JP6506529B2 - Resin composition containing oxocarbon-based compound and molded article comprising the same - Google Patents

Description

  The present invention relates to a resin composition containing an oxocarbon compound and a resin component, and a molded article made of the same.

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

  A typical compound as a compound which is excellent in the absorption characteristic in a near infrared region among the many squalilium type or croconium type compounds is a squarylium type or croconium type pigment | dye represented by a following formula. However, all of the dyes shown below have low resistance to light, and thus 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, examples of the compound having excellent light resistance include the following compounds disclosed in Patent Documents 6 to 8. However, each of these compounds has a maximum absorption wavelength (λmax) in the region of 650 nm or less, and is inferior to the absorption characteristics in the near infrared region (about 700 nm or more).

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

Unexamined-Japanese-Patent No. 1-230674 JP, 2008-308602, A JP, 2011-208101, A JP 2007-169315 A JP, 2008-1754, A JP 2001-183522 A Japanese Patent Application Publication No. 2005-520835 JP, 2008-184606, A

Raymond, 2 others, "Squaraines based on 2-arylpyrroles", Tetrahedron, August 23 (2004), 60, pp 8913-8918 Luca, 14 others, "Assessment of Water-Soluble pi-Extended Squares as One-and Two-Photon Singlet Oxygen Photosensitizers: Design, Synthesis, and Characterization", JACS, January 19 (2008), 130, pp 1894-1902 Fabio, 8 others, "A squaraine-phthalocyanine ensemble: towards molecular molecular sensitivity in solar cells", Chem. Commun. , April 20 (2009), pp 4500-4502. Michael, 3 others, "Redox-Switchable Squares with Extended Conjugation", Org. Lett. , July 19 (2003), 5 (17), pp 2975-2978.

  As described above, conventionally, squarylium-based or croconium-based compounds having a maximum absorption wavelength (λmax) in the near infrared region while having good light resistance have not been widely known. Moreover, coexistence of light resistance and an absorption region is similarly requested | required also to the resin composition containing these compounds. Therefore, the present invention has an object to provide a resin composition capable of achieving both light resistance and an absorption region while containing a squarylium-based or croconium-based dye.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition comprising a specific oxocarbon compound and a resin component has a maximum absorption wavelength in the near infrared region. And, it found that it was excellent also in light resistance, and completed the present 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 formula (3), R ^{b1 to} R ^b4 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, a substituent An aryloxycarbonyl group which may have, an acyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a substituent Or 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). The R ^b1 and R ^b2 , R ^b2 and R ^b3 , and R ^b3 and R ^b4 may be combined with 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 as defined above, or * -CH = N-R ^d (wherein R ^d is as defined above), R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 And at least one ring to which is attached is present] an oxocarbon-based compound represented by
It is characterized by including a resin component.
Furthermore, the resin composition contains at least one or more solvents 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, it is preferable that the usage-amount of said amides is 80 mass% or less in 100 mass% of resin compositions.
The present application also encompasses a molded body and a planar molded body made of the resin composition.

  According to the present invention, a resin composition capable of absorbing a near infrared region having light resistance can be obtained.

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

  The resin composition according to the present invention contains, as a dye, an oxocarbon-based compound represented by the general formula (1) and / or the general formula (2), and a resin component. The dye is preferably dispersed or dissolved in the resin composition. The dye and the resin component may be used alone or in combination of two or more. 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. An oxocarbon-based compound having a pyrrole-based structural unit In the resin composition, 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 formula (3), R ^{b1 to} R ^b4 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, a substituent An aryloxycarbonyl group which may have, an acyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a substituent Optionally substituted 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 ^b1 and R ^b2 , R ^b2 and R ^b3 , and R ^b3 and R ^b4 , which are each other, are each —R ^d (wherein R ^d is an amino group which may have a substituent); And 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 as defined above, or * -CH = N-R ^d (wherein R ^d is as defined above), R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 At least one ring to which is attached is present] is included.

  The oxocarbon-based compound described in detail below has a squarylium skeleton or a croconium skeleton, and the compounds represented by the formulas (1) or (2) have a conjugated relationship with these compounds, respectively. There may be compounds present in Examples of the compound in a conjugated relationship include the following (1a), (1b), (2a), (2b), and (2c). Hereinafter, in the specification of the application, a compound represented by the formula (1) (sometimes referred to as a compound (1)) even if it is an oxocarbon-based compound in which a compound having such a conjugated relationship is present Although the compound represented by the formula (2) (sometimes referred to as a compound (2)) is exemplified, the compound represented by the following formulas (1a) and (1b) is exemplified in the compound (1). The compound (2) also 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, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and 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 -A linear or branched alkyl group such as -ethylheptyl group, 4-ethylheptyl group, trimethylhexyl group, 3, 3-diethylpentyl group, decyl group, undecyl group, dodecyl group and the like can be mentioned. Among them, an alkyl group having 1 to 15 carbon atoms is preferable, and more preferably 1 to 12 carbon atoms. The alkyl group may be linear or branched, but is more preferably linear. The alkyl group may have a substituent, and as the substituent, those other than the alkyl group among those described later can be used.

Examples of the alkyloxycarbonyl group represented by R ^{b1 to} R ^b4 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, and an octyloxy group. And alkyloxycarbonyl groups such as carbonyl group, decyloxycarbonyl group and 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 among these described below, ones other than an alkyl group can be used as the substituent. Examples of substituents include trihalo substituents such as 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 group And phenyloxycarbonyl groups such as 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like; 1-naphthyloxy Naphthyloxycarbonyl group such as 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.

The acyl group represented by R ^{b1 to} R ^b4 is, for example, an alkanoyl group such as acetyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, trifluoroacetyl group and the like And Aroyl groups such as benzoyl group, 1-naphthoyl group and 2-naphthoyl group. Among these, a C2-C15 acyl group is preferable, and a C2-C10 thing is more preferable. Among them, an alkanoyl group is preferable, more preferably an acetyl group, a propanoyl group or a butanoyl group. 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), and specific examples thereof include phenyl group, naphthyl group, pentarenyl group, indenyl group, anthracenyl group, phenanthryl group, fluorenyl group, And biphenylyl group, biphenyl group and the like. Among them, preferred is a phenyl group or a naphthyl group. 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, and more preferably 5 to 10 carbon atoms. The alicyclic hydrocarbon group is more preferably unsaturated. As the unsaturated cyclic hydrocarbon group, for example, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group and the like Examples of cycloalkenyl groups having one double bond; cycloalkenyl groups having two or more double bonds such as 1,3-cyclohexadiene-1-yl group and 1,4-cyclohexadiene-1-yl group; it can. In addition, this alicyclic hydrocarbon group may have a substituent, and this substituent is suitably selected from what is mentioned later.

The heteroaryl group represented by R ^{b1 to} R ^b4 is preferably a heteroaryl group having a carbon number of 2 to 20, and examples thereof include a thienyl group, a thiopyranyl group, an isothiochromenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group and a pyridyl group. And pyrarizinyl groups, pyrimidinyl groups, pyridazinyl groups, thiazolyl groups, isothiazolyl groups, furanyl groups, pyranyl groups 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 a carbon number of 7 to 18, 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 to which the substituent is attached, 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 -Butyl, tert-butyl and sec-butyl. These alkyl groups may be substituted by a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
As a cycloalkyl group, a C3-C20 cycloalkyl group is preferable, For example, a cyclopropyl group, cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, cyclooctyl group, cyclododecyl group etc. are mentioned. The number of constituent atoms of the ring skeleton of the cycloalkyl group is preferably 3 to 15, more preferably 5 to 9, and still more preferably 6 (cyclohexyl group).
Further, as the alkoxy group, a substituent in which an alkyl group is bonded via an oxygen atom is used, and specifically exemplified one having 1 to 18 carbon atoms, and examples thereof include a methoxy group, an ethoxy group and a propoxy group, Isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, 2-methylpentyloxy, 3-methylpentyloxy , 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, heptyloxy, 2-methylhexyloxy, 3-methylhexyloxy, 2,2-dimethylpentyloxy, 2,3-dimethyl Pentyloxy group, 2,4-dimethyl pentyloxy group, 3-ethyl pentyloxy group, 2 2,3-Trimethylbutyloxy, octyloxy, methylheptyloxy, dimethylhexyloxy, 2-ethylhexyloxy, 3-ethylhexyloxy, trimethylpentyloxy, 3-ethyl-2-methylpentyloxy 2-ethyl-3-methylpentyloxy group, 2,2,3,3-tetramethylbutoxy group, nonyloxy group, methyloctyloxy group, 3,7-dimethyloctyloxy group, dimethylheptyloxy group, 3- Ethyl heptyloxy group, 4-ethyl heptyloxy group, trimethylhexyloxy group, 3, 3-diethyl pentyloxy group, decyloxy group, undecyloxy group, dodecyloxy group etc. are mentioned. Among them, 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) The group (C) will be described. In the ethylene-containing group (C), as the aliphatic hydrocarbon group, for example, one having 1 to 20 carbon atoms is preferable, and one having 1 to 10 carbon atoms is more preferable.

The aliphatic hydrocarbon group may be either 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, including, for example, vinyl groups.

  The aryl group preferably has 1 to 5 rings (more preferably 1 to 3 rings), and specific examples thereof include phenyl group, naphthyl group, pentarenyl group, indenyl group, anthracenyl group, phenanthryl group, fluorenyl group. And biphenyl group and biphenyl group.

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

  As ethylene containing group (C), each group represented by a following formula can be illustrated, for example.

Furthermore, a group represented by * -CH = N-R ^d (D) (in the formula (D), R ^d is an amino group which may have a substituent) (hereinafter referred to as an imine-containing group I will explain about D). Examples of the amino group which may have a substituent of 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. A group represented by the alkyl group which may be substituted or an aryl group which may have a substituent.

  As an imine containing group (D), each group represented by a following formula can be illustrated, for example.

Among these, more preferable R ^b1 is 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, or an aralkyl group, and among them, a hydrogen atom or a group represented by the following formulas (B1-1) to (B1-15) (wherein * represents A binding site is preferably exemplified.

Further, preferable R ^b2 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 aryl group which may have a group, * -CH = CH-R ^c (wherein R ^c is as defined above), or * -CH = N-R ^d (wherein R ^d is as defined above) Among them, hydrogen atoms or groups represented by the following formulas (B2-1) to (B2-14) (wherein, * represents a bonding site) can be preferably exemplified.

Further, preferable 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 linear chain of 1 to 5 carbon atoms which may have a substituent, or It is a branched alkyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an acetyl group or a propanoyl group.

Further 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 linear chain of 1 to 5 carbon atoms which may have a substituent, or It is a branched alkyl group, a phenyl group, a 4-biphenyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an acetyl group or a propanoyl group.

Also, R ^b1 and R ^b2 , R ^b2 and R ^b3 , and R ^b3 and R ^b4 may be combined with each other to form a ring. As an example in which R ^b1 and R ^b2 combine to form a ring, for example, a structural unit (3) represented by the following formula is mentioned (in the following formula, * is a binding site). These rings may optionally have a substituent.

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

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

(In the formula (4),
A represents a ring structure formed by two carbon atoms at the β-position of the pyrrole ring 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 above formula (4) in which R ^b3 and R ^b4 are combined to form a ring is particularly preferable. An oxocarbon 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 being excellent in light resistance. Hereinafter, the novel oxocarbon-based compound will be described in detail.

  The novel oxocarbon compounds are characterized by being 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 the formula (4),
Ring A represents a ring structure formed by two carbon atoms at the β-position of the pyrrole ring 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, a structural unit represented by the formula (4) which can be bonded to a squarylium skeleton or a 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 with other atoms. A is preferably, for example, a 5- to 7-membered ring, more preferably a 5- or 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 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 an aromatic ring, C6-C10 aromatic rings, such as a benzene ring, are preferable, for example. Further, as the alicyclic hydrocarbon ring, for example, cycloalkanes such as cyclopentane, cyclohexane, cycloheptane and the like having 3 to 10 carbon atoms; cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene (eg, 1,3-cyclohexadiene), Cycloheptene, cycloheptadiene, etc. Cycloalkene having 3 to 10 carbon atoms such as cycloalkene; etc .; Monocyclic ring such as bicyclo [2.2.1] pentane, bicyclo [2.2.1] pent-2-ene, bicyclo [2 .2.2] Octane, cyclic alkanes having a bridge such as bicyclo [2.2.2] octa-2-ene, and the like. Among them, aromatic rings having 6 to 7 carbons, cycloalkanes having 5 to 7 carbons, cycloalkenes having 5 to 7 carbons, and cyclic alkanes having 5 to 9 carbons having a bridge are preferable. Also preferably, a five-membered ring (for example, cyclopentene (following A-1) and the like), a six-membered ring (for example cyclohexane (following A-2), cyclohexene (following A-3) and cyclohexadiene (following A-4) , Bicyclo [2.2.2] octane (following A-5), bicyclo [2.2.2] octa-2-ene (following A-6), bicyclo [2.1.2] heptane (following A-) 7), bicyclo [2.1.2] hept-2-ene (the following A-8) and the like). Among them, 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 to the β carbon atom of the pyrrole ring, and may be any of two β carbon atoms. Further, the bonding site is bonded to two carbon atoms located at the β-position of the pyrrole ring to form a ring.

  In the ring A, at least one or more of carbon atoms constituting the above-mentioned aromatic ring or alicyclic hydrocarbon ring (with the exception of the carbon atom shared with the pyrrole ring) are N (nitrogen atom), S ( It may be a heterocycle substituted by at least one or more atoms selected from sulfur atom) and O (oxygen atom). As such a heterocyclic ring, for example, at least one or more carbon atoms constituting the cycloalkane having 5 to 7 carbon atoms or the cycloalkene having 5 to 7 carbon atoms is at least one selected from N, S and O. Heterocycles substituted by the above atoms are preferable, and more preferably, at least one or more of carbon atoms constituting cyclohexane, cyclohexene and cyclohexadiene are at least one or more atoms selected from N, S and O. Heterocycles which are substituted are preferred. The number of N, S and O per A1 ring depends on the skeleton constituting A, but is 1 or more (especially 1 or 2), and may be 2 or more (especially 2). When N, S and O contained in A1 ring are 2 or more, 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 carbon atom at position β of the pyrrole ring is N, S or O (for example, the following (B-1), (B-3), (B- 5) to (B-17) and the like, and heterocyclic rings in which the other carbon atom is N, S or O can be exemplified (for example, the following (B-2), (B-4) and the like). Among them, 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 to the β carbon atom of the pyrrole ring, and may be any of two β carbon atoms. Further, the bonding site is bonded to two carbon atoms located at the β-position of the pyrrole ring to form a ring.

  Furthermore, ring A may be fused with another ring B. By condensation of the other ring B, the wavelength of the resulting oxocarbon-based compound can be increased, so that molecular design according to the color tone of the compound can be easily performed. For the ring B, for example, an aromatic ring, an alicyclic hydrocarbon ring or a heterocyclic ring described in detail in the section of the ring A can be appropriately selected, and among them, an aromatic ring having 6 to 10 carbon atoms, carbon A cycloalkane of 5 to 10, a cycloalkene of 5 to 10 carbons, a cyclic alkane of 5 to 12 carbons having a bridge, and at least one of carbon atoms constituting these rings is N, S And a heterocyclic ring substituted by at least one or more atoms selected from O and O is preferable. In addition, what is described as a ring in the column of A is read in B as containing any two adjacent carbon atoms present in A. In addition, the structure exemplified by the binding site is read as B in which the binding site bonds with any two adjacent carbon atoms present in A to form a ring.

  The ring A in which the ring B is fused is, for example, a fused polycyclic hydrocarbon or (for example, the following (C-1), (C-2), (C-5), (C-6), (C- 8), (C-9), etc., condensed heteropolycyclic compounds (eg, the following (C-3), (C-4), (C-7) etc.), and among them, the following formula (C-) 1) Structural formula selected from (C-9) is preferable. In the following formulas (C-1) to (C-9), * is a bonding site to the β carbon atom of the pyrrole ring, and may be any of two β carbon atoms. Further, the bonding 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 by an electron withdrawing group and / or an organic substituent.

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

  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, trifluoroacetyl group and the like; And substituted or unsubstituted aroyl groups such as 1-naphthoyl group and 2-naphthoyl group. Among these, a C2-C15 acyl group is preferable, and a C2-C10 thing 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 octadecyloxycarbonyl groups, and substituted or unsubstituted alkyloxycarbonyl groups such as trifluoromethyloxycarbonyl groups. The alkyl group in the alkyloxycarbonyl group may be linear or branched.

  As the aryloxycarbonyl group, for example, a phenoxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyl group Oxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxy group Substituted or unsubstituted phenyloxycarbonyl group 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 carbamoyl group, N-ethylcarbamoyl group, N-phenylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group and the like. Groups are mentioned.

  Examples of the alkylsulfinyl group include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, octylsulfinyl group, cyanomethylsulfinyl group. And 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 phenylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 2-fluorophenylsulfinyl group, 3-methylphenyl group Phenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-methylphenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyano A substituted or unsubstituted phenylsulfinyl group such as phenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, etc .; Iniru group, 2-naphthylsulfinyl substituted or unsubstituted naphthylsulfinyl group such as Le group; and the like.

  As the alkylsulfonyl group, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, octylsulfonyl group, cyanomethylsulfonyl group Groups, 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 phenylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 2-fluorophenylsulfonyl group, 3-methyl Phenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 3-fluorophenylsulfonyl group, 4-methylphenylsulfonyl group, 4-fluorophenyl A substituted or unsubstituted phenylsulfonyl group such as phenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc .; 1-naphthylsulfone 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 sulfamoyl group (-SOONH ₂ ) is substituted or a disubstituted sulfamoyl group in which two hydrogen atoms are substituted. As a monosubstituted sulfamoyl group, for example, sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group N-phenylsulfamoyl group substituted with an alkyl group such as 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 sulfamoyl groups substituted with a substituted or unsubstituted aryl group such as a moyl group, N-4-phenylsulfanylphenylsulfamoyl group, and the like. As a disubstituted sulfamoyl group, for example, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group Etc.

  The organic substituent capable of substituting the hydrogen atom of ring A and / or ring B is, for example, an alkyl group, an alkoxy group, a thioalkoxy group, an aryl group, an aralkyl group, an aryloxy group, an arylthiooxy group, etc. Can be mentioned.

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

  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. And tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, icosyloxy, methoxyethoxy, ethoxyethoxy and the like. Among these, a C1-C20 alkoxy group is preferable, and a C1-C10 thing is more preferable. The alkyl group in the alkoxy group may be either linear or branched.

  As the thioalkoxy group, for example, methylthiooxy group, ethylthiooxy group, propylthiooxy group, butylthiooxy group, pentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthiooxy group, nonylthio Oxy group, decylthiooxy group, undecylthiooxy group, dodecylthiooxy group, tridecylthiooxy group, tetradecylthiooxy group, pentadecylthiooxy group, hexadecylthiooxy group, heptadecylthiooxy group, 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. The alkyl group in the thioalkoxy group may be either linear or branched.

  Examples of the aryl group include phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl group, azulenyl group, fluorenyl group, terphenyl group, quarter phenyl group, pentalenyl group, heptarenyl group, biphenylenyl group. Groups, indasenyl groups, acenaphthylenyl groups, phenalenyl groups, fluorenyl groups, phenanthryl groups and the like. Among these, a C6-C30 aryl group is preferable, and a C6-C15 thing is more preferable. This aryl group may have a substituent. As a substituent which an aryl group has, 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, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an aryl 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 a carbon number of 7 to 18, 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, A carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a sulfamoyl group can be mentioned.

  Examples of the aryloxy group include phenyloxy group, biphenyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, pyrenyloxy group, indenyloxy group, azulenyloxy group, fluorenyloxy group, ter Phenyloxy group, quarter phenyloxy group, pentalenyloxy group, heptarenyloxy group, biphenylenyloxy group, indacenyloxy group, acenaphthyryloxy group, phenarenyloxy group, fluorenyloxy group Groups, phenanthryloxy groups and the like. Among these, a C1-C25 aryloxy group is preferable, and a C1-C15 thing is more preferable.

  Examples of the arylthiooxy group include phenylthiooxy group, biphenylthiooxy group, naphthylthiooxy group, anthrylthiooxy group, phenanthrylthiooxy group, pyrenylthiooxy group, indenylthiooxy group, and the like. Renylthiooxy group, fluorenylthiooxy group, terphenylthiooxy group, quarter phenylthiooxy group, pentalenylthiooxy group, heptarenylthiooxy group, biphenylenylthiooxy group, indasenylthiooxy group, acenaphthyreni And luthiooxy group, phenalenylthiooxy group, fluorenylthiooxy group, phenanthrylthiooxy group and the like. Among these, a C1-C25 arylthiooxy group is preferable, and a C1-C15 thing 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 in particular, in the case where the ring A is a ring having poor solubility such as acenaphthene In particular, bulky groups such as t-butyl group or isobutyl group are preferable from the viewpoint of solubility improvement.

Although the bonding position of the organic substituent is not particularly limited, for example, it is preferable that it is bonded to 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).

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

  Next, X in equation (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 or an alkoxyalkyl group.

  As the alkyl group, for example, an alkyl group having 1 to 20 carbon atoms is preferable, and specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, 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, methylheptyl, dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, trimethylpentyl, 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 phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl group, azulenyl group, fluorenyl group, terphenyl group, quarter phenyl group, pentalenyl group, heptarenyl group, biphenylenyl group. Groups, indasenyl groups, acenaphthylenyl groups, phenalenyl groups, fluorenyl groups, phenanthryl groups and the like. Among these, a C6-C30 aryl group is preferable, and a C6-C15 thing is more preferable. This aryl group may have a substituent. As a substituent which an aryl group has, 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, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an aryl 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 a carbon number of 7 to 18, 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, A carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a sulfamoyl group can be mentioned.

  As the alkylsulfonyl group, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, octylsulfonyl group, cyanomethylsulfonyl group Groups, 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 phenylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 2-fluorophenylsulfonyl group, 3-methyl Phenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 3-fluorophenylsulfonyl group, 4-methylphenylsulfonyl group, 4-fluorophenyl A substituted or unsubstituted phenylsulfonyl group such as phenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc .; 1-naphthylsulfone Group, a substituted or unsubstituted naphthylsulfonyl group and a 2-naphthylsulfonyl group; and the like.

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

(Wherein, Z ¹ and Z ² are each independently an alkylene group, Z ³ is an alkyl group, and n is an integer of 0 to 4).
Each of Z ¹ and Z ² is 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. are mentioned. Among them, -CH _2- (methylene group), -CH ₂ CH _2- (ethylene group), -CH (CH ₂ ) CH _2- (propylene group) or -CH ₂ CH ₂ CH _2- (trimethylene group) is preferable, More preferably, they are -CH _2- (methylene group) or -CH ₂ CH _2- (ethylene group).
Further, Z ³ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and a preferable alkyl group is exemplified by, for example, a methyl group, an ethyl group, and n-propyl It is a group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, more preferably methyl group or ethyl group.
n is an integer of 0 to 4, more preferably 0 to 2, and still more preferably 0 or 1.
As such an alkoxyalkyl group, a methoxyethyl group, an ethoxyethyl group, a methoxyethoxymethyl group, a methoxyethoxymethyl group, an ethoxyethoxyethyl group etc. are mentioned, for example.

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

  Next, Y in equation (4) will be described. Y is a hydrogen atom, an electron withdrawing group or an organic substituent, and as the electron withdrawing group, for example, the aforementioned halogen, cyano group, nitro group, thiocyanate group, trifluoromethyl group, acyl group, alkyl It is preferable to select an oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group and the like. Similarly, as the organic substituent, for example, the alkyl group, alkoxy group, thioalkoxy group, aryl group, aralkyl group, aryloxy group, arylthiooxy group and the like described above may be selected. 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 And more preferably a methyl group, an ethyl group, or a phenyl group substituted with an alkoxy group, and particularly preferably a methyl group, an ethyl group, (o-, m-, p-) methoxyphenyl, or (o -, M-, p-) ethoxyphenyl.

  As a particularly preferred compound as such an oxocarbon compound, for example, in the compound having a squarylium skeleton,

Examples of compounds having a croconium skeleton include, 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, and for example, long-wavelength light is produced by converting a cyclic alkane bridged in the molecule to an aromatic ring or the like. It is also possible to set the wavelength to 600 to 800 nm. In the case of a croconium dye, the maximum absorption wavelength (λmax) of the dye is 700 to 1200 nm, and the cyclic alkane of the bridge in the molecule is further converted to an aromatic ring to lengthen the compound. , 800 to 950 nm.

  Furthermore, these oxocarbon compounds are excellent in light resistance, and when a coating film containing the oxocarbon compound is set in a xenon weather meter and light resistance test is conducted by irradiating light in a 60 ° C. atmosphere for 24 hours. 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):

[Wherein, in the formula (5), A, X and Y are as defined above] can be produced by reacting the pyrrole derivative represented by the formula (5) with squaric acid or croconic acid.

  In the step of reacting squaric acid or croconic acid with pyrrole derivative (5) (hereinafter referred to as "step 1"), the amount of pyrrole derivative (5) used is 0.8 relative to squaric acid or croconic acid Double mol or more is preferable, More preferably, it is 1.2 times mol or more, More preferably, it is 1.5 times mol or more, 5 times mol or less is preferable, More preferably, it is 4 times mol or less, More preferably, It is 3 times mol or less.

  The reaction is preferably carried out in the presence of a solvent, and examples of usable solvents include chlorinated hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; THF, Ethers such as dioxane, cyclopentyl methyl ether, diisopropyl ether, diethyl ether and the like; alcohols such as methanol, ethanol, propanol, butanol and the like; amides such as dimethylformamide, dimethylacetamide and the like. These solvents may be used alone or in combination of two or more.

  The amount (total) of the solvent used is preferably at least 1 time by weight, more preferably 10 times by weight or more, still more preferably 20 times by weight or more, based on squaric acid or croconic acid, and the upper limit is, for example, It is less than 100 times its weight.

  The reaction temperature may be appropriately set, for example, preferably 0 ° C. or more, more preferably 25 ° C. or more, preferably 170 ° C. or less, more preferably 140 ° C. or less. This reaction may be carried out under reflux to remove reaction product water. The reaction time is also not particularly limited, and is, for example, preferably 0.1 hours or more, more preferably 0.5 hours or more, and preferably 24 hours or less, more preferably 12 hours or less.

  It is recommended to carry out step 1 particularly under 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, reprecipitation and the like.

  In addition, when ring A and / or ring B of formula (4) contains a cyclic alkane having a bridge, an oxocarbon compound having a cyclic alkane bridged in the molecule was produced in step 1 Thereafter, the obtained oxocarbon compound is subjected to a heat treatment (hereinafter referred to as “step 2”) to convert the bridged cyclic alkane into an aromatic ring.

  The heat treatment temperature at this time is preferably 160 ° C. or more, more preferably 210 ° C. or more, and preferably 280 ° C. or less, more preferably 270 ° C. or less. The heat treatment time is preferably 0.2 hours or more, more preferably 0.5 hours or more, and preferably 10 hours or less, more preferably 6 hours or less.

  It is recommended to carry out step 2 particularly under an inert gas (nitrogen, argon, etc.) atmosphere.

  In the oxocarbon compounds (1) and (2), either one of (1) or (2) may be added to the resin composition, and both (1) and (2) may be added to the resin composition. You may add it. The content of the oxocarbon 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 exert the effects of the present invention sufficiently. It is more preferably 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 dyes 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 squarylium dyes having no structural unit as described above, croconium dyes having no structural unit as described above, copper as a central metal ion , Cu (II), zinc (for example, Zn (II)), etc. Cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, cholines, etc.), cyanine dyes, quaterrylene dyes Dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes and the like may be mentioned, and one or more of these may be used in combination. It is desirable that these other dyes have an absorption maximum wavelength in the wavelength range of 400 to 1000 nm so as not to impair the effects of the present invention.

  The content of the other dye is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass with respect to 100% by mass of the total amount of the dye in order to sufficiently exert the effects of the present invention. It is preferably at most mass%, particularly preferably substantially free of these other dyes.

  The concentration (content) of these dyes is, for example, preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more 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, it may be difficult to form a film with a uniform film thickness, so the content 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 contains a resin component. As the resin component, those which can sufficiently dissolve or disperse the various dyes described above are preferable. By selecting a resin component suitable for such purpose, it is possible to achieve both high transmittance in the wavelength range to be transmitted and high absorption in the wavelength range to be blocked.

  Examples of the resin component include (meth) acrylic resins, (meth) acrylic urethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins (for example, polyethylene resins, polypropylene resins), 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, modified silicone resins such as silicone acrylic resins; fluorinated aromatic polymers, polytetrafluoroethylene (PTFE) Fluorine-based resins such as perfluoroalkoxy fluorine resin (PFA), fluorinated polyarylether ketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorinated polyether nitrile (FPEN)) 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, or the like, and a resin composition that has been made into a coating material so that coating can be performed by spin coating method, solvent casting method, etc. It may be

  By using the thermoplastic resin composition, a molded article can be obtained by injection molding, extrusion molding, vacuum molding, compression molding, blow molding, and the like. In this method, a molded product is obtained by kneading an oxocarbon-based compound into a thermoplastic resin among the above-mentioned resins and performing heat molding. That is, the oxocarbon compound may be added to the powder or pellet of the base resin, heated at 150 to 350 ° C. for dissolution, and then molded. The shape of the molded product is not particularly limited, but a film having a thickness of 200 μm or less, a planar molded product such as a plate-shaped product having a thickness of 200 μm or more; a molded product such as an irregular product; Further, when the resin is kneaded, an additive used for normal resin molding such as an ultraviolet absorber, a plasticizer and the like may be added.

  Further, a resin composition made into a paint is a liquid or paste composition containing an oxocarbon compound, and the resin composition made into a paint is coated on a resin plate, a film, a glass plate, etc. By doing this, it is possible to form a planar molded body such as a film having a thickness of 200 μm or less and a plate-like material having a thickness of 200 μm or more. The resin composition made into a paint is, for example, one obtained by dissolving an oxocarbon-based compound in a solvent containing a base resin to make a paint, or atomizing the oxocarbon-based compound to several μm or less into an emulsion of a base resin. The thing etc. which were disperse | distributed are mentioned.

  The resin component to be the base resin needs to have high dispersibility to the pigment so that the pigment can be dissolved or dispersed at a high concentration. In addition, it is preferable that the coatability is also good so that a film can be formed by a spin coating method, a 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 solvent-soluble resins soluble in organic solvents, solvent-soluble resin raw materials, and liquid resin raw materials is preferably used. These resins are more preferable because they can form a film even under relatively low temperature conditions. Depending on the structure of the dye, some or all of the dye may be degraded by impurities present during polymerization (eg, unreacted substances that promote decomposition, reactive terminals, ionic groups, catalysts, acid / basic groups, etc.) Since it is possible that the light resistance may deteriorate, it is desirable to combine such a dye with a solvent-soluble resin which has already been polymerized (if necessary, purified).

In addition, the above-mentioned "solvent soluble resin" means resin soluble in an organic solvent, for example, resin which dissolves 1 mass part or more to 100 mass parts of various organic solvents mentioned below is preferred.
The above-mentioned "solvent-soluble resin raw material" means a resin raw material soluble in an organic solvent, that is, a resin raw material which is solvent-soluble, and for example, 1 mass per 100 mass parts of various organic solvents described later. Those which dissolve in part or more are preferable.
Furthermore, the above-mentioned "liquid resin raw material" means a liquid resin raw material, that is, a resin raw material which is liquid. The substance being “liquid” means that the viscosity of the substance itself is 100 Pa · s or less at normal temperature (25 ° C.). The viscosity can be measured by a B-type viscometer.
In the present specification, the “resin raw material” includes a precursor of a resin, a raw material of the precursor, and a monomer (curable monomer or the like) for forming a resin.

  Examples of the solvent-soluble resin include poly (amide) imide resin, fluorinated aromatic polymer, (meth) acrylic resin, polyamide resin, aramid resin, polycycloolefin resin and the like. Among them, poly (amide) imide resin, fluorinated aromatic polymer, (meth) acrylic resin or polycycloolefin resin is preferable, and polyimide resin, (meth) acrylic resin or poly is more preferable, from the viewpoint of being more excellent in light resistance. It is a cycloolefin resin, more preferably a (meth) acrylic resin or a polycycloolefin resin.

The solvent-soluble resin may also be 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, or an ethylene sulfide group, an acrylic group, a methacrylic group, a vinyl group Etc. and may have a radical curable group and / or an addition curable group).
When a solvent-soluble resin is used as the resin component, the solvent-soluble resin may be the resin component constituting the resin layer as it is, or the solvent-soluble resin may be changed by a crosslinking reaction or the like. It may be a resin component constituting a layer.
Although the amount of the crosslinkable reactive group and the degree to which the crosslinking reaction in film formation proceeds is not particularly limited, 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 solvent soluble resin, is the polyimide resin of narrow sense (the resin which includes the imide bond, does not contain the amide bond, the amide bond here is the amic acid Means an amide bond which can not form an imide bond by dehydration reaction), and a polyamideimide resin (a resin containing an amide bond and an imide bond which can not form an imide bond by a dehydration reaction of an amic acid) ) Is included.

  The imide bond in the polyimide resin is usually a bond chain having an amide bond and a carboxyl group adjacent thereto (in the present invention, the bond chain is also referred to as an amic acid. Usually, carbon adjacent to a carbon atom to which the amide bond is bonded) It is a structure in which a carboxyl group is bonded to an atom. When a polyimide resin is produced from polyamic acid by dehydration reaction, some amount of amic acid may remain in the molecule. Therefore, in the present invention, when referred to as "polyimide resin", although it contains an imide bond and does not contain an amide bond which can not form an imide bond by dehydration of an amic acid, it can form an imide bond by dehydration of an amic acid The amide bond may or may not contain a slight amount. Preferred is a polyimide resin having an imide bond content (the ratio of the number of imide bonds to the total of 100 mol% of the number of amide bonds imidizable by imidization and the number of imide bonds) in the polyimide resin is 80 mol% or more. More preferably, it is 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 98 mol% or more.

  Moreover, although the polyamide imide resin contains the amide bond and the imide bond which can not form an imide bond by the dehydration reaction of an amic acid, the amide bond which can form an imide bond by the dehydration reaction of the amic acid is not included May be included. In the case of containing an amide bond capable of forming an imide bond by dehydration reaction of an amic acid, the number of amide bonds (a number of amide bonds which can not form an imide bond by dehydration reaction The content of the amide bond capable of forming an imide bond by the dehydration reaction of an amic acid is preferably less than 20 mol% with respect to the total amount of 100 mol% of the sum and the imide bond number. More preferably, it is less than 10 mol%, still more preferably less than 5 mol%, particularly preferably less than 2 mol%.

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

  The poly (amide) imide resin is not particularly limited as long as it is a compound having an imide bond, and, for example, the following formula (10):

A compound having a repeating unit represented by (wherein R ^p1 is the same or different and 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 is preferably one containing one or more hydrocarbon skeletons. The hydrocarbon backbone 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) is also the same or different two or more kinds selected from the above hydrocarbon skeleton and / or heterocyclic skeleton, and they have a carbon-carbon bond, or carbon Preferred is one comprising a backbone linked via a linking group which is different from the-carbon bond. The bonding group, for _{example, -O -, - SO 2 -} , - CO -, - Si (CH 3) 2 -, - C 2 H 4 O -, - S- , and the like. In addition, as each R ^p1 in the repeating unit represented by said Formula (10), it may be same or different.

The organic group represented by the above 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- , etc. may be included. In addition, although one part or all part of the hydrogen atom in the cyclohexyl ring in Formula (10) may be substituted, what is unsubstituted (a form which is all hydrogen atoms) is 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 or random.

  Among the above poly (amide) imide resins, preferable ones are, for example, the following formula (10-1):

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

2-2. Fluorinated Aromatic Polymers Next, fluorinated aromatic polymers that can be used as solvent soluble resins are described. The fluorinated aromatic polymer includes an aromatic ring having at least one or more fluorine group, and at least one bond selected from the group of ether bond, ketone bond, sulfone bond, amide bond, imide bond and ester bond And the like. Examples thereof include polyimides having a fluorine atom, polyethers, polyether imides, polyether ketones, polyether ketones, polyether sulfones, polyamide ethers, polyamides, polyethers, etc. A nitrile, polyester etc. are mentioned. Among these, a polymer having, as an essential part, a repeating unit containing an aromatic ring having at least one or more fluorine groups and an ether bond is preferable, and the following formula (11-1) or (11-2) The polyether ketone which has a fluorine atom containing the repeating unit represented by is more preferable. Among these, fluorinated polyether ketone (FPEK) is particularly preferable. The repeating units represented by formula (11-1) or (11-2) may be the same or different, and may be in any form such as block or random.

In said formula (11-1), ^Rq1 represents the bivalent organic chain which has a C1-C150 aromatic ring. 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 the degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.
In the above formula (11-2), R ^q2 is 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 which may have a substituent. Group, alkylthio group having 1 to 12 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, arylamino group having 6 to 20 carbon atoms or arylthio group having 6 to 20 carbon atoms . R ^q3 represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. z is the number of fluorine atoms bonded to the aromatic ring and is 1 or 2; n ¹ represents the degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.

In said Formula (11-1), the inside of the range of 2-8 is preferable, and x + y has more preferable inside of the range of 4-8. Moreover, as a position which an ether structure part (-O- ^Rq1- O-) couple ^| bonds with an aromatic ring, it is preferable that it is a para-position with respect 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 of groups represented by the following structural formula group (11-3) It is preferable that it is or the organic chain of the combination.

In the above 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 And 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 the above R ^q1 and R ^q3 include organic chains represented by the following structural formula group (11-4).

  In Formula (11-1) above, Z represents a divalent chain or direct bonding. As the bivalent chain, for example, a chain represented by the following structural formula group (11-5) is preferable.

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

The alkyl group in R ^q2 in the above formula (11-2) is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl Groups, 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 a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group and an undecyloxy group. , Dodecyloxy group, flufuryloxy group, allyloxy group and the like are preferable.

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

  Examples of the aryl group include 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, Biphenylyl, benzhydryl, trityl, pyrenyl and the like are preferred.

  The aryloxy group is a group derived from phenoxy group, benzyloxy group, hydroxybenzoic acid and esters thereof (eg, methyl ester, ethyl ester, methoxyethyl ester, ethoxyethyl ester, furfuryl ester, phenyl ester and the like), Preferred are naphthoxy group, o-, m- or p-methyl phenoxy group, o-, m- or p-phenyl phenoxy group, phenylethynyl phenoxy group, groups derived from cresotine acid and esters thereof, and the like.

  Examples of the arylamino group include anilino, o-, m- or p-toluidino, 1,2- or 1,3-xylidino, o-, m- or p-methoxyanilino, anthranilic acid and the like Groups derived from esters and the like are preferred.

  As the above 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.

Among them, an alkoxy group, an aryloxy group, an arylthio group and an arylamino group which may have a substituent are preferable as R ^q2 above. However, R ^q2 may or may not contain a double bond or a triple bond.

The substituent for R ^q2 in the above formula (11-2) is an alkyl group having 1 to 12 carbon atoms as described above; halogen atoms such as fluorine, chlorine, bromine and iodine; cyano group, nitro group, carboxy ester Preferred are groups and the like. In addition, hydrogens of these substituents may or may not be halogenated. Among these, preferably, a halogen atom and hydrogen may or may not be halogenated methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl and carboxy ester 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 the present 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 it is preferable to use (meth) acrylic acid ester or (meth) acrylic acid It may have a structural unit derived from a derivative. In addition, "(meth) acryl" shall mean "acryl" and / or "methacryl."

  Examples of (meth) acrylic acid esters or (meth) acrylic acid ester derivatives include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, 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 with hydroxyhydrocarbons (alkyl (meth) acrylate, aryl (meth) acrylate, aralkyl (meth) acrylate, etc.), dicyclopentanyloxy (meth) acrylate Ether bond-introduced derivatives such as ethyl; chloromethyl (meth) acrylate, (meth) acrylic acid Halogen-introduced derivatives such as 2-chloroethyl; and hydroxy-introduced derivatives. Examples of the hydroxy group-introduced derivatives include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, (meth) (Meth) acrylic acid hydroxyalkyls such as acrylic acid 2,3,4,5-tetrahydroxypentyl; alkyl 2- (hydroxymethyl) acrylate (eg methyl 2- (hydroxymethyl) acrylate, 2- (hydroxy) Methyl) ethyl acrylate, isopropyl 2- (hydroxymethyl) acrylate, n-butyl 2- (hydroxymethyl) acrylate, t-butyl 2- (hydroxymethyl) acrylate, etc.), 2- (hydroxyethyl) acrylic acid Alkyl (eg, methyl 2- (hydroxyethyl) acrylate etc.) 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 viewpoint of heat resistance and transparency.
The (meth) acrylic acid ester (unit), the (meth) acrylic acid (unit) and the derivative (unit) thereof may have only one type or two or more types.

  The (meth) acrylic resin may have another structural unit introduced by copolymerizing the (meth) acrylic acid-based monomer described above with another monomer. As such other monomers, for example, styrene, vinyltoluene, α-methylstyrene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, acrylonitrile, methacrylonitrile, methallyl alcohol, allyl alcohol, ethylene, propylene, Monomers having a polymerizable double bond such as 4-methyl-1-pentene, vinyl acetate, 2-hydroxymethyl-1-butene, methyl vinyl ketone, N-vinyl pyrrolidone, N-vinyl carbazole and the like can be mentioned. These other monomers (constituent units) may have only one type or two or more types.

  Constituent units derived from (meth) acrylic acid-based monomers in all constitutional units of (meth) acrylic resin (that is, (meth) acrylic acid ester units, (meth) acrylic acid units and constituent units derived from these derivatives) 50 mass% or more is preferable, More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more. There is no particular upper limit, and most preferably 100% by mass.

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

  The lactone ring structure is not particularly limited, and may be, for example, any of a 4- to 8-membered ring, but is preferably a 5- or 6-membered ring because the ring structure is excellent in stability. And 6-membered rings are more preferred. Examples of the lactone ring structure that is a six-membered ring include the structures disclosed in JP-A-2004-168882, but the introduction of the lactone ring structure is easy, specifically, the precursor ( The polymerization yield of the polymer before lactone cyclization is high, that the lactone ring content in the cyclization condensation reaction of the precursor can be increased, and that the 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 preferable because of 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 It is also good.
Examples of the organic residue in the formula (12-1) include saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms such as methyl group, ethyl group and propyl group (such as alkyl group), ethenyl group and propenyl group. In addition to C2-C20 unsaturated aliphatic hydrocarbon groups (such as alkenyl groups) and C6-C20 aromatic hydrocarbon groups such as phenyl and naphthyl groups (such as aryl groups), these saturated aliphatic carbon compounds A group in which one or more of hydrogen atoms in a hydrogen group, an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group is substituted by at least one group selected from a hydroxy group, a carboxyl group, an ether group and an ester group Can be mentioned.

  The lactone ring structure is obtained by, for example, polymerizing (preferably copolymerizing) a (meth) acrylic acid-based monomer A having a hydroxy group with a (meth) acrylic acid-based monomer B to form a hydroxy group and an ester group or a carboxyl group in a molecular chain. After introducing a group, it can be formed by causing dealcoholation or dehydrating cyclocondensation between these hydroxy group and an ester group or a carboxyl group. As a polymerization component, a (meth) acrylic acid-based monomer A having a hydroxy group is essential, and a (meth) acrylic acid-based monomer B includes the monomer A. Monomer B may or may not correspond to monomer A. When monomer B matches with monomer A, homopolymerization of monomer A results.

Examples of the (meth) acrylic acid-based monomer A having a hydroxy group include hydroxy group-introduced derivatives of (meth) acrylic acid esters described above, hydroxyalkylated (meth) acrylic acids, and the like, preferably monomers having a hydroxyallyl moiety. Is included. Specific examples of the (meth) acrylic acid-based monomer A having a hydroxy group include 2- (hydroxymethyl) acrylic acid, 2- (hydroxyethyl) acrylic acid and alkyl 2- (hydroxymethyl) acrylate (for example, 2- (hydroxymethyl) acrylic acid). Methyl (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, n-butyl 2- (hydroxymethyl) acrylate, t- 2- (hydroxymethyl) acrylate Butyl), alkyl 2- (hydroxyethyl) acrylate (eg, methyl 2- (hydroxyethyl) acrylate, ethyl 2- (hydroxyethyl) acrylate), etc., preferably a monomer having a hydroxyallyl moiety. Some 2- (hydroxymethyl) acrylic acid and Rokishimechiru) include alkyl acrylate. Particularly preferred are methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate. The (meth) acrylic acid monomer B is preferably a monomer having a vinyl group and an ester group or a carboxyl group, and examples thereof include (meth) acrylic acid and alkyl (meth) acrylate (for example, methyl (meth) acrylate, Ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate etc, preferably methyl methacrylate), (meth) Aryl acrylate (eg, phenyl (meth) acrylate, benzyl (meth) acrylate etc.), alkyl 2- (hydroxyalkyl) acrylate (eg, methyl 2- (hydroxymethyl) acrylate, 2- (hydroxymethyl) Ethyl acrylate, isopropyl 2- (hydroxymethyl) acrylate, -2- (Hydroxyethyl) alkyl such as 2- (hydroxymethyl) acrylic acid such as n-butyl (hydroxymethyl) acrylate and t-butyl 2- (hydroxymethyl) acrylate, 2- (hydroxyethyl) such as methyl 2- (hydroxyethyl) acrylate And the like) and the like.
More specifically, (meth) acrylic polymers having a lactone ring structure in the main chain can be prepared, for example, by the methods described in JP-A-2006-96960, JP-A-2006-171464, and JP-A-2007-63541. It can be manufactured by

  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 5 to 90% by mass, more preferably 10 The content is 80 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass.

The content of lactone ring structure in the (meth) acrylic resin is the same as that of monomers involved in lactone cyclization ((meth) acrylic acid monomer A and (meth) acrylic acid monomer B having a hydroxy group). It can be determined from the amount of copolymerization 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
(In the formula, Z ₁ is a raw material monomer involved in lactone cyclization in the polymer before lactone cyclization ((meth) acrylic acid type monomer A having a hydroxy group and (meth) acrylic acid type monomer B) M _R is a formula weight of a lactone ring structure unit to be generated (specifically, a total formula weight of a lactone ring-forming element and a group other than the main chain bonded to the lactone ring) M _m is the molecular weight (total) of the raw material monomers (hydroxy group-containing (meth) acrylic acid type monomer A and (meth) acrylic acid type monomer B) involved in lactone cyclization, and Z ₂ is Lactone cyclization rate)
It can be calculated by

  The lactone cyclization rate is, for example, based on the amount of mass loss that occurs when all hydroxy groups are dealcoholized or dehydrated as alcohol or water from the polymer composition obtained by polymerization, and mass loss begins in dynamic TG measurement It can be determined from the weight loss due to the dealcoholization reaction up to 300 ° C. before 150 ° C. before decomposition of the polymer starts. That is, in the dynamic TG measurement of the 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 (that is, 100% in the composition) assuming that all the hydroxyl groups contained in the polymer composition participate in the formation of the lactone ring to dealcoholate or dehydrate. Let (Y) be the mass loss rate calculated assuming that dealcoholation or dehydration reaction has occurred. More specifically, the theoretical mass reduction rate (Y) is the molar ratio of the raw material monomer having a structure (hydroxy group) involved in the dealcoholization or dehydration reaction in the polymer, that is, in the polymer composition. It can calculate from the content rate of the said raw material monomer. Substituting these values (X, Y) into the formula: 1- (measured mass reduction rate (X) / theoretical mass reduction rate (Y)), the value is determined, and expressed as "%", the lactone cyclization rate (Dealcoholization or dehydration reaction rate) is obtained.

As the glutaric anhydride structure or the glutarimide structure, for example, when X ^s1 is an oxygen atom in a structure represented by the following formula (12-2) (in the following formula (12-2), a glutaric anhydride structure And preferably a glutarimide structure when X ^s1 is a nitrogen atom.

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

The glutaric anhydride structure in which X ^s1 in the above formula (12-2) is an oxygen atom causes, for example, intramolecular dealcoholization cyclocondensation of a copolymer of (meth) acrylic acid ester and (meth) acrylic acid It can be formed by
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, (meth) acrylic resins having a glutaric anhydride structure or a glutarimide structure in the main chain can be produced, for example, by the method described in WO 2007/26659 and WO 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, but is, for example, 5 to 90 mass %, 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, for example by the method of Unexamined-Japanese-Patent No. 2006-131689.

As the maleic anhydride structure or the N-substituted maleimide structure, for example, when X ^s2 is an oxygen atom in a structure represented by the following formula (12-3) (in the following formula (12-3), maleic anhydride And X-substituted maleimide structure when X ^s2 is a nitrogen atom.

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

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 and a (meth) acrylic acid ester or the like to polymerization.
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 phenyl maleimide and the like to (meth) acrylic acid ester and the like to polymerization.
More specifically, (meth) acrylic resins having a maleic anhydride structure or an N-substituted maleimide structure in the main chain can be prepared, for example, by the methods described in JP-A-57-153008 and JP-A-2007-31537. It 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 preferably -90% by mass, more preferably 10 to 70% by mass, still more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass.

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

2-4. Solvent-Soluble Resin Raw Material and Liquid Resin Raw Material Next, the solvent-soluble resin raw material and the liquid resin raw material will be described. Examples of solvent-soluble resin raw materials or liquid resin raw materials include epoxy compounds serving as raw materials for epoxy resins, vinyl compounds (such as (meth) acrylic compounds and styrenic compounds) serving as raw materials for vinyl polymer resins, and poly (amides) And imide precursors. Preferred are epoxy compounds and vinyl compounds.

  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 photo and / or heat curing of an epoxy compound in the presence of a cationic curing catalyst, and a form of a cured product obtained by reacting an epoxy compound with an additional curing agent. In the latter case, conventionally known curing accelerators may be used in combination to accelerate the curing reaction. Examples of the additional curing agent include, for example, acid anhydrides, polyhydric phenol compounds, polyhydric amines and the like, among which acid anhydrides are preferred.

  As the epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, a hydrogenated epoxy compound, and the like are preferable. For example, fluorene epoxy (Oncoat EX-1) manufactured by Osaka Gas Chemical Co., Ltd. Bisphenol A type epoxy compound (epicoat 828EL) manufactured by Japan Epoxy Resins Co., Ltd .; Hydrogenated bisphenol A type epoxy compound (epicoat YX 8000) manufactured by Japan Epoxy Resins Co., Ltd .; Alicyclic liquid epoxy compound (Celloxide 2021) manufactured by Daicel Industries, etc. Is preferably used. In the present specification, an epoxy group includes an oxirane ring which is a three-membered ether, and includes a glycidyl group (including a glycidyl ether group and a glycidyl ester group) in addition to an epoxy group in a narrow sense. 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 that does not break when molded or removed from a substrate, a mold or the like, does not lose its shape, easily peels off, or has flexibility. 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 (meth) acryloyl group-containing compound (also referred to as a (meth) acryloyl group-containing compound or a (meth) acrylic compound), and a styrene resin is styrene And a cured product of a curable composition containing a styrene-based monomer (also referred to as a styrene-based compound) such as divinylbenzene, and the acrylic-styrene resin is a curable composition containing a (meth) acryloyl group-containing compound and a styrene-based monomer It is a cured product of the composition. Among the above 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 (but having a (meth) acryloyl group) obtained by (co) polymerizing a (meth) acrylate monomer can also be suitably used. An acrylic composition containing a polymerizable oligomer such as urethane (meth) acrylate, polyester (meth) acrylate, (meth) acrylate (co) polymer, and (meth) acrylate monomer, in that a coating film can be easily formed. It is preferable to use as a resin raw material. As said acryl- styrene resin raw material, the composition which further used the styrene-type monomer 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 to be subjected to an imidization reaction, and for example, 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 (that is, one containing a solvent) diluted with a solvent (organic solvent) in order to easily carry out the subsequent coating operation. The solvent that can be used is not particularly limited and can be appropriately selected according to the type of the resin component etc. For example, ketones such as methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), cyclohexanone etc. 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.

  The amount of the solvent used is preferably 50% by mass or more in 100% by mass of the resin composition, and preferably less than 100% by mass. More preferably, it is 70 mass% or more, and may be 95 mass% or less. By adjusting in the said range, it becomes possible to obtain a resin composition with high pigment concentration.

  In addition, since there exists a possibility that amides, such as N, N- dimethylacetamide, may decompose | disassemble the oxo carbon type compound described by the said General formula (1) or (2), the one with a small usage is preferable. Therefore, the amount of the 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 (i.e. without amides).

  In addition, the resin composition according to the present invention may contain, for example, a compound having an absorbing ability in a wavelength range of 350 to 400 nm. The presence of these compounds makes it possible to sufficiently suppress the deterioration of the resin sheet (and the light selective transmission filter) caused by the light in the 350-400 nm wavelength region (almost violet light). When a compound having absorption in the wavelength range of 350 to 400 nm is used in combination, as compounds having absorption in the wavelength range of 350 to 400 nm, for example, TINUVIN P, TINUVIN 234, TINUVIN 329, TINUVIN 213, TINUVIN 571, TINUVIN One or two or more types of ultraviolet light absorbing compounds such as 326 (manufactured by BASF) can be used.

  The resin composition according to the present invention may also contain various additives such as surfactants, dispersants, surface tension modifiers, viscosity modifiers, antifoaming agents, preservatives, specific resistance modifiers and the like. .

<4. Applications>
The resin composition according to the present invention can be preferably used as a resin composition for forming a filter which is used in various applications such as opto device applications, display device applications, machine parts, and electric / electronic parts.

  Usually, filters used in these applications are integrated with a support and used as a resin sheet. The resin sheet may be, for example, a spin coat method or a solvent cast method on the surface of the support (or, if there is another layer between the support and the resin layer, the surface of the resin composition). Other than the method of forming by applying (coating method or coating method) by applying by drying, and curing or forming the resin film formed from the resin composition against the support by thermocompression bonding And can be manufactured by a kneading method or the like. The coating thickness (film thickness) is not particularly limited, but is preferably a thin film to obtain a member with good light resistance, so the coating thickness (film thickness) is preferably 5 μm or less, for example. And more preferably 3 μm or less. Moreover, it is preferable that it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more.

  In addition, as said support body, the thing of a film form (support body film) is preferable. 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) ) Imide resin, polyamide resin, aramid resin, cycloolefin resin, etc. can be used. Among these, fluorinated aromatic polymers, poly (amides) imide resins, polyamide resins, aramid resins, cycloolefin resins, epoxy resins and / or acrylic resins are preferred in that they are excellent in heat resistance when forming a reflective layer 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 excellent in light resistance, the coating film obtained by solidifying the resin composition also exhibits good light resistance.

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is of course not limited by the following examples, and appropriate modifications may be made as long as the present invention can be applied to the purpose. Of course, implementation is also possible, and all of them are included in the technical scope of the present invention. In the following, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise noted.

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

  The compound 20 used in this synthesis example is Tetsuo, 9 others, “Acenaphthylene-Fused Cyclo [8] pyrroles with Intense Near-IR-Region Absorption Bands”, Chemistry-A European Journal, August 26 (2013), 19 (41)), pp. 13970-13978, prepared in the same manner as 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-dipyrromethene as an NIR dye”, Tetrahedron, May 6 (2001), 67 (18), pp 3187- Prepared in a similar manner to the method of synthesis of compound 3b on page 3188 described in 3193.

  The pyrrole 13 used in this synthesis example is described in Schultz, et al., "Application of In-situ-Generated Rh-Bound Trimethylethylenemethane Variants to the Synthesis of 3,4-Fused Pyrroles", J. Chem. Am. Chem. Soc. (2013), 135, pp. 4696-4699. The compound was prepared by the same method as the synthesis method of compound 13a on page 4697.

<< Synthesis example of squarylium dye >>
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 purged with nitrogen. 30 mL of dryTHF was added to shield light, LiAlH ₄ (213 mg, 5.6 mmol) was added, and the mixture was heated to reflux overnight. After cooling to room temperature, the reaction solution was quenched with saturated aqueous sodium tartrate solution, extracted with ethyl acetate and washed with water and saturated brine. Drying over Na ₂ SO ₄ and concentration under reduced pressure gave the desired acenaphthopyrrole 2 (yield 356 mg, 1.1 mmol, yield quant.).
Mol. Form. : (Exact Mass: 317.2143, Mol. Wt .: 317.4672)
Appearance: light yellowish green solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.72 (brs, 1 H), 7.60 (d, J = 1.2 Hz, 1 H), 7.52 (m, 2 H), 7.50 (m , 1H), 6.85 (d, J = 2.3 Hz, 1 H), 2.54 (s, 3 H), 1.45 (s, 9 H), 1.43 (s, 9 H)

[Step 2]
Squaric acid 1 (62.4 mg, 0.547 mmol) and acenaphthopyrrole 2 (0.356 g, 1.13 mmol) were added to a reaction vessel and purged with nitrogen. 20 mL of n-BuOH and toluene were added at a ratio of 1: 1, and the mixture was heated to reflux. After confirming that the raw material acenaphthopyrrole had disappeared after 1 hour by TLC, the heating was stopped and the temperature was returned to room temperature and concentrated under reduced pressure. The product was washed with MeOH to give a dark green solid which was considered to be a product, and further recrystallized with CHCl ₃ / MeOH to give compound 3 (yield 0.2744 g, 0.383 mmol, 70% yield). The rotamer abundance ratio 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, 1 H, minor), 9.97 (brs, 1 H, major), 9.42 (s, 1 H, 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, 36 H)
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 purged 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 starting material o-methoxyphenylbicyclopyrrole had disappeared, and then the heating was stopped and the temperature 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, 1 H), 10.38 (brs, 1 H), 7.78 (m, 2 H), 7.36 (m, 2 H), 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, 2 H), 4.07 (s, 3 H), 4.03 (s, 3 H), 1.79 to 1.56 (m, 8 H)
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 rotomers present when dissolved 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, 1 H, major), 8.14-8.06 (m, 4 H), 7.51-7.38 (m, 6 H), 7.20-7. 10 (m, 4 H), 4. 19 (s, 3 H, major), 4. 10 (s, 3 H, 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 purged 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 starting material pyrrole had disappeared, heating was discontinued, the temperature was returned to room temperature, concentration was carried out under reduced pressure, and recrystallization with chloroform / hexane gave compound 8 (yield 0.3133 g, 0 .787 mmol, yield 78%).
Mol. Form. : (Exact Mass: 580.2362, Mol. Wt .: 396.4810)
Appearance: color powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 9.61 (brs, 1 H), 9.39 (brs, 1 H), 6.56-6.46 (m, 4 H), 4.94 (m, 1 H) ), 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 a 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 placed in a 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 product was returned to room temperature, concentrated under reduced pressure, and washed with MeOH to obtain the desired product 14. The ratio of rotomers present when dissolved 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 Dyes >>
Synthesis Example 7 Synthesis of croconium dye having o-methoxyphenyl-bicyclopyrrole

In a reaction vessel, croconic acid (101 mg, 0.402 mmol) and o-methoxyphenylbicyclopyrrole 4 (30.3 mg, 0.213 mol) are placed, n-BuOH / toluene (1: 1, 5 mL) is added, and 2 hours Refluxed. After completion of the reaction, the reaction solution was returned to room temperature, concentrated under reduced pressure, and washed with IPA to obtain compound 10 (yield 105 mg, 81%). The rotomer abundance ratio 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
1 H NMR: (CDCl ₃ , 400 MHz): δ = 13.14 (brs, 1 H), 12.83 (brs, 1 H), 12.76 (brs, 1 H), 12. 60 (brs, 1 H), 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, 1 H), 5.72 (m, 1 H), 5. 65 (m, 1 H), 4.47-4.41 (m, 2 H + 2 H), 4. 17 (s, 3 H), 4 .16 (s, 3 H), 4. 14 (s, 3 H), 4. 10 (s, 3 H), 1.69-1.56 (m, 8 H + 8 H)
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

The reaction vessel was charged with compound 10 (6.5 mg, 0.011 mmol) and heated in vacuum at 230 ° C. for 2 hours. It returned to room temperature and the target object 11 was obtained.
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

In a reaction vessel, croconic acid (243 mg, 1.71 mmol) and acenaphthopyrrole 2 (1.09 g, 3.42 mol) were placed, n-BuOH / toluene (1: 1, 10 mL) was added, and the mixture was refluxed for one and a half hours. . After completion of the reaction, the reaction product was returned to room temperature, concentrated under reduced pressure, and washed with IPA to obtain Target 12 (yield 1.15 g, 91%). The rotamer abundance ratio at the time of dissolution 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
1 H NMR: (CDCl ₃ , 400 MHz): δ (syn) = 12.60 (brs, 2 H, major), 9.67 (s, 2 H, major), 7.82 (s, 2 H, major), 7. 68 (s, 2 H, major), 7.43 (s, 2 H, major), 2.5 5 (s, 6 H, major), 1.62 (s, 18 H, major), 1.41 (s, 18 H, major), δ (anti) = 13.41 (brs, 1 H, minor), 11. 76 (brs, 1 H, minor), 9.74 (s, 1 H, minor), 9.64 (s, 1 H, minor) ), 7.86 (s, 1 H, minor), 7.83 (s, 1 H, minor), 7.77 (s, 1 H, minor), 7.72 (s, 1 H, minor), 7.69 ( s, 1 H, mino r), 7.63 (s, 1 H, minor), 2.82 (s, 3 H, minor), 2.57 (s, 3 H, minor), 1.64 (s, 9 H, 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 placed in a 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 reaction product was concentrated under reduced pressure and washed with MeOH to obtain the desired product 15. The rotomer abundance ratio 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 coatings obtained by the following formulations 1 to 5 were set in a xenon weather meter (X75 SC, manufactured by Suga Test Instruments Co., Ltd.), and a light resistance test was conducted. 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 (manufactured by Tokyo Chemical Industry, purity 98%, Mw = 260.20) and 44 parts of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) in a flask and stirred. While replacing the inside of the reactor with nitrogen gas. The temperature was raised to the reflux temperature of the solvent under nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. The mixture was cooled to room temperature while stirring to precipitate crystals. The precipitated crystals were solid-liquid separated and dried to obtain crystals of the desired product (1,2,4,5-cyclohexanetetracarboxylic acid dianhydride). In a flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with a side tube, a Dean Stark, and a condenser, under a nitrogen stream, 4,4'-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd., Mw = 200.24 8.9 parts and 76 parts of dimethylacetamide as a solvent are charged and dissolved, and 10 parts of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (Mw = 224.17) at room temperature The solid was dividedly charged over 1 hour, and stirred at room temperature for 2 hours. 26 parts of toluene was added as an azeotropic dehydrating agent, and reaction was carried out at 130 ° C. for 3 hours, and refluxing with Dean-Stark was performed to separate azeotropically formed water. After distilling off xylene while raising the temperature to 194 ° C., the solution was cooled to obtain a dimethylacetamide solution of polyimide.

Preparation Example 2 (Acriva in dioxane)
As a (meth) acrylic resin having a lactone ring structure in its main chain, Acrivaa (registered trademark: "RN") manufactured by Nippon Shokuhin Co., Ltd. was used. By mixing 10 parts of the acribia with 90 parts of dioxane and stirring, a solution of acribia (RN) in dioxane was obtained.

«Method of manufacturing coating film»
Example 1 (Resin composition containing compound 3)
The dimethylacetamide solution of the polyimide obtained in Preparation Example 1 was diluted with dimethylacetamide to adjust the concentration to 8%. 12.31 parts of this solution and 0.015 parts of the compound (3) obtained in Synthesis Example 1 were mixed to dissolve the compound. The solution was filtered to remove insolubles and the like, and then spin coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coated film.

Example 2 (Resin composition containing compound 3)
9.85 parts of a dioxane solution of Acruria obtained in Production Example 2 and 0.015 parts of the compound (3) obtained in Synthesis Example 1 were mixed to dissolve the compound. The solution was filtered to remove insolubles and the like, and then spin coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coated film.

Example 3 (Resin composition containing compound 12)
9.85 parts of a dioxane solution of Acruria obtained in Production Example 2 and 0.015 parts of the compound (12) obtained in Synthesis Example 9 were mixed to dissolve the compound. The solution was filtered to remove insolubles and the like, and then spin coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coated film.

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

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

The peaks obtained before and after the light resistance test were measured, and the respective results are shown in FIGS. 1 to 5 (solid lines in the attached chart indicate spectra before the test and dotted lines indicate spectra after the test). The peak tops obtained before and after the light resistance test were respectively determined, and (the value of peak top before test−value of peak top after test) was divided by the value of peak top before test to obtain a peak remaining rate. The results of peak residual rate are 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 to 2 and Comparative Example 1, in the compound in which the pyrrole ring is bonded to the squarylium skeleton, the compound in which the cyclic substituent is introduced to two β-position carbons of the pyrrole ring is a compound other than That is, it was found that the peak residual ratio is higher and the light resistance is excellent as compared with the compound formed through the methine group. Similarly, from the results of Example 3 and Comparative Example 2, also in the compound having a croconium skeleton, it is found that the compound in which a cyclic substituent is introduced to two β-position carbons of the pyrrole ring is excellent in light resistance. The

  Since the resin composition according to the present invention contains a dye excellent in weather resistance and color tone, an optical filter for a semiconductor light receiving element having a function of absorbing and cutting visible light and near infrared rays; blocking heat rays for energy saving Near infrared ray absorbing film or near infrared ray absorbing plate; information display material as security ink or invisible bar code ink; solar cell material using visible light and near infrared light; specified for plasma display panel (PDP) or CCD Wavelength absorbing filter; Photothermal conversion material for laser welding; Photofixing method (toner for electrostatic charge development for flash fusing method) using light which hardly causes problems due to pressure or heating; be able to.

Claims (6)

An oxocarbon-based compound represented by the following formula (1) having a squarylium skeleton and having a maximum absorption wavelength of 639 to 1000 nm in CHCl ₃ and / or a 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 formula (3), R ^{b1 to} R ^b4 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, a substituent An aryloxycarbonyl group which may have, an acyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a substituent Optionally substituted 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). The R ^b1 and R ^b2 , R ^b2 and R ^b3 , and R ^b3 and R ^b4 may be combined with 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 as defined above, or * -CH = N-R ^d (wherein R ^d is as defined above), R ^b1 and R ^b2 , R ^b2 and R ^b3 , R ^b3 and R ^b4 There exist at least one or more rings to which is attached . When Formula (3) represents R ^a1 and R ^a2 , a ring in which R ^b3 and R ^b4 are bonded is present in the structural unit of Formula (3) . And an oxocarbon compound represented by
Resin component,
A resin composition comprising at least one solvent selected from ketones, glycol derivatives, amides, esters, pyrrolidones, aromatic hydrocarbons, aliphatic hydrocarbons and ethers.   The resin component is at least one selected from poly (amide) imide resin, fluorinated aromatic polymer, (meth) acrylic resin, polyamide resin, aramid resin and polycycloolefin resin. Resin composition.   The resin composition according to claim 1 or 2, wherein the amount of the amide used is 80% by mass or less in 100% by mass of the resin composition. The maximum absorption wavelength in CHCl ₃ of the oxocarbon compound represented by the formula (1) is 651 to 1000 nm,
The resin composition according to any one of claims 1 to ₃ , wherein the maximum absorption wavelength in CHCl3 of the oxocarbon-based compound represented by the formula (2) is 700 to 1200 nm. 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 .