JP2005234558A - Diimonium salt compound, and near-ir absorbing filter and optical information recording medium using the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-IR absorbing filter having excellent heat resistance. <P>SOLUTION: The filter contains a compound expressed by formula (1), wherein each of R<SB>1</SB>to R<SB>8</SB>represents a branched chain alkyl group, however, not all of R<SB>1</SB>to R<SB>8</SB>are iso-butyl groups, a ring A and a ring B may have a substituent, and X represents an anion necessary to neutralize electric charges. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a diimonium salt compound excellent in heat resistance and having a near-infrared absorption ability, a near-infrared absorption filter, a near-infrared absorption composition, and an optical information recording medium, and in particular, a plasma comprising the near-infrared absorption filter The present invention relates to a near infrared absorption filter for a display panel.

  Conventionally, the diimonium salt compound which is a near-infrared absorber is widely used for a near-infrared absorption filter, a heat insulating film, sunglasses, and the like. However, in the conventional diimonium salt compound, there are many compounds having a linear alkyl group at the end group, and the near-infrared absorption filter using these compounds generally has a material that is easily changed by heat and light. For this reason, there was a problem that the near-infrared absorption ability was lowered. Especially for heat, there was a serious problem that the visible transmittance of the filter itself decreased with decomposition and the color of the filter became greenish. Near-infrared absorption filters are also used for plasma display panels. A plasma display panel is a panel that displays an image by using plasma emission. Since the emission of plasma includes light in the infrared region (800 to 1100 nm), various infrared rays that can exist around the panel. In order to eliminate malfunctions of devices that use the remote control, such as remote controllers, automatic doors, and entry detectors, it is necessary to cut light in the infrared region using a near infrared absorption filter. However, the conventional near-infrared absorber has a problem that a satisfactory filter cannot be provided for the reasons described above.

  Also, various organic dyes such as cyanine dyes have been proposed as dyes for use in optical recording media containing organic dyes, particularly optical disks such as CD-R and DVD-R that can be recorded only once and optical cards. However, in general, there has been a problem that the recording / reproducing characteristics and the storage stability are lowered due to the fact that these dyes are easily changed by light. As means for solving such problems, it is already known to add a diimonium salt having a linear end group, as described in JP-B-6-26028 and JP-A-1-99885. ing. However, when a heat resistance test and a moist heat resistance test are performed on a recording medium prepared using these compounds, the diimonium salt generally deteriorates first, and the cyanine dye is extremely deteriorated in the subsequent light resistance test. There was a problem of becoming.

  The present invention has been made in view of such a situation, and an object of the present invention is to absorb near infrared rays with improved stability, particularly heat resistance, as compared with a conventional diimonium salt having a linear alkyl group. To provide a near-infrared absorption filter improved in heat resistance suitable for a near-infrared absorption filter for a plasma display panel, and an optical recording medium, prepared using the compound (dimonium salt), such a near-infrared absorption compound is there.

As a result of diligent efforts to solve the problems as described above, the present inventors have found that a near-infrared absorbing compound having the structure of the following formula (1) has excellent stability, particularly excellent heat resistance. Completed the invention. That is, the present invention
(1) The following formula (1):

〔式（１）中、Ｒ_１〜Ｒ_８はそれぞれ同じであっても異なっていても良く、その少なくとも１つが分岐鎖状アルキル基であり、環Ａ及びＢは置換基を有していても良く、Ｘは電荷を中和させるのに必要なアニオンを表す〕
で示される少なくとも一種の化合物を含有することを特徴とする近赤外線吸収フィルター；
（２） 環Ａ及びＢの１，４−位以外が無置換であるか、又は置換基として１〜４個のハロゲン原子、低級アルキル基、低級アルコキシ基、シアノ基及び／又はヒドロキシル基を有する、上記（１）に記載の近赤外線吸収フィルター；
（３） Ｒ_１〜Ｒ_８における分岐鎖状アルキル基が、１−メチルエチル基、１，１−ジメチルエチル基、１−メチルプロピル基、２−メチルプロピル基、１−メチルブチル基、２−メチルブチル基、３−メチルブチル基、又は２−エチルブチル基である、上記（１）又は（２）に記載の近赤外線吸収フィルター；
（４） プラズマディスプレーパネル用である、上記（１）から（３）のいずれかに記載の近赤外線吸収フィルター；
（５） 樹脂中に式（１）で表される化合物を添加してなることを特徴とする近赤外線吸収組成物；
（６） 下記式（１）：

[In Formula (1), R _{1 to} R ₈ may be the same or different, and at least one of them is a branched alkyl group, and Rings A and B may have a substituent. Well, X represents the anion necessary to neutralize the charge.
A near infrared absorbing filter comprising at least one compound represented by:
(2) Rings A and B other than the 1,4-position are unsubstituted or have 1 to 4 halogen atoms, lower alkyl groups, lower alkoxy groups, cyano groups and / or hydroxyl groups as substituents. The near-infrared absorption filter according to (1) above;
(3) The branched alkyl group in R _{1 to} R ₈ is 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl. A near-infrared absorbing filter according to (1) or (2) above, which is a group, a 3-methylbutyl group, or a 2-ethylbutyl group;
(4) The near-infrared absorption filter according to any one of (1) to (3), which is for a plasma display panel;
(5) A near-infrared absorbing composition obtained by adding a compound represented by formula (1) to a resin;
(6) The following formula (1):

〔式（１）中、Ｒ_１〜Ｒ_８はそれぞれ同じであっても異なっていても良く、その少なくとも１つが下記式（２）：

[In formula (1), R _{1 to} R ₈ may be the same or different, and at least one of them may be represented by the following formula (2):

（式（２）中、ｎは１以上の整数を表し、Ｒは分岐鎖状アルキル基を表す）で表される分岐鎖状アルキル基であり、環Ａ及びＢは置換基を有していても良く、Ｘは電荷を中和させるのに必要なアニオンを表す〕
で表されるジイモニウム塩化合物；及び
（７） 上記（６）に記載の少なくとも一種のジイモニウム塩化合物を記録層に含有することを特徴とする光情報記録媒体；
に関する。

(In formula (2), n represents an integer of 1 or more, R represents a branched alkyl group), and rings A and B have a substituent. X represents an anion necessary to neutralize the charge.
And (7) an optical information recording medium characterized in that the recording layer contains at least one diimonium salt compound as described in (6) above;
About.

The near-infrared absorption filter of the present invention uses at least one compound having a structure represented by the general formula (1). In the general formula (1), the rings A and B may or may not have 1 to 4 substituents other than the 1,4-position. Examples of the substituent that can be bonded 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 lower alkoxy group include a methoxy group, and an alkoxy group of C ₁ -C _5, such as ethoxy groups, the lower alkyl group include an alkyl group of C ₁ -C ₅ such as a methyl group, an ethyl group Is mentioned. Preferably, both A and B do not have a substituent, or are substituted with a halogen atom (especially a chlorine atom or a bromine atom), a methyl group or a cyano group. In addition, when B has a substituent, all four B rings are the same, and further, the position of the substituent is m-position with respect to the nitrogen atom bonded to the phenylenediamine skeleton. preferable. In addition, rings A and B preferably have no substituent other than the 1,4-position in terms of synthesis.

In the general formula (1), R _{1 to} R ₈ may be the same or different, at least one of which is a branched alkyl group, and the rest are carbons that may have a substituent. The linear alkyl group of number 1-8 is represented.

  Specific examples of such branched alkyl groups include 1-methylethyl group (i-propyl group), 1,1-dimethylethyl group (t-butyl group), 1-methylpropyl group (sec-butyl). 1,1-dimethylpropyl group, 2-methylpropyl group (iso-butyl group), 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl Carbon number such as a group (iso-amyl group), 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, and 2-ethylbutyl group Examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms.

The remaining substituents other than the branched alkyl group in R _{1 to} R ₈ are preferably selected from linear alkyl groups having 1 to 8 carbon atoms that may have a substituent. Specific examples of these linear alkyl groups include an ethyl group, an n-propyl group, and an n-butyl group, and examples of the substituent that can be bonded to these groups include a cyano group; a hydroxyl group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, n-propoxy group and n-butoxy group; methoxymethoxy group, ethoxymethoxy group and methoxyethoxy group C2-C8 alkoxyalkoxy groups such as ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxybutoxy group; carbons such as methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group An alkoxyalkoxy group of 3 to 15; an allyloxy group; Aryloxy groups having 6 to 12 carbon atoms such as xy group, tolyloxy group, xylyloxy group, naphthyloxy group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, etc. An alkoxycarbonyl group having 2 to 7 carbon atoms; an alkylcarbonyloxy group having 2 to 7 carbon atoms such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, and an n-butylcarbonyloxy group; and methoxycarbonyl Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an oxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, and an n-butoxycarbonyloxy group.

Among the branched alkyl substituents of R _{1 to} R ₈ described above, preferable examples include 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1 -A methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, etc. are mentioned.

  X is an anion necessary for neutralizing the electric charge, and one molecule is required when the anion is divalent, and two molecules are required when the anion is monovalent. These anions are selected from, for example, organic acid anions or inorganic anions. Specifically, examples of the organic acid anion include organic carboxylate ions such as acetate ion, lactate ion, trifluoroacetate ion, propionate ion, benzoate ion, oxalate ion, succinate ion and stearate ion; Methanesulfonate ion, toluenesulfonate ion, naphthalene monosulfonate ion, naphthalene disulfonate ion, chlorobenzenesulfonate ion, nitrobenzenesulfonate ion, dodecylbenzenesulfonate ion, benzenesulfonate ion, ethanesulfonate ion, trifluoromethanesulfone Organic sulfonate ions such as acid ions; and organic borate ions such as tetraphenylborate ions and butyltriphenylborate ions. Preferred are trifluoromethanesulfonate ions. , Alkyl sulfonate ion, and alkyl aryl sulfonate ion such as toluenesulfonate ion.

  Examples of inorganic anions include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion; thiocyanate ion, hexafluoroantimonate ion, perchlorate ion, periodate ion, nitrate ion and tetrafluoroborate. Ion, hexafluorophosphate ion, molybdate ion, tungstate ion, titanate ion, vanadate ion, phosphate ion, borate ion and the like, and preferable ones include perchlorate ion, iodine ion, Tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion and the like can be mentioned.

  Preferred examples of these anions include perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, trifluoromethanesulfonate ion, and toluenesulfonate ion. Is mentioned.

  In Formula (2), n is an integer of 1-17, Preferably it is 1-7. R is a branched alkyl group, and the number of carbon atoms as a whole of the formula (2) is 4 to 20.

Next, specific examples of the near-infrared absorbing compound represented by the general formula (1) of the present invention are shown in Tables 1 to 3. In Tables 1 to 3, i- represents a branched state such as iso-, s- represents sec-, t- represents tert-, and TsO represents a toluenesulfonate ion. In addition, regarding A and B, when there is no substitution at positions other than the 1,4-positions, “4H” is indicated. Moreover, regarding R _{1 to} R ₈ , when R _{1 to} R ₈ are all iso-butyl groups, that is, (R ₁ , R ₂ ), (R ₃ , R ₄ ), (R ₅ , R ₆ ) and When the combination of the four substituents of (R ₇ , R ₈ ) is an iso-butyl group, it is abbreviated as “4 (i-C ₄ H ₉ , i-C ₄ H ₉ )” and similarly In the case where all are iso-amyl groups (—C ₂ H ₄ CH (CH ₃ ) ₂ ), they are abbreviated as “4 (i-C ₅ H ₁₁ , i-C ₅ H ₁₁ )”. Further, among R _{1 to} R ₈ , for example, when one is an n-butyl group and the rest is an iso-butyl group, that is, n-butyl is contained in one of the four combinations of substituents, and the rest In the case where all three pairs are iso-butyl groups, they are abbreviated as “3 (i-C ₄ H ₉ , i-C ₄ H ₉ ) (i-C ₄ H ₉ , n-C ₄ H ₉ )”. .

  In addition, Compound No. In 23 and 24, all four B rings are the same, and the position of the substituent is the m-position with respect to the nitrogen atom bonded to the phenylenediamine skeleton.

  The compound represented by the general formula (1) used in the near-infrared absorption filter of the present invention can be obtained by the following method described in, for example, Japanese Patent Publication No. 43-25335. That is, the following formula (3) obtained by reducing a product obtained by Ullmann reaction of p-phenylenediamine and 1-chloro-4-nitrobenzene:

（式（３）中、環Ａ及びＢは前記で定義された通りである）
で表されるアミノ体を、有機溶媒中、好ましくはＤＭＦ、ＤＭＩ又はＮＭＰ等の水溶性極性溶媒中、３０〜１６０℃、好ましくは５０〜１４０℃で、所望のＲ_１〜Ｒ_８に対応するハロゲン化化合物（例えば、Ｒ_１がｉ−Ｃ_４Ｈ_９のときはＢｒＣＨ_２ＣＨ（ＣＨ_３）_２）と反応させて、全ての置換基（Ｒ_１〜Ｒ_８）が同一である化合物（以下、全置換体と記す）を得ることができる。また、全置換体以外の化合物を合成する場合、例えばＮｏ．２５の化合物を合成する場合には、先に所定のモル数（上記式（３）のアミン体１モル当たり７モル）の試薬（ＢｒＣＨ_２ＣＨ（ＣＨ_３）_２）と反応させてＲ_１〜Ｒ_８のうち７つにｉｓｏ−ブチル基を導入した後、残りの置換基（ｎ−ブチル基）を導入するのに必要なモル数（上記式（３）のアミン体１モル当たり１モル）の対応する試薬（ＢｒＣ_４Ｈ_９）と反応させる。例示したＮｏ．２５の化合物の製造方法と同様の方法により、全置換体以外の任意の化合物を得ることができる。

(In formula (3), rings A and B are as defined above.)
Corresponding to the desired R _{1 to} R ₈ in an organic solvent, preferably in a water-soluble polar solvent such as DMF, DMI or NMP at 30 to 160 ° C., preferably 50 to 140 ° C. Halogenated compound (for example, when R ₁ is i-C ₄ H ₉ , it is reacted with BrCH ₂ CH (CH ₃ ) ₂ ), and all the substituents (R _{1 to} R ₈ ) are the same Can be obtained as a total substitution product). In the case of synthesizing compounds other than all substitution products, for example, In the case of synthesizing 25 compounds, the compound is first reacted with a reagent (BrCH ₂ CH (CH ₃ ) ₂ ) in a predetermined number of moles (7 mol per 1 mol of the amine compound of the above formula (3)), R ₁ to After introducing an iso-butyl group into seven of R _8, the number of moles necessary to introduce the remaining substituent (n-butyl group) (1 mole per mole of amine of the above formula (3)) With the corresponding reagent (BrC ₄ H ₉ ). No. illustrated Any compound other than all substituted compounds can be obtained by a method similar to the method for producing compound 25.

  Thereafter, the compound synthesized above corresponds to X in formula (1) at 0-100 ° C., preferably 5-70 ° C. in an organic solvent, preferably in a water-soluble polar solvent such as DMF, DMI or NMP. An oxidizing agent (for example, silver salt) is added to carry out the oxidation reaction. If the equivalent of the oxidizing agent is 2 equivalents, the diimonium salt compound represented by the general formula (1) of the present invention is obtained. If it is 1 equivalent, a monovalent aminium salt compound (hereinafter referred to as an aminium body) is obtained. It is done.

  Further, by oxidizing the compound synthesized above with an oxidizing agent such as silver nitrate, silver perchlorate, cupric chloride, etc., and then adding the acid or salt of the desired anion to the reaction solution, and performing salt exchange In addition, a compound represented by the general formula (1) can be synthesized.

  The near-infrared absorbing filter of the present invention may be one in which a layer containing the above-mentioned near-infrared absorbing compound is provided on a substrate, and the substrate itself contains a near-infrared absorbing compound (or a cured product thereof). ). 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 near-infrared absorbing compound-containing layer is generally about 0.1 μm to 10 mm, but is appropriately determined according to the purpose such as the near-infrared cut rate. Moreover, content of a near-infrared absorption compound is also suitably determined according to the target near-infrared cut rate.

  The resin used as the base material is preferably as highly transparent as possible when molded into a resin plate or resin film. Specific examples include polyethylene, polystyrene, polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, and polyacrylonitrile. , Vinyl compounds such as polyvinyl chloride and polyvinyl fluoride, and addition polymers of those vinyl compounds; polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride, polyvinylidene fluoride, polycylidene vinylidene, vinylidene fluoride / trifluoro Copolymers of vinyl compounds or fluorine compounds such as ethylene copolymers, vinylidene fluoride / tetrafluoroethylene copolymers, vinylidene cyanide / vinyl acetate copolymers; polytrifluoroethylene, polytetrafluoroethylene, polyhexa Fluorine-containing resins such as fluoropropylene; polyamides such as nylon 6 and nylon 66; polyimides; polyurethanes; polypeptides; polyesters such as polyethylene terephthalate; polycarbonates; polyethers such as polyoxymethylene; Examples include butyral.

  The method for producing the near-infrared absorption filter of the present invention is not particularly limited, but for example, the following method can be used. For example, (1) a method in which the above-mentioned near-infrared absorbing compound is kneaded into a resin and thermoformed to produce a resin plate or film; (2) a prepolymer of the compound and resin monomer or resin monomer is present in the presence of a polymerization catalyst A method of producing a resin plate or film by cast polymerization below; (3) a method of producing a paint containing the above compound and coating it on a transparent resin plate, a transparent film, or a transparent glass plate; and (4) the above For example, a compound resin is contained in an adhesive to produce a laminated resin plate, a laminated resin film, or a laminated glass plate.

  As a production method of (1), the processing temperature, filming (resin plate) conditions and the like are slightly different depending on the resin used, but the compound of the present invention is usually added to the base resin powder or pellets, and 150- Examples include a method of heating and dissolving at 350 ° C. and then molding to produce a resin plate, or forming a film (resin plate) with an extruder. The amount of the above-mentioned near infrared absorbing compound added varies depending on the thickness, absorption strength, visible light transmittance, etc. of the resin plate or film to be produced, but is generally 0.01 to 30 weights with respect to the weight of the binder resin. %, Preferably 0.03 to 15% by weight.

  In the method (2), which is prepared by cast polymerization of the above compound and a resin monomer or a prepolymer of a resin monomer in the presence of a polymerization catalyst, the mixture is injected into a mold and allowed to react and cure. Alternatively, it is poured into a mold and solidified until it becomes a hard product in the mold and molded. Many resins can be molded by this method, and specific examples of such resins include acrylic resins, diethylene glycol bis (allyl carbonate) resins, epoxy resins, phenol-formaldehyde resins, polystyrene resins, and silicon resins. . 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.

  As the polymerization catalyst, known radical thermal polymerization initiators can be used, for example, peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, and azo compounds such as azobisisobutyronitrile. Can be mentioned. The amount used is generally 0.01 to 5% by weight, based on the total amount of the mixture. The heating temperature in thermal polymerization is generally 40 to 200 ° C., and the polymerization time is generally 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 used.

  Examples of the method (3) include a method in which the compound used in the present invention is dissolved in a binder resin and an organic solvent to form a paint, and a method in which the compound of the present invention is microparticulated and dispersed in water to obtain a water-based paint. There is. In the former method, for example, aliphatic ester resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, polycarbonate resin, polyvinyl resin, aliphatic polyolefin resin, aromatic polyolefin resin, polyvinyl alcohol resin, polyvinyl modification Resins or the like or copolymer resins thereof can be used as a binder.

  As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof can be used. Although the density | concentration of the near-infrared absorption compound of this invention changes with thickness of the coating to produce, absorption intensity, and visible light transmittance | permeability, it is 0.1-30 weight% generally with respect to binder resin.

  Using the coating material thus produced, a near-infrared absorbing filter is obtained by coating on a transparent resin film, transparent resin plate, or transparent glass with a spin coater, bar coater, roll coater, spray, or the like. Can do.

  In the method (4), as an adhesive, a general silicon-based, urethane-based, acrylic-based resin or laminated glass polyvinyl butyral adhesive, ethylene-vinyl acetate adhesive, and other laminated glass A known transparent adhesive can be used. Transparent adhesive between resin plates, resin plate and resin film, resin plate and glass, resin film, resin film and glass, or glass using an adhesive containing 0.1 to 30% by weight of the compound of the present invention. Adhere to make a filter.

  In addition, at the time of kneading and mixing by each method, usual additives used for resin molding such as an ultraviolet absorber and a plasticizer may be added.

  Thus, in each method of (1) to (4), the near-infrared absorption composition which added this invention compound represented by Formula (1) in resin is also contained in this invention.

  The near-infrared absorption filter of the present invention preferably uses a diimonium salt compound represented by the general formula (1), but an aminium body having a corresponding structure may be used. When the aminium body is used, the aminium body may be used alone or in combination with the diimonium compound of the general formula (1). Furthermore, you may mix and produce with another near-infrared absorption compound. Examples of other near-infrared absorbing compounds that can be used in combination include phthalocyanine dyes, cyanine dyes, and dithiol nickel complexes. In addition, near-infrared absorbing compounds of inorganic metals can be used in combination. Examples of such inorganic metals include copper compounds such as copper metal, copper sulfide or copper oxide, metal mixtures based on zinc oxide, tungsten compounds, ITO, ATO, etc. are mentioned.

  In order to change the color tone of the filter, it is also preferable to add a dye having absorption in the visible region within a range that does not impair the effects of the present invention. It is also possible to produce a filter containing only the color-adjusting dye, and then attach the near-infrared absorption filter of the present invention later.

  When such a near-infrared absorption filter is used for the front plate of a 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 800 to 900 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. Therefore, it is preferable to use a diimonium compound of the general formula (1) without using an aminium body which generally has a low visible light transmittance.

  The optical recording medium of the present invention has a recording layer on a substrate, and the recording layer contains at least one diimonium compound of the general formula (1) and / or an aminium body. The diimonium compound and / or aminium compound of the general formula (1) may be used alone, but if necessary, one or more compounds selected from the compound of the general formula (1) and / or the aminium compound may be mixed. May be used.

  In the recording layer of the optical recording medium of the present invention, the diimonium compound of the general formula (1) and / or the aminium body may be contained singly or mixed with various additives such as a binder. Also good. In this case, information is recorded by the diimonium compound of the general formula (1) and / or the aminium body.

  Furthermore, the light resistance of the optical recording medium can be improved by including the diimonium compound of the general formula (1) and / or the aminium in the recording layer of the optical recording medium on which information is recorded by the organic dye. . Such an optical recording medium is also a kind of the optical recording medium of the present invention.

  In an optical recording medium using the diimonium compound and / or aminium compound of the general formula (1) for improving light resistance, organic dyes that can be used in combination with these compounds are generally known dyes, for example, Examples include cyanine dyes, squarylium dyes, indoaniline dyes, phthalocyanine dyes, azo dyes, merocyanine dyes, polymethine dyes, naphthoquinone dyes, and pyrylium dyes.

  With respect to 1 mol of these organic dyes, the diimonium compound and / or aminium compound of the general formula (1) is generally used in an amount of 0.01 to 10 mol, preferably 0.03 to 3 mol.

  The optical recording medium of the present invention has a recording layer containing a diimonium compound of the general formula (1) and / or an aminium body and, if desired, a dye, provided on a substrate. A reflective layer and a protective layer are provided as necessary. It is done. 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 resins, polycarbonate resins, methacrylic resins, polysulfone resins, polyimide resins, amorphous polyolefin resins, polyester resins. And polypropylene resin. As for the shape of the substrate, various shapes such as a disk shape, a card shape, a sheet shape, and a roll film shape are exemplified.

  A guide groove may be formed on a glass or plastic substrate to facilitate tracking during recording. The glass or plastic substrate may be provided with a subbing layer such as a plastic binder, inorganic oxide, or inorganic sulfide, and the subbing layer preferably has a lower thermal conductivity than the substrate.

  The recording layer in the optical recording medium of the present invention is, for example, a dimonium compound and / or aminium compound of the general formula (1), and more preferably a dimonium compound and / or aminium compound of the general formula (1) and other organic dyes. Is dissolved in a known organic solvent such as tetrafluoropropanol (TFP), octafluoropentanol (OFP), diacetone alcohol, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, dichloroethane, isophorone, or cyclohexanone. If necessary, an appropriate binder can be added, and the solution can be obtained by applying the solution onto a substrate with a spin coater, bar coater, roll coater or the like. The recording layer in the optical recording medium of the present invention can also be obtained by other methods, for example, vacuum deposition, sputtering, doctor blade, casting, or dipping in which the substrate is immersed in a solution. Here, an acrylic resin, a urethane resin, an 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 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. I can do it. When the reflective layer is provided, the reflective layer is composed of a metal such as gold, silver, copper, or aluminum, preferably gold, silver, or aluminum, but these metals may be used alone or in combination of two or more. It may be used as an alloy. The reflective layer is formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like. The thickness of such a reflective layer is 0.02 to 2 μm. The protective layer that may be provided on the reflective layer is generally formed by applying an ultraviolet curable resin by a spin coating method and then irradiating the ultraviolet ray 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.

  The recording of information or the formation of images on the optical recording medium of the present invention is carried out by using a focused spot-like high energy beam such as a laser, for example, a semiconductor laser, a helium-neon laser, a He-Cd laser, a YAG laser, or an Ar laser. Is irradiated to the recording layer through the substrate or from the opposite side of the substrate, and the reading of information or image is performed by irradiating a low-power laser beam to reflect the pit portion and the portion where no pit is formed. This is done by detecting the difference in light quantity or transmitted light quantity.

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

  The near-infrared absorption filter of the present invention is an excellent near-infrared absorption filter that absorbs a wide range of wavelengths of near-infrared light while exhibiting very high transmittance in the visible light region. Compared with a near-infrared absorption filter made of a diimonium salt having a linear end group, the solubility is high and the processability is also excellent. In particular, the near-infrared absorbing compound of the present invention is very excellent in heat resistance and hardly undergoes a reaction such as decomposition during a heat resistance test, so that a near-infrared absorbing filter that hardly causes coloring in the visible region can be obtained. . Furthermore, since it has such characteristics, it can be suitably used for a near infrared absorption filter and a near infrared absorption film such as a heat insulating film and sunglasses, particularly for a near infrared absorption filter for plasma display. Is preferred.

  The optical recording medium of the present invention can provide an optical recording medium having remarkably improved durability, resistance to moist heat and light resistance during repeated reproduction.

(Example)
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” represents “parts by weight” unless otherwise specified.

(Synthesis Example 1)
(1) Synthesis of N, N, N ′, N′-tetrakis [di {p-di (iso-butyl) aminophenyl} aminophenyl] -p-phenylenediamine In 30 parts of DMF, N, N, N ′, Add 3.8 parts N'-tetrakis (aminophenyl) -p-phenylenediamine, 21 parts iso-butyl bromide, and 15 parts potassium carbonate, 1 hour at 80 ° C, 7 hours at 90 ° C, and 1 at 130 ° C. Reacted for hours. After cooling, the mixture was filtered, 30 parts of isopropanol was added to the reaction solution (filtrate), and the mixture was stirred at 5 ° C. or lower for 1 hour. The produced crystals were washed with methanol and dried to obtain 2.5 parts of light brown crystals.
Melting point 159-167 ° C (DSC)

(2) No. Synthesis of 1 compound 1 part of the compound synthesized in (1) above was added to 10 parts of DMF, heated and dissolved at 60 ° C., 0.78 parts of silver hexafluoroantimonate dissolved in 10 parts of DMF was added, and 30 minutes Reacted. After cooling, the precipitated silver was filtered off. To this reaction liquid (filtrate), 10 parts of water was slowly added dropwise and stirred for 15 minutes after the addition. The produced black crystals were filtered, washed with 50 parts of water, and the resulting cake was dried. 0.5 parts of compound 1 were obtained.
λmax 1104nm (dichloromethane)
Absorption coefficient 100,000
Decomposition temperature 259 ° C (TG-DTA)

(Synthesis Example 2)
Synthesis was performed in the same manner as in Synthesis Example 1 except that in the reaction of Synthesis Example 1 (2), 0.56 parts of silver hexafluorophosphate was used instead of silver hexafluoroantimonate. 0.5 part of compound 2 was obtained.
λmax 1104nm (dichloromethane)
Absorption coefficient 93,200
Decomposition temperature 205 ° C (TG-DTA)

(Synthesis Example 3)
Synthesis was performed in the same manner as in Synthesis Example 1 except that in the reaction of Synthesis Example 1 (1), iso-amyl bromide was used instead of iso-butyl bromide, N, N, N ′, N′-tetrakis [di {P-di (iso-amyl) aminophenyl} aminophenyl] -p-phenylenediamine was obtained.
Melting point 104-107 ° C (DSC)

Further, this compound was reacted with silver hexafluoroantimonate in the same manner as in the reaction of the synthesis example 1 (2). 5 compounds were obtained.
λmax 1106nm (dichloromethane)
Absorption coefficient 109,000
Decomposition temperature 278 ° C (TG-DTA)

(Synthesis Example 4)
Synthesis was performed in the same manner as in Synthesis Example 3 except that silver hexafluorophosphate was replaced with silver hexafluoroantimonate instead of silver hexafluoroantimonate in the reaction of Synthesis Example 3. 6 compounds were obtained.
λmax 1102 nm (dichloromethane)
Absorption coefficient 107,000
Decomposition temperature 220 ° C (TG-DTA)

  For other compound examples, the corresponding phenylenediamine derivative was synthesized in the same manner as in Synthesis Example 1, and after oxidizing the corresponding silver salt and other various oxidizing agents as described above, the reaction with the corresponding anion was performed. Can be synthesized.

(Near infrared absorption filter and heat stability test)
In 10 parts of tetrafluoropropanol, no. 1, no. 2, no. 5 and no. 0.1 part of each compound of 6 was dissolved, and about 1 mg of the solution was spin-coated on a polycarbonate substrate at a rotational speed of 2000 rpm to obtain a near-infrared absorption filter of the present invention. About the obtained near-infrared absorption filter, the heat stability test was done in each period of 1st, 4th, 7th, 11th, and 14th using a 80 degreeC hot air dryer. After the test, the dye residual ratio was measured with a spectrophotometer for each near infrared absorption filter. Table 4 shows the results of the heat resistance test.

  A dye film was prepared and evaluated in the same manner except that tetrakis {p-di (n-butyl) aminophenyl} phenylenediimonium hexafluoride antimonate (comparative sample) was used instead of the above compound.

(Near infrared absorption filter)
No. obtained in Example 1 above. 1 was added in an amount of 0.03% with respect to PMMA (polymethyl methacrylate), and injection molding was performed at a temperature of 200 ° C. to obtain filters having a thickness of 1 mm and 3 mm. When the average light transmittance at 800 to 1000 nm of the obtained filter was measured with a spectrophotometer, it was 20% for a filter having a thickness of 1 mm and 3% for a filter having a thickness of 3 mm.

(Optical recording medium and heat stability test)
No. obtained in Synthesis Example 1 0.02 part of compound 1 and 0.10 part of cyanine dye (OM-57, manufactured by Fuji Photo Film Co., Ltd.) were dissolved in 10 parts of tetrafluoropropanol and passed through a 0.2 μm filter to obtain a coating solution. 5 ml of this solution was dropped with a pipette onto a 5 inch polycarbonate resin substrate with a groove, and applied and dried with a spin coater to form an organic thin film recording layer. The maximum absorption wavelength of the coating film was 719 nm. A gold layer was formed on the obtained coating film by a sputtering method to form a reflective layer, thereby producing an optical recording medium. When the obtained optical recording medium was evaluated with a CD-R recording / reproducing apparatus, recording and reproduction were possible.

  In 15 parts of tetrafluoropropanol, 0.3 part of a cyanine dye (OM-57) was dissolved. 1 (sample 1), No. 1 2 (Sample 2), No. 2 5 (Sample 3), No. 5 1 (sample 4), and No. 1 compound. The aminium body (sample 5) of compound 2 was added in an amount of 0.04 parts to prepare a coating solution. The obtained coating solution was spin-coated on a polycarbonate substrate to prepare a dye film. The obtained dye film was first subjected to a moisture and heat resistance test for 4 days under conditions of 60 ° C. and 95% RH. After the test was completed, the dye film was placed in a UV long life carbon arc light resistance tester (black panel temperature 63 ° C.) manufactured by Suga Test Instruments, and irradiated with light from the substrate side for 10 hours, 20 hours, and 40 hours. The light stability test was performed at the irradiation time. Thereafter, the residual ratio of the cyanine dye was measured with a spectrophotometer. The results are shown in Table 7.

  For comparison, no. 1, no. 2 and no. In place of compound No. 5, tetrakis {p-di (n-butyl) aminophenyl} phenylenediimonium hexafluoroantimonate (Comparative Sample 1) was used. 1 and no. A dye film was prepared in the same manner except that tetrakis {p-di (n-butyl) aminophenyl} phenyleneaminium hexafluoride antimonate (Comparative Sample 2) was used instead of the aminium compound of Compound 2. ,evaluated. The results are shown in Table 5. In addition, Table 6 shows the results of the light resistance test without passing through the moisture resistance test.

(The invention's effect)
The diimonium salt compound of the present invention has higher solubility and excellent processability than the conventional diimonium salt having a linear end group, and is extremely excellent in heat and heat resistance. Near-infrared absorption filter using this is a near-infrared absorption filter with extremely excellent heat resistance. Even when a heat test is performed, reaction such as decomposition is difficult to occur during the test, and coloring in the visible part is hardly recognized. . Because of having such characteristics, the diimonium salt compound of the present invention can be suitably used for a near-infrared absorbing filter, a near-infrared absorbing film such as a heat insulating film and sunglasses, in particular, plasma. Suitable for near infrared absorption filter for display. In addition, when the above-mentioned compound is contained in, for example, an organic dye thin film corresponding to the recording layer of the optical recording medium, an optical recording medium can be provided in which durability in repeated reproduction, heat and humidity resistance, and light stability are remarkably improved.

Claims (7)

Following formula (1):

[In formula (1), R _{1 to} R ₈ may be the same or different, and at least one of them is a branched alkyl group, but all of R _{1 to} R ₈ are iso-butyl groups. Rings A and B may have a substituent, and X represents an anion necessary for neutralizing the charge.
The near-infrared absorption filter characterized by containing the at least 1 type of compound shown by these.   Rings A and B other than the 1,4-position are unsubstituted or have 1 to 4 halogen atoms, lower alkyl groups, lower alkoxy groups, cyano groups and / or hydroxyl groups as substituents. The near-infrared absorption filter according to 1. The branched alkyl group in R _{1 to} R ₈ is 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3 The near-infrared absorption filter according to claim 1 or 2, which is a methylbutyl group or a 2-ethylbutyl group.   The near-infrared absorption filter according to claim 1, which is used for a plasma display panel. In the resin, the following formula (1):

[In Formula (1), R _{1 to} R ₈ may be the same or different, and at least one of them is a branched alkyl group, and Rings A and B may have a substituent. Well, X represents the anion necessary to neutralize the charge.
A near-infrared absorbing composition comprising: at least one compound represented by the formula: Following formula (1):

[In formula (1), R _{1 to} R ₈ may be the same or different, and at least one of them may be represented by the following formula (2):

(In formula (2), n represents an integer of 1 or more, R represents a branched alkyl group), and rings A and B have a substituent. X represents an anion necessary to neutralize the charge.
The diimonium salt compound represented by these.   An optical information recording medium comprising the recording layer containing at least one diimonium salt compound according to claim 6.