 4 D or less And the other solvent) is preferably 10 to 4000 parts by mass.

More preferably 300 to 3,000 parts by mass, and still more preferably 500 to 2,000 parts by mass. When the composition contains no resin, the total amount of the solvent is preferably 1 to 10000 parts by mass based on 1 part by mass of the total amount of the oxocarbon compound. More preferably from 10 to 8,000 parts by mass, and still more preferably from 100 to 5,000 parts by mass.

Particularly, when amides are used alone or in combination with other solvents as solvents, there is a fear that the amides may decompose the oxocarbon-based compounds. Therefore, the amount of amides to be used is preferably small, . Specifically, the amount of the amide to be used is preferably 60 mass% or less, more preferably 40 mass% or less, further preferably 20 mass% or less, in 100 mass% of the resin composition (total amount containing the solvent) By mass, particularly preferably not more than 5% by mass, and most preferably 0% by mass (i.e., does not contain amides).

3.4. Various additives

The resin composition according to the present invention may contain an ultraviolet absorber, a plasticizer, a surfactant, a dispersant, a surface tension adjuster, a viscosity adjuster, a defoaming agent, an antiseptic agent, a resistivity adjuster, And the like.

4. Molded body, surface molded body

The resin composition is useful for producing a molded article, a coating of a molded part, a resin film, or a surface molded article. The molded article is obtained by molding the resin composition of the present invention into a predetermined shape by a known method such as injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or solvent casting. In the present invention, in particular, those molded in the form of a film or a plate are sometimes referred to as " surface-formed bodies ". The above "surface-formed article" also includes a film-shaped molded article of the resin composition of the present invention formed on a support and a support integrated with each other (sometimes referred to as a "laminated sheet").

There is no particular limitation on the shape of the molded article or the formed article in accordance with the present invention, but examples thereof include a film having a thickness of less than 200 탆 and a plate having a thickness of 200 탆 or more.

Particularly preferred molded articles are surface-formed articles, more preferably optical filters. The optical filter of the present invention preferably has a resin layer or resin film formed from the resin composition of the present invention. The transmittance of the resin layer or the resin film at the maximum absorption wavelength is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, particularly preferably 5% or less , Still more preferably not more than 2.5%, and most preferably not more than 1%. The optical filter preferably comprises a support and a film-like resin layer formed on one or both sides of the support, and the resin composition of the present invention is used for the resin layer. Such a laminated sheet or filter can be obtained by, for example, a method of forming a resinous resin composition by coating on a support by a spin coating method or a solvent casting method and drying or curing the resin, or a method of forming a resin A film can be formed by thermocompression bonding, a kneading method, or the like. The thickness of the resin layer formed by the resin composition is not particularly limited. For example, it is preferably 0.5 占 퐉 or more and 15 占 퐉 or less, more preferably 1 占 퐉 or more and 10 占 퐉 or less, further preferably 1 占 퐉 Or more and 5 m or less, and most preferably 1 m or more and 3 m or less. As the support, a resin plate, a film, a glass substrate or the like can be used, but it is preferably a glass substrate or a film, more preferably a film. The film for a support is preferably formed of, for example, the resin described above as a preferable resin component.

As another form of the above, a single-layer resin film (surface-formed article) formed from the resin composition of the present invention is also a preferable form. The film thickness of the single-layer resin film (surface-formed article) formed by the resin composition is not particularly limited, but is preferably 30 占 퐉 or more and 200 占 퐉 or less, more preferably 50 占 퐉 or more and 150 占 퐉 or less.

Such a laminated sheet, a filter, and a single-layer resin film can be preferably used for various applications such as opto-device use, display device use, machine parts, electric / electronic parts, and the like.

5. Characteristics in absorption spectrum

INDUSTRIAL APPLICABILITY The oxocarbon-based compound of the present invention and the resin composition of the present invention containing the same and the molded product thereof are free of (or significantly reduced) shoulder peaks in the absorption spectrum of the visible and near infrared regions, And more selectively absorbs light.

The oxocarbon-based compound of the present invention and the resin composition of the present invention containing the same and the molded product thereof are characterized in that when the absorbance is 0.1 in the chart corrected for the absorption spectrum in the visible and near infrared region so as to have an absorption maximum of 1.000 a wavelength (λ _0.1) wavelength (λ _0.5) peak area (Fig. S ₁ of 2) up to the time the absorption is to be 0.5 from a S _1, and the absorbance from the wavelength (λ _0.5) at which the absorbance is 0.5 when a is 1, the peak area to the wavelength (λ ₁₎ of the time a (Fig. 2 in S ₂₎ in S _2, the following formula: and preferably at least X = S ₂ / S ratio X is 128 indicated by _1, More preferably 130 or more. Normally, the shoulder peak is seen in the absorption region (area S ₁ ) from the rise of the peak to the absorbance of 0.5, and the smaller the area (area S ₁ ) of the absorption region (in other words, The larger the area ratio X is), and the shoulder peak is reduced, which is advantageous for more selectively absorbing light in the absorption maximum region.

The maximum absorption wavelength (? Max) of the oxocarbon compound in the present invention is preferably 550 to 1000 nm (more preferably 600 to 900 nm) in the case of the squarylium compound, and in the case of the chromium compound , Preferably 700 to 1200 nm (more preferably 750 to 1100 nm).

The optical filter of the present invention has a maximum absorption wavelength (λmax) within a range of 550 to 1200 nm and has excellent absorption characteristics of red light because the resin layer contains a specific oxocarbon compound. In particular, when a squarylium compound is contained as the oxocarbon compound, it is preferably 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 the compound has a maximum absorption wavelength and contains a chromium compound as the oxocarbon compound, it preferably has a maximum absorption wavelength in the range of 700 to 1200 nm, more preferably 750 to 1100 nm. Since the optical filter contains a specific oxocarbon compound, the optical filter has a high light absorption characteristic at the maximum absorption wavelength and a high average transmittance of light at 400 to 450 nm. have. In order to exhibit sufficient performance as an optical filter, the spectroscopic light transmittance at the maximum absorption wavelength of the optical filter is preferably 20% or less, more preferably 15% or less, further preferably 10% , Preferably not more than 5%, even more preferably not more than 2.5%, and most preferably not more than 1%. In the optical filter exhibiting such a spectral light transmittance at the maximum absorption wavelength, the average transmittance of the spectral light at a wavelength of 400 to 450 nm is preferably 81% or more (preferably 82% or more, more preferably, Is 83% or more). When the filter of the present invention as described above is used, the average transmittance of 400 to 450 nm is increased, while the absorption rate of light of a red wavelength is increased, so that it has high selective permeability. On the other hand, if the average transmittance of the spectral light at a wavelength of 400 to 450 nm is less than 81%, the transmission of blue light is insufficient and the color tone of the light transmitted through the filter may change. Further, since the optical filter of the present invention can reduce the angle dependence of the transmitted light and the reflected light, it is possible to obtain a near-infrared ray cut filter suitable for use in visibility correction with little change in brightness or color tone. A method of obtaining the average transmittance and the maximum absorption wavelength of light at 400 to 500 nm will be described later.

It is preferable that the filter of the present invention has no (or substantially reduced) shoulder peaks in the absorption spectrum of the visible / near infrared region. Whereby the light in the absorption maximum region can be more selectively absorbed.

6. Other

An example of the filter of the present invention includes a support and a resin layer formed on one side or both sides of the support, but a base layer may be formed between the support and the resin layer. The base layer may be provided only on one side of the support or on both sides. The base layer may be either a single-layer structure or a multi-layer structure.

The base layer is preferably formed of a composition containing a silane coupling agent. By incorporating such a silane coupling agent in the composition for the underlayer, it has the effect of improving the adhesion with the support and the effect of suppressing the penetration of water into the underlayer due to the water repellency. As a result, A filter can be obtained. Specifically, peeling and the like can be suppressed in the solder reflow process and the use in a humid environment. The silane coupling agent may be used alone or in combination of two or more.

The method for preparing the composition for a foundation layer is not particularly limited and can be obtained by adding a liquid medium and a catalyst to a silane coupling agent and mixing them by a conventional method. The liquid medium may be water, alcohol or the like, and one or more liquid media may be used. The catalyst may be either an organic acid or an inorganic acid.

As a method for forming the base layer, a known method can be used, but it is preferable to form the base layer by applying the base layer composition (undercoat solution) on a support and heating and drying.

In the case where the support is a glass substrate, from the viewpoint of improving the adhesion, the base layer is preferably formed of a composition for ground layer containing a silane coupling agent having an amino group, an epoxy group or a mercapto group. It is preferably a silane coupling agent having a primary amino group when it is formed from a composition containing a silane coupling agent having an amino group. When the composition for ground layer containing a silane coupling agent having a primary amino group is used, adhesiveness to a glass substrate is much better than that in the case of containing a silane coupling agent having an amino group other than the primary amino group. The liquid medium is preferably at least one selected from water, ethanol, and isopropyl alcohol. By adding a liquid medium, an alkoxy group is hydrolyzed in an amino group, an epoxy group, or a mercapto group-containing silane coupling agent to produce a silanol group, and this silanol group is bonded to a glass substrate To the surface. Then, after the dehydration condensation reaction of the silanol groups, a strong covalent bond is formed on the surface of the glass substrate, whereby the adhesion between the glass substrate and the ground layer is improved. The catalyst may be any one that acts as a catalyst in the hydrolysis reaction of an amino group, an epoxy group or a mercapto group-containing silane coupling agent, and may be any of an organic acid and an inorganic acid, but it is preferable to use formic acid.

The silane coupling agent may be added to the composition for the resin layer instead of the composition for the base layer to improve the adhesiveness of the filter. In this case, the resin layer is preferably formed from a composition for a resin layer to which a silane coupling agent having an amino group, an epoxy group, or a mercapto group is added from the viewpoint of improvement in adhesion. When the silane coupling agent is mixed with the oxocarbon compound represented by the above formula (1) or (2), the amino group-containing silane coupling agent reacts with the oxocarbon compound to cause precipitation of the reactant and spectrum of the composition for the resin layer It is preferable to use a mercapto group-containing silane coupling agent. When a mixture of the oxocarbon-based compound and the mercapto group-containing silane coupling agent is used, the mercapto group-containing silane coupling agent is preferable because the transmittance of 400 to 600 nm can be improved.

Since the resin composition of the present invention may cause appearance defects such as stratification or depression after film formation, it is preferable to add additives such as a leveling agent (surface control agent) and a surfactant as necessary. As the additive, a silicon-based additive, an acrylic-based additive, a fluorine-based additive and the like are effective, but from the viewpoints of adhesion of the resin layer and prevention of bleed-out of the additive in the resin layer, a silicone additive or an acrylic additive is preferable. Examples of the additive include BYK (registered trademark) series of Big Chemie which is a surface conditioner, and BYK (registered trademark) 306, 330, 337, 354, 355, 378 and 392 are preferable. The amount of the additive is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the resin. If the amount of the additive to be added is excessive, turbidity may occur in the resin layer after application, and if the amount of the additive to be added is too small, defects in appearance can not be sufficiently solved.

The optical filter of the present invention may further comprise a resin layer or a resin film formed by using the resin composition of the present invention, a layer having antireflection properties and / or antireflection properties for reducing non-exposure to fluorescent lamps, Layers having other functions may be laminated, or a transparent substrate, a glass substrate, a filter, or the like may be laminated.

The optical filter of the present invention preferably includes an ultraviolet ray reflecting film for reflecting ultraviolet rays and / or a near-infrared ray reflecting film for reflecting near-infrared rays (hereinafter collectively referred to as an "invisible light reflecting film"). Examples of such an invisible light reflective film include an aluminum evaporated film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and containing a small amount of tin oxide are dispersed, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated Etc. may be used. The non-visible light reflective film may be formed on one side of the resin layer or the support, or on both sides. When formed on one side, it is possible to obtain an ultraviolet ray cut filter or a near-infrared ray cut filter which has excellent manufacturing cost and easiness of manufacture and has high strength and is less prone to warping when formed on both sides. Further, when the near-infrared reflection film is laminated, a near-infrared ray cut filter capable of more reliably cutting the near-infrared ray can be obtained.

As the non-visible light reflective film, it is preferable to use a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated. As the 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 usually 1.7 to 2.5 is 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; (ITO), antimony doped tin oxide (ATO)) doped with a metal or carbon such as aluminum or copper, or a mixture of the above oxides or nitrides, have. 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 usually 1.2 to 1.6 is selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, aluminum sodium hexafluoride, and the like.

The optical filter of the present invention preferably includes an antireflection film. As the antireflection film, it is preferable to use a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated. As the 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 usually 1.7 to 2.5 is 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; (ITO), antimony doped tin oxide (ATO)) doped with a metal or carbon such as aluminum or copper, or a mixture of the above oxides or nitrides, have. 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 usually 1.2 to 1.6 is selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, aluminum sodium hexafluoride, and the like.

It is preferable that the invisible light reflecting film and / or the antireflection film is a laminated film in which oxygen is not transmitted (oxygen can be blocked) from the air layer (outside air side) to the resin layer. As described above, since the durability of the oxocarbon compound is improved as the oxygen concentration is lowered, it is preferable to laminate an invisible light reflecting film or an antireflection film having a high oxygen blocking ability. In order to increase the oxygen barrier performance, 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 It is preferable to increase the thickness of the layer), and it is also preferable to use both in combination. As a method for producing a dense film, a well-known technique can be used. For example, the vacuum degree at the time of vapor deposition is set to a high vacuum, the vapor deposition temperature is raised, and the vapor deposition is performed by the ion assist method (IAD) However, a dense film may be produced by a method other than the above. Concretely, the degree of vacuum is preferably not more than 5 × 10 ^-2 Pa, and the deposition temperature is preferably not less than 80 ° C. and not more than 300 ° C. In the deposition by the IAD method, the assist accelerating voltage is preferably 500 V or more and 1200 V or less, and the assist accelerating current is preferably 500 mA or more and 1200 mA or less. When the deposition temperature is too high, the temperature of the resin layer becomes higher than the Tg of the resin used as the resin layer. Therefore, the resin layer may be deteriorated by vapor deposition. If the deposition temperature is too low, Antireflection film) may not become a dense film. In the case of depositing by the IAD method, the evaporation film (the invisible light reflection film and / or the antireflection film) is not a dense film (film having a high filling density) if the assist voltage is too weak or the assist current is the same as the deposition temperature If the assist voltage / assist current is too strong, the resin layer may be deteriorated. It is preferable to produce a dense film having a high oxygen blocking ability by optimizing various conditions and to not deteriorate the resin layer or to reduce deterioration.

By laminating an invisible light reflecting film, an antireflection film or other layer having a high oxygen blocking ability to the optical filter of the present invention, the durability of the oxocarbon compound of the present invention can be remarkably improved, and an optical filter having excellent durability and optical characteristics, A near-infrared cut filter can be obtained. It is also possible to use the optical filter of the present invention or an imaging element including a near-infrared cut filter in which a dielectric multi-layer film is laminated on the optical filter.

An infrared ray cut filter, a near-infrared ray cut filter, a security filter, a heat ray blocking / heat ray absorbing filter, a band-pass filter, a heat ray absorbing filter, or the like by laminating an invisible light reflecting film, , A filter for a surveillance camera (Day & Night), a filter for an obscene camera, a dual band filter, a filter for a visible light image sensor, an infrared sensor, a neon light or a fluorescent light sensor .

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples, and it is of course possible to carry out the present invention by appropriately modifying it within a range that is suitable for the purposes of the former and latter cases All of which are included in the technical scope of the present invention.

In the following description, "%" represents "mass%" and "part" represents "mass part".

(Method of analysis of chemical structure)

Approximately 1 mg of the obtained compound was applied to a glass rod and adhered and ionized by a direct ionization unit (DART) ("DART-OS" manufactured by Shimadzu Corporation, heater temperature: 500 ° C) and analyzed by a mass spectrometer ("LCMS- 2020 ", M / Z = 50-2000, positive and negative simultaneous scanning), MS spectra of the obtained compounds were measured.

(Method of measuring maximum absorption wavelength and transmittance)

Using a spectrophotometer (UV-1800 manufactured by Shimadzu Corporation), the absorption spectrum (transmission spectrum) of the resin layer laminate substrate was measured at a measurement pitch of 1 nm to obtain the transmittance of light at a wavelength of 200 to 1100 nm. The wavelength at which the absorption maximum was obtained at a wavelength of 650 to 750 nm was defined as the maximum absorption wavelength. The average value of the 51 transmittances measured at a measurement pitch of 1 nm at a wavelength of 400 to 450 nm was regarded as an average transmittance of 400 to 450 nm.

(PCT (Pressure Cooker Test) test)

(Resin layer laminated substrate) was cut with a cutter (A-300, manufactured by Enuti Co., Ltd.) into the resin layer formed on the sealing material, and ten cross cut lines were formed at intervals of 2 mm each in a row and a row, ² squares were formed on a scale of 81 to prepare a sample substrate for evaluation. Next, the sample substrate for evaluation was immersed in a high-pressure high-temperature high-humidity tank (Personal Pressure Cooker PC-242HS-E (manufactured by Hirayama Seiyaku Co., Ltd., operating mode 1) at 120 ° C and 2 atmospheric pressure and 100% Time. Subsequently, a tape (Scotch (registered trademark) transparent adhesive tape transparent off-color (registered trademark) manufactured by 3M (Sri Lanka)) was stuck at room temperature for 10 seconds to prevent air from entering. Thereafter, peeling of the tape from the substrate was carried out within one second, and evaluation was made based on the following criteria. Further, the peeling of the tape was carried out so that the peeling force became constant even at any scale.

○: Among the squares of the 81 scales produced, there was no scaling even at 1 scale.

?: Peeling occurred in the 1 to 9 scale among the square of the 81 scale produced.

X: Peeling occurred in 10 to 81 scale out of the square of 81 scale produced.

Structural formulas of comparative squarylium compounds 3 and 4 used in the examples are shown below. As the comparative squarylium compound 3, the squarylium compound disclosed in the formula 17 of the specification of U.S. Patent No. 5,543,086 was used.

Further, the comparative squarylium compounds 3 and 4 were analyzed by the above-mentioned method, and it was confirmed that they had the structures shown below.

(35)

(Example 1-1)

The squarylium compound 01 was synthesized on the basis of the following schematic diagram. The details are as follows.

(36)

1) Synthesis of intermediate material 01 (4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

A raw material composition comprising 14.46 g (0.100 mol) of phenylhydrazine hydrochloride and 11.22 g (0.100 mol) of 2-methylcyclohexanone and 130 g of acetic acid as a solvent was added to a 300 ml four-necked flask, Ml / min) and reacted for 2 hours under reflux using a magnetic stirrer while stirring. After the completion of the reaction, the reaction solution, 200 ml of ethyl acetate and 300 ml of water were added to the separating funnel and vigorously stirred to extract only the organic phase. The extracted organic phase was dehydrated by adding magnesium sulfate (anhydrous). The solid matter (inorganic matter) was separated from the organic phase by filtration, and then the solvent was distilled off using an evaporator. After distilling off the solvent, the residue was dried at 60 ° C for 12 hours using a vacuum drier to obtain 12.50 g of an intermediate raw material 01 (4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) (phenylhydrazine hydrochloride Yield: 67.5 mol%).

2) Synthesis of squarylium compound 01

12.50 g (0.068 mol) of the intermediate raw material 01, 3.31 g (0.029 mmol) of squaric acid, 130 g of 1-butanol and 130 g of toluene obtained above were added to a 500 ml four-necked flask, 10 ml / min), the mixture was stirred using a magnetic stirrer, and the mixture was reacted under reflux conditions for 3 hours while removing water eluted with a Dean-Stark apparatus. After completion of the reaction, the solvent was distilled off by an evaporator. Then, 50 g of methanol was added thereto, and crystallization and washing treatment were carried out with stirring for 30 minutes under reflux conditions. The solution was cooled to room temperature and then the cake obtained by filtration was dried at 60 ° C for 12 hours using a vacuum drier to obtain 8.0 g of the objective squarylium compound 01 (yield relative to squaric acid: 62.3 mol%) .

The MS spectrum of the obtained compound was measured by the above-mentioned method. As a result, as shown in Fig. 1, a signal originating from the object was detected in both the positive and negative modes, and it was confirmed that it had the structure shown in Table 1.

(Example 1-2)

1) Synthesis of intermediate material 02 (4a- (sec-butyl) -2,3,4,4a-tetrahydro-1H-carbazole)

Except that 4.34 g (0.03 mol) of phenylhydrazine hydrochloride and 4.63 g (0.03 mol) of 2-sec-butylcyclohexanone were used as the raw material composition in the same manner as in Example 1-1 To obtain 3.57 g of an intermediate material 02 (4a (sec-butyl) -2,3,4,4a-tetrahydro-1H-carbazole) (yield to phenylhydrazine hydrochloride: 52.3 mol%).

2) Synthesis of squarylium compound 02

Except that 0.28 g (0.001 mol) of the intermediate raw material 02 obtained above was used in place of the intermediate raw material 01 and 0.06 g (0.001 mol) of squalic acid was used in place of the intermediate raw material 01, 01), 0.15 g of the objective squarylium compound 02 (yield relative to squaric acid: 46.4 mol%) was obtained.

(Example 1-3)

1) Synthesis of intermediate material 03 (4a-isopropyl-2-methyl-2,3,4,4a-tetrahydro-1H-carbazol-

Except that 0.45 g (0.004 mol) of phenylhydrazine hydrochloride and 0.70 g (0.004 mol) of 5-hydroxy-2-isopropyl-5-methylcyclohexanone were used as the raw material composition. 01) was obtained in the same manner as in the synthesis of Intermediate Material 03 (4a-isopropyl-2-methyl-2,3,4,4a-tetrahydro-1H-carbazol- Yield: 50.9 mol%).

2) Synthesis of squarylium compound 03

Except that 0.43 g (0.002 mol) of the intermediate raw material 03 obtained above was used in place of the intermediate raw material 01 and 0.10 g (0.001 mol) of squalic acid was used in place of the intermediate raw material 01, 01), 0.02 g of the objective squarylium compound 03 (yield relative to squaric acid: 4.0 mol%) was obtained.

(Examples 1-4)

1) Synthesis of intermediate material 04 (4a-isopropyl-2-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

Except that 2.16 g (0.020 mol) of phenylhydrazine hydrochloride and 3.09 g (0.020 mol) of 2-isopropyl-5-methylcyclohexanone were used as the raw material composition in Example 1-1 (synthesis of Intermediate Material 01) According to the same procedure, 4.05 g of the intermediate raw material 04 (4a-isopropyl-2-methyl-2,3,4,4a-tetrahydro-1H-carbazole) (yield to phenylhydrazine hydrochloride: 89.1 mol%) was obtained .

2) Synthesis of squarylium compound 04

Except that 4.05 g (0.018 mol) of the intermediate raw material 04 obtained above was used instead of the intermediate raw material 01 and the amount of squalic acid was changed to 1.03 g (0.009 mol) instead of the intermediate raw material 01, 01), 0.51 g of the objective squarylium compound 04 (yield relative to squaric acid: 10.6 mol%) was obtained.

(Example 1-5)

1) Synthesis of intermediate raw material 05 (2,3,4,4a-tetrahydro-1H-carbazole-4-carboxylate)

Except that 4.34 g (0.03 mol) of phenylhydrazine hydrochloride and 5.11 g (0.03 mol) of ethyl 2-oxocyclohexanecarboxylate were used as the raw material composition in the same manner as in Example 1-1 (synthesis of the intermediate raw material 01) 5.44 g (yield based on phenylhydrazine hydrochloride: 74.5 mol%) of the intermediate raw material 05 (2,3,4,4a-tetrahydro-1H-carbazole-4-carboxylate) was obtained.

2) Synthesis of squarylium compound 05

Except that 1.32 g (0.005 mol) of the intermediate raw material 05 obtained above was used in place of the intermediate raw material 01 and 0.27 g (0.002 mol) of squalic acid was used. 01), 0.32 g of the objective squarylium compound 05 (yield relative to squaric acid: 21.3 mol%) was obtained.

(Examples 1-6)

1) Synthesis of intermediate material 06 (4a-phenyl-2,3,4,4a-tetrahydro-1H-carbazole)

By the same procedure as in Example 1-1 (synthesis of the intermediate raw material 01), except that 4.09 g (0.028 mol) of phenylhydrazine hydrochloride and 4.93 g (0.028 mol) of 2-phenylcyclohexanone were used as the raw material composition, 5.71 g of intermediate material 06 (4a-phenyl-2,3,4,4a-tetrahydro-1H-carbazole) (yield to phenylhydrazine hydrochloride: 81.5 mol%) was obtained.

2) Synthesis of squarylium compound 06

Except that 3.46 g (0.014 mol) of the intermediate raw material 06 obtained above was used in place of the intermediate raw material 01 and 0.80 g (0.007 mol) of squalic acid was used as the intermediate raw material 06 in Example 1-1 (squarylium compound 01), 1.12 g of the objective squarylium compound 06 (yield based on squaric acid: 28.0 mol%) was obtained.

(Example 1-7)

1) Synthesis of intermediate material 07 (6,8-difluoro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

Except that 3.97 g (0.022 mol) of 2,4-difluorophenylhydrazine hydrochloride and 4.94 g (0.044 mol) of 2-methylcyclohexanone were used as the raw material composition in Example 1-1 (Synthesis of Intermediate Material 01 ), An intermediate material 07 (6,8-difluoro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) was reacted with 4.63 g (2,4-difluoro Phenylhydrazine hydrochloride: 95.1 mol%).

2) Synthesis of squarylium compound 07

Except that 4.43 g (0.020 mol) of the intermediate raw material 07 obtained above was used in place of the intermediate raw material 01 and 1.14 g (0.010 mol) of squalic acid was used. 01), 0.80 g of the objective squarylium compound 07 (yield relative to squaric acid: 15.6 mol%) was obtained.

(Examples 1-8)

1) Synthesis of intermediate material 08 (6,8-dichloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

Except that 1.71 g (0.008 mol) of 2,4-dichlorophenylhydrazine hydrochloride and 1.08 g (0.01 mol) of 2-methylcyclohexanone were used as a raw material composition in Example 1-1 (synthesis of Intermediate Material 01) According to the same procedure, 2.07 g of intermediate material 08 (6,8-dichloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) was reacted with 2,4,7- : 89.7 mol%).

2) Synthesis of squarylium compound 08

Except that 1.91 g (0.008 mol) of the intermediate raw material 08 obtained above was used in place of the intermediate raw material 01 and 0.43 g (0.004 mol) of squalic acid was used. 01), 0.80 g of the objective squarylium compound 08 (yield of 32.6 mol% based on squaric acid) was obtained.

(Examples 1-9)

1) Synthesis of intermediate material 09 (5,7-dichloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

Except that 1.93 g (0.009 mol) of 3,5-dichlorophenylhydrazine hydrochloride and 1.22 g (0.011 mol) of 2-methylcyclohexanone were used as a raw material composition, and in Example 1-1 (synthesis of Intermediate Material 01) By the same procedure, the intermediate material 09 (5,7-dichloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) was reacted with 2.09 g (yield for 3,5-dichlorophenylhydrazine hydrochloride : 91.0 mol%).

2) Synthesis of squarylium compound 09

Except that 1.27 g (0.005 mol) of the intermediate raw material 09 obtained above was used in place of the intermediate raw material 01 and 0.29 g (0.003 mol) of squalic acid was used as the intermediate raw material 09, 01), 0.30 g of the objective squarylium compound 09 (yield relative to squaric acid: 19.8 mol%) was obtained.

(Examples 1-10)

1) Synthesis of intermediate raw material 10-1 (2,4,5-trichlorophenylhydrazine hydrochloride)

100 ml of hydrochloric acid was added to a 500 ml four-necked flask, and the internal temperature was cooled to 5 캜 or lower with an ice water bath. Then, 8.64 g (0.044 mol) of 2,4,5-trichloroaniline was added and dissolved so that the internal temperature did not exceed 5 캜. After the exothermic calming, a mixed solution of 3.28 g (0.048 mol) of sodium nitrite and 25 g of distilled water was added dropwise over 1 hour while the internal temperature was maintained at 5 캜 or lower. After completion of the dropwise addition, a mixed solution of 49.64 g (0.220 mol) of tin chloride dihydrate and 50 ml of hydrochloric acid was added dropwise over 1 hour while keeping the internal temperature at 5 ° C or lower. After completion of the reaction, the resulting cake was separated by filtration and dried in a vacuum drier at 60 ° C for 12 hours to obtain 8.50 g (2,4,5-trichlorophenylhydrazine hydrochloride) of the intermediate raw material 10-1 - < / RTI > trichloroaniline: 78.0 mol%).

2) Synthesis of intermediate material 10-2 (5,6,8-trichloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

Except that 3.69 g (0.015 mol) of the intermediate raw material 10-1 (2,4,5-trichlorophenylhydrazine hydrochloride) obtained above and 3.34 g (0.030 mol) of 2-methylcyclohexanone were used as the raw material composition. Example 1-1 (Synthesis of Intermediate Material 01) By the same procedure as in Intermediate Material 10-2 (5,6,8-trichloro-4a-methyl-2,3,4,4a-tetrahydro- Carbazole) (4.09 g, yield based on 2,4,5-trichlorophenylhydrazine hydrochloride: 95.1 mol%).

3) Synthesis of squarylium compound 10

Except that 4.33 g (0.015 mol) of the intermediate raw material 10-2 obtained above was used in place of the intermediate raw material 01 and 0.86 g (0.008 mol) of squalic acid was used. (Synthesis of Compound 01) By the same procedure as in the above, 1.30 g of the objective squarylium compound 10 (yield relative to squaric acid: 26.3 mol%) was obtained.

(Example 1-11)

1) Synthesis of intermediate material 11-1 (2,4-dibromophenylhydrazine hydrochloride)

Was obtained in the same manner as in Example 1-10 (synthesis of intermediate raw material 10-1), except that 2,4-dibromoaniline was used in place of 2,4,5-trichloroaniline. 1 (2,4-dibromophenylhydrazine hydrochloride) was obtained in an amount of 10.20 g (yield based on 2,4-dibromoaniline: 84.3 mol%).

2) Synthesis of intermediate material 11-2 (6,8-dibromo-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

Except that 12.10 g (0.040 mol) of the intermediate raw material 11-1 (2,4-dibromophenylhydrazine hydrochloride) obtained above and 6.73 g (0.060 mol) of 2-methylcyclohexanone were used as the raw material composition According to the same procedure as in Example 1-1 (synthesis of intermediate raw material 01), an intermediate material 11-2 (6,8-dibromo-4a-methyl-2,3,4,4a-tetrahydro-1H- ) Was obtained in an amount of 10.81 g (yield 78.8 mol% based on 2,4-dibromophenylhydrazine hydrochloride).

3) Synthesis of squarylium compound 11

Except that 10.63 g (0.031 mol) of the intermediate raw material 11-2 obtained above was used in place of the intermediate raw material 01 and 1.77 g (0.016 mol) of squalic acid was used as the intermediate raw material 11-2. (Yield of squaric acid: 31.2 mol%) was obtained in the same manner as in the synthesis of squarylium compound 11 as a starting material.

(Example 1-12)

1) Synthesis of intermediate raw material 12-1 (4-methylthiophenylhydrazine hydrochloride)

Was obtained in the same manner as in Example 1-10 (synthesis of intermediate raw material 10-1) except that 4-methylthioaniline was used in place of 2,4,5-trichloroaniline. -Methylthiophenylhydrazine hydrochloride) was obtained in an amount of 5.50 g (yield relative to 4-methylthioaniline: 65.7 mol%).

2) Synthesis of intermediate material 12-2 (4a-methyl-6- (methylthio) -2,3,4,4a-tetrahydro-1H-carbazole)

Except that 2.86 g (0.015 mol) of the intermediate raw material 12-1 (4-methylthiophenylhydrazine hydrochloride) obtained above and 1.68 g (0.015 mol) of 2-methylcyclohexanone were used as the raw material composition. (4a-methyl-6- (methylthio) -2,3,4,4a-tetrahydro-1H-carbazole) was obtained as a white solid from intermediate material 12-2 (Yield based on 4-methylthiophenylhydrazine hydrochloride: 72.6 mol%).

3) Synthesis of squarylium compound 12

Except that 2.31 g (0.010 mol) of the intermediate raw material 12-2 obtained above was used in place of the intermediate raw material 01 and the amount of squalic acid was changed to 0.57 g (0.005 mol). (Synthesis of Compound 01) 0.50 g of the objective squarylium compound 12 (yield relative to squaric acid: 17.4 mol%) was obtained in the same manner as in the above.

(Example 1-13)

1) Synthesis of intermediate material 13 (4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole-8-carboxylic acid)

The same procedure as in Example 1-1 (synthesis of the intermediate raw material 01) was carried out except that 4.53 g (0.024 mol) of 2-carboxyphenylhydrazine hydrochloride and 2.69 g (0.024 mol) of 2-methylcyclohexanone were used as a raw material composition (Yield: 89.6 mol% based on 2-carboxyphenylhydrazine hydrochloride) of the intermediate raw material 13 (4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole- ).

2) Synthesis of squarylium compound 13

Except that 3.44 g (0.015 mol) of the intermediate raw material 13 obtained above was used in place of the intermediate raw material 01 and 0.86 g (0.008 mol) of squalic acid was used. 01), 2.40 g (yield relative to squaric acid: 58.6 mol%) of the objective squarylium compound 13 was obtained.

(Example 1-14)

1) Synthesis of intermediate material 14 (4a-methyl-6-nitro-2,3,4,4a-tetrahydro-1H-carbazole)

As a raw material composition, 4.45 g (0.023 mol) of 4-nitrophenylhydrazine hydrochloride and 5.16 g (0.046 mol) of 2-methylcyclohexanone were used, and a mixed solution of acetic acid and hydrochloric acid (4-methyl-6-nitro-2,3,4,4a-tetrahydro-naphthalen-2-ylmethyl) -thiophene was obtained in the same manner as in Example 1-1 (synthesis of intermediate raw material 01) 1H-carbazole) (5.05 g, yield based on 4-nitrophenylhydrazine hydrochloride: 95.4 mol%).

2) Synthesis of squarylium compound 14

Except that 4.00 g (0.017 mol) of the intermediate raw material 14 obtained above was used in place of the intermediate raw material 01 and 0.99 g (0.009 mol) of squalic acid was used in place of the intermediate raw material 01, 01), 3.10 g of the objective squarylium compound 14 (yield relative to squaric acid: 65.5 mol%) was obtained.

(Examples 1-15)

1) Synthesis of Intermediate Material 15 (6b-methyl-7,8,9,10-tetrahydro-6bH-benzo [a] carbazole)

As a raw material composition, there were used 2.00 g (0.01 mol) of 1-naphthylhydrazine hydrochloride and 2.31 g (0.021 mol) of 2-methylcyclohexanone as a solvent, and a mixed solution of acetic acid and hydrochloric acid (6b-methyl-7,8,9,10-tetrahydro-6bH-benzo [l, 5] naphthyridin- a] carbazole) was obtained in an amount of 1.50 g (yield based on 1-naphthylhydrazine hydrochloride: 62.0 mol%).

2) Synthesis of squarylium compound 15

Except that 1.41 g (0.006 mol) of the intermediate raw material 15 obtained above was used in place of the intermediate raw material 01 and 0.34 g (0.003 mol) of squalic acid was used. 01), 0.40 g of the objective squarylium compound 15 (yield based on squaric acid: 23.1 mol%) was obtained.

(Example 1-16)

1) Synthesis of Intermediate Material 16 (8b-cyclopentyl-1,2,3,8b-tetrahydrocyclopenta [b] indole)

Except that 4.34 g (0.030 mol) of phenylhydrazine hydrochloride and 4.57 g (0.030 mol) of 2-cyclopentylcyclopentanone were used as the raw material composition in the same manner as in Example 1-1 (synthesis of the intermediate raw material 01) , And 1.57 g (yield to phenylhydrazine hydrochloride: 23.2 mol%) of the intermediate raw material 16 (8b-cyclopentyl-1,2,3,8b-tetrahydrocyclopenta [b] indole).

2) Synthesis of squarylium compound 16

Except that 0.94 g (0.004 mol) of the intermediate raw material 16 obtained above was used in place of the intermediate raw material 01 and 0.24 g (0.002 mol) of squalic acid was used. 01), 0.495 g (yield relative to squaric acid: 22.5 mol%) of the objective squarylium compound 16 was obtained.

(Examples 1-17)

1) Synthesis of intermediate raw material 17-1 (2-methylcycloheptanone)

In a 300 ml four-necked flask, 7.21 g (0.120 mol) of potassium hydroxide and 150 cc of dimethyl sulfoxide were added, and the mixture was stirred at room temperature for 30 minutes. Subsequently, a mixed solution of 5.68 g (0.040 mol) of iodomethane and 4.49 g (0.040 mol) of cycloheptanone was added dropwise, and the mixture was heated to an internal temperature of 40 ° C and reacted with stirring for 2 hours. After the completion of the reaction, the reaction solution, 200 ml of ethyl acetate and 300 ml of water were added to the separating funnel and vigorously stirred. Only the organic phase was extracted, and the extracted organic phase was dehydrated by adding magnesium sulfate (anhydrous). The solid component (inorganic component) was separated from the organic phase by filtration, and then the solvent was distilled off using an evaporator. After the solvent was distilled off, the residue was dried at 40 DEG C for 12 hours using a vacuum drier to obtain 2.85 g of an intermediate raw material 17-1 (2-methylcycloheptanone) (yield to cycloheptanone: 56.5 mol%).

2) Synthesis of intermediate material 17-2 (10a-methyl-6,7,8,9,10,10a-hexahydrocyclohepta [b] indole)

Except that 2.54 g (0.024 mol) of phenylhydrazine hydrochloride and 2.97 g (0.024 mol) of the intermediate material 17-1 (2-methylcycloheptanone) obtained above were used as the raw material composition in Example 1-1 01) was obtained in the same manner as in the synthesis of the intermediate raw material 17-2 (10a-methyl-6,7,8,9,10,10a-hexahydrocyclohepta [b] indole) Yield: 87.6 mol%).

3) Synthesis of squarylium compound 17

Except that 2.09 g (0.011 mol) of the intermediate raw material 17-2 obtained above was used in place of the intermediate raw material 01 and the amount of squalic acid was changed to 0.60 g (0.005 mol). The reaction solution was concentrated in an evaporator, and the resulting solid was purified by column chromatography. The purified product was recrystallized in methanol to obtain the target compound, squaryl 0.04 g (yield based on squalic acid: 1.5 mol%) of Compound 17 was obtained.

(Example 1-18)

1) Synthesis of intermediate raw material 18-1 (2-methylcyclooctanone)

Was obtained in the same manner as in Example 1-17 (synthesis of intermediate raw material 17-1) except that 5.55 g (0.044 mol) of cyclooctanone was used in place of cycloheptanone, Cyclohexanone) was obtained in an amount of 5.75 g (yield based on cyclooctanone: 92.7 mol%).

2) Synthesis of intermediate material 18-2 (11a-methyl-7,8,9,10,11,11a-hexahydro-6H-cycloocta [b] indole)

Except that 4.30 g (0.040 mol) of phenylhydrazine hydrochloride and 5.58 g (0.040 mol) of the intermediate raw material 18-1 (2-methylcyclooctanone) obtained above were used as the raw material composition in Example 1-1 (11a-methyl-7,8,9,10,11,11a-hexahydro-6H-cycloocta [b] indole) was dissolved in 7.00 g (phenylhydrazine Yield to hydrochloride: 82.5 mol%).

3) Synthesis of squarylium compound 18

Except that 3.52 g (0.017 mol) of the intermediate raw material 18-2 obtained above was used instead of the intermediate raw material 17-2 and 0.94 g (0.008 mol) of squalic acid was used. Synthesis of squarylium compound 17) 0.04 g (yield relative to squaric acid: 0.9 mol%) of the objective squarylium compound 18 was obtained by the same procedure as in the above.

(Comparative Example 1-1: Synthesis of Comparative Squarylium Compound 1)

Except that 6.98 g (0.044 mol) of 2,3,3-trimethyl-3H-indole was used in place of the intermediate raw material 01 and 2.5 g (0.022 mol) of squalic acid was used. (Synthesis of squarylium compound 01), 7.63 g (yield relative to squaric acid: 87.8 mol%) of the comparative squarylium compound 1 as the target product was obtained.

(Comparative Example 1-2: synthesis of comparative squarylium compound 2)

Except that 2.43 g (0.014 mol) of 2-ethyl-3,3-dimethyl-3H-indole was used in place of the intermediate raw material 01 and 0.80 g (0.007 mol) of squalic acid was used. -1 (synthesis of squarylium compound 01), 2.30 g of the objective squarylium compound 2 (yield relative to squaric acid: 76.1 mol%) was obtained.

(Example 1-19)

1) Synthesis of Intermediate Material 19 (6-Chloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

The same procedure as in Example 1-1 (synthesis of Intermediate Material 01) was carried out except that 5.37 g (0.030 mol) of 4-chlorophenylhydrazine hydrochloride and 3.37 g (0.030 mol) of 2-methylcyclohexanone were used as a raw material composition To obtain 4.73 g (yield based on 4-chlorophenylhydrazine hydrochloride: 71.8 mol%) of the intermediate material 19 (6-chloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) .

2) Synthesis of squarylium compound 19

Except that 4.61 g (0.021 mol) of the intermediate raw material 19 obtained above was used in place of the intermediate raw material 01 and 1.20 g (0.011 mol) of squalic acid was used as the intermediate raw material 19. 01), 2.1 g (the yield relative to squaric acid: 39.4 mol%) of the objective squarylium compound 19 was obtained.

(Example 1-20)

1) Synthesis of intermediate material 20 (4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole-6-carboxylic acid)

The same procedure as in Example 1-1 (synthesis of intermediate raw material 01) was carried out except that 5.97 g (0.031 mol) of 4-carboxyphenylhydrazine hydrochloride and 3.48 g (0.031 mol) of 2-methylcyclohexanone were used as a raw material composition 7.06 g (yield based on 4-carboxyphenylhydrazine hydrochloride: 99.3 mol%) of the intermediate raw material 20 (4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole- ).

2) Synthesis of squarylium compound 20

Except that 3.44 g (0.015 mol) of the intermediate raw material 20 obtained above was used in place of the intermediate raw material 01 and 0.86 g (0.008 mol) of squalic acid was used. 01), 2.0 g of the objective squarylium compound 20 (yield relative to squaric acid: 49.7 mol%) was obtained.

(Example 1-21)

1) Synthesis of Intermediate Material 21 (4a, 6-dimethyl-2,3,4,4a-tetrahydro-1H-carbazole)

Except that 4.53 g (0.028 mol) of 4-methylphenylhydrazine hydrochloride and 3.14 g (0.028 mol) of 2-methylcyclohexanone were used as a raw material composition in the same manner as in Example 1-1 (synthesis of Intermediate Material 01) (Yield: 57.3 mol% based on 4-methylphenylhydrazine hydrochloride) of Intermediate Material 21 (4a, 6-dimethyl-2,3,4,4a- tetrahydro-1H-carbazole).

2) Synthesis of squarylium compound 21

Except that 2.85 g (0.010 mol) of the intermediate raw material 21 obtained above was used in place of the intermediate raw material 01 and the amount of squalic acid was changed to 0.57 g (0.005 mol). 01), 1.1 g of the objective squarylium compound 21 (yield relative to squaric acid: 46.2 mol%) was obtained.

(Example 1-22)

1) Synthesis of intermediate material 22 (6-bromo-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

Was the same as that of Example 1-1 (synthesis of the intermediate raw material 01), except that 5.25 g (0.023 mol) of 4-bromophenylhydrazine hydrochloride and 2.58 g (0.023 mol) of 2-methylcyclohexanone were used as a raw material composition 5.68 g (yield based on 4-bromophenylhydrazine hydrochloride: 93.5 mol) of the intermediate raw material 22 (6-bromo-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) %).

2) Synthesis of squarylium compound 22

Except that 5.66 g (0.015 mol) of the intermediate raw material 22 obtained above was used in place of the intermediate raw material 01 and 0.86 g (0.008 mol) of squalic acid was used. 01), 2.7 g of the objective squarylium compound 22 (yield relative to squaric acid: 60.0 mol%) was obtained.

(Example 1-23)

1) Synthesis of intermediate raw material 23-1 (4-trifluoromethylphenylhydrazine hydrochloride)

By the same procedure as in Example 1-10 (synthesis of intermediate raw material 10-1), except that 4-trifluoromethylaniline was used in place of 2,4,5-trichloroaniline, the intermediate raw material 23-1 (4-trifluoromethylphenylhydrazine hydrochloride) was obtained in an amount of 8.0 g (yield based on 4-trifluoromethylaniline: 62.4 mol%).

2) Synthesis of intermediate material 23-2 (6-Trifluoromethyl-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

The procedure of Example 1 was repeated except that 3.47 g (0.016 mol) of the intermediate raw material 23-1 (4-trifluoromethylphenylhydrazine hydrochloride) obtained above and 1.79 g (0.016 mol) of 2-methylcyclohexanone were used as the raw material composition. -14 (Synthesis of Intermediate Material 14) The intermediate material 23-2 (6-trifluoromethyl-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) g (yield based on 4-trifluoromethylphenylhydrazine hydrochloride: 98.7 mol%).

3) Synthesis of squarylium compound 23

Except that 4.00 g (0.016 mol) of the intermediate raw material 23-2 obtained above was used in place of the intermediate raw material 01 and 0.90 g (0.008 mol) of squalic acid was used. (Synthesis of Sodium Compound 01) 0.20 g of the objective squarylium compound 23 (yield relative to squaric acid: 4.5 mol%) was obtained in the same manner as in the above.

(Examples 1-24)

1) Synthesis of intermediate raw material 24-1 (2-phenylphenylhydrazine hydrochloride)

An intermediate raw material 24-1 (2- (2-phenylaniline) was obtained in the same manner as in Example 1-10 (synthesis of intermediate raw material 10-1), except that 2-phenylaniline was used in place of 2,4,5- Phenylphenylhydrazine hydrochloride) (13.0 g, yield based on 2-phenylaniline: 99.2 mol%).

The squarylium compound 24 was synthesized on the basis of the following schematic diagram. The details are as follows.

(37)

A raw material composition composed of 5.08 g (0.023 mol) of the intermediate raw material 24-1 (2-phenylphenylhydrazine hydrochloride) obtained above and 2.58 g (0.023 mol) of 2-methylcyclohexanone, And 58 g of 1-butanol was added thereto. The mixture was reacted for 6 hours at an internal temperature of 80 占 폚 with stirring using a magnetic stirrer under nitrogen flow (5 ml / min). After the completion of the reaction, the solution was cooled to room temperature, and the filtrate obtained by filtration was transferred to a 300 ml four-necked flask. 2.00 g (0.018 mol) of squalic acid and 92 g of toluene were added thereto, (5 ml / min) and stirred using a magnetic stirrer, and the mixture was reacted under reflux conditions for 6 hours while removing water eluted with a Dean-Stark apparatus. After the completion of the reaction, the solution was cooled to room temperature, and then the cake obtained by filtration was sprayed with 50 g of methanol, washed, and washed. The obtained cleansing cake was dried in a vacuum drier at 60 占 폚 for 12 hours to obtain 2.45 g of the objective squarylium compound 24 (yield relative to squaric acid: 23.2 mol%).

(Examples 1-25)

1) Synthesis of intermediate material 25 (6-methoxy-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

Was the same as that of Example 1-1 (synthesis of the intermediate raw material 01) except that 4.99 g (0.028 mol) of 4-methoxyphenylhydrazine hydrochloride and 3.14 g (0.028 mol) of 2-methylcyclohexanone were used as a raw material composition By the procedure, 3.20 g of intermediate material 25 (6-methoxy-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) (yield to 4-methoxyphenylhydrazine hydrochloride: 53.1 mol %).

2) Synthesis of squarylium compound 25

Except that 2.46 g (0.008 mol) of the intermediate raw material 25 obtained above was used in place of the intermediate raw material 01 and 0.46 g (0.004 mol) of squalic acid was used. 01), 0.30 g of the objective squarylium compound 25 (yield relative to squaric acid: 14.7 mol%) was obtained.

(Example 1-26)

1) Synthesis of intermediate material 26-1 (5-hydrazinylquinoline hydrochloride)

The same procedure as in Example 1-10 (synthesis of intermediate raw material 10-1) was repeated except that 5-aminoquinoline was used instead of 2,4,5-trichloroaniline to obtain an intermediate raw material 26-1 (5- Hydrazinyl quinoline hydrochloride) was obtained in an amount of 6.5 g (yield based on 5-aminoquinoline: 95.6 mol%).

2) Synthesis of intermediate material 26-2 (6b-methyl-7,8,9,10-tetrahydro-6bH-pyrido [3,2-a] carbazole)

Except that 6.5 g (0.033 mol) of the intermediate raw material 26-1 (5-hydrazinyl quinoline hydrochloride) obtained above and 3.70 g (0.033 mol) of 2-methylcyclohexanone were used as the raw material composition. (6b-methyl-7,8,9,10-tetrahydro-6bH-pyrido [3,2-a] carbazole) was reacted in the same manner as in the synthesis of Intermediate Material 01 g (yield based on 5-hydrazinylquinoline hydrochloride: 60.1 mol%).

3) Synthesis of squarylium compound 26

Except that 4.25 g (0.018 mol) of the intermediate raw material 26-2 obtained above was used in place of the intermediate raw material 01 and the amount of squalic acid was changed to 1.03 g (0.009 mol). (Yield of squaric acid: 15.5 mol%) was obtained in the same manner as in the synthesis of the target compound, squarylium compound 26.

(Examples 1-27)

1) Synthesis of intermediate raw material 27-1 (8-hydrazinylquinoline hydrochloride)

Was obtained in the same manner as in Example 1-10 (synthesis of intermediate raw material 10-1), except that 8-aminoquinoline was used in place of 2,4,5-trichloroaniline to obtain an intermediate raw material 27-1 (8- Hydrazinylquinoline hydrochloride) was obtained in an amount of 11.27 g (yield relative to 8-aminoquinoline: 96.0 mol%).

2) Synthesis of intermediate material 27-2 (6b-methyl-7,8,9,10-tetrahydro-6bH-pyrido [2,3-a] carbazole)

Except that 4.99 g (0.025 mol) of the intermediate raw material 27-1 (8-hydrazinylquinoline hydrochloride) obtained above and 2.80 g (0.025 mol) of 2-methylcyclohexanone were used as the raw material composition. (6b-methyl-7,8,9,10-tetrahydro-6bH-pyrido [2,3-a] carbazole) was obtained in a similar manner to Intermediate Material 27-2 g (yield based on 8-hydrazinylquinoline hydrochloride: 57.0 mol%).

3) Synthesis of squarylium compound 27

Except that 2.13 g (0.009 mol) of the intermediate raw material 27-2 obtained above was used in place of the intermediate raw material 01 and the amount of squalic acid was changed to 0.51 g (0.005 mol). (Synthesis of Sodium Compound 01) By the same procedure as in the above, 1.19 g of the objective squarylium compound 27 (yield relative to squaric acid: 48.0 mol%) was obtained.

(Examples 1-28)

1) Synthesis of intermediate material 28 (6-cyano-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

The same procedure as in Example 1-14 (synthesis of Intermediate Material 14) was repeated except that 5.43 g (0.032 mol) of 4-cyanophenylhydrazine hydrochloride and 3.59 g (0.032 mol) of 2-methylcyclohexanone were used as the raw material composition. According to the procedure, 1.82 g of the intermediate material 28 (6-cyano-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) (yield to 25.9 mol of 4-cyanophenylhydrazine hydrochloride %).

2) Synthesis of squarylium compound 28

Except that 1.68 g (0.008 mol) of the intermediate raw material 28 obtained above was used instead of the intermediate raw material 01 and 0.046 g (0.004 mol) of squalic acid was used instead of the intermediate raw material 01, 01), 0.15 g of the objective squarylium compound 28 (yield relative to squaric acid: 7.2 mol%) was obtained.

(Example 1-29)

1) Synthesis of intermediate material 29 (6-fluoro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole)

The same procedure as in Example 1-1 (synthesis of the intermediate raw material 01) was carried out except that 5.09 g (0.031 mol) of 4-fluorophenylhydrazine hydrochloride and 3.51 g (0.031 mol) of 2-methylcyclohexanone were used as the raw material composition 6.15 g (yield to 4-fluorophenylhydrazine hydrochloride: 96.7 mol) of intermediate material 29 (6-fluoro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole) %).

2) Synthesis of squarylium compound 29

Except that 6.15 g (0.030 mol) of the intermediate raw material 29 obtained above was used in place of the intermediate raw material 01 and 1.79 g (0.016 mol) of squalic acid was used. 01), 2.7 g of the objective squarylium compound 29 (yield relative to squaric acid: 38.9 mol%) was obtained.

(Example 1-30)

1) Synthesis of intermediate material 30-1 (2- (4-aminophenyl) benzothiazole)

A raw material composition composed of 6.26 g (0.05 mol) of 2-aminothiophenol and 6.86 g (0.05 mol) of 4-aminobenzoic acid and 125 g of polyphosphoric acid as a solvent was added to a 200 ml four-necked flask, 5 ml / min), and the mixture was warmed to 195 deg. C while stirring with a magnetic stirrer, and the mixture was reacted for about 5 hours. After completion of the reaction, the reaction solution was poured into about 1 L of a 3 M aqueous sodium hydroxide solution to crystallize. The precipitated object was separated by filtration, and the cake was washed with about 500 ml of distilled water. The resulting wet cake was dried at 40 占 폚 for 12 hours to obtain 10.8 g of an intermediate raw material 30-1 (2- (4-aminophenyl) benzothiazole) (yield relative to 2-aminothiophenol: 95.3 mol%).

2) Synthesis of intermediate material 30-2 (2- (4-hydrazinylphenyl) benzo [d] thiazole hydrochloride)

Was obtained in the same manner as in Example 1-10 (synthesis of the intermediate raw material 10-1) except that 2- (4-aminophenyl) benzothiazole was used in place of 2,4,5-trichloroaniline. 10.0 g (yield based on 2- (4-aminophenyl) benzothiazole: 81.3 mol%) of the raw material 30-2 (2- (4-hydrazinylphenyl) benzo [d] thiazole hydrochloride) was obtained.

3) Synthesis of intermediate material 30-3 (2- (4a-methyl-2,3,4,4a-tetrahydro-1H-carbazol-6-yl) benzo [d] thiazole)

5.56 g (0.015 mol) of the intermediate raw material 30-2 (2- (4-hydrazinylphenyl) benzo [d] thiazole hydrochloride) obtained above and 2.96 g (0.030 mol) of 2-methylcyclohexanone as the raw material composition The same procedure as in Example 1-1 (synthesis of intermediate raw material 01) was repeated except that the intermediate raw material 30-3 (2- (4a-methyl-2,3,4,4a-tetrahydro-1H- 6-yl) benzo [d] thiazole) was obtained in an amount of 1.45 g (yield based on 2- (4-hydrazinylphenyl) benzo [d] thiazole hydrochloride: 30.8 mol%).

4) Synthesis of squarylium compound 30

Except that 1.45 g (0.003 mol) of the intermediate raw material 30-3 obtained above was used in place of the intermediate raw material 01 and the amount of squalic acid was changed to 0.24 g (0.002 mol). (Synthesis of Sulfur compound 01) In accordance with the same procedure as in the above, 0.9 g of the objective squarylium compound 30 (yield relative to squaric acid: 71.6 mol%) was obtained.

The squarylium compounds 02 to 30 and the comparative squarylium compounds 1 and 2 obtained as described above were analyzed by the above analysis method, and as a result, it was confirmed that they had the structures shown in Table 1 or Table 2.

The maximum absorption wavelengths of the oxocarbon compounds (squarylium compounds 01 to 30) and the comparative squarylium compounds 1 and 2 thus obtained were measured by the following methods. Specifically, about 1 mg of the obtained compound was dissolved in about 3 g of chloroform to prepare a measurement solution. The solution for measurement was placed in a quartz cell having a width of 1 cm and an absorbance in the maximum absorption range was in a range of 0.950 to 1.050 And the concentration thereof was adjusted by adding chloroform as needed. Then, the absorption spectrum was measured using a spectrophotometer ("UV-1800" manufactured by Shimadzu Corporation). Then, an absorption spectrum obtained by correcting the obtained absorption spectrum so that the absorbance of the absorption maximum was 1.000 was obtained. Table 3 shows the absorption maximum wavelength and the area ratio X of each compound. The absorption spectrum of the squarylium compound 01 and the comparative squarylium compounds 1 and 2 is shown in FIG.

(Example 2-1)

1) Preparation of dimethylacetamide solution of alicyclic polyimide

5 parts by mass of 1,2,4,5-cyclohexanetetracarboxylic acid (manufactured by TOKYO CHEMICAL CORPORATION: purity: 98%, Mw = 260.20) and 44 parts by mass of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) The interior of the reactor was replaced with nitrogen gas. The mixture was heated in a nitrogen gas atmosphere and refluxed for 10 minutes. Subsequently, the crystals were precipitated by cooling to room temperature with stirring, and the precipitated crystals were separated by solid-liquid separation and dried to obtain crystals of 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

Next, to a flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, a Dean Stark and a cooling tube, 4,4'-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd.: Mw = 200.24) and 76 parts by mass of dimethylacetamide as a solvent were charged into a solution, and then 10 mass parts of the 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (Mw = 224.17) obtained above Was added portionwise over 1 hour while being solid at room temperature, and the mixture was stirred at room temperature for 2 hours. Subsequently, 26 parts by mass of toluene was added as an azeotropic dehydrating agent, and the reaction was carried out at 130 DEG C for 3 hours, and refluxing with a Dean Starck to separate the azeotropic water. Then, while the temperature was raised to 194 占 폚, xylene was distilled off and then cooled to obtain a dimethylacetamide solution of alicyclic polyimide.

2) Preparation of resin composition and production of a face-to-face molded article

The dimethylacetamide solution of the alicyclic polyimide obtained above was diluted with dimethylacetamide and the resin solid content concentration was adjusted to 8 mass%. 0.015 parts by mass of the squarylium compound 01 obtained in Example 1-1 was mixed and dissolved in 12.31 parts by mass of the 8 mass% solution, and then the resulting solution was filtered to remove insoluble matter and the like to obtain Resin Composition 01 .

Next, the obtained resin composition was applied on a glass substrate by spin coating and baked at 150 占 폚 for 20 minutes to prepare a 2 占 퐉 thick coating film (surface-formed article).

(Examples 2-2 to 2-30 and Comparative Examples 2-1 to 2-2)

Except that the squarylium compound 02 to the squarylium compound 30, the comparative squarylium compound 1 or the comparative squarylium compound 2 was used in place of the squarylium compound 01 in Example 2-1, 02 to 30 and resin compositions C1 and C2 were prepared. Using the resin compositions thus obtained, a planar molding (coating film) was produced in the same manner as in Example 1.

The maximum absorption wavelengths of the resin compositions 01 to 30 and the resin compositions C1 and C2 thus obtained were measured by the following methods. Specifically, absorption spectra were measured using a spectrophotometer (" UV-1800 " manufactured by Shimadzu Corporation) for each of the face-to-face molded products (coating films) prepared from the respective resin compositions. Then, an absorption spectrum obtained by correcting the obtained absorption spectrum so that the absorbance of the absorption maximum was 1.000 was obtained. Table 3 shows the absorption maximum wavelength and the area ratio X of each resin composition. The absorption spectrum of the resin composition 01 and the resin compositions C1 and C2 is shown in Fig.

3, a large shoulder peak is observed on the shorter wavelength side than the maximum absorption wavelength in the comparative squarylium compounds 1 and 2 (denoted by "comparative compound 1" and "comparative compound 2" in the figure) It can be seen that the same shoulder peak almost disappears and a smooth absorption waveform is obtained in the arylium compound 01 (represented by " Compound 01 " in the figure). This is also evident from the slope of the tangent line of the shoulder peak given in the figure. The squarylium compound 01 according to the present invention as described above can absorb light in the maximum absorption region more selectively than the comparative squarylium compounds 1 and 2. In comparison of the structures of the comparative squarylium compounds 1 and 2 and the squarylium compound 01, the smooth absorption waveforms such as the squarylium compound 01 show that the squarylium skeleton or the croconium skeleton and the indole ring Can be said to be expressed by designing the structure so that the binding site of the protein is part of the ring structure.

As shown in Table 3, the area ratio X of the compound group of the present invention (squarylium compounds 01 to 30) is larger than the area ratio X of the comparative squarylium compounds 1 and 2. Therefore, it can be seen that the compound group of the present invention can more selectively absorb light in the absorption maximum region.

4, a large shoulder peak is observed on the shorter wavelength side than the maximum absorption wavelength in the comparative resin compositions C1 and C2 (denoted as "comparative compound 1" and "comparative compound 2" in the drawings) In the composition 01 (represented by " Compound 01 " in the figure), it is found that the same shoulder peak almost disappears and a smooth absorption waveform is obtained.

As shown in Table 3, the area ratio X of the resin composition groups (resin compositions 01 to 30) of the present invention is larger than the area ratio X of the comparative resin compositions C1 and C2. Therefore, it can be seen that the resin composition group of the present invention can more selectively absorb light in the absorption maximum region.

In view of the above, it can be said that the effect of the compound group of the present invention described above (selective absorption of light in the absorption maximum region) is also exerted in the case of a resin composition.

Examples 3-1 to 54 and Comparative Examples 3-1 to 10 will be described below.

(Production of polyimide resin A)

5 parts of 1,2,4,5-cyclohexanetetracarboxylic acid (Aldrich, purity 95%) and 44 parts of acetic anhydride (manufactured by Wako Pure Chemical Industries) were poured into a flask, and the inside of the reactor was replaced with nitrogen gas did. The temperature was raised to the reflux temperature of the solvent in a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. Thereafter, the mixture was cooled to room temperature while stirring to precipitate crystals. The precipitated crystals were separated by solid-liquid separation and dried to obtain crystals of the objective product (1,2,4,5-cyclohexanetetracarboxylic dianhydride). Subsequently, 4,4'-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 0.89 (product of Wako Pure Chemical Industries, Ltd.) was added to a flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, And 7.6 parts of N-methyl-2-pyrrolidone as a solvent were dissolved and injected. Then, 1 part of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride was dispersed at room temperature for 1 hour And the mixture was stirred at room temperature for 2 hours. 2.6 parts of xylene was added as an azeotropic dehydrating agent, and the mixture was reacted at 180 DEG C for 3 hours, and refluxed with Dean Stark to separate azeotropic water. After raising the temperature to 190 캜, xylene was distilled off and then cooled to obtain an N-methyl-2-pyrrolidone solution of polyimide. This N-methyl-2-pyrrolidone solution was further diluted with? -Butyrolactone to obtain a polyimide resin solution having a solid content of 3%. 1 part of the polyimide resin solution was re-dissolved in 50 parts of methanol, and solid-liquid separation was carried out. The solid-liquid separated polyimide resin was dissolved in? -Butyrolactone, and again as a polyimide resin solution having a solid content of 3%, and again with 50 parts of methanol in the same manner as described above. The resin obtained by reprecipitation was dried to obtain polyimide resin A. The glass transition temperature (Tg) of the polyimide resin A was measured by a differential scanning calorimeter and found to be 297 ° C.

(Synthesis method of acrylic resin B)

60 parts of α-allyloxymethyl acrylate (AMA) and 140 parts of 4-methyl-2-pentanone (methyl isobutyl ketone, methyl isobutyl ketone) as a polymerization solvent were added to a reactor equipped with a stirrer, a temperature sensor, MIBK) (initial monomer concentration = 30% by mass), and the mixture was heated to 100 DEG C while passing nitrogen through it. Then, 0.12 part of 1,1'-azobis (cyclohexane-1-carbonitrile V-40, manufactured by Junya Kogyo Co., Ltd.) was added to initiate polymerization. The polymerization reaction was carried out for 6 hours. As a result, a polymer having a polymerization conversion rate of 97%, an allyl conversion rate of 96%, and a Mw of 21,000 was obtained. As a result of measuring a 5% mass reduction temperature of this polymer, it was 360 ° C. 5 parts of the obtained acrylic polymer solution was reprecipitated with 500 parts of methanol to carry out solid-liquid separation. The acrylic resin which had been separated by solid-liquid separation was again dissolved in MIBK, and an acrylic resin solution having a solid content of 10% was reprecipitated with 500 parts of methanol in the same manner as described above, and solid-liquid separation was carried out. The resin obtained by reprecipitation was dried to obtain an acrylic resin B. The Tg of the acrylic resin B was measured by a differential scanning calorimeter and found to be 70 캜.

(Synthesis method of acrylic resin B ') [

21.0 parts of methyl α-allyloxymethyl acrylate (AMA) and 9.0 parts of N-cyclohexylmaleimide as monomers and 45.0 parts of ethyl acetate as a polymerization solvent were added to a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a gas- And stirring and heating were started while flowing nitrogen gas. After confirming that the internal temperature was stable at 70 占 폚, 0.03 part of an azo radical polymerization initiator (ABN-V manufactured by Nippon Fine Chemical 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 the reaction was cooled to room temperature. Reprecipitation operation was performed using tetrahydrofuran as a diluting solvent and n-hexane as a poor solvent, and the precipitate was separated by suction filtration. The precipitate was dried at 80 DEG C for 2 hours under reduced pressure using a vacuum dryer to obtain an acrylic resin B '.

The weight average molecular weight of the obtained acrylic resin B 'was measured by a gel permeation chromatography apparatus and found to be 50,400. Further, Tg was measured by a differential scanning calorimeter and found to be 134 deg.

(Method for synthesizing fluorinated aromatic polymer C)

16.74 parts of BPDE (4,4'-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether) was added to a reactor equipped with a thermometer, a cooling tube, a gas introducing tube and a stirrer, (9,9-bis (4-hydroxyphenyl) fluorene), 4.34 parts of potassium carbonate, and 90 parts of DMAc (dimethylacetamide). The mixture was heated to 80 DEG C and reacted for 8 hours. After completion of the reaction, the reaction solution was added (added) in 1% aqueous acetic acid solution while vigorously 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 polyaryl ether ketone (FPEK)). The Tg of the obtained polymer was 242 占 폚, and the number average molecular weight (Mn) was 70770. The number average molecular weight in the above Synthesis Example was measured by the following method. (2 columns, TSKgel SuperMultipore HZ-N 4.6 * 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard) by gel permeation chromatography.

(Example 3-1)

≪ Preparation and Coating of Composition Solution for Resin Layer >

0.6 part of squarylium compound 01 was mixed and dissolved in a resin solution obtained by dissolving 6 parts of polyimide resin A in 94 parts of cyclopentanone to prepare a composition solution for a resin layer. The composition solution for the resin layer was filtered to remove insolubles and the like, and a composition solution for a resin layer was prepared. After 0.6 cc of the composition solution for the resin layer was flowed on the glass substrate, the resin solution was spun for 0.2 seconds using a spin coater (1H-D7, manufactured by Mikasa Co., Ltd.) for 1000 seconds and maintained at that number of revolutions for 10 seconds. The resin layer was formed so as to be rotated at 0 revolution (rpm). The glass substrate on which the resin layer was formed was dried at 100 占 폚 for 3 minutes by using a precision thermostat (DH611 manufactured by Yamato Scientific Co., Ltd.), and then subjected to nitrogen substitution at 50 占 폚 for 30 minutes using an inert gas oven (DN610I, After that, the temperature was raised to 200 占 폚 for about 15 minutes and further dried (under a nitrogen atmosphere) at 200 占 폚 for 30 minutes to obtain a glass substrate (hereinafter referred to as a resin layer laminated substrate) having a resin layer. As a result of measuring the transmittance of this resin layer laminated substrate, the transmittance of the maximum absorption wavelength (peak top) was 2.5%. The film thickness of the resin layer after drying was 1 占 퐉. The film thickness of the resin layer after drying was measured by using a micrometer to measure the thickness of the resin layer laminated substrate and the thickness of the glass substrate, and the difference between them was taken as 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 4 below.

(Examples 3-2 to 11 and Comparative Examples 3-1 and 2)

A resin layer laminated substrate was obtained in the same manner as in Example 3-1 except that the amount of the resin, the kind and amount of the solvent, and the kind and amount of the dye were changed as shown in Table 4 in Example 3-1 . In Examples 2 to 11 and Comparative Examples 3-1 and 2, a composition solution for a resin layer was prepared and applied such that the transmittance of 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.

(Examples 3-12 to 16 and Comparative Examples 3-3 to 7)

The same procedure as in Example 3-1 was repeated except that the kind and amount of the resin, the kind and amount of the solvent, and the kind and amount of the pigment were changed as shown in Table 5, To obtain a substrate. However, in Examples 3-16 and Comparative Examples 3-7, heating was performed without applying initial drying at 100 ° C for 3 minutes after application. In Examples 3-12 to 16 and Comparative Examples 3-3 to 7, a composition solution for a resin layer was prepared and applied such that the transmittance of the maximum absorption wavelength was 2.5%. (Acrylic resin B), a polysulfone resin (UDEL (registered trademark) P-1700 manufactured by SOLVAY SPECIALTY POLYMERS), a polycarbonate resin P (ARTON (registered trademark) (modified norbornene resin) manufactured by JSR Corporation) The fluorinated aromatic polymer C and an epoxy resin (EHPE3150, manufactured by Daicel Chemical Industries, Ltd., and Celloxide (registered trademark) 2021P, manufactured by Daicel Chemical Industries, Ltd.) were used. As the solvent, cyclopentanone, o-dichlorobenzene, and PGMEA (2-acetoxy-1-methoxypropane) were used. The cationic curing catalyst D added in Examples 3-16 and 3-7 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 5 below.

Preparation Example 1 (Synthesis of TPB-containing powder)

According to the synthetic method described in International Publication No. 1997/031924, 255 g of Isopar (registered trademark) E solution (manufactured by Ando Parachemis) having a content of TPB (tris (pentafluorophenyl) borane) of 7% was prepared. Water was added dropwise to this solution at 60 占 폚. White crystals precipitated during the dropwise addition. After cooling the reaction solution to room temperature, the resulting slurry was suction filtered and washed with n-heptane. The obtained cake was dried under reduced pressure at 60 캜 to obtain 18.7 g of a white crystal, TPB-water complex (TPB-containing powder B). The complex had a water content of 9.2% (Curfischer moisture meter) and a TPB content of 90.8%. ¹⁹ F-NMR analysis and GC analysis were performed on the complex after drying, but peaks other than TPB were not detected.

The measurement results of ¹⁹ F-NMR are shown below.

^{19 F-NMR (CDCl 3)} ppm ( standard: CFCl ³ 0 ppm)

[delta] = -135.6 (6F, m)

[delta] = -156.5 (3F, dd)

[delta] = -163.5 (6F, d)

Preparation Example 2 (Preparation of Cationic Curing Catalyst D)

1.1 g of? -Butyrolactone was added to 2 g of TPB-containing powder B (1.816 g (3.547 mmol) of TPB and 0.184 g (10.211 mmol) of water obtained in Preparation Example 1) Mixed. Thereafter, 2.6 g of a 2 mol / l ammonia-ethanol solution was added and mixed at room temperature for 60 minutes to obtain a homogeneous solution of the cationic curing catalyst D (TPB catalyst). This was used as a cationic curing catalyst D.

(Example 3-17)

The polyimide resin A was dissolved in N, N-dimethylacetamide, and film formation was performed using the solvent casting method, and a film was produced so that the thickness after drying was 100 占 퐉. Further, the drying was sufficiently carried out at 250 캜 under nitrogen, and the residual solvent was 1.5%. On both sides of the polyimide film, the same resin composition as in Example 3-1 was used and both sides of the polyimide film were coated so that the transmittance of the maximum absorption wavelength (peak top) was 2.5%. The obtained absorbing film is obtained by applying a resin composition containing a dye to a film which becomes a substrate (support). The results of the average transmittance and the maximum absorption wavelength of 400 to 450 nm are summarized in Table 6 below.

(Comparative Example 3-8)

A polyimide film was obtained in the same manner as in Example 3-17, and then the same resin composition as in Comparative Example 3-1 was used to apply on both sides in the same manner as in Examples 3-17 to obtain an absorbent film. The results of the average transmittance and the maximum absorption wavelength of 400 to 450 nm are summarized in Table 6 below.

(Examples 3-18)

The polycycloolefin resin P was dissolved in o-dichlorobenzene and the squarylium compound 01 was dissolved. This resin solution was filtered and applied to a glass substrate so as to have a thickness after drying of 50 mu m and a transmittance of 2.5% at a maximum absorption wavelength (peak top) using a solvent casting method. After drying for 30 minutes at 120 DEG C, And peeled off from the glass substrate. The peeled film was further dried again under nitrogen at 150 DEG C for 30 minutes. The obtained absorbent film is not coated on a support but is a film having absorption as a single layer. The results of the average transmittance and the maximum absorption wavelength of 400 to 450 nm are summarized in Table 6 below.

(Comparative Example 3-9)

An absorbent film was obtained in the same manner as in Example 3-18 except that the comparative squarylium compound 3 was used. The results of the average transmittance and the maximum absorption wavelength of 400 to 450 nm are summarized in Table 6 below.

(Examples 3-19 to 30)

A resin layer laminated substrate was obtained in the same manner as in Example 3-1 except that the amount of the resin, the amount of the solvent, and the kind and amount of the dye were changed as shown in Table 7. In Examples 3-19 to 30, a composition solution for a resin layer was prepared and applied such that the transmittance of the maximum absorption wavelength was 2.5%. The structures 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 3-31)

(Composition for undercoat layer (undercoat solution))

<Production of undercoat solution>

1.52 parts of a silane coupling agent (KBM-903 (3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Silicone Co., Ltd.), 2 parts of ethanol, 0.455 parts of water and 0.26 parts of formic acid solution were mixed and dissolved. Next, 1 part of the mixed solution S was diluted with 99 parts of ethanol to prepare Undercoat Solution No. 1. [

&Lt; Application of undercoat solution &gt;

The undercoat solution was flowed 1 cc onto a glass substrate (D263Teco, manufactured by SCHOTT Co., Ltd., 60 mm x 60 mm x 0.3 mm), followed by 3 seconds of spinning at 2200 rpm using a spin coater (1H- And kept at that number of revolutions for 20 seconds. Thereafter, the base layer was formed in such a manner that it was rotated at 0 revolutions (rpm) for 3 seconds. The glass substrate after the base layer film formation was dried at 100 占 폚 for 10 minutes using a precision thermostat (DH611, manufactured by Yamato Scientific Co., Ltd.) to obtain a glass substrate having a base layer (hereinafter referred to as base layer laminate substrate).

&Lt; Preparation and Coating of Composition Solution for Resin Layer &gt;

Except that the composition solution for a resin layer was allowed to flow over the base layer of the base layer laminated substrate (surface directly contacting the base layer) in place of flowing the solution for the resin layer onto the glass substrate in Example 3-1 , And a resin layer laminated substrate was obtained in the same manner as in Example 3-1. In Example 3-31, a composition solution for a resin layer was prepared and applied such that the transmittance of 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 8 below.

(Examples 3-32 to 36)

A resin layer laminated substrate was obtained in the same manner as in Example 3-31, except that the kind and amount of the dye were changed as shown in Table 8 in Example 3-31. In Examples 3-32 to 36, a composition solution for a resin layer was prepared and applied such that the transmittance of 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 8 below.

(Examples 3-37 to 39, 42, and 43)

In the same manner as in Example 3-31, except that the kind and amount of the resin, the kind and amount of the solvent, and the kind and amount of the pigment were changed as shown in Table 6, To obtain a substrate. In Examples 3-37 to 39, 42 and 43, a composition solution for a resin layer was prepared and applied such that the transmittance of the maximum absorption wavelength was 2.5%. As the resin, a polycycloolefin resin P (ARTON (registered trademark) (modified norbornene resin) manufactured by JSR Corporation) RX4500, a polycycloolefin resin Q (TOPAS (registered trademark) (cyclic olefin copolymer resin) 5013F04). As the solvent, o-dichlorobenzene and xylene were used. The results of 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 9 below.

(Examples 3-40 and 41)

In the same manner as in Example 3-1, except that the kind and amount of the resin, the kind and amount of the solvent, and the kind and amount of the pigment were changed as shown in Table 9, To obtain a substrate. In Examples 3-40 and 41, a composition solution for a resin layer was prepared and applied such that the transmittance of the maximum absorption wavelength was 2.5%. As the resin, the polycycloolefin resin P and the polycycloolefin resin Q were used. As the solvent, o-dichlorobenzene and xylene were used. The results of 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 9 below.

(Examples 3-44 to 47)

In Example 3-1, the kind and amount of the resin were changed to 15 parts of the acrylic resin B ', the kind and amount of the solvent were changed to 85 parts of cyclopentanone, and the kinds and amounts of the pigments were changed as shown in Table 10 A resin layer laminated substrate was obtained in the same manner as in Example 3-1 except for the above. In Examples 3-44 to 47, a composition solution for a resin layer was prepared and applied such that the transmittance of 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 10 below.

(Example 3-48, Comparative Example 3-10)

The procedure of Example 3-1 was repeated, except that the kind and amount of the resin, the kind and amount of the solvent, and the kind and amount of the colorant were changed as shown in Table 11, To obtain a substrate. In Example 3-48 and Comparative Example 3-10, a composition solution for a resin layer was prepared and applied such that the transmittance of the maximum absorption wavelength was 12%. The results of the average transmittance of 400 to 450 nm and the maximum absorption wavelength are summarized in Table 11 below.

(Examples 3-49 to 54)

Example 3-31 was repeated except that the kind and amount of the resin, the kind and amount of the solvent, the kind and amount of the pigment were changed as shown in Table 12, and the curing agent and the additive were added. The resin layer-laminated substrates of Examples 3-49 to 52 were obtained. In addition, in Examples 3-16, except that the type and amount of the resin, the kind and amount of the solvent, the kind and amount of the curing agent, the kind and amount of the curing agent were changed as shown in Table 12 and the additives were added , And the resin layer-laminated boards of Examples 3-53 to 54 were obtained in the same manner as in Example 3-16. In Examples 3-49 to 54, a composition solution for a resin layer was prepared and applied such that the transmittance of 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 12 below. In Examples 3-53 to 54, Z-6062 (3-mercaptopropyltrimethoxysilane) manufactured by Toray Dow Corning Inc. was used as the silane coupling agent. In Examples 3-49 to 54, BYK (registered trademark) -306 (a silicone additive) manufactured by Big Chemie was used as an additive, and the catechin curing catalyst D described above or catechin curing catalyst On Curing Catalyst E was used.

Preparation Example 3 (Preparation of cationic curing catalyst E)

A homogeneous solution of a cationic curing catalyst (TPB catalyst) was prepared in the same manner as in Preparation Example 2, except that? -Butyrolactone was changed to toluene in Preparation Example 2. This was designated as cation cation curing catalyst E.

5 is a graph showing the relationship between the wavelength and the transmittance in the resin layer of Example 3-12 and the resin layer of Comparative Example 3-3. 5, in the resin layer of Comparative Example 3-3 containing the comparative squarylium compound 3, the transmittance at the maximum absorption wavelength is 2.5%, but the average transmittance at 400 to 450 nm is only about 76%. However, in the resin layer of Examples 3-12 containing the squarylium compound 01, the transmittance at the maximum absorption 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 the squarylium compound 01 has a higher selective permeability than the resin layer containing the comparative squarylium compound 3.

5 shows that the resin layer of Comparative Example 3-3 containing the comparative squarylium compound 3 has a larger shoulder peak on the shorter wavelength side than the absorption maximum wavelength. However, in Example 3-12 containing the squarylium compound 01 The same shoulder peak almost disappears, and a smooth absorption waveform can be obtained. Therefore, the resin layer containing the squarylium compound 01 can absorb light in the absorption maximum region more selectively than the resin layer containing the comparative squarylium compound 3.

Fig. 6 is a graph showing the relationship between the amount of the polycycloolefin resin P contained in the resin layer containing the squarylium compound 01 and the amount of the squarylium compound represented by the following formula (18) (hereinafter referred to as comparative squarylium compound 5) Fig. 3 is a graph showing the relationship between the wavelength and the absorbance in the sample. In Fig. 6, similarly to Fig. 5, it can be seen that the resin layer containing the squarylium compound 01 has excellent selective permeability.

From FIG. 6, similarly to FIG. 5, in the resin layer containing the comparative squarylium compound 5 in the polycycloolefin resin P, a large shoulder peak is observed on the shorter wavelength side than the absorption maximum wavelength, but the squarylium compound 01 It can be seen that the same shoulder peak is almost lost in the resin layer containing it and a smooth absorption waveform can be obtained. Therefore, the resin layer containing the squarylium compound 01 can absorb light in the absorption maximum region more selectively than the resin layer containing the comparative squarylium compound 5.

(38)

An antireflection film was laminated on one surface of the optical filter obtained in Examples 3-1 to 54 and a near infrared reflecting film was laminated on the other surface thereof to prepare a near infrared ray cut filter. A near infrared ray reflection film and an antireflection film were produced by alternately depositing a silica layer and a titanium oxide layer by the IAD method. The deposition temperature at the time of depositing the silica layer and the titanium oxide layer was set to be Tg or less of each resin.

All of the near-infrared cut filters manufactured using the optical filters obtained in Examples 3-1 to 54 exhibited good transmittance characteristics and had almost no dependency on angle of transmitted light. As a representative, the near-infrared cut filter obtained by depositing the antireflection film and the near-infrared reflection film on the optical filters of Examples 3-12, the transmittance at each wavelength when light was incident at an incident angle of 0, Table 13 shows the results of measurement of the transmittance at each wavelength when the incident light is incident. The wavelength at which light is incident at an incident angle of 0 DEG is 50% at 631 nm, the wavelength at which light is incident at an incident angle of 30 DEG at 50% is 629 nm, Regardless of the angle, the wavelength at which the transmittance was 50% was almost the same.

The near-infrared cut filter produced using the optical filters obtained in Examples 3-1 to 54 was evaluated for resistance to ultraviolet rays, wet heat resistance, water resistance, weather resistance, impact resistance and heat resistance. As a result, , No deterioration of the dye was observed, and it was found that the durability was very excellent.

Industrial availability

The novel oxocarbon compound according to the present invention can be used as a colorant absorbing visible light and near-infrared light because there is no (or significantly reduced) shoulder appearing in the peak of the absorption spectrum in the visible-near infrared region. In addition, the resin composition of the present invention has a higher average transmittance of light at a wavelength of 400 to 450 nm than a filter using a conventional oxocarbon compound, and eliminates a shoulder peak near the maximum absorption wavelength It is possible to efficiently absorb the light of the desired near infrared region with good color purity. Therefore, the novel oxocarbon compound and the resin composition using the compound according to the present invention are excellent in optical filter for semiconductor light-receiving element having a function of absorbing and cutting near infrared rays and a part of visible light, An information display material as a security ink or an invisible barcode ink, a material for a solar cell using visible light and near-infrared light, a specific wavelength absorption filter for a plasma display panel (PDP) or a CCD, A transferring material, and an optical fixing method (a toner for electrostatic charge developing for a flash fixing method) using light which hardly causes problems due to pressurization or heating.

Claims (17)

An oxocarbon-based compound represented by the following formula (1) or (2)
[Chemical Formula 1]

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

(In the formula (3)
Ring A is an unsaturated hydrocarbon ring of 4-9 atoms.
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 (provided that m is a value obtained by subtracting 3 from the number of constituent atoms of the ring A). When n is 2 or more, a plurality of Ys may be the same or different.
Ring B is an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures, which may have a substituent.
And * represents a bonding site of a four-membered ring in formula (1) or a five-membered ring in formula (2)). The method according to claim 1,
And the ring B is a benzene ring or a naphthalene ring. 3. The method according to claim 1 or 2,
And Y is an alkyl group or a hydroxyl group. 4. The method according to any one of claims 1 to 3,
And X is an alkyl group or an aryl group. A resin composition comprising the oxocarbon compound according to any one of claims 1 to 4 and a resin component. 6. The method of claim 5,
Further, the resin composition contains at least one solvent selected from ketones, glycol derivatives, amides, esters, pyrrolidones, aromatic hydrocarbons, aliphatic hydrocarbons and ethers. The method according to claim 5 or 6,
Wherein the resin component is at least one resin selected from a poly (amide) imide resin, a fluorinated aromatic polymer, a (meth) acrylic resin, a polyamide resin, an aramid resin, a polysulfone resin, an epoxy resin, and a polycycloolefin resin Composition. 8. The method according to claim 6 or 7,
Wherein the amide is used in an amount of 60 mass% or less based on 100 mass% of the resin composition. A molded article comprising the resin composition according to any one of claims 5 to 8. An in-plane formed article comprising the resin composition according to any one of claims 5 to 8. An optical filter having a resin layer formed from the resin composition according to any one of claims 5 to 8. An optical filter comprising a support and a resin layer formed on one side or both sides of the support, wherein the resin layer is formed from the resin composition according to any one of claims 5 to 8. 13. The method according to claim 11 or 12,
Wherein an average transmittance of the spectroscopic light at a wavelength of 400 to 450 nm of the resin layer is 81% or more. An optical filter comprising a resin film formed from the resin composition according to any one of claims 5 to 8. 15. The method of claim 14,
Wherein an average transmittance of a spectroscopic ray at a wavelength of 400 to 450 nm of the resin film is 81% or more. A near infrared ray cut filter, characterized in that the optical filter according to any one of claims 11 to 15 is provided with a dielectric multilayer film. An image pickup device comprising at least one of the optical filter according to any one of claims 11 to 15 and the near-infrared cut filter according to claim 16.

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