JP2016079331A - Resin composition including oxocarbon compound and molded product formed from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that achieves both light fastness and absorption region although it contains a squarylium-based or croconium-based dye.SOLUTION: The resin composition includes an oxocarbon compound represented by formula (1) having a squarylium skeleton and/or formula (2) having a croconium skeleton (Rto Rare each independently a pyrrole group or a substituted pyrrole group) and a resin component.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition containing an oxocarbon-based compound and a resin component, and a molded body comprising the same.

  Conventionally, an oxocarbon compound having a squarylium skeleton or a croconium skeleton in a compound has been provided. These oxocarbon compounds are generally produced by using squaric acid or croconic acid as raw materials and introducing heterocyclic groups at both ends of the raw materials (Patent Documents 1 to 5).

  Among the many squarylium-based or croconium-based compounds, a typical compound having excellent absorption characteristics in the near-infrared region is a squarylium-based or croconium-based dye represented by the following formula. However, since all of the dyes shown below have low resistance to light, they have the property of being easily decomposed by light and have a problem of lack of versatility.

  On the other hand, among the squarylium-based or croconium-based compounds, those having excellent light resistance include, for example, the following compounds disclosed in Patent Documents 6 to 8. However, these compounds all have a maximum absorption wavelength (λmax) in the region of 650 nm or less, and have poor absorption characteristics in the near infrared region (about 700 nm or more).

  Further, although light resistance is unknown, Non-Patent Documents 1 to 4 disclose various compounds having a maximum absorption wavelength in the near infrared region.

Japanese Patent Laid-Open No. 1-230674 JP 2008-308602 A JP 2011-208101 A JP 2007-169315 A JP 2008-1754 A JP 2001-183522 A JP 2005-520835 A JP 2008-184606 A

Raymond, two others, “Squaraines based on 2-arypyrroles”, Tetrahedron, August 23 (2004), 60, pp 8913-8918. Luca, 14 others, “Assessment of Water-Soluable π-Extended Squares as One, and Two-Photon Single oxygen Photosensorizers: Design, 19 Fabio, et al., “A squaraine-phthalocyanine ensemble: tow molecular molecular sensitizers in solar cells”, Chem. Commun. , April 20 (2009), pp 4500-4502. Michael, three others, “Redox-Switchable Squares with Extended Conjugation”, Org. Lett. , July 19 (2003), 5 (17), pp 2975-2978.

  As described above, a squarylium-based or croconium-based compound having a maximum absorption wavelength (λmax) in the near-infrared region while having good light resistance has not been widely known. Similarly, resin compositions containing these compounds are also required to have both light resistance and an absorption region. Then, this invention raise | lifts as a subject the resin composition which can make light resistance and an absorption region compatible, including a squarylium type | system | group or a croconium type pigment | dye.

  As a result of intensive research to solve the above problems, the present inventors have found that a resin composition comprising a specific oxocarbon-based compound and a resin component has a maximum absorption wavelength in the near infrared region. And it discovered that it was excellent also in light resistance, and completed this invention.

  That is, the resin composition according to the present invention has the following formula (1) having a squarylium skeleton and / or the following formula (2) having a croconium skeleton:

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

[In the formula (3), R ^{b1 to} R ^b4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, or a substituent. Aryloxycarbonyl group which may have, acyl group which may have substituent, aryl group which may have substituent, heteroaryl group which may have substituent, substituent An aralkyl group, * —CH═CH—R ^c (wherein R ^c is an aliphatic hydrocarbon group, an aryl group, or a heterocyclic substituent), or * —CH═N— R ^d (wherein R ^d is an amino group which may have a substituent). R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 may be bonded to each other to form a ring.
* Represents a binding site.
However, at least one of R ^{b1 to} R ^b4 is an aryl group which may have a substituent, a heteroaryl group which may have a substituent, * —CH═CH—R ^c (wherein R ^c is the same as above), or * —CH═N—R ^d (wherein R ^d is the same as above), or R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 An oxocarbon-based compound represented by the formula:
A resin component is included.
Furthermore, the resin composition contains at least one solvent selected from ketones, glycol derivatives, amides, esters, pyrrolidones, aromatic hydrocarbons, aliphatic hydrocarbons, and ethers. Also good.
The resin component is preferably at least one selected from poly (amide) imide resins, fluorinated aromatic polymers, (meth) acrylic resins, polyamide resins, aramid resins, and polycycloolefin resins.
Furthermore, the amount of the amide used is preferably 80% by mass or less in 100% by mass of the resin composition.
The present application also includes a molded body and a planar molded body made of the resin composition.

  According to the present invention, a resin composition that absorbs light in the near infrared region can be obtained.

It is the peak contrast result of Example 1 measured before and after the light resistance test. It is a peak contrast result of Example 2 measured before and after the light resistance test. It is a peak contrast result of Example 3 measured before and after the light resistance test. It is the peak contrast result of the comparative example 1 measured before and after the light resistance test. It is the peak contrast result of the comparative example 2 measured before and after the light resistance test.

  The resin composition which concerns on this invention contains the oxocarbon type compound represented by General formula (1) and / or General formula (2), and a resin component as a pigment | dye. The pigment is preferably dispersed or dissolved in the resin composition. In addition, a pigment | dye and a resin component may be used individually by 1 type, respectively, and may be used in combination of 2 or more type. Below, each component contained in a resin composition is demonstrated in detail.

<1. Dye>
First, the pigment contained in the resin composition according to the present invention will be described.

1-1. The oxocarbon-based compound having a pyrrole-based structural unit The resin composition includes the following formula (1) having a squarylium skeleton and / or the following formula (2) having a croconium skeleton:

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

[In the formula (3), R ^{b1 to} R ^b4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, or a substituent. Aryloxycarbonyl group which may have, acyl group which may have substituent, aryl group which may have substituent, heteroaryl group which may have substituent, substituent aralkyl group which may have a, * - CH = (wherein R ^c is an aliphatic hydrocarbon group, an aryl group, or a heterocyclic substituent) CH-R ^c, or * -CH = N R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 are —R ^d (wherein R ^d is an amino group which may have a substituent), May combine to form a ring,
* Represents a binding site,
However, at least one of R ^{b1 to} R ^b4 is an aryl group which may have a substituent, a heteroaryl group which may have a substituent, * —CH═CH—R ^c (wherein R ^c is the same as above), or * —CH═N—R ^d (wherein R ^d is the same as above), or R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 At least one ring to which is attached] is included.

  Note that the oxocarbon-based compound described in detail below has a squarylium skeleton or a croconium skeleton, and the compound represented by the formula (1) or (2) has a conjugated relationship with these compounds, respectively. In some cases. Examples of the compound having a conjugated relationship include the following (1a), (1b), (2a), (2b), and (2c). Hereinafter, in the present specification, even an oxocarbon-based compound in which a compound having such a conjugated relationship exists is a compound represented by the formula (1) (sometimes referred to as a compound (1)). The compound represented by the formula (2) (sometimes referred to as the compound (2)) will be described. The compound represented by the following formulas (1a) and (1b) The compound (2) includes the following formulas (2a), (2b), and (2c).

  First, the structure of the formula (3) will be described.

The alkyl group represented by R ^{b1 to} R ^b4 is preferably an alkyl group having 1 to 20 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, or a tert-butyl group. Group, sec-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl Group, octyl group, methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl 2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, nonyl group, methyloctyl group, 3,7-dimethyloctyl group, dimethylheptyl group, 3 Examples include linear or branched alkyl groups such as -ethylheptyl group, 4-ethylheptyl group, trimethylhexyl group, 3,3-diethylpentyl group, decyl group, undecyl group, dodecyl group, and the like. Especially, a C1-C15 alkyl group is preferable, More preferably, it is C1-C12. The alkyl group may be linear or branched, but more preferably is linear. In addition, this alkyl group may have a substituent, and the substituent other than the alkyl group can be used as the substituent.

Examples of the alkyloxycarbonyl group represented by R ^{b1 to} R ^b4 include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxy Examples thereof include alkyloxycarbonyl groups such as a carbonyl group, a decyloxycarbonyl group, and an octadecyloxycarbonyl group. Among them, an alkyloxycarbonyl group having 1 to 5 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group is preferable, and a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group is more preferable. The alkyl group in the alkyloxycarbonyl group may be either linear or branched. The alkyloxycarbonyl group may have a substituent, and as the substituent, those other than the alkyl group can be used among those described later. Examples having a substituent include trihalo substituents such as a trifluoromethyloxycarbonyl group.

Examples of the aryloxycarbonyl group represented by R ^{b1 to} R ^b4 include phenoxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxy Carbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl Groups, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, phenyloxycarbonyl group such as 4-methoxyphenyloxycarbonyl group; 1-naphthyloxy Naphthyloxycarbonyl groups such as a carbonyl group and 2-naphthyloxycarbonyl group; and the like. The aryloxycarbonyl group may have a substituent, and the substituent is appropriately selected from those described later.

Examples of the acyl group represented by R ^{b1 to} R ^b4 include alkanoyl groups such as acetyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, and trifluoroacetyl group. An aroyl group such as a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group; Among these, an acyl group having 2 to 15 carbon atoms is preferable, and an acyl group having 2 to 10 carbon atoms is more preferable. Among these, an alkanoyl group is preferable, and an acetyl group, a propanoyl group, or a butanoyl group is more preferable. The acyl group may have a substituent, and the substituent is appropriately selected from those described later.

The aryl group represented by R ^{b1 to} R ^b4 is preferably an aromatic hydrocarbon group having 6 to 16 carbon atoms. The aryl group preferably has 1 to 5 rings (more preferably 1 to 3 rings). Specific examples include a phenyl group, a naphthyl group, a pentarenyl group, an indenyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, Biphenylyl group, biphenyl group and the like can be mentioned. Among these, a phenyl group or a naphthyl group is preferable. The aryl group may have a substituent, and the substituent is appropriately selected from those described later.

The alicyclic hydrocarbon group represented by R ^{b1 to} R ^b4 is preferably a saturated or unsaturated cyclic hydrocarbon group having 3 to 16 carbon atoms, more preferably 5 to 10 carbon atoms. The alicyclic hydrocarbon group is more preferably unsaturated. Examples of the unsaturated cyclic hydrocarbon group include a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group. A cycloalkenyl group having one double bond; a cycloalkenyl group having two or more double bonds such as a 1,3-cyclohexadien-1-yl group and a 1,4-cyclohexadien-1-yl group; it can. The alicyclic hydrocarbon group may have a substituent, and the substituent is appropriately selected from those described later.

The heteroaryl group represented by R ^{b1 to} R ^b4 is preferably a heteroaryl group having 2 to 20 carbon atoms, such as a thienyl group, a thiopyranyl group, an isothiochromenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, or a pyridyl group. And pyralidinyl group, pyrimidinyl group, pyridazinyl group, thiazolyl group, isothiazolyl group, furanyl group, pyranyl group and the like. The heteroaryl group may have a substituent, and the substituent is appropriately selected from those described later.

The aralkyl group represented by R ^{b1 to} R ^b4 is preferably an aralkyl group having 7 to 18 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylpentyl group. Groups are preferred. The aralkyl group may have a substituent, and the substituent is appropriately selected from those described later.

Each group represented by R ^{b1 to} R ^b4 may have a substituent as described above. The substituent means an atomic group belonging to a group different from the group from which the group is bonded, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, and a cyano group.
As an alkyl group, a C1-C20 alkyl group is preferable, More preferably, it is a C1-C10 alkyl group, More preferably, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n -A butyl group, a tert-butyl group, and a sec-butyl group. These alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group. The number of atoms constituting the ring skeleton of the cycloalkyl group is preferably from 3 to 15, more preferably from 5 to 9, and even more preferably 6 (cyclohexyl group).
In addition, as the alkoxy group, a substituent in which an alkyl group is bonded through an oxygen atom is used. Specifically, those having 1 to 18 carbon atoms are preferable. For example, a methoxy group, an ethoxy group, a propoxy group, Isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group Group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, heptyloxy group, 2-methylhexyloxy group, 3-methylhexyloxy group, 2,2-dimethylpentyloxy group, 2,3-dimethyl Pentyloxy group, 2,4-dimethylpentyloxy group, 3-ethylpentyloxy group, 2 2,3-trimethylbutyloxy group, octyloxy group, methylheptyloxy group, dimethylhexyloxy group, 2-ethylhexyloxy group, 3-ethylhexyloxy group, trimethylpentyloxy group, 3-ethyl-2-methylpentyloxy group 2-ethyl-3-methylpentyloxy group, 2,2,3,3-tetramethylbutoxy group, nonyloxy group, methyloctyloxy group, 3,7-dimethyloctyloxy group, dimethylheptyloxy group, 3- Examples include ethyl heptyloxy group, 4-ethylheptyloxy group, trimethylhexyloxy group, 3,3-diethylpentyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like. Of these, a methoxy group or an ethoxy group is preferable.

* —CH═CH—R ^c (C) (in the formula (C), R ^c is an aliphatic hydrocarbon group, an aryl group, or a heterocyclic substituent) (hereinafter referred to as ethylene-containing group) Group (C)) will be described. In the ethylene-containing group (C), as the aliphatic hydrocarbon group, for example, those having 1 to 20 carbon atoms are preferable, and those having 1 to 10 carbon atoms are more preferable.

The aliphatic hydrocarbon group may be saturated or unsaturated, but is more preferably unsaturated. Specifically, such an aliphatic hydrocarbon group has a repeating unit represented by — (CH═CH) _n — (n is an integer of 1 to 10, more preferably 1 to 5). Groups are preferred, for example vinyl groups.

  In addition, the aryl group preferably has 1 to 5 rings (more preferably 1 to 3 rings). Specific examples include a phenyl group, a naphthyl group, a pentarenyl group, an indenyl group, an anthracenyl group, a phenanthryl group, and a fluorenyl group. Group, biphenylyl group, biphenyl group and the like.

  Furthermore, examples of the heterocyclic substituent include hetero-element heterocyclic substituents such as pyrrole, pyridine, pyrrolidine, piperidine, piperazine, thiophene, and furan.

  Examples of the ethylene-containing group (C) include each group represented by the following formula.

Further, * —CH═N—R ^d (D) [in the formula (D), R ^d is an amino group which may have a substituent] (hereinafter, an imine-containing group ( D)) will be described. Examples of the amino group which may have a substituent for R ^d include, for example, * —N—R ^d1 R ^d2 (wherein R ^d1 and R ^d2 each independently have a hydrogen atom or a substituent). An alkyl group that may be substituted, or an aryl group that may have a substituent).

  Examples of the imine-containing group (D) include groups represented by the following formulas.

Among these, R ^b1 is more preferably a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent (for example, a cycloalkylalkyl group) or a substituent (for example, CF ₃ , an alkoxy group, cyano. Group, a linear or branched alkyl group) is an aralkyl group, and among them, a hydrogen atom or a group represented by the following formulas (B1-1) to (B1-15) (wherein, * is It represents a binding site).

Preferred R ^b2 is a hydrogen atom, an ^optionally substituted alkyl group, an optionally substituted alkyloxycarbonyl group, an optionally substituted aryloxycarbonyl group, substituted An aryl group optionally having a group, * —CH═CH—R ^c (wherein R ^c is the same as above), or * —CH═N—R ^d (wherein, R ^d is the same as above) Among them, a hydrogen atom or a group represented by the following formulas (B2-1) to (B2-14) (wherein * represents a binding site) can be preferably exemplified.

Preferred R ^b3 is a hydrogen atom, an alkyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, a substituent An acyl group which may have a group or an aryl group which may have a substituent, more preferably a hydrogen atom, a straight chain having 1 to 5 carbon atoms which may have a substituent or A branched alkyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an acetyl group or a propanoyl group;

More preferable R ^b4 is a hydrogen atom, an alkyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, a substituent An acyl group which may have a group or an aryl group which may have a substituent, more preferably a hydrogen atom, a straight chain having 1 to 5 carbon atoms which may have a substituent or A branched alkyl group, phenyl group, 4-biphenyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetyl group or propanoyl group.

R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 may be bonded to each other to form a ring. As an example in which R ^b1 and R ^b2 are bonded to form a ring, for example, there is a structural unit (3) represented by the following formula (in the following formula, * is a binding site). These rings may have a substituent as appropriate.

Next, as an example in which R ^b2 and R ^b3 are bonded to form a ring, for example, there is a structural unit (3) represented by the following formula (in the following formula, * is a binding site). These rings may have a substituent as appropriate.

Furthermore, as an example in which R ^b3 and R ^b4 are bonded to form a ring, for example, there is a structural unit (4) represented by the following formula (in the following formula, * is a binding site).

(In formula (4),
A represents a ring structure formed by two carbon atoms at the β-position of the pyrrole ring together with other atoms;
X is a hydrogen atom or an organic group,
Y is a hydrogen atom, an electron withdrawing group or an organic substituent,
* Represents a binding site. )

In the present invention, the structural unit represented by the formula (4) in which R ^b3 and R ^b4 are bonded to form a ring is particularly preferable. An oxocarbon-based compound having a squarylium skeleton or a croconium skeleton and further having a structural unit (4) is a novel compound not described in the literature. This compound has a maximum absorption wavelength (λmax) between 550 and 950 nm, and is further characterized by excellent light resistance. Hereinafter, this novel oxocarbon compound will be described in detail.

  The novel oxocarbon-based compound is represented by the following formula (1) having a squarylium skeleton or the following formula (2) having a croconium skeleton.

(In the formulas (1) and (2), R ^{a1 to} R ^a4 are each independently a structural unit represented by the following formula (4).)

(In formula (4),
Ring A represents a ring structure formed by two carbon atoms at the β-position of the pyrrole ring together with other atoms,
X is a hydrogen atom or an organic group,
Y is a hydrogen atom, an electron withdrawing group or an organic substituent,
* Represents a binding site. )

  First, the structural unit represented by the formula (4) that can be bonded to the squarylium skeleton or the croconium skeleton will be described. In the structural unit represented by the formula (4), A is a ring structure formed by two carbon atoms at the β-position of the pyrrole ring together with other atoms. A is, for example, preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring.

  In the following, when A is described as a ring, it includes two carbon atoms located at the β-position of the pyrrole ring.

  A is not particularly limited as long as the two carbon atoms at the β-position of the pyrrole ring form a ring with other atoms, but an aromatic ring or an alicyclic hydrocarbon ring is preferable. As the aromatic ring, for example, an aromatic ring having 6 to 10 carbon atoms such as a benzene ring is preferable. Examples of the alicyclic hydrocarbon ring include cycloalkanes having 3 to 10 carbon atoms such as cyclopentane, cyclohexane and cycloheptane; cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene (for example, 1,3-cyclohexadiene), Cycloalkene having 3 to 10 carbon atoms such as cycloheptene, cycloheptadiene, and the like; monocyclic ring such as bicyclo [2.2.1] pentane, bicyclo [2.2.1] pent-2-ene, bicyclo [2 And 2.2] octane, and bicyclic [2.2.2] oct-2-ene and other cyclic alkanes having a bridge. Among them, an aromatic ring having 6 to 7 carbon atoms, a cycloalkane having 5 to 7 carbon atoms, a cycloalkene having 5 to 7 carbon atoms, and a cyclic alkane having 5 to 9 carbon atoms having a bridge are preferable. Also preferably, a five-membered ring (for example, cyclopentene (following A-1) etc.), a six-membered ring (for example, cyclohexane (following A-2), cyclohexene (following A-3), cyclohexadiene (following A-4) , Bicyclo [2.2.2] octane (A-5 below), bicyclo [2.2.2] oct-2-ene (A-6 below), bicyclo [2.1.2] heptane (A- below) 7), bicyclo [2.1.2] hept-2-ene (the following A-8) and the like. Among these, structural formulas selected from the following formulas (A-1) to (A-8) are preferable. In the following formulas (A-1) to (A-8), * is a bonding site with the β carbon atom of the pyrrole ring and may be any of the two β carbon atoms. In addition, the binding site is bonded to two carbon atoms located at the β-position of the pyrrole ring to form a ring.

  In ring A, at least one of the carbon atoms constituting the aromatic ring or alicyclic hydrocarbon ring (excluding the carbon atom shared with the pyrrole ring) is N (nitrogen atom), S ( It may be a heterocyclic ring substituted with at least one atom selected from sulfur atom) and O (oxygen atom). As such a heterocyclic ring, for example, at least one of carbon atoms constituting a cycloalkane having 5 to 7 carbon atoms or a cycloalkene having 5 to 7 carbon atoms is at least one selected from N, S and O A heterocyclic ring substituted with the above atoms is preferable, and more preferably, at least one of carbon atoms constituting cyclohexane, cyclohexene, and cyclohexadiene is at least one atom selected from N, S, and O. Substituted heterocycles are preferred. Although the number of N, S, and O per A1 ring depends on the skeleton constituting A, it is 1 or more (especially 1 to 2), and may be 2 or more (particularly 2). Further, when there are two or more N, S, and O contained in the A1 ring, N, S, and O may be the same or different. Such a heterocyclic ring is, for example, a heterocyclic ring in which the atom bonded to the β-position carbon atom of the pyrrole ring is N, S, or O (for example, (B-1), (B-3), (B- 5) to (B-17), etc.), and other heterocycles in which the carbon atom is N, S or O can be exemplified (for example, the following (B-2), (B-4) and the like). Among these, structural formulas selected from the following formulas (B-1) to (B-17) are preferable. In the following formulas (B-1) to (B-17), * is a bonding site with the β carbon atom of the pyrrole ring and may be any of the two β carbon atoms. In addition, the binding site is bonded to two carbon atoms located at the β-position of the pyrrole ring to form a ring.

  Further, the ring A may be condensed with another ring B. When the other ring B is condensed, the resulting oxocarbon-based compound can have a longer wavelength, so that it is easy to design a molecule according to the color tone of the compound. For the ring B, for example, the aromatic ring, alicyclic hydrocarbon ring, and heterocyclic ring described in detail in the column of ring A can be appropriately selected. Among them, the aromatic ring having 6 to 10 carbon atoms, carbon A cycloalkane having 5 to 10 carbon atoms, a cycloalkene having 5 to 10 carbon atoms, a cyclic alkane having 5 to 12 carbon atoms having a bridge, and at least one of carbon atoms constituting these rings are N, S And a heterocyclic ring substituted with at least one atom selected from O and O is preferred. In addition, what is described as a ring in the column of A is read in B as including any two adjacent carbon atoms present in A. Moreover, the structure illustrated using the coupling | bonding site | part is read in B as this coupling | bonding site | part couple | bonds with arbitrary two adjacent carbon atoms which exist in A, and forms a ring.

  Examples of the ring A condensed with the ring B include condensed polycyclic hydrocarbons (for example, the following (C-1), (C-2), (C-5), (C-6), (C- 8), (C-9), etc.), condensed heteropolycyclic compounds (for example, the following (C-3), (C-4), (C-7), etc.), among others, the following formula (C- A structural formula selected from 1) to (C-9) is preferred. In the following formulas (C-1) to (C-9), * is a bonding site with the β carbon atom of the pyrrole ring and may be any of the two β carbon atoms. In addition, the binding site is bonded to two carbon atoms located at the β-position of the pyrrole ring to form a ring.

  The hydrogen atom of ring A and / or ring B may be substituted with an electron withdrawing group and / or an organic substituent.

  The electron withdrawing group is not particularly limited as long as it can be introduced by an electrophilic substitution reaction. In the electron withdrawing group, the Hammett's rule substituent constant σ is known as an electron withdrawing index, and a functional group having a positive Hammett's substituent constant σ is used as the electron withdrawing group. Can be mentioned. Examples of the electron withdrawing group include halogen such as fluorine, chlorine, bromine and iodine, cyano group, nitro group, thiocyanate group, trifluoromethyl group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, Examples include a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

  Examples of the acyl group include substituted or unsubstituted alkanoyl groups such as acetyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group and trifluoroacetyl group; benzoyl Groups, substituted or unsubstituted aroyl groups such as 1-naphthoyl group and 2-naphthoyl group. Among these, an acyl group having 2 to 15 carbon atoms is preferable, and an acyl group having 2 to 10 carbon atoms is more preferable.

  Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, and a decyloxycarbonyl group. And substituted or unsubstituted alkyloxycarbonyl groups such as octadecyloxycarbonyl group and trifluoromethyloxycarbonyl group. The alkyl group in the alkyloxycarbonyl group may be linear or branched.

  Examples of the aryloxycarbonyl group include phenoxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyl. Oxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxy Substituted or unsubstituted phenyloxycarbonyl groups such as carbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc .; 1-naphthyloxy Carbonyl group, a substituted or unsubstituted naphthyl oxycarbonyl group such as a 2-naphthyloxycarbonyl group; and the like.

  Examples of the carbamoyl group include substituted or unsubstituted carbamoyl groups such as a carbamoyl group, an N-ethylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-dibutylcarbamoyl group, and an N- (2-dodecyloxyethyl) carbamoyl group. Groups.

  Examples of the alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a hexylsulfinyl group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, an octylsulfinyl group, and a cyanomethylsulfinyl group. Group, a substituted or unsubstituted alkylsulfinyl group of a methoxymethylsulfinyl group, and the like. The alkyl group in the alkylsulfinyl group may be linear or branched.

  Examples of the arylsulfinyl group include a phenylsulfinyl group, a 2-chlorophenylsulfinyl group, a 2-methylphenylsulfinyl group, a 2-methoxyphenylsulfinyl group, a 2-butoxyphenylsulfinyl group, a 2-fluorophenylsulfinyl group, and 3-methyl. Phenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-methylphenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyano Substituted or unsubstituted phenylsulfinyl group such as phenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group; 1-naphthylsulfur Iniru group, 2-naphthylsulfinyl substituted or unsubstituted naphthylsulfinyl group such as Le group; and the like.

  Examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, octylsulfonyl group, and cyanomethylsulfonyl. Group, methoxymethylsulfonyl group, trifluoromethylsulfonyl group and the like. The alkyl group in the alkylsulfonyl group may be linear or branched.

  Examples of the arylsulfonyl group include a phenylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, a 2-butoxyphenylsulfonyl group, a 2-fluorophenylsulfonyl group, and 3-methyl. Phenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 3-fluorophenylsulfonyl group, 4-methylphenylsulfonyl group, 4-fluoro Substituted or unsubstituted phenylsulfonyl group such as phenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group; 1-naphthylsulfo Group, a substituted or unsubstituted naphthylsulfonyl group and a 2-naphthylsulfonyl group; and the like.

The sulfamoyl group may be a monosubstituted sulfamoyl group in which one hydrogen atom in the sulfamoyl group (—SOONH ₂ ) is substituted, or a disubstituted sulfamoyl group in which two hydrogen atoms are substituted. Examples of monosubstituted sulfamoyl groups include sulfamoyl groups; N-methylsulfamoyl groups, N-ethylsulfamoyl groups, N-propylsulfamoyl groups, N-butylsulfamoyl groups, and N-hexylsulfamoyl groups. A sulfamoyl group substituted with an alkyl group such as a group, N-cyclohexylsulfamoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group; Famoyl group, N-2-methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N- 3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3- Anophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfa And a sulfamoyl group substituted with a substituted or unsubstituted aryl group such as a moyl group and an N-4-phenylsulfanylphenylsulfamoyl group. Examples of the disubstituted sulfamoyl group include N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, and N, N-diphenylsulfamoyl group. Etc.

  Examples of the organic substituent that can replace the hydrogen atom of the ring A and / or ring B include, for example, an alkyl group, an alkoxy group, a thioalkoxy group, an aryl group, an aralkyl group, an aryloxy group, an arylthiooxy group, and the like. Is mentioned.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Examples thereof include linear or branched alkyl groups such as dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group. Among these, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, or t-butyl is more preferable. A propyl group, isopropyl group, butyl group, isobutyl group or t-butyl group, more preferably a t-butyl group. This alkyl group may have a substituent. Examples of the substituent that the alkyl group has include a halogen and an alkoxy group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. , Tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, icosyloxy group, methoxyethoxy group, ethoxyethoxy group and the like. Among these, a C1-C20 alkoxy group is preferable and a C1-C10 thing is more preferable. Further, the alkyl group in the alkoxy group may be either linear or branched.

  Examples of the thioalkoxy group include a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, a butylthiooxy group, a pentylthiooxy group, a hexylthiooxy group, a heptylthiooxy group, an octylthiooxy group, and a nonylthio group. Oxy, decylthiooxy, undecylthiooxy, dodecylthiooxy, tridecylthiooxy, tetradecylthiooxy, pentadecylthiooxy, hexadecylthiooxy, heptadecylthiooxy, octadecyl A thiooxy group, a nonadecyl thiooxy group, an icosyl thiooxy group, etc. are mentioned. Among these, a C1-C20 thioalkoxy group is preferable and a C1-C10 thing is more preferable. Further, the alkyl group in the thioalkoxy group may be either linear or branched.

  Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, an azulenyl group, a fluorenyl group, a terphenyl group, a quarterphenyl group, a pentarenyl group, a heptaenyl group, and a biphenylenyl group. Group, indacenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, phenanthryl group and the like. Among these, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 15 carbon atoms is more preferable. This aryl group may have a substituent. The substituents of the aryl group include alkyl groups, alkoxy groups, halogens, cyano groups, nitro groups, thiocyanate groups, acyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfo groups, alkylsulfinyl groups, and aryl groups. A sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group can be mentioned.

  The aralkyl group is preferably an aralkyl group having 7 to 18 carbon atoms, and examples thereof 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 include an alkyl group, an alkoxy group, a halogen, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples thereof include a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

  Examples of the aryloxy group include phenyloxy group, biphenyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, pyrenyloxy group, indenyloxy group, azulenyloxy group, fluorenyloxy group, Phenyloxy group, quarterphenyloxy group, pentarenyloxy group, heptaenyloxy group, biphenylenyloxy group, indacenyloxy group, acenaphthylenyloxy group, phenalenyloxy group, fluorenyloxy Group, phenanthryloxy group and the like. Among these, an aryloxy group having 1 to 25 carbon atoms is preferable, and an aryloxy group having 1 to 15 carbon atoms is more preferable.

  Examples of the arylthiooxy group include phenylthiooxy group, biphenylthiooxy group, naphthylthiooxy group, anthrylthiooxy group, phenanthrylthiooxy group, pyrenylthiooxy group, indenylthiooxy group, azene Renylthiooxy group, fluorenylthiooxy group, terphenylthiooxy group, quarterphenylthiooxy group, pentarenylthiooxy group, heptalenylthiooxy group, biphenylenylthiooxy group, indacenylthiooxy group, acenaphthyleni Examples include a ruthiooxy group, a phenalenylthiooxy group, a fluorenylthiooxy group, and a phenanthrylthiooxy group. Among these, an arylthiooxy group having 1 to 25 carbon atoms is preferable, and an arylthiooxy group having 1 to 15 carbon atoms is more preferable.

  The organic substituent is preferably an alkyl group, an alkoxy group, a thioalkoxy group, an aryl group, or an aryloxy group, more preferably an alkyl group, and particularly when ring A is a ring having poor solubility such as acenaphthene. From the viewpoint of improving solubility, a bulky group such as a t-butyl group or an isobutyl group is particularly preferable.

The bonding position of the organic substituent is not particularly limited, but is preferably bonded to, for example, ring B (for example, in the case of formulas (C-1) to (C-9), R ^{c2 to} R ^c5 , R ^{c8 ~R c11, R c13 ~R c40} , R c42 ~R c47, R c50 ~R c57).

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

  Next, X in Formula (4) will be described. X is a hydrogen atom or an organic group, and examples of the organic group include an alkyl group, an aryl group, an aralkyl group, an alkylsulfonyl group, an arylsulfonyl group, and an alkoxyalkyl group.

  As the alkyl group, for example, an alkyl group having 1 to 20 carbon atoms is preferable. Specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, sec-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2- Methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, Octyl group, methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2 Methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, nonyl group, methyloctyl group, 3,7-dimethyloctyl group, dimethylheptyl group, 3-ethylheptyl And linear or branched alkyl groups such as 4-ethylheptyl group, trimethylhexyl group, 3,3-diethylpentyl group, decyl group, undecyl group, and dodecyl group.

  Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, an azulenyl group, a fluorenyl group, a terphenyl group, a quarterphenyl group, a pentarenyl group, a heptaenyl group, and a biphenylenyl group. Group, indacenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, phenanthryl group and the like. Among these, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 15 carbon atoms is more preferable. This aryl group may have a substituent. The substituents of the aryl group include alkyl groups, alkoxy groups, halogens, cyano groups, nitro groups, thiocyanate groups, acyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfo groups, alkylsulfinyl groups, and aryl groups. A sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group can be mentioned.

  The aralkyl group is preferably an aralkyl group having 7 to 18 carbon atoms, and examples thereof 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 include an alkyl group, an alkoxy group, a halogen, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples thereof include a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

  Examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, octylsulfonyl group, and cyanomethylsulfonyl. Group, methoxymethylsulfonyl group, trifluoromethylsulfonyl group and the like. The alkyl group in the alkylsulfonyl group may be linear or branched.

  Examples of the arylsulfonyl group include a phenylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, a 2-butoxyphenylsulfonyl group, a 2-fluorophenylsulfonyl group, and 3-methyl. Phenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 3-fluorophenylsulfonyl group, 4-methylphenylsulfonyl group, 4-fluoro Substituted or unsubstituted phenylsulfonyl group such as phenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group; 1-naphthylsulfo Group, a substituted or unsubstituted naphthylsulfonyl group and a 2-naphthylsulfonyl group; and the like.

  Examples of the alkoxyalkyl group include the following formula (6):

(Wherein, Z ¹ and Z ² are each independently an alkylene group, Z ³ is an alkyl group, and n represents an integer of 0 to 4).
Z ¹ and Z ² are preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 5 carbon atoms. To illustrate the preferred alkylene group _{include, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 2) CH 2 - _{, -CH (C 2 H 5)} CH 2 -, - C (CH 2) 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, Etc. Among them, -CH ₂ - _{(methylene), - CH 2 CH 2 -} ( ethylene _{group), - CH (CH 2)} CH 2 - ( propylene), or -CH ₂ CH ₂ CH ₂ - (trimethylene group) are preferred, More preferred is —CH ₂ — (methylene group) or —CH ₂ CH ₂ — (ethylene group).
Z ³ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Examples of preferable alkyl groups include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and n-pentyl group, more preferably methyl group or ethyl group.
Although n is an integer of 0-4, More preferably, it is 0-2, More preferably, it is 0 or 1.
Examples of such an alkoxyalkyl group include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxymethyl group, a methoxyethoxymethyl group, and an ethoxyethoxyethyl group.

  Among these, in the present invention, X is preferably a hydrogen atom, an alkyl group or an alkoxyalkyl group, more preferably a hydrogen atom.

  Next, Y in Formula (4) will be described. Y is a hydrogen atom, an electron withdrawing group or an organic substituent. Examples of the electron withdrawing group include the halogen, cyano group, nitro group, thiocyanate group, trifluoromethyl group, acyl group, alkyl group described above. An oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like may be selected. Similarly, the above-mentioned alkyl group, alkoxy group, thioalkoxy group, aryl group, aralkyl group, aryloxy group, arylthiooxy group, etc. may be selected as the organic substituent. Among them, an alkyl group having 1 to 4 carbon atoms or an aryl group which may have a substituent is preferable, and more preferably an aryl group having 6 to 10 carbon atoms substituted with a methyl group, an ethyl group or an alkoxy group. More preferably, it is a phenyl group substituted with a methyl group, an ethyl group or an alkoxy group, and particularly preferably a methyl group, an ethyl group, (o-, m-, p-) methoxyphenyl, or (o -, M-, p-) ethoxyphenyl.

  As such an oxocarbon-based compound, a particularly preferable compound is exemplified. In a compound having a squarylium skeleton, for example,

As a compound having a croconium skeleton, for example,

Etc. can be illustrated.

  The maximum absorption wavelength (λmax) of these oxocarbon-based compounds is 550 to 1000 nm for squarylium-based dyes. For example, by converting a bridged cyclic alkane in the molecule to an aromatic ring, the compound has a long wavelength. It is also possible to set the thickness to 600 to 800 nm. In the case of a croconium-based dye, the maximum absorption wavelength (λmax) of the dye is 700 to 1200 nm, and the compound is made longer by, for example, converting a bridged cyclic alkane in the molecule into an aromatic ring. 800 to 950 nm.

  Furthermore, these oxocarbon compounds are excellent in light resistance, and when a light resistance test is performed in which a coating film containing the oxocarbon compounds is set in a xenon weather meter and irradiated with light for 24 hours in an atmosphere of 60 ° C. The peak residual ratio obtained from the peak top obtained before and after the light resistance test can achieve 30% or more, more preferably 50% or more, and still more preferably 60% or more.

  The oxocarbon compound having the structural unit (4) is represented by the following formula (5):

(In formula (5), A, X, and Y are the same as above), and can be manufactured by reacting squaric acid or croconic acid.

  In the step of reacting squaric acid or croconic acid with the pyrrole derivative (5) (hereinafter referred to as “step 1”), the amount of the pyrrole derivative (5) used is 0.8 relative to squaric acid or croconic acid. Is preferably at least 1.2 times mol, more preferably at least 1.5 times mol, preferably at most 5 times mol, more preferably at most 4 times mol, still more preferably It is 3 times mol or less.

  This reaction is preferably carried out in the presence of a solvent. Examples of the solvent that can be used include chlorine-based hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; THF, And ethers such as dioxane, cyclopentyl methyl ether, diisopropyl ether, and diethyl ether; alcohols such as methanol, ethanol, propanol, and butanol; amides such as dimethylformamide and dimethylacetamide; These solvents may be used alone or in combination of two or more.

  The amount of the solvent used (total) is preferably 1 times or more weight, more preferably 10 times weight or more, still more preferably 20 times weight or more, relative to squaric acid or croconic acid, and the upper limit is, for example, The weight is 100 times or less.

  The reaction temperature may be appropriately set. For example, it is preferably 0 ° C. or higher, more preferably 25 ° C. or higher, 170 ° C. or lower, and more preferably 140 ° C. or lower. This reaction may be performed in a reflux state in order to remove reaction product water. The reaction time is not particularly limited, and is preferably 0.1 hour or longer, more preferably 0.5 hour or longer, preferably 24 hours or shorter, more preferably 12 hours or shorter.

  It is recommended that Step 1 be performed in an inert gas (nitrogen, argon, etc.) atmosphere.

  The oxocarbon compound obtained by the above reaction may be appropriately purified after the reaction. Examples of the purification means include filtration, silica gel column chromatography, alumina column chromatography, recrystallization, crystallization, and reprecipitation.

  In addition, when ring A and / or ring B of formula (4) includes a cyclic alkane having a bridge, an oxocarbon-based compound having a bridged cyclic alkane in the molecule was produced in step 1. Thereafter, the resulting oxocarbon-based compound is subjected to a heat treatment (hereinafter referred to as “Step 2”), whereby the bridged cyclic alkane can be converted into an aromatic ring.

  In this case, the heat treatment temperature is preferably 160 ° C. or higher, more preferably 210 ° C. or higher, preferably 280 ° C. or lower, more preferably 270 ° C. or lower. The heat treatment time is preferably 0.2 hours or longer, more preferably 0.5 hours or longer, preferably 10 hours or shorter, more preferably 6 hours or shorter.

  It is recommended that step 2 be performed in an inert gas (nitrogen, argon, etc.) atmosphere.

  In the oxocarbon compounds (1) and (2), either (1) or (2) may be added to the resin composition, and both (1) and (2) are added to the resin composition. May be added. The content of the oxocarbon-based compounds (1) and (2) is preferably 40% by mass or more, more preferably 60% by mass or more, based on 100% by mass of the total amount of the dye in order to sufficiently exhibit the effects of the present invention. More preferably, it is 80% by mass or more, particularly preferably 100% by mass, but may be 95% by mass or less.

1-2. Other dyes In the resin composition according to the present invention, in addition to the oxocarbon compounds (1) and / or (2) described above, other dyes other than these may be used in combination. That is, the resin composition according to the present invention may contain other pigments as long as the effects of the present invention are not impaired. Examples of the dye that may be contained in the resin composition of the present invention include a squarylium dye that does not have the structural unit shown above, a croconium dye that does not have the structural unit shown above, and copper (for example, , Cu (II)) or zinc (for example, Zn (II)), etc., cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, cholines, etc.), cyanine dyes, quaterylenes Examples include dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes, and the like, and one or more of these may be used in combination. In order not to impair the effects of the present invention, these other dyes desirably have an absorption maximum wavelength in the wavelength region of 400 to 1000 nm.

  The content of the other pigment is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% with respect to 100% by mass of the total amount of the pigment in order to sufficiently exhibit the effects of the present invention. It is not more than mass%, and it is particularly preferable that these other dyes are not substantially contained.

  The concentration (content) of these pigments is, for example, preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more, in 100% by mass of the resin composition. The upper limit is not particularly limited, but if the dye concentration is too high, film formation may be difficult with a uniform film thickness. Therefore, the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. More preferably, it is 15% by mass or less.

<2. Resin component>
The resin composition according to the present invention includes a resin component. As the resin component, those capable of sufficiently dissolving or dispersing the various dyes described above are preferable. By selecting a resin component suitable for such a purpose, it is possible to achieve both high transmittance in the wavelength range desired to be transmitted and high absorbency in the wavelength range desired to be blocked.

  Examples of the resin component include (meth) acrylic resins, (meth) acrylurethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins (for example, polyethylene resins and polypropylene resins), and polycycloolefin resins. , Melamine resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (for example, nylon), aramid resin, polyimide resin, alkyd resin, phenol resin, epoxy resin, polyester resin (for example, Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), etc.), butyral resin, polycarbonate resin, polyether resin, ABS resin (acrylonitrile butadiene styrene resin), AS resin (acrylonitrile-styrene) Polymers); (meth) acrylic silicone resins, alkylpolysiloxane resins, silicone resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins and other modified silicone resins; fluorinated aromatic polymers, polytetrafluoroethylene (PTFE) ), Perfluoroalkoxy fluororesin (PFA), fluorinated polyaryletherketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorinated polyethernitrile (FPEN)), etc. And the like.

  The resin composition according to the present invention may be a thermoplastic resin composition that can be used for molding such as injection molding, and is a resin composition that is made into a paint so that it can be applied by a spin coating method, a solvent casting method, or the like. It may be.

  By using the thermoplastic resin composition, a molded product can be obtained by injection molding, extrusion molding, vacuum molding, compression molding, blow molding or the like. In this method, a molded product can be obtained by kneading an oxocarbon-based compound in a thermoplastic resin among the above-described resins and then heat-molding it. That is, an oxocarbon compound is added to the base resin powder or pellets, heated and dissolved at 150 to 350 ° C., and then molded. The shape of the molded product is not particularly limited, but is preferably a film having a thickness of 200 μm or less, a planar molded product such as a plate having a thickness of 200 μm or more, or a molded product such as a deformed product. Moreover, when kneading | mixing resin, you may add the additive used for normal resin shaping | molding, such as a ultraviolet absorber and a plasticizer.

  The paint resin composition is a liquid or paste composition containing an oxocarbon-based compound, and the paint resin composition is applied onto a resin plate, film, glass plate or the like. By doing so, a planar molded body such as a film having a thickness of 200 μm or less and a plate-like product having a thickness of 200 μm or more can be formed. Painted resin compositions include, for example, those prepared by dissolving an oxocarbon-based compound in a solvent containing a base resin, or by atomizing the oxocarbon-based compound to several μm or less into an emulsion of the base resin. Examples are dispersed.

  The resin component serving as the base resin needs to have high dispersibility with respect to the dye so that the dye can be dissolved or dispersed at a high concentration. Also, it is preferable that the coating property is good so that a film can be formed by the spin coating method, the solvent casting method, or the like using the resin composition of the present invention. From these viewpoints, as the resin component, at least one selected from the group consisting of a solvent-soluble resin soluble in an organic solvent, a solvent-soluble resin raw material, and a liquid resin raw material is preferably used. These resins are more preferable because a film can be formed even under relatively low temperature conditions. Depending on the structure of the dye, some or all of the dye may be decomposed by impurities present during polymerization (for example, unreacted substances that promote decomposition, reactive ends, ionic groups, catalysts, acid / basic groups, etc.). Since the light resistance may deteriorate, it is desirable to combine such a dye with a solvent-soluble resin that has already been polymerized (purified as necessary).

The “solvent-soluble resin” means a resin that is soluble in an organic solvent. For example, a resin that dissolves 1 part by mass or more with respect to 100 parts by mass of various organic solvents described later is preferable.
The “solvent-soluble resin raw material” means a resin raw material that is soluble in an organic solvent, that is, a resin raw material that is solvent-soluble, and for example, 1 mass with respect to 100 parts by mass of various organic solvents described later. Those that dissolve at least part are preferred.
Further, the “liquid resin raw material” means a liquid resin raw material, that is, a resin raw material that is liquid. The term “liquid” means that the viscosity of the product itself is 100 Pa · s or less at room temperature (25 ° C.). The viscosity can be measured with a B-type viscometer.
In the present specification, the “resin raw material” includes a resin precursor, a raw material of the precursor, and a monomer (such as a curable monomer) for forming the resin.

  Examples of the solvent-soluble resin include poly (amide) imide resins, fluorinated aromatic polymers, (meth) acrylic resins, polyamide resins, aramid resins, and polycycloolefin resins. Among these, from the viewpoint of superior light resistance, a poly (amide) imide resin, a fluorinated aromatic polymer, a (meth) acrylic resin or a polycycloolefin resin is preferable, and more preferably a polyimide resin, a (meth) acrylic resin or a poly A cycloolefin resin, more preferably a (meth) acrylic resin or a polycycloolefin resin.

The solvent-soluble resin also has a reactive group capable of undergoing a crosslinking reaction (curing reaction) (for example, a ring-opening polymerizable group such as an epoxy group, an oxetane ring, an ethylene sulfide group, an acrylic group, a methacryl group, a vinyl group). Or a radical curable group such as an addition curable group).
When a solvent-soluble resin is used as the resin component, the solvent-soluble resin may be used as it is as a resin component constituting the resin layer, or the resin-soluble resin is changed by a crosslinking reaction or the like. It may be a resin component constituting the layer.
The amount of reactive groups that can be cross-linked and the extent of the cross-linking reaction during film formation are not particularly limited, but it is preferable that the solvent solubility of the resin can be maintained.

2-1. Poly (amide) imide resin Poly (amide) imide resin, which is a solvent-soluble resin, means a narrowly defined polyimide resin (resin that contains an imide bond and does not contain an amide bond, and the amide bond here refers to an amic acid Means an amide bond that cannot form an imide bond by dehydration reaction), and a polyamide-imide resin (means a resin that contains an amide bond and an imide bond that cannot form an imide bond by a dehydration reaction of an amic acid) .)).

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

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

The poly (amide) imide resin is a poly (amide) imide resin raw material (poly (amide) imide precursor) obtained by reacting a polyvalent carboxylic acid compound with a polyvalent amine compound and / or a polyvalent isocyanate compound. Can be obtained by imidization reaction.
The poly (amide) imide resin also preferably has transparency. In order to improve transparency, it is preferable that there are few aromatic rings. Among them, it is preferable to have a structure in which the aromatic ring is replaced with an alicyclic ring or a fatty chain. More preferably, the weight of the aromatic ring in the total weight of 100% is 65% or less, more preferably 45% or less, and particularly preferably 30% or less.

  Although it will not specifically limit if it is a compound which has an imide bond as said poly (amide) imide resin, For example, following formula (10):

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

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

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

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

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

2-2. Fluorinated aromatic polymer Next, a fluorinated aromatic polymer that can be used as a solvent-soluble resin will be described. The fluorinated aromatic polymer includes an aromatic ring having at least one fluorine group and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. Specifically, for example, a polyimide having a fluorine atom, polyether, polyetherimide, polyetherketone, polyethersulfone, polyamide ether, polyamide, polyether A nitrile, polyester, etc. are mentioned. Among these, it is preferable that it is a polymer which has as an essential part the repeating unit containing the aromatic ring which has an at least 1 or more fluorine group, and an ether bond, and following formula (11-1) or (11-2) A polyether ketone having a fluorine atom, which contains a repeating unit represented by Among these, fluorinated polyether ketone (FPEK) is particularly preferable. In addition, the repeating unit represented by Formula (11-1) or (11-2) may be the same or different, and may have any form such as a block form or a random form.

In the above formula (11-1), R ^q1 represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. Z represents a divalent chain or a direct bond. x and y are integers of 0 or more, satisfy x + y = 1 to 8, and are the same or different and represent the number of fluorine atoms bonded to the aromatic ring. n ¹ represents a degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.
In the above formula (11-2), R ^q2 may have a substituent, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkylamino having 1 to 12 carbon atoms. Group, an alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms. . R ^q3 represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. z is the number of fluorine atoms bonded to the aromatic ring and is 1 or 2. n ¹ represents a degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.

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

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

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

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

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

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

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

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

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

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

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

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

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

  As the arylthio group, a phenylthio group, a phenylmethanethio group, an o-, m- or p-tolylthio group, a group derived from thiosalicylic acid and esters thereof, and the like are preferable.

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

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

2-3. (Meth) acrylic resin Next, a (meth) acrylic resin that can be used as a solvent-soluble resin will be described. In this specification, the (meth) acrylic resin has a (meth) acrylic acid ester unit and / or a (meth) acrylic acid unit as an essential constituent unit, and is a (meth) acrylic acid ester or (meth) acrylic acid. You may have the structural unit derived from a derivative | guide_body. “(Meth) acryl” means “acryl” and / or “methacryl”.

  Examples of the (meth) acrylic acid ester or (meth) acrylic acid ester derivative include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate. , T-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopenta (meth) acrylate Esters of (meth) acrylic acid and hydroxy hydrocarbons such as nyl (alkyl (meth) acrylate, aryl (meth) acrylate, aralkyl (meth) acrylate), dicyclopentanyloxy (meth) acrylate Ether-linked derivatives such as ethyl; chloromethyl (meth) acrylate, (meth) acrylic acid And halogen-introduced derivatives such as 2-chloroethyl; and hydroxy group-introduced derivatives. The hydroxy group-introduced derivatives include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2,3,4,5-tetrahydroxypentyl acrylate; 2- (hydroxymethyl) alkyl acrylate (eg, methyl 2- (hydroxymethyl) acrylate, 2- (hydroxy Methyl) ethyl acrylate, 2- (hydroxymethyl) isopropyl acrylate, 2- (hydroxymethyl) acrylate n-butyl, 2- (hydroxymethyl) acrylate t-butyl, etc.), 2- (hydroxyethyl) acrylic acid 2- (Hydroxy) of alkyl (for example, methyl 2- (hydroxyethyl) acrylate) Rokishiarukiru) include alkyl acrylate.

Examples of (meth) acrylic acid or (meth) acrylic acid derivatives include (meth) acrylic acids such as acrylic acid and methacrylic acid; alkylated (meth) acrylic acids such as crotonic acid; 2- (hydroxymethyl) acrylic acid And hydroxyalkylated (meth) acrylic acids such as 2- (hydroxyethyl) acrylic acid. Among these, methyl methacrylate is preferable from the viewpoints of heat resistance and transparency.
Each of the (meth) acrylic acid ester (unit), (meth) acrylic acid (unit), and derivatives (units) thereof may be only one kind or two or more kinds.

  The (meth) acrylic resin may have other structural units introduced by copolymerizing the above-described (meth) acrylic acid monomer with another monomer. Examples of such other monomers include styrene, vinyl toluene, α-methyl styrene, α-hydroxymethyl styrene, α-hydroxyethyl styrene, acrylonitrile, methacrylonitrile, methallyl alcohol, allyl alcohol, ethylene, propylene, Examples thereof include monomers having a polymerizable double bond such as 4-methyl-1-pentene, vinyl acetate, 2-hydroxymethyl-1-butene, methyl vinyl ketone, N-vinyl pyrrolidone, and N-vinyl carbazole. These other monomers (structural units) may have only one type or two or more types.

  Structural units derived from (meth) acrylic acid monomers in all structural units of (meth) acrylic resins (that is, structural units derived from (meth) acrylic acid ester units, (meth) acrylic acid units and derivatives thereof) Is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. There is no particular upper limit, and most preferably 100% by mass.

  The main chain constituting the (meth) acrylic resin preferably includes a ring structure. The main chain ring structure in the (meth) acrylic resin is not particularly limited, and examples thereof include a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, a maleic anhydride structure, and an N-substituted maleimide structure. More preferred is a lactone ring structure, a glutaric anhydride structure, or a glutarimide structure, and particularly preferred is a lactone ring structure.

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

In the above formula (12-1), R ^s1 , R ^s2 and R ^s3 are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue contains an oxygen atom. Also good.
Examples of the organic residue in the formula (12-1) include a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms (such as an alkyl group) such as a methyl group, an ethyl group, and a propyl group, an ethenyl group, and a propenyl group. In addition to C2-C20 unsaturated aliphatic hydrocarbon groups (alkenyl groups, etc.), phenyl groups, naphthyl groups, C6-C20 aromatic hydrocarbon groups (aryl groups, etc.), these saturated aliphatic carbon groups A group in which one or more hydrogen atoms in a hydrogen group, an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group are substituted with at least one group selected from a hydroxy group, a carboxyl group, an ether group and an ester group, etc. Is mentioned.

  For example, the lactone ring structure is obtained by polymerizing (preferably copolymerizing) a (meth) acrylic acid monomer A having a hydroxy group and a (meth) acrylic acid monomer B to form a hydroxy group and an ester group or a carboxyl group in the molecular chain. After introducing a group, it can be formed by causing dealcoholization or dehydration-cyclization condensation between these hydroxy group and ester group or carboxyl group. As the polymerization component, the (meth) acrylic acid monomer A having a hydroxy group is essential, and the (meth) acrylic acid monomer B includes the monomer A. Monomer B may or may not coincide with monomer A. When monomer B coincides with monomer A, monomer A is homopolymerized.

Examples of the (meth) acrylic acid monomer A having a hydroxy group include hydroxy group-introduced derivatives of the above (meth) acrylic acid esters, hydroxyalkylated (meth) acrylic acids, and the like, and preferably a monomer having a hydroxyallyl moiety Is included. Specific examples of the (meth) acrylic acid monomer A having a hydroxy group include 2- (hydroxymethyl) acrylic acid, 2- (hydroxyethyl) acrylic acid, and alkyl 2- (hydroxymethyl) acrylate (for example, 2- (Hydroxymethyl) methyl acrylate, 2- (hydroxymethyl) ethyl acrylate, 2- (hydroxymethyl) isopropyl acrylate, 2- (hydroxymethyl) acrylate n-butyl, 2- (hydroxymethyl) acrylate t- Butyl), 2- (hydroxyethyl) alkyl acrylate (for example, 2- (hydroxyethyl) methyl acrylate, 2- (hydroxyethyl) ethyl acrylate), and the like, preferably a monomer having a hydroxyallyl moiety. Some 2- (hydroxymethyl) acrylic acid and 2- ( Rokishimechiru) include alkyl acrylate. Particularly preferred are methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate. As the (meth) acrylic acid monomer B, a monomer having a vinyl group and an ester group or a carboxyl group is preferable. For example, (meth) acrylic acid, alkyl (meth) acrylate (for example, methyl (meth) acrylate, (Meth) ethyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, preferably methyl methacrylate), (meth) Aryl acrylate (eg phenyl (meth) acrylate, benzyl (meth) acrylate), 2- (hydroxyalkyl) alkyl acrylate (eg methyl 2- (hydroxymethyl) acrylate, 2- (hydroxymethyl) Ethyl acrylate, 2- (hydroxymethyl) isopropyl acrylate, -2- (hydroxyethyl) such as n-butyl (hydroxymethyl) acrylate, 2- (hydroxymethyl) alkyl acrylate such as t-butyl 2- (hydroxymethyl) acrylate, and 2- (hydroxyethyl) methyl acrylate ) Alkyl acrylate) and the like.
More specifically, the (meth) acrylic polymer having a lactone ring structure in the main chain is, for example, a method described in JP-A-2006-96960, JP-A-2006-171464, or JP-A-2007-63541. Can be manufactured.

  When the (meth) acrylic resin has a lactone ring structure in the main chain, the content of the lactone ring structure in the resin is not particularly limited, but is preferably, for example, 5 to 90% by mass, and more preferably 10 -80 mass%, More preferably, it is 10-70 mass%, Most preferably, it is 20-60 mass%.

In addition, the content rate of the lactone ring structure in the (meth) acrylic resin is that of the monomers involved in the lactone cyclization (the (meth) acrylic acid monomer A and the (meth) acrylic acid monomer B having a hydroxy group). It can be determined from the copolymerization amount and the lactone cyclization rate. That is, assuming that the lactone cyclization reaction has been performed by the lactone cyclization rate, the following formula:
Content of lactone ring structure (% by mass) = Z ₁ × Z ₂ × M _R / M _m
(Wherein Z ₁ is a raw material monomer involved in lactone cyclization in the polymer before lactone cyclization ((meth) acrylic acid monomer A and (meth) acrylic acid monomer B having a hydroxy group)) the mass content of the structural unit derived from the formula weight of the lactone ring structural units M _R of generating (specifically, a lactone ring-forming elements, the total formula weight of groups other than the main chain which binds to the lactone ring) M _m is the molecular weight (total) of raw material monomers (hydroxy group-containing (meth) acrylic acid monomer A and (meth) acrylic acid monomer B) involved in lactone cyclization, and Z ₂ is Lactone cyclization rate)
Can be calculated.

  The lactone cyclization rate is, for example, based on the amount of mass loss that occurs when all hydroxy groups are dealcoholated or dehydrated as alcohol or water from the polymer composition obtained by polymerization, and mass loss starts in dynamic TG measurement. It can be determined from the mass reduction due to the dealcoholization reaction from the previous 150 ° C. to 300 ° C. before the decomposition of the polymer begins. That is, in the dynamic TG measurement of a polymer having a lactone ring structure, the mass reduction rate between 150 ° C. and 300 ° C. is measured, and the obtained actual mass reduction rate is defined as (X). On the other hand, from the composition of the polymer, the theoretical mass reduction rate when assuming that all the hydroxyl groups contained in the polymer composition are dealcoholized or dehydrated because they are involved in the formation of the lactone ring (that is, 100% on the composition) (Mass reduction rate calculated assuming that dealcoholization or dehydration reaction has occurred) is defined as (Y). The theoretical mass reduction rate (Y) is more specifically the molar ratio of raw material monomers having a structure (hydroxy group) involved in dealcoholization or dehydration reaction in the polymer, that is, in the polymer composition. It can be calculated from the content of the raw material monomer. Substituting these values (X, Y) into the formula: 1- (actually measured mass reduction rate (X) / theoretical mass reduction rate (Y)) to obtain the value and expressing it as “%”, the lactone cyclization rate (Dealcoholation or dehydration rate) is obtained.

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

In the above formula (12-2), R ^s4 and R ^s5 are each independently a hydrogen atom or a methyl group, and X ^s1 is an oxygen atom or a nitrogen atom. When X ^s1 is an oxygen atom, R ^s6 does not exist, and when X ^s1 is a nitrogen atom, R ^s6 is a hydrogen atom, a straight-chain alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group). Butyl group, pentyl group, hexyl group), cyclopentyl group, cyclohexyl group or phenyl group.

The glutaric anhydride structure in which X ^s1 in the above formula (12-2) is an oxygen atom is, for example, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid is subjected to dealcoholization cyclocondensation in the molecule. Can be formed.
The glutarimide structure in which X ^s1 in the above formula (12-2) is a nitrogen atom can be formed, for example, by imidizing a (meth) acrylic acid ester polymer with an imidizing agent such as methylamine.
More specifically, a (meth) acrylic resin having a glutaric anhydride structure or a glutarimide structure in the main chain can be produced, for example, by the method described in International Publication No. 2007/26659 and International Publication No. 2005/108438.

  When the (meth) acrylic resin has a glutaric anhydride structure or a glutarimide structure in the main chain, the content of the glutaric anhydride structure or the glutarimide structure in the polymer is not particularly limited. %, More preferably 10 to 70% by mass, still more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass.

  In addition, the content rate of the glutaric anhydride structure and glutarimide structure in (meth) acrylic-type resin can be calculated | required by the method as described in Unexamined-Japanese-Patent No. 2006-131589, for example.

Examples of the maleic anhydride structure or the N-substituted maleimide structure include a structure represented by the following formula (12-3) (in the following formula (12-3), when X ^s2 is an oxygen atom, maleic anhydride Preferred is an acid structure, and an N-substituted maleimide structure when X ^s2 is a nitrogen atom.

In the above formula (12-3), R ^s7 and R ^s8 are each independently a hydrogen atom or a methyl group, and X ^s2 is an oxygen atom or a nitrogen atom. When X ^s2 is an oxygen atom, R ^s9 does not exist, and when X ^s2 is a nitrogen atom, R ^s9 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group). Butyl group, pentyl group, hexyl group), cyclopentyl group, cyclohexyl group, benzyl group or phenyl group.

The maleic anhydride structure in which X ^s2 in the above formula (12-3) is an oxygen atom can be formed, for example, by subjecting maleic anhydride to polymerization together with (meth) acrylic acid ester and the like.
The N-substituted maleimide structure in which X ^s2 in the above formula (12-3) is a nitrogen atom can be formed, for example, by subjecting an N-substituted maleimide such as phenylmaleimide to polymerization together with a (meth) acrylic acid ester or the like.
More specifically, a (meth) acrylic resin having a maleic anhydride structure or an N-substituted maleimide structure in the main chain can be obtained, for example, by the method described in JP-A-57-153008 and JP-A-2007-31537. Can be manufactured.

  When the (meth) acrylic resin has a maleic anhydride structure or an N-substituted maleimide structure in the main chain, the content of the maleic anhydride structure or the N-substituted maleimide structure in the resin is not particularly limited. It is preferable that it is -90 mass%, More preferably, it is 10-70 mass%, More preferably, it is 10-60 mass%, Most preferably, it is 20-50 mass%.

  The content of the maleic anhydride structure or N-substituted maleimide structure in the (meth) acrylic resin can be determined from the copolymerization amount of maleic anhydride or N-substituted maleimide.

2-4. Next, the solvent-soluble resin material and the liquid resin material will be described. Examples of the solvent-soluble resin raw material or liquid resin raw material include, for example, epoxy compounds used as raw materials for epoxy resins, vinyl compounds ((meth) acrylic compounds, styrene compounds, etc.) used as raw materials for vinyl polymer resins, and poly (amides). ) Imide precursors and the like. An epoxy compound and a vinyl compound are preferable.

  The said epoxy resin is a hardened | cured material of the curable composition containing the compound (epoxy compound) which has an epoxy group. Examples of the form of the cured product include a form obtained by curing the epoxy compound with light and / or heat in the presence of a cationic curing catalyst, a form of a cured product obtained by reacting the epoxy compound with an additional curing agent, and the like. In the latter case, a conventionally known curing accelerator can be used in combination for accelerating the curing reaction. Examples of the additional curing agent include acid anhydrides, polyhydric phenol compounds, polyhydric amines, etc. Among them, acid anhydrides are preferable.

  As said epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, a hydrogenated epoxy compound etc. are suitable, For example, Osaka Gas Chemical Co., Ltd. fluorene epoxy (Oncoat EX-1); Bisphenol A epoxy compound (Epicoat 828EL) manufactured by Japan Epoxy Resin; Hydrogenated bisphenol A epoxy compound (Epicoat YX8000) manufactured by Japan Epoxy Resin; Alicyclic liquid epoxy compound (Celoxide 2021) manufactured by Daicel Industries Can be preferably used. In addition, in this specification, an epoxy group includes an oxirane ring that is a three-membered ether, and includes a glycidyl group (including a glycidyl ether group and a glycidyl ester group) in addition to a narrowly defined epoxy group. Means.

  The curable composition containing the epoxy compound preferably contains a component having flexibility (flexible component). By including a flexible component, it is possible to obtain a resin composition having a sense of unity, such as not cracking, not losing shape, being easily peeled off, and having flexibility when being removed from molding or from a substrate or mold. The flexible component may be a compound different from the epoxy compound, or at least one of the epoxy compounds may be a flexible component.

  The vinyl polymer resin is a polymer obtained by (co) polymerizing a vinyl compound as a polymerization raw material, and examples thereof include an acrylic resin, a styrene resin, and an acrylic-styrene resin. An acrylic resin is a cured product of a curable composition containing a compound having a (meth) acryloyl group (also referred to as a (meth) acryloyl group-containing compound or a (meth) acrylic compound). A styrene resin is a styrene resin. Is a cured product of a curable composition containing a styrene monomer (also referred to as a styrene compound) such as divinylbenzene, and acrylic-styrene resin is a curable composition containing a (meth) acryloyl group-containing compound and a styrene monomer. It is a cured product of the composition. Among the vinyl polymer resins, acrylic resins and acrylic-styrene resins are preferable.

  Preferred examples of the (meth) acryloyl group-containing compound include (meth) acrylate monomers, urethane (meth) acrylates, polyester (meth) acrylates, and epoxy (meth) acrylates. A (meth) acrylate (co) polymer (having a (meth) acryloyl group) obtained by (co) polymerizing a (meth) acrylate monomer can also be suitably used. A composition containing a polymerizable oligomer such as urethane (meth) acrylate, polyester (meth) acrylate, (meth) acrylate (co) polymer, and (meth) acrylate monomer is acrylic in that a coating film can be easily formed. It is preferable to use it as a resin raw material. As said acrylic-styrene resin raw material, the composition which used the styrene-type monomer further in the suitable form of the said acrylic resin raw material is preferable.

  The poly (amide) imide precursor is a raw material for forming a poly (amide) imide resin, that is, a compound that is subjected to an imidization reaction. For example, a polyamic acid is preferable. Specifically, for example, HPC-7000-30 manufactured by Hitachi Chemical Co., Ltd. is preferably used.

<3. Solvent>
The resin composition according to the present invention may be a composition diluted with a solvent (organic solvent) (that is, a solvent-containing one) in order to easily carry out the subsequent coating operation. Solvents that can be used are not particularly limited, and can be appropriately selected according to the type of resin component. For example, ketones such as methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), and cyclohexanone. Class: PGMEA (2-acetoxy-1-methoxypropane), glycol derivatives such as ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol ethyl ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); Amides such as N, N-dimethylacetamide; Esters such as ethyl acetate, propyl acetate and butyl acetate; Pyrrolidones such as N-methyl-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone and the like); Toluene, xylene, etc. Aromatic hydrocarbons; cyclohexane, aliphatic hydrocarbons such as heptane; tetrahydrofuran, dioxane, diethyl ether, ethers such as Djibouti ether; and the like.

  As the usage-amount of the said solvent, it is preferable that it is 50 mass% or more in 100 mass% of resin compositions, and less than 100 mass% is preferable. More preferably, it is 70 mass% or more, and may be 95 mass% or less. By adjusting within the said range, it becomes possible to obtain a resin composition with a high pigment concentration.

  It should be noted that amides such as N, N-dimethylacetamide and the like may decompose the oxocarbon-based compound described in the above general formula (1) or (2), so that the amount used is preferably small. Therefore, the amount of amides used is preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 40% by mass or less, and particularly preferably 20% by mass or less, in 100% by mass of the resin composition. And most preferably 0% by weight (ie not containing amides).

  Moreover, the resin composition which concerns on this invention may contain the compound which has an absorptivity in the wavelength range of 350-400 nm, for example. Due to the presence of these compounds, it is possible to sufficiently suppress the deterioration of the resin sheet (and the light selective transmission filter) due to light in the wavelength range of 350 to 400 nm (substantially purple light). When a compound having an absorption ability in the wavelength range of 350 to 400 nm is used in combination, examples of the compound having an absorption ability in the wavelength range of 350 to 400 nm include TINUVIN P, TINUVIN 234, TINUVIN 329, TINUVIN 213, TINUVIN 571, and TINUVIN. One type or two or more types of ultraviolet absorbing compounds such as 326 (manufactured by BASF) can be used.

  The resin composition according to the present invention may contain various additives such as a surfactant, a dispersant, a surface tension adjuster, a viscosity adjuster, an antifoaming agent, an antiseptic, and a specific resistance adjuster. .

<4. Application>
The resin composition according to the present invention can be preferably used as a resin composition for forming a filter used in various applications such as an optical device application, a display device application, a machine part, and an electric / electronic part.

  Usually, a filter used in these applications is integrated with a support and used as a resin sheet. For example, the resin sheet may be formed by applying a resin composition on the surface of the support (or on the surface of the other layer when the support and the resin layer have other layers) by spin coating or solvent casting. In addition to a method of forming by coating and drying or curing (referred to as a coating method or a coating method) or a method of forming by thermocompression bonding a resin film formed from a resin composition to a support It can be produced by a kneading method or the like. Although the coating thickness (film thickness) is not particularly limited, it is preferable that the coating thickness (film thickness) is, for example, 5 μm or less because a thin film is preferable to obtain a light-resistant member. More preferably, it is 3 μm or less. Moreover, it is preferable that it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more.

  The support is preferably a film (support film). As the support film, it is preferable to use a resin having excellent transparency. Specifically, for example, (meth) acrylic resin, epoxy resin, polycarbonate resin, polyester resin, fluorinated aromatic polymer, poly (amide) are used. ) Imide resin, polyamide resin, aramid resin, cycloolefin resin and the like can be used. Among these, fluorinated aromatic polymer, poly (amide) imide resin, polyamide resin, aramid resin, cycloolefin resin, epoxy resin and / or acrylic resin are excellent in heat resistance when the reflective layer is formed by vapor deposition. preferable. More preferably, at least a poly (amide) imide resin is used.

  Since the resin composition according to the present invention contains a dye having excellent light resistance, a coating film obtained by solidifying the resin composition also exhibits good light resistance.

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

In addition, the following apparatus was used for the analysis about the compound synthesize | combined.
Ultraviolet-visible absorption spectrum: model “U-2810” manufactured by Hitachi High-Technologies Corporation, model “v-570 model” manufactured by JASCO Corporation
Infrared absorption spectrum: HORIBA, Ltd. Model “FT-720”
NMR spectrum: “JNM-AL400” manufactured by JEOL Ltd., “JNM-EX400” manufactured by JEOL Ltd., “Mercury 2000” manufactured by Varian Technologies, Inc.
Mass spectrum: manufactured by JEOL Ltd. Model “JMS-MS 700”
(MALDI-TOF) mass spectrum; manufactured by Applied Biosystems, model “Voyager-DE ^™ -PRO”

  Further, compound 20 used in this synthesis example is Tetsuo, Nine others, “Acenaphthylene-Fused Cyclo [8] polaris with Intense Near-IR-Region Absorption Bands”, Chemistry-AuropJu 19 (41)), pp 13970-13978, and was produced by a method similar to the method for synthesizing compound 5 on page 13971.

  Compound 4 used in this synthesis example is Yuya, 6 others, “Synthesis of π-expanded O-chelated boron-dipyrrothene as an NIR dye”, Tetrahedron, May 6 (2001), 67 (18), pp 3187. 3193, described in 3193, on a similar method to the synthesis of compound 3b.

  The pyrrole 13 used in this synthesis example is Schultz, 1 other, “Application of In Situ-Generated Rh-Bound Trimethylene methane Variants to the Synthesis of 3, 4-Fused Pyroles”. Am. Chem. Soc. (2013), 135, pp 4696-4699, prepared in the same manner as the method for synthesizing compound 13a on page 4697.

≪Synthesis example of squarylium dyes≫
Synthesis Example 1 Synthesis of squarylium dye having acenaphthopyrrole

[Step 1]
Acenaphthopyrrole 20 (413 mg, 1.1 mmol) was added to the reaction vessel, and the atmosphere was replaced with nitrogen. 30 mL of dryTHF was added to protect from light, LiAlH ₄ (213 mg, 5.6 mmol) was added, and the mixture was heated to reflux overnight. After returning to room temperature, the reaction mixture was quenched with a saturated aqueous sodium tartrate solution, extracted with ethyl acetate, and washed with water and saturated brine. The extract was dried over Na ₂ SO ₄ and concentrated under reduced pressure to obtain the desired acenaphthopyrrole 2 (yield 356 mg, 1.1 mmol, yield quant.).
Mol. Form. : (Exact Mass: 317.2143, Mol. Wt .: 317.4672)
Appearance: pale yellowish green solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.72 (brs, 1H), 7.60 (d, J = 1.2 Hz, 1H), 7.52 (m, 2H), 7.50 (m , 1H), 6.85 (d, J = 2.3 Hz, 1H), 2.54 (s, 3H), 1.45 (s, 9H), 1.43 (s, 9H)

[Step 2]
Squaric acid 1 (62.4 mg, 0.547 mmol) and acenaphthopyrrole 2 (0.356 g, 1.13 mmol) were added to the reaction vessel and purged with nitrogen. 20 mL of n-BuOH and toluene were added at a ratio of 1: 1 and heated to reflux. After 1 hour, it was confirmed by TLC that the raw material acenaphthopyrrole had disappeared, and then the heating was stopped and the mixture was returned to room temperature and concentrated under reduced pressure. The product was washed with MeOH to obtain a dark green solid which was considered to be a product, and further recrystallized with CHCl ₃ / MeOH to obtain Compound 3 (yield 0.2744 g, 0.383 mmol, yield 70%). The ratio of rotational isomers at the time of dissolution in chloroform was 5: 3.
Mol. Form. : (Exact Mass 712.4029 :, Mol. Wt .: 712.9601)
Appearance: Green powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 10.19 (brs, 1H, minor), 9.97 (brs, 1H, major), 9.42 (s, 1H, major), 9.24 (s) , 1H, minor), 7.80-7.78 (m, 2H), 7.73-7.68 (m, 4H), 2.76 (s, 3H, minor), 2.64 (s, 3H) , Major), 1.63-1.48 (m, 36H)
UV-vis (CHCl ₃ ) λmax, 709 nm
MS (MALDI-TOF MS): 713.0355 (M ^<+> )

  Synthesis Example 2 Synthesis of squarylium dye having o-methoxyphenylbicyclopyrrole

Squaric acid 1 (29.5 mg, 0.26 mmol) and o-methoxyphenylbicyclopyrrole 4 (126.3 mg, 0.5 mmol) were added to the reaction vessel, and the atmosphere was replaced with nitrogen. 10 mL of n-BuOH and toluene were added at a ratio of 1: 1, and the mixture was heated to reflux. After 30 minutes, it was confirmed by TLC that the raw material o-methoxyphenylbicyclopyrrole had disappeared, and then the heating was stopped and the mixture was returned to room temperature and concentrated under reduced pressure. Washing with isopropanol gave compound 5 (yield 0.0925 g, 0.16 mmol, 62% yield).
Mol. Form. : (Exact Mass: 580.2362, Mol. Wt .: 580.6722)
Appearance: Green powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 10.66 (brs, 1H), 10.38 (brs, 1H), 7.78 (m, 2H), 7.36 (m, 2H), 7. 09 (m, 2H), 7.04 (m, 2H), 6.63 (m, 2H), 6.53 (m, 2H), 5.06 (m, 1H), 4.92 (m, 1H) ), 4.38 (m, 2H), 4.07 (s, 3H), 4.03 (s, 3H), 1.79-1.56 (m, 8H)
UV-vis (CHCl ₃ ) λmax, 639 nm
MS (MALDI-TOF MS): 581.8236 (M ⁺ ), 553.8042 (M ⁺ -28), 524.7811 (M ⁺ -56)

  Synthesis Example 3 Synthesis of squarylium dye having o-methoxyphenyl-benzopyrrole

Compound 5 (15.6 mg, 0.027 mmol) was added to the reaction vessel and purged with nitrogen. The mixture was heated at 230 ° C. for 1 hour and allowed to cool to room temperature to obtain Compound 6 (yield 14 mg, 0.027 mmol, yield quant). The ratio of rotational isomers at the time of dissolution in chloroform was 2: 1.
Mol. Form. : (Exact Mass: 524.1736, Mol. Wt .: 524.5654)
Appearance: Black powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 12.38 (brs, 1H, major), 12.12 (brs, 1H, minor), 8.94 (d, J = 8.1 Hz, 1H, minor) , 8.80 (d, J = 8.1 Hz, 1H, major), 8.14-8.06 (m, 4H), 7.51-7.38 (m, 6H), 7.20-7. 10 (m, 4H), 4.19 (s, 3H, major), 4.10 (s, 3H, minor)
UV-vis (CHCl ₃ ) λmax, 740 nm
MS (MALDI-TOF MS): 546.03 (M ⁺ +23)

  Synthesis Example 4 Synthesis of squarylium dye having α-methylbicyclopyrrole

Squaric acid 1 (57.9 mg, 0.5 mmol) and α-methylbicyclopyrrole 7 (160 mg, 1.0 mmol) were added to the reaction vessel, and the atmosphere was replaced with nitrogen. 10 mL of n-BuOH and toluene were added at a ratio of 1: 1, and the mixture was heated to reflux. After confirming the disappearance of the pyrrole starting material by TLC after 30 minutes, heating was stopped, the temperature was returned to room temperature, the solution was concentrated under reduced pressure, and recrystallized with chloroform / hexane to obtain Compound 8 (yield 0.3133 g, 0 787 mmol, 78% yield).
Mol. Form. : (Exact Mass: 580.2362, Mol. Wt .: 396.4810)
Appearance: Color powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 9.61 (brs, 1H), 9.39 (brs, 1H), 6.56-6.46 (m, 4H), 4.94 (m, 1H) ), 4.80 (m, 1H), 3.90 (s, 2H), 2.36 (s, 6H), 1.65 to 1.26 (m, 8H)
UV-vis (CHCl ₃ ) λmax, 563 nm
MS (MALDI-TOF): 368.84 (M ⁺ -28)
MS (FAB): 396 (M ^<+> ), 340 (M ^<+>- 56)

  Synthesis Example 5 Synthesis of squarylium dye having α-methylbenzopyrrole

Compound 8 (12.0 mg, 0.03 mmol) was added to the reaction vessel and purged with nitrogen. The mixture was heated at 230 ° C. for 1 hour and allowed to cool to room temperature to obtain Compound 9 (yield 10 mg, 0.03 mmol, yield quant.).
Mol. Form. : (Exact Mass: 340.1212, Mol. Wt .: 340.3746)
Appearance: Black powder UV-vis (CHCl ₃ ) λmax, 650 nm

  Synthesis Example 6

Squaric acid (56 mg, 0.493 mmol) and pyrrole 13 (295 mg, 0.985 mol) were added to the reaction vessel, n-BuOH / toluene (1: 1, 10 mL) was added, and the mixture was refluxed for 30 minutes. After completion of the reaction, the reaction solution was returned to room temperature, concentrated under reduced pressure, and washed with MeOH to obtain the target product 14. The ratio of rotational isomers at the time of dissolution in chloroform was 2: 1.
yield: 109 mg (41%)
Mol. Form. : C ₃₄ H ₃₄ N ₂ O ₄ (Exact Mass: 534.25, Mol. Wt .: 534.64)
Appearance: green powder
UV-vis (CHCl ₃ ): 651 nm

≪Synthesis example of croconium dye≫
Synthesis Example 7 Synthesis of croconium dye having o-methoxyphenyl-bicyclopyrrole

Croconic acid (101 mg, 0.402 mmol) and o-methoxyphenylbicyclopyrrole 4 (30.3 mg, 0.213 mol) were placed in the reaction vessel, and n-BuOH / toluene (1: 1, 5 mL) was added for 2 hours. Refluxed. After completion of the reaction, the mixture was returned to room temperature, concentrated under reduced pressure, and washed with IPA to obtain Compound 10 (yield 105 mg, 81%). The ratio of rotational isomers at the time of dissolution in chloroform was 1: 1.
Mol. Form. : C ₃₉ H ₃₂ N ₂ O ₅ (Exact Mass: 608.23, Mol. Wt .: 608.68)
Appearance: brown-red powder
1H NMR: (CDCl ₃ , 400 MHz): δ = 13.14 (brs, 1H), 12.83 (brs, 1H), 12.76 (brs, 1H), 12.60 (brs, 1H), 7. 94-7.83 (m, 2H + 2H), 7.47-7.40 (m, 2H + 2H), 7.15-7.06 (m, 4H + 4H), 6.71-6.52 (m, 4H + 4H), 5.81 (m, 1H), 5.72 (m, 1H), 5.65 (m, 1H), 4.47-4.41 (m, 2H + 2H), 4.17 (s, 3H), 4 .16 (s, 3H), 4.14 (s, 3H), 4.10 (s, 3H), 1.69-1.56 (m, 8H + 8H)
MS (MALDI-TOF): 579.49 (M ⁺ -28)
UV-vis (CHCl ₃ ) λmax, 794 nm

  Synthesis Example 8 Synthesis of croconium dye having o-methoxyphenyl-benzopyrrole

Compound 10 (6.5 mg, 0.011 mmol) was placed in a reaction vessel and heated in vacuum at 230 ° C. for 2 hours. It returned to room temperature and obtained the target object 11.
yield: trace (trace)
Mol. Form. _{: C 39 H 32 N 2 O} 5 (Exact Mass: 552.17, Mol.Wt:. 552.58)
Appearance: block solid
UV-vis (CHCl ₃ ) λmax, 866 nm

  Synthesis Example 9 Synthesis of croconium dye having acenaphthopyrrole

Croconic acid (243 mg, 1.71 mmol) and acenaphthopyrrole 2 (1.09 g, 3.42 mol) were added to the reaction vessel, n-BuOH / toluene (1: 1, 10 mL) was added, and the mixture was refluxed for 1.5 hours. . After completion of the reaction, the reaction solution was returned to room temperature, concentrated under reduced pressure, and washed with IPA to obtain the target compound 12 (yield 1.15 g, yield 91%). The abundance ratio of rotamers when dissolved in chloroform was 10: 7.
Mol. Form. : C ₅₁ H ₅₄ N ₂ O ₃ (Exact Mass: 742.41, Mol. Wt .: 742.99)
Appearance: brown-red powder
1H NMR: (CDCl ₃ , 400 MHz): δ (syn) = 12.60 (brs, 2H, major), 9.67 (s, 2H, major), 7.82 (s, 2H, major), 7. 68 (s, 2H, major), 7.43 (s, 2H, major), 2.55 (s, 6H, major), 1.62 (s, 18H, major), 1.41 (s, 18H, major), δ (anti) = 13.41 (brs, 1H, minor), 11.76 (brs, 1H, minor), 9.74 (s, 1H, minor), 9.64 (s, 1H, minor) ), 7.86 (s, 1H, minor), 7.83 (s, 1H, minor), 7.77 (s, 1H, minor), 7.72 (s, 1H, minor), 7.69 ( s, 1H, mino r), 7.63 (s, 1H, minor), 2.82 (s, 3H, minor), 2.57 (s, 3H, minor), 1.64 (s, 9H, minor), 1.60 (S, 9H, minor), 1.50 (s, 9H, minor), 1.47 (s, 9H, minor)
MS (FAB): 742 (M ^<+> )
UV-vis (CHCl ₃ ) λmax, 854 nm

  Synthesis Example 10

Croconic acid (182 mg, 1.28 mmol) and pyrrole 13 (582 mg, 2.56 mol) were added to the reaction vessel, n-BuOH / toluene (1: 1, 10 mL) was added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the product was concentrated under reduced pressure and washed with MeOH to obtain the target product 15. The ratio of rotational isomers at the time of dissolution in chloroform was 1: 1.
yield: 408 mg (57%)
Mol. Form. : C ₃₅ H ₃₂ N ₂ O ₅ (Exact Mass: 560.23, Mol. Wt .: 560.64)
Appearance: brown-red powder
UV-vis (CHCl ₃ ): 800 nm

<Light resistance test>
The coating film obtained by the following prescriptions 1-5 was set in a xenon weather meter (X75SC, manufactured by Suga Test Instruments Co., Ltd.), and a light resistance test was performed. The evaluation conditions were light irradiation for 24 hours in a 60 ° C. atmosphere.

≪Method for producing resin composition≫
Production Example 1 (Dimethylacetamide solution of alicyclic polyimide)
A flask was charged with 5 parts of 1,2,4,5-cyclohexanetetracarboxylic acid (Tokyo Chemical Industry, purity 98%, Mw = 260.20) and 44 parts of acetic anhydride (Wako Pure Chemical Industries, Ltd.) and stirred. The inside of the reactor was replaced with nitrogen gas. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. While stirring, the mixture was cooled to room temperature to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain crystals of the desired product (1,2,4,5-cyclohexanetetracarboxylic dianhydride). In a flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a dropping funnel with a side tube, Dean Stark, and a cooling tube, 4,4′-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Mw = 200.24) under a nitrogen stream. ) 8.9 parts and 76 parts of dimethylacetamide as a solvent were dissolved and then 10 parts of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (Mw = 224.17) were added at room temperature. The solid was added in portions over 1 hour and stirred at room temperature for 2 hours. 26 parts of toluene was added as an azeotropic dehydrating agent, the reaction was performed at 130 ° C. for 3 hours, and the product water to be azeotroped was separated by refluxing with Dean Stark. Xylene was distilled off while the temperature was raised to 194 ° C., and then cooled to obtain a dimethylacetamide solution of polyimide.

Production Example 2 (Acrybure Dioxane Solution)
As a (meth) acrylic resin having a lactone ring structure in the main chain, AKRIVIEWA (registered trademark: “RN”) manufactured by Nippon Shokubai was used. By mixing and stirring 10 parts of the above-mentioned Acryviewer with 90 parts of dioxane, a dioxane solution of Acryviewer (RN) was obtained.

≪Method for producing coating film≫
Example 1 (resin composition containing compound 3)
The dimethylacetamide solution of polyimide obtained in Production Example 1 was diluted with dimethylacetamide to adjust the concentration to 8%. 12.31 parts of this solution and 0.015 part of the compound (3) obtained in Synthesis Example 1 were mixed to dissolve the compound. This solution was filtered to remove insoluble components, and then spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

Example 2 (resin composition containing compound 3)
9.85 parts of acrylobium dioxane solution obtained in Production Example 2 and 0.015 part of Compound (3) obtained in Synthesis Example 1 were mixed to dissolve the compound. This solution was filtered to remove insoluble components, and then spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

Example 3 (resin composition containing compound 12)
9.85 parts of the dioxane solution of Acribure obtained in Production Example 2 and 0.015 part of Compound (12) obtained in Synthesis Example 9 were mixed to dissolve the compound. This solution was filtered to remove insoluble components, and then spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

Comparative Example 1
The dimethylacetamide solution of polyimide obtained in Production Example 1 was diluted with dimethylacetamide to adjust the concentration to 8%. 12.31 parts of this solution and 0.015 part of squarylium dye represented by the following formula were mixed to dissolve the dye. This solution was filtered to remove insoluble components, and then spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

Comparative Example 2
The dimethylacetamide solution of polyimide obtained in Production Example 1 was diluted with dimethylacetamide to adjust the concentration to 8%. 12.31 parts of this solution and 0.015 part of a croconium dye represented by the following formula were mixed to dissolve the dye. This solution was filtered to remove insoluble components, and then spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

The peaks obtained before and after the light resistance test are measured, and the results are shown in FIGS. 1 to 5 (the solid line in the attached chart indicates the spectrum before the test, and the dotted line indicates the spectrum after the test). The peak tops obtained before and after the light resistance test were respectively obtained, and (peak top value before test−peak top value after test) was divided by the peak top value before the test to obtain the peak residual rate. The result of peak residual ratio is shown below.
Example 1 (FIG. 1) 44%
Example 2 (FIG. 2) 72%
Example 3 (FIG. 3) 92%
Comparative Example 1 (FIG. 4) 2%
Comparative Example 2 (FIG. 5) 56%

  From the results of Examples 1 and 2 and Comparative Example 1, in the compound in which the pyrrole ring is bonded to the squarylium skeleton, the compound in which a cyclic substituent is introduced into the two β-position carbons of the pyrrole ring is a compound that is not so, That is, it was found that the peak residual ratio was high and the light resistance was excellent as compared with a compound via a methine group. Similarly, from the results of Example 3 and Comparative Example 2, it was found that a compound having a croconium skeleton also had excellent light resistance when a compound having a cyclic substituent introduced into two β-position carbons of the pyrrole ring. It was.

  Since the resin composition according to the present invention contains a pigment having excellent weather resistance and color tone, it is an optical filter for a semiconductor light-receiving element having a function of absorbing and cutting visible light and near infrared rays; Near-infrared absorbing film and near-infrared absorbing plate; information display material as security ink and invisible barcode ink; solar cell material using visible light and near-infrared light; specific for plasma display panel (PDP) and CCD It is preferably used as a material capable of forming a wavelength absorption filter; a photothermal conversion material for laser welding; a photofixing method (light developing toner for flash fixing method) using light that does not easily cause problems due to pressurization and heating; be able to.

Claims (6)

The following formula (1) having a squarylium skeleton and / or the following formula (2) having a croconium skeleton:
(In the formulas (1) and (2), R ^{a1 to} R ^a4 are each independently a structural unit represented by the following formula (3).)
[In the formula (3), R ^{b1 to} R ^b4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, or a substituent. Aryloxycarbonyl group which may have, acyl group which may have substituent, aryl group which may have substituent, heteroaryl group which may have substituent, substituent aralkyl group which may have a, * - CH = (wherein R ^c is an aliphatic hydrocarbon group, an aryl group, or a heterocyclic substituent) CH-R ^c, or * -CH = N -R ^d (wherein R ^d is an amino group which may have a substituent). R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 may be bonded to each other to form a ring.
* Represents a binding site.
However, at least one of R ^{b1 to} R ^b4 is an aryl group which may have a substituent, a heteroaryl group which may have a substituent, * —CH═CH—R ^c (wherein R ^c is the same as above), or * —CH═N—R ^d (wherein R ^d is the same as above), or R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 An oxocarbon-based compound represented by the formula:
A resin composition comprising a resin component.   The resin composition according to claim 1, further comprising at least one solvent selected from ketones, glycol derivatives, amides, esters, pyrrolidones, aromatic hydrocarbons, aliphatic hydrocarbons, and ethers. object.   3. The resin component according to claim 1 or 2, wherein the resin component is at least one selected from a poly (amide) imide resin, a fluorinated aromatic polymer, a (meth) acrylic resin, a polyamide resin, an aramid resin, and a polycycloolefin resin. The resin composition as described.   The resin composition according to claim 2 or 3, wherein the amount of the amide used is 80% by mass or less in 100% by mass of the resin composition.   The molded object which consists of a resin composition of any one of Claims 1-4.   The planar molded object which consists of a resin composition of any one of Claims 1-4.