JP2006347938A - Diimmonium compound and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near infrared light absorbing compound having excellent solubility in an alcohol, such as methanol, without containing antimony nor arsenic, and to provide an infrared light absorbing filter manufactured by using the near infrared light absorbing compound and having excellent resistance, such as light resistance. <P>SOLUTION: A diimmonium compound expressed formula (1) (R<SB>1</SB>to R<SB>8</SB>are each H or an aliphatic hydrocarbon residue which may be substituted; R<SB>9</SB>and R<SB>10</SB>are each an aliphatic hydrocarbon residue which may have a halogen; and ring A and ring B each may be further substituted) and the near infrared light absorbing filter obtained by using the compound are provided, respectively. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a diimonium compound having absorption in the infrared region and its use. In particular, the present invention relates to a diimonium compound that does not correspond to a deleterious substance and has excellent solubility in an organic solvent such as alcohol, a resin composition using the same, an infrared absorption filter, and an optical information recording medium.

  Conventionally, the diimonium compound as a near-infrared absorber is known widely (for example, refer patent documents 1-3), and is widely utilized for a near-infrared absorption filter, a heat insulation film, sunglasses, etc. And as a diimonium compound, the compound whose counter ion is a hexafluoroantimonate ion was mainly used. However, since compounds containing antimony fall under the category of deleterious substances, diimonium compounds that do not contain these metals have been desired in the industrial field where the use of heavy metals and the like is restricted, particularly in the field of electrical materials. As means for solving this, a method using perchlorate ion, hexafluorophosphate ion, borofluoride ion, trifluoromethanesulfonate ion, bis (trifluoromethane) sulfonateimide, etc. as a counter ion has been proposed. (See, for example, Patent Documents 1, 4, and 5), in handling these compounds, compounds having these counter ions are insufficient in view of solubility in alcohol, which is a commonly used solvent. Furthermore, although compounds using an organic counter ion such as naphthalenedisulfonic acid have been proposed (see, for example, Patent Document 2), from the viewpoint of low molar extinction coefficient and ease of handling in actual use, methanol, There is a difficulty in solubility in alcohol such as ethanol.

Japanese Patent Publication No. 7-51555 (2nd page) JP 10-316633 A (page 5) Japanese Patent Publication No. 43-25335 (pages 7-14) International Publication WO 2004/068199 Pamphlet International Publication WO2004 / 048480 Pamphlet

  The present invention has been made in view of the above situation, and an object of the present invention is to provide diimonium which does not contain antimony, has a high molar extinction coefficient, and has excellent solubility, and An object of the present invention is to provide an infrared absorption filter, an optical recording medium, and a resin composition using such a diimonium compound.

As a result of diligent efforts to solve the above-described problems, the present inventors have found that a diimonium compound having a specific counterion structure can solve the above-mentioned problems, and have completed the present invention. . That is, the present invention
(1) A diimonium compound represented by the following formula (1)

(In the formula (1), R _{1 to} R ₈ each independently represents an aliphatic hydrocarbon residue which may have a hydrogen atom or a substituent, and R ₉ and R ₁₀ each independently have a halogen atom. Each represents an aliphatic hydrocarbon residue that may be present, and rings A and B may each independently further have a substituent).
(2) The diimonium compound according to (1), wherein R ₉ and R _{1O in} the formula (1) are aliphatic hydrocarbon residues having a fluorine atom,
(3) The diimonium compound according to (2), wherein the aliphatic hydrocarbon residue having a fluorine atom is a trifluoromethyl group,
(4) The diimonium compound according to any one of (1) to (3), wherein at least one of R _{1 to} R _{8 in} the formula (1) is a linear or branched (C1-C6) alkyl group. (5) The diimonium compound according to (4), wherein all of R _{1 to} R _{8 in} the formula (1) are iso-butyl groups,
(6) The substituent in the aliphatic hydrocarbon residue which may have a substituent of R _{1 to} R _{8 in} the formula (1) is a halogen atom, cyano group, nitro group, hydroxyl group, carboxyl group, carbonamide A diimonium compound according to any one of (1) to (3), which is a group, an alkoxycarbonyl group, an acyl group, an aryl group or an alkoxyl group;
(7) The diimonium compound according to (6), wherein all of R _{1 to} R _{8 in} formula (1) are cyanopropyl groups,
(8) R _{1 to} R _{8 in} Formula (1) are each independently a cyano (C1-C4) alkyl group, a (C1-C3) alkoxy (C1-C4) alkyl group, or an unsubstituted (C1-C6) alkyl. Group, (C2-C4) unsaturated alkyl group or perfluoro (C1-C4) alkyl group, R ₉ and R ₁₀ are each independently a perfluoro (C1-C4) alkyl group, and ring A is unsubstituted. The diimonium compound according to claim 1, wherein the substituent of ring B is a bromine atom or a (C1-C3) alkyl group,
(9) A resin composition comprising the diimonium compound according to any one of (1) to (8) and a resin,
(10) A near-infrared absorption filter comprising a layer containing the diimonium compound according to any one of (1) to (8),
(11) An optical information recording medium comprising the recording layer containing the diimonium compound according to any one of (1) to (8),
About.

The near-infrared absorptive diimonium compound of the present invention does not contain antimony, arsenic or the like, and does not correspond to a deleterious substance. In addition, the molar extinction coefficient is as high as 90,000 or more, and it has a higher solubility in alcohols than conventional organic acid salts such as bis (trifluoromethane) sulfonic acid imide. Therefore, the diimonium compound of the present invention has high processing properties because of its high solubility in alcohols, and is suitable as a material for near-infrared absorption filters and near-infrared absorption films such as heat insulating films and sunglasses. Can be used.
Further, the optical information recording medium of the present invention is characterized in that the light resistance can be greatly improved as compared with the conventional optical information recording medium containing a diimonium compound. The diimonium compound of the present invention has sufficient solubility for preparing an optical information recording medium and is excellent in processing characteristics. In addition, for example, when this compound is contained in an organic dye thin film corresponding to the recording layer of an optical information recording medium, an optical information recording medium can be provided in which durability in repeated reproduction and light resistance stability are remarkably improved. .

  The diimonium compound of the present invention is a salt composed of one diimonium cation and two anions, as represented by the formula (1).

In the formula (1), R ₉ and R ₁₀ independently represent an aliphatic hydrocarbon residue which may have a halogen atom. Examples of the aliphatic hydrocarbon residue include saturated and unsaturated linear, branched and cyclic alkyl groups, and the number of carbon atoms is preferably 1 to 36, more preferably saturated which may have a substituent. In which the number of carbon atoms is 1 to 20, and the number of carbon atoms is most preferably 1-4. The halogen atom is preferably a fluorine, chlorine, bromine or iodine atom, more preferably a fluorine, chlorine or bromine atom, and most preferably a fluorine atom.
In the description of the present invention, the aliphatic hydrocarbon residue and the alkyl group represent the same group.
As specific examples, R _{9 to} R ₁₀ are each independently a methyl group, a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group, a dichloromethyl group, a monochloromethyl group, a dibromomethyl group, a difluorochloromethyl group, Ethyl group, pentafluoroethyl group, tetrafluoroethyl group, trifluoroethyl group, trifluorochloroethyl group, difluoroethyl group, monofluoroethyl group, trifluoroiodoethyl group, propyl group, heptafluoropropyl group, hexafluoropropyl Group, pentafluoropropyl group, tetrafluoropropyl group, trifluoropropyl group, difluoropropyl group, monofluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorooctylethyl group, etc. Saturated linear alkyl group, allyl group, tetrafluoroallyl group, trifluoroethylene group, perfluorobutylethylene group and other unsaturated alkyl groups, isopropyl group, pentafluoroisopropyl group, heptafluoroisopropyl group, perfluoro-3- Examples thereof include branched alkyl groups such as methylbutyl group and perfluoro-3-methylhexyl group, and cyclic alkyl groups such as cyclohexyl group. R ₉ and R ₁₀ are preferably the same group. Further, R ₉ and R ₁₀ may be bonded to form a cyclic alkyl group.

More preferable as R ₉ and R ₁₀ are aliphatic hydrocarbon residues having a fluorine atom, which are a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group, a pentafluoroethyl group, a tetrafluoroethyl group, a trifluoroethyl group, Specific examples thereof include fluoroethyl group, difluoroethyl group, heptafluoropropyl group, hexafluoropropyl group, pentafluoropropyl group, tetrafluoropropyl group, trifluoropropyl group, perfluorobutyl group, more preferably trifluoro A methyl group, a difluoromethyl group, a pentafluoroethyl group, a trifluoroethyl group, a heptafluoropropyl group, a tetrafluoropropyl group, and a perfluorobutyl group, and most preferred is a trifluoromethyl group. In each of the above groups, unless otherwise specified, the alkylene part and the alkyl part are normal (straight chain).

In the formula (1), the rings A and B may have 1 to 4 substituents in addition to the 1- and 4-positions, respectively. Specific examples of the substituent include a halogen atom, a hydroxyl group, a lower alkoxy group, a cyano group, and a lower alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include C1-C5 alkoxy groups such as methoxy group and ethoxy group, and examples of the lower alkyl group include C1-C5 alkyl groups such as methyl group and ethyl group. It is preferable that both A and B have no substituent other than the 1- and 4-positions, or are substituted with a halogen atom (especially a chlorine atom, a bromine atom or a fluorine atom), a methyl group or a cyano group. .
When B has a substituent, it is preferable that all four B rings have the same substituent, and that the position of the substituent is m-position with respect to the nitrogen atom bonded to the phenylenediamine skeleton. .

R _{1 to} R ₈ each independently represent a hydrogen atom or an aliphatic hydrocarbon residue which may have a substituent. An aliphatic hydrocarbon residue means a group obtained by removing one hydrogen atom from a saturated and unsaturated linear, branched or cyclic aliphatic hydrocarbon. Examples of the carbon number include those having 1 to 36, preferably 1 to 20 carbon atoms.

  Specific examples of the aliphatic hydrocarbon residue having no substituent include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, s-butyl group, and ter-butyl. Group, n-pentyl group, iso-pentyl group, ter-pentyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, propenyl group, pentynyl group, Butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl, cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, hexynyl, isohexynyl, cyclohexynyl, etc. Can be mentioned. Among these, preferred are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, ter-butyl group, n-pentyl group. , Iso-pentyl group, ter-pentyl group, vinyl group, allyl group, propenyl group, pentynyl group, etc., C1-C5 straight chain, branched chain saturated aliphatic hydrocarbon residue or unsaturated aliphatic hydrocarbon residue Groups and the like.

In the present invention, R ₁ at least one of to R ₈ is intended a linear or branched (C1-C6) alkyl group, more at least one straight-chain (C1-C4 of R ₁ to R ₈ ) An alkyl group is preferred, and at least one of R _{1 to} R ₈ is a branched alkyl group, and in particular, R _{1 to} R ₈ are all alkyl groups branched at the terminal. preferable. As R _{1 to} R ₈ , all of which are alkyl groups branched at the terminals, it is particularly preferable that R _{1 to} R ₈ are all iso-butyl groups.

  Examples of the substituent in the aliphatic hydrocarbon residue having a substituent include, for example, a halogen atom (eg, F, Cl, Br), a hydroxy group, an alkoxy group (eg, a methoxy group, an ethoxy group, an isobutoxy group), An alkoxyalkoxy group (eg, methoxyethoxy group, etc.), an aryl group (eg, substituted phenyl group, substituted naphthyl group, etc.) which may have a substituent, an aryloxy group (eg, substituted) which may have a substituent Phenoxy group, etc.), acyloxy group (eg, acetyloxy group, butyryloxy group, hexyloxy group), aryloxy group (such as substituted benzoyloxy group) which may have a substituent, amino group, alkyl-substituted amino group ( Eg, methylamino group, dimethylamino group, etc.), cyano group, nitro group, carboxyl group, carbonamido group, alkoxycarbo Le group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), an acyl group, an amido group (e.g., such as acetamido group), a sulfonamido group (e.g., a methanesulfonamido group), such as a sulfo group. Among these substituents, preferred examples include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a carbonamido group, an alkoxycarbonyl group, an acyl group, an aryl group, or an alkoxyl group.

  These groups can exist independently, for example, one amino group substituted with an unsubstituted linear alkyl group and a cyano-substituted alkyl group, an unsubstituted branched chain alkyl group and a cyano-substituted group. It may be substituted with an alkyl group or substituted with an unsubstituted linear alkyl group and an unsubstituted branched alkyl group.

  Specific examples of the aliphatic hydrocarbon residue having a substituent include a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 2-cyanopropyl group, a 4-cyanobutyl group, a 3-cyanobutyl group, and a 2-cyanobutyl group. Cyano-substituted (C1-C6) alkyl groups such as 5-cyanopentyl group, 4-cyanopentyl group, 3-cyanopentyl group, 2-cyanopentyl group, 3,4-dicyanobutyl group, methoxyethyl group, ethoxyethyl Group, 3-methoxypropyl group, 3-ethoxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, 5-methoxypentyl group and other alkoxy-substituted (C1-C6) alkyl groups, tri Fluoromethyl group, monofluoromethyl group, pentafluoroethyl group, tetrafluoroethyl group, trifluoroethylene Group, heptafluoropropyl group, perfluorobutyl group, perfluorobutyl ethyl group, perfluorohexyl group, perfluorohexyl ethyl group, perfluorooctyl group, fluoride, such as perfluorooctyl ethyl (C1 to C8) alkyl group, and the like.

In the present invention, all of R _{1 to} R ₈ are diimonium compounds which are alkyl groups substituted with a cyano group, or at least one of R _{1 to} R ₈ is an alkyl group substituted with a cyano group, and at least one Is preferably a diimonium compound which is an alkyl group. In particular, those in which all of R _{1 to} R ₈ are cyanopropyl groups are preferred.

  The diimonium compound represented by Formula (1) of this invention can be manufactured by the method according to the method described in patent document 3, for example. That is, the following formula (4) obtained by reducing the product obtained by the Ullmann reaction of p-phenylenediamine and 1-chloro-4-nitrobenzene.

(In Formula (4), Ring A and Ring B are as defined in Formula (1) above.)
In an organic solvent, preferably in a water-soluble polar solvent such as DMF (dimethylformamide), DMI (dimethylimidazolinone) or NMP (N-methylpyrrolidone) at 30 to 160 ° C., preferably 50 to 140. ℃ in, is reacted with a halogenating compound corresponding to the desired R ₁ to R ₈ (e.g., n-C ₄ H ₉ Br when the R ₁ to R ₈ is n-C ₄ H _9), all permutations A compound represented by the formula (2) in which the groups (R _{1 to} R ₈ ) are the same (hereinafter, referred to as all substituents) can be obtained. In addition, when synthesizing a compound of the following formula (2) other than a compound in which all of R _{1 to} R ₈ are the same substituents (for example, a precursor of the compound of the following compound example No. 19), first, a predetermined mole Reaction with a number (4 moles per mole of the above formula (4)) (n-C ₄ H ₉ Br) to introduce n-butyl groups into four of R _{1 to} R ₈ , then the remaining By reacting with the corresponding reagent (iso-C ₄ H ₉ Br) in the number of moles necessary to introduce the substituent (iso-butyl group) (4 moles per mole of amine of the above formula (4)). Can also be synthesized. Arbitrary compounds other than all substitution products can be obtained by the same method as the method for producing the compound of Compound Example No. 19 exemplified here.

(In formula (2), R _{1 to} R ₈ and ring A and ring B are as defined in formula (1).)
The compound of the formula (2) synthesized as described above is represented by the following formula (0) to 100 ° C., preferably 5 to 70 ° C. in an organic solvent, preferably a water-soluble polar solvent such as DMF, DMI, NMP or the like. The oxidation reaction is performed by adding 2 equivalents of an oxidizing agent (for example, silver salt) corresponding to 3). Further, after oxidizing the compound of formula (2) with an oxidizing agent such as silver nitrate, silver perchlorate, cupric chloride, etc., an acid or salt of an anion of formula (3) is added to the reaction solution for salt exchange. Do. Alternatively, the compound of formula (2) may be added by adding an acid or alkali metal salt of an anion of formula (3), and an oxidation reaction with an oxidizing agent such as silver nitrate, silver perchlorate, or mineral acid. ) Can also be synthesized.

(In the formula (3), R _{9 to} R ₁₀ are as defined in the formula (1).)
Next, specific examples of the diimonium compound of the present invention represented by the formula (1) are shown in Table 1. In the table, regarding R _{1 to} R ₈ , i- means “iso” and n- means “normal”. Regarding A and B, when the positions other than the 1- and 4-positions are unsubstituted, it is expressed as “4H”, and the substitution position is a substitution position with respect to the nitrogen atom bonded to the phenylenediamine skeleton. Further, when all of R _{1 to} R ₈ are n-butyl groups, they are abbreviated as “4 (n—C ₄ H ₉ , n—C ₄ H ₉ )”, and for example, one is an iso-pentyl group. When the rest is an n-butyl group, that is, when an iso-pentyl group is included in one of the four combinations of substituents and all the remaining three pairs are n-butyl groups, “3 (n -C ₄ H ₉ , n-C ₄ H ₉ ) 1 (n-C ₄ H ₉ , i-C ₅ H ₁₁ ) Further, Cy means cyclo, and R _{9 to} R ₁₀ The C ₃ F ₇ group is “normal”.

The resin composition of the present invention contains a resin and a diimonium compound represented by the formula (1) of the present invention.
Specific examples of resins that can be used include, for example, vinyl compounds such as polyethylene, polystyrene, polyacrylic acid, polyacrylic acid esters, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, and polyvinyl fluoride, and addition weights of these vinyl compounds. Polymer, Polymethacrylic acid, Polymethacrylate, Polyvinylidene chloride, Polyvinylidene fluoride, Polyvinylidene fluoride, Vinylidene fluoride / Trifluoroethylene copolymer, Vinylidene fluoride / Tetrafluoroethylene copolymer, Vinylidene cyanide / Acetic acid Vinyl copolymers such as vinyl copolymers or copolymers of fluorine compounds, resins containing fluorine such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, polyamides such as nylon 6 and nylon 66 Polyimides, polyurethanes, polypeptides, polyesters such as polyethylene terephthalate, polycarbonate, polyether polyoxymethylene or the like, epoxy resins, polyvinyl alcohol, polyvinyl butyral, and the like.

The method for preparing the resin composition of the present invention is not particularly limited. For example, the following methods known per se can be employed.
(1) A method of obtaining the resin composition of the present invention as a resin plate or film by kneading the diimonium compound of the present invention into the resin and thermoforming it,
(2) A method in which the diimonium compound of the present invention and the monomer of the resin or a prepolymer of the monomer of the resin are cast polymerized in the presence of a polymerization catalyst to obtain the resin composition of the present invention as a resin plate or film,
(3) A method of obtaining the resin composition of the present invention as a coating film by preparing a paint containing the diimonium compound of the present invention and coating the transparent resin plate, transparent film, or transparent glass plate,
(4) Using the composition containing the diimonium compound of the present invention and a resin (adhesive), a laminated resin plate, a laminated resin film, or a laminated glass plate is produced, and the resin composition of the present invention is used as an adhesive layer. How to get,
Etc.

  In the method (1), the processing temperature, filming (resin plate) conditions and the like differ somewhat depending on the resin used, but usually the diimonium compound of the formula (1) of the present invention is added to the powder or pellets of the base resin. Then, after heating and dissolving at 150 to 350 ° C., a method of forming a resin plate by molding, or a method of forming a film (resin plate) with an extruder, and the like can be mentioned. The diimonium compound of the present invention varies depending on the thickness of the resin plate or film to be produced, the absorption intensity with respect to near infrared rays, the visible light transmittance, etc., but is usually 0.01 to 30% by mass with respect to the mass of the base resin, preferably Is used in an amount of 0.03 to 15% by mass.

  In the method (2), the diimonium compound of the formula (1) of the present invention and a resin monomer or a prepolymer of a resin monomer are injected into a mold in the presence of a polymerization catalyst and reacted to be cured, or a mold is used. And solidify until a hard product is formed in the mold. Many resins can be molded in this process, and specific examples of resins that can employ such a method include acrylic resins, diethylene glycol bis (allyl carbonate) resins, epoxy resins, phenol-formaldehyde resins, polystyrene resins, silicon Resin, and the like. Among them, the casting method by bulk polymerization of methyl methacrylate, which can obtain an acrylic sheet excellent in hardness, heat resistance, and chemical resistance, is preferable. The diimonium compound of the present invention varies depending on the thickness of the resin plate or film to be produced, the absorption intensity with respect to near infrared rays, the visible light transmittance, and the like, but is usually 0. 0 relative to the total mass of the resin monomer or resin monomer prepolymer. 01 to 30% by mass, preferably 0.03 to 15% by mass is used.

  A known radical thermal polymerization initiator can be used as the polymerization catalyst. Specific examples of the radical thermal polymerization initiator that can be used include peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide and diisopropyl peroxycarbonate, and azo compounds such as azobisisobutyronitrile. . The amount used is usually 0.01 to 5% by mass relative to the total mass of the resin monomer or resin monomer prepolymer. The heating temperature in the thermal polymerization is usually 40 to 200 ° C., and the polymerization time is usually about 30 minutes to 8 hours. In addition to thermal polymerization, a method of photopolymerization by adding a photopolymerization initiator or a sensitizer can also be employed.

  In the method (3), the dimonium compound represented by the formula (1) of the present invention is dissolved in a binder resin and an organic solvent to form a paint, and the dimonium compound represented by the formula (1) is finely dispersed in the presence of the resin. There are methods such as water-based paints. The former is preferred. Among these, in the method of dissolving the diimonium compound of the formula (1) in a binder resin and an organic solvent to form a paint, for example, an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, A polyvinyl resin, an aliphatic polyolefin resin, an aromatic polyolefin resin, a polyvinyl alcohol resin, a polyvinyl modified resin, or a copolymer resin thereof can be used as a binder.

  As the organic solvent, halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, or mixtures thereof can be used. The concentration of the diimonium compound of the present invention varies depending on the thickness of the coating to be produced, the absorption strength, and the visible light transmittance, but is usually 0.1 to 30% by mass with respect to the binder resin.

A near-infrared absorption filter can be obtained, for example, by coating the thus-prepared coating on a transparent resin film, transparent resin plate, transparent glass or the like with a spin coater, bar coater, roll coater, spray or the like.
In the method (4), as the resin for the adhesive, a transparent adhesive such as a silicone adhesive for resin, a urethane adhesive, an acrylic adhesive, or a polyvinyl butyral adhesive for laminated glass, ethylene- Transparent adhesives such as vinyl acetate adhesives can be used. Bonding transparent resin plates, resin plates and resin films, resin plates and glass, resin films, resin films and glass, and glasses using an adhesive added with 0.1 to 30% by mass of the dimonium compound of the present invention Thus, for example, a filter is produced.
In the above methods (1) to (4), usual additives used for resin molding such as an ultraviolet absorber and a plasticizer may be added during kneading and mixing.

Next, the near-infrared absorption filter of the present invention prepared by the above methods (1) to (4) will be described in detail.
The near-infrared absorption filter of the present invention may be one in which the resin layer containing the diimonium salt of the present invention is provided on a base material, or the base material itself from a resin composition (or a cured product thereof) containing a near-infrared absorption compound. It may be a layer. The substrate is not particularly limited as long as it can be generally used for a near-infrared absorption filter, but a resin substrate is usually used. The thickness of the layer containing the diimonium compound of the present invention is usually about 0.1 μm to 10 mm, but is appropriately determined according to the purpose such as the near infrared cut rate. Further, the content of the diimonium compound of the present invention is also appropriately determined according to the target near-infrared cut rate. Examples of the resin that can be used include the above-mentioned resins. When the resin is molded into a resin plate or a resin film, a resin that is as transparent as possible is preferable.

  The infrared absorption filter of the present invention may contain only the diimonium compound of the formula (1) of the present invention as an infrared absorption compound, but it is also possible to use two or more kinds of the diimonium compounds of the present invention in combination. You may produce combining a compound and near-infrared absorption compounds other than the diimonium compound of this invention. Other near-infrared absorbing compounds that can be used in combination include, for example, phthalocyanine dyes, cyanine dyes, dithiol nickel complexes as organic compounds, or copper compounds such as metal copper or copper sulfide, copper oxide as metal compounds, oxidation Examples thereof include a metal mixture mainly composed of zinc, a tungsten compound, ITO (indium-tin oxide), and ATO (antimony-tin oxide).

In order to change the color tone of the near-infrared filter, a dye having a visible region absorption (toning dye) may be added as long as the effect of the present invention is not impaired, or only the toning dye is contained. A filter may be produced and the near-infrared absorption filter of the present invention may be attached later.
When such a near-infrared absorption filter is used for the front plate of a plasma display, the higher the visible light transmittance, the better, and a transmittance of at least 40% or more, preferably 50% or more is required. The near infrared cut region is preferably 750 to 1200 nm, more preferably 800 to 1000 nm, and the average near infrared transmittance of the region is 50% or less, more preferably 30% or less, still more preferably 20% or less, Particularly preferably, it is desirable to be 10% or less.

  The near-infrared absorption filter of the present invention is not limited to uses such as the front plate of a display, but can also be used for filters and films that need to cut infrared rays, such as heat insulating films, optical products, and sunglasses.

Next, the optical information recording medium of the present invention will be described.
The optical information recording medium of the present invention has a recording layer on a substrate, and the recording layer contains the diimonium compound of the present invention. This recording layer may be composed of only a diimonium compound, or may be mixed with various additives such as a binder. In this case, information is recorded by the diimonium compound of the present invention.

In addition, the light resistance of the optical information recording medium is improved by including the diimonium compound of the present invention and the organic dye as described below in the recording layer of the optical information recording medium on which information is recorded by the dye. Can be made. Examples of organic dyes used for recording information in such optical information recording media include cyanine dyes, squarylium dyes, indoaniline dyes, phthalocyanine dyes, azo dyes, merocyanine dyes, and polymethine dyes. Naphthoquinone dyes, pyrylium dyes, and the like.
In such a method, the diimonium compound of the present invention is generally used in an amount of 0.01 to 10 mol, preferably 0.03 to 3 mol, per 1 mol of these organic dyes.

  The optical information recording medium of the present invention comprises a substrate provided with a recording layer containing the diimonium compound of the present invention and, if desired, a dye other than this, and a reflective layer and a protective layer are provided as necessary. Any known substrate can be used. For example, a glass plate, a metal plate, a plastic plate or a film can be mentioned, and plastics for producing these include acrylic resin, polycarbonate resin, methacrylic resin, polysulfone resin, polyimide resin, amorphous polyolefin resin, polyester resin, polypropylene Examples thereof include resins. Examples of the shape of the substrate include various shapes such as a disk shape, a card shape, a sheet shape, and a roll film shape.

  A guide groove may be formed on the substrate to facilitate tracking during recording, and an undercoat layer such as a plastic binder, an inorganic oxide, or an inorganic sulfide may be provided. Those having a lower thermal conductivity than the substrate used are preferred.

The recording layer in the optical information recording medium of the present invention contains, for example, the diimonium compound of the formula (1) of the present invention, and more preferably a diimonium compound of the present invention and other organic dyes in a known organic solvent such as tetrafluoropropanol ( (TFP), octafluoropentanol (OFP), diacetone alcohol, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, dichloroethane, isophorone, cyclohexanone, etc., if necessary, add a binder and spin the solution It can be obtained by coating on a substrate with a coater, bar coater, roll coater or the like. As other methods, it can also be obtained by a vacuum deposition method, a sputtering method, a doctor blade method, a casting method, or a dipping method in which the substrate is immersed in a solution. Here, acrylic resin, urethane resin, epoxy resin, or the like can be used as the binder.
The film thickness of the recording layer is preferably 0.01 μm to 5 μm, more preferably 0.02 μm to 3 μm in consideration of recording sensitivity and reflectance.

  In the optical information recording medium of the present invention, if necessary, an undercoat layer can be provided below the recording layer, and a protective layer can be provided on the recording layer, and a reflective layer can be provided between the recording layer and the protective layer. However, when a reflective layer is provided, the reflective layer is composed of gold, silver, copper, aluminum or the like, preferably gold, silver, or aluminum. These metals may be used alone or in combination of two or more. An alloy may be used. This layer is formed by vacuum deposition, sputtering, ion plating, or the like. The thickness of such a reflective layer is usually 0.02 to 2 μm. The protective layer that may be provided on the reflective layer is usually formed by applying an ultraviolet curable resin or the like by spin coating, and then irradiating with ultraviolet rays to cure the coating film. In addition, an epoxy resin, an acrylic resin, a silicone resin, a urethane resin, or the like is also used as a protective film forming material. The thickness of such a protective film is usually 0.01 to 100 μm.

  Information recording or image formation in the optical information recording medium of the present invention is performed by collecting a laser, for example, a semiconductor laser, a helium-neon laser, a He-Cd (helium-cadmium) laser, a YAG laser, an Ar (argon) laser, or the like. The recording layer is irradiated with a light spot-like high-energy beam directly or through the substrate. Information or images are read out by irradiating a low-power laser beam. This is done by detecting the difference in the amount of reflected light or the amount of transmitted light in the part where no is formed.

  The diimonium compound of the present invention has a maximum absorption wavelength of 900 nm or more, and has a large molar extinction coefficient of 100,000 or more. Moreover, it has sufficient solvent solubility with respect to alcohols, such as methanol, and can be used for uses, such as an infrared absorption filter, as an infrared absorber with good workability.

  The diimonium compound of the formula (1) of the present invention has sufficient solubility in a solvent used when producing an optical information recording medium, and is excellent in workability. Further, for example, when these compounds are contained as a light stabilizer in an organic dye thin film (recording layer) of an optical information recording medium, an optical information recording medium having remarkably improved durability in repeated reproduction and light resistance stability is obtained. be able to

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” are based on mass unless otherwise specified. Further, the following difference of ± 4 nm in the measured value of λmax and ± 5% in the measured value of the molar extinction coefficient is an allowable range depending on the measurement conditions.

Example 1 (Synthesis of No. 2 compound in Table 1)
In 20 parts of DMF, 3 parts of N, N, N ′, N′-tetrakis (p-di (iso-butyl) aminophenyl) -p-phenylenediamine is added and dissolved by heating at 60 ° C. 2.1 parts of -trifluoro-N- (trifluoromethanesulfonyl) acetamide potassium salt were added. Subsequently, 1.25 parts of silver nitrate dissolved in 20 parts of DMF was added and stirred with heating for 30 minutes. After filtering the insoluble matter, water and methanol were added to the reaction solution to precipitate crystals. The precipitated crystals were filtered, washed with methanol, washed with water and dried. 2.3 parts of compound 2 were obtained. The maximum absorption wavelength and the molar extinction coefficient at the same wavelength for this compound are as follows.
λmax 1105 nm (dichloromethane) molar extinction coefficient (ε) 105,000

Example 2 (Synthesis of compound No. 3 in Table 1)
After adding 3.28 parts of N, N, N ′, N′-tetrakis (p-di (cyanopropyl) aminophenyl) -p-phenylenediamine in 20 parts of DMF and heating and dissolving at 60 ° C., 2,2, 2.1 parts of 2-trifluoro-N- (trifluoromethanesulfonyl) acetamide potassium salt was added. Subsequently, 1.25 parts of silver nitrate dissolved in 20 parts of DMF was added and stirred with heating for 30 minutes. After filtering the insoluble matter, water and methanol were added to the reaction solution to precipitate crystals. The precipitated crystals were filtered, washed with methanol, washed with water and dried. 2.7 parts of compound 2 were obtained. The maximum absorption wavelength and the molar extinction coefficient at the same wavelength for this compound are as follows.
λmax 1063 nm (dichloromethane) molar extinction coefficient (ε) 102,000

  Other compound examples can also be synthesized by oxidizing the corresponding phenylenediamine derivative with an oxidizing agent and reacting with the corresponding anion, as in Example 1.

Comparative Examples 1-6
(1) Comparison of solubility in methanol In 20 parts of methanol, 0.5 parts of each compound obtained in Examples 1 and 2 and the following comparative compound were stirred at room temperature (20 to 25 ° C.). While throwing. After stirring at room temperature for 20 minutes, the insoluble matter was collected by filtration and dried, and the weight of the insoluble matter was measured. The solubility was calculated from the weight of insoluble matter. The results are shown in Table 1.

Comparative Example 1: N, N, N ′, N′-tetrakis {p-di (iso-butyl) aminophenyl} phenylenediimonium hexafluoroantimonate (Compound No. 21)
Comparative Example 2: N, N, N ′, N′-tetrakis {p-di (iso-butyl) aminophenyl} phenylenediimonium bis (trifluoromethanesulfonyl) imidate (Compound No. 22)
Comparative Example 3: N, N, N ′, N′-tetrakis {p-di (cyanopropyl) aminophenyl} phenylenediimonium hexafluoroantimonate (Compound No. 23)
Comparative Example 4: N, N, N ′, N′-tetrakis {p-di (cyanopropyl) aminophenyl} phenylenediimonium bis (trifluoromethanesulfonyl) imidate (Compound No. 24)

Table 1
Compound No. Solubility in methanol No. 2 (Example 1) 0.32 g / 20 ml
No. 3 (Example 2) 0.17 g / 20 ml
No. 21 (Comparative Example 1) 0.02 g / 20 ml
No. 22 (Comparative Example 2) 0.16 g / 20 ml
No. 23 (Comparative Example 3) 0.09 g / 20 ml
No. 24 (Comparative Example 4) 0.13 g / 20 ml

(2) Comparison of Solubility in Ethanol In 20 parts of ethanol, at room temperature (20 to 25 ° C.), 0.5 parts of each of the compound obtained in Example 1 and the following comparative compound were added with stirring. After stirring at room temperature for 20 minutes, the insoluble matter was collected by filtration and dried, and the weight of the insoluble matter was measured. The solubility was calculated from the weight of insoluble matter. The results are shown in Table 2.

Comparative Example 5: N, N, N ′, N′-tetrakis {p-di (iso-butyl) aminophenyl} phenylenediimonium hexafluoroantimonate (Compound No. 21)
Comparative Example 6 N, N, N ′, N′-Tetrakis {p-di (iso-butyl) aminophenyl} phenylenediimonium bis (trifluoromethanesulfonyl) imido salt (Compound No. 22)

Table 2
Compound No. Solubility in ethanol no. 2 (Example 1) 0.15 g / 20 ml
No. 21 (Comparative Example 5) 0.03 g / 20 ml
No. 22 (Comparative Example 6) 0.10 g / 20 ml

  As is apparent from the results in Tables 1 and 2, it can be seen that the diimonium compound in the present invention has higher solubility in alcohols such as methanol and ethanol than known diimonium compounds.

Claims (11)

Diimonium compound represented by the following formula (1)

(In the formula (1), R _{1 to} R ₈ each independently represents an aliphatic hydrocarbon residue which may have a hydrogen atom or a substituent, and R ₉ and R ₁₀ each independently have a halogen atom. Each represents an aliphatic hydrocarbon residue that may be present, and rings A and B may each independently further have a substituent.) The diimonium compound according to claim 1, wherein R ₉ and R _{10 in} the formula (1) are aliphatic hydrocarbon residues having a fluorine atom. The diimonium compound according to claim 2, wherein the aliphatic hydrocarbon residue having a fluorine atom is a trifluoromethyl group. The diimonium compound according to any one of claims 1 to 3, wherein at least one of R _{1 to} R _{8 in} the formula (1) is a linear or branched (C1-C6) alkyl group. All of R < ₁ > -R < ₈ > of Formula (1) is an iso-butyl group, The diimonium compound of Claim 4 The substituent in the aliphatic hydrocarbon residue which may have a substituent of R _{1 to} R _{8 in} the formula (1) is a halogen atom, cyano group, nitro group, hydroxyl group, carboxyl group, carbonamido group, alkoxy The diimonium compound according to any one of claims 1 to 3, which is a carbonyl group, an acyl group, an aryl group, or an alkoxyl group. All of R < ₁ > -R < ₈ > of Formula (1) is a cyanopropyl group, The diimonium compound of Claim 6 R _{1 to} R _{8 in the} formula (1) are each independently a cyano (C1-C4) alkyl group, a (C1-C3) alkoxy (C1-C4) alkyl group, an unsubstituted (C1-C6) alkyl group, ( C2-C4) an unsaturated alkyl group or a perfluoro (C1-C4) alkyl group, R ₉ and R ₁₀ are each independently a perfluoro (C1-C4) alkyl group, ring A is unsubstituted, The diimonium compound according to claim 1, wherein the substituent of B is a bromine atom or a (C1-C3) alkyl group. A resin composition comprising the diimonium compound according to any one of claims 1 to 8 and a resin. A near-infrared absorption filter comprising a layer containing the diimonium compound according to any one of claims 1 to 8. An optical information recording medium comprising the diimonium compound according to any one of claims 1 to 8 in a recording layer.