KR20080007333A - Dimonium Compounds and Uses thereof - Google Patents

Abstract

PROBLEM: To provide an infrared absorption filter and an optical recording medium which do not contain antimony or arsenic and which have excellent stability, in particular, a near infrared absorbing compound having heat resistance, light resistance, and heat and moisture resistance, and heat resistance produced using a near infrared absorbing compound.

Solution: A dimonium compound represented by the following formula (1) and a near infrared absorption filter obtained by using the same:

(1)

(One)

In formula (1),

R ₁ to R ₈ are each independently an aliphatic hydrocarbon group which may have a hydrogen atom or a substituent, R ₉ to R ₁₀ are each independently an aliphatic hydrocarbon group which may have a halogen atom, and R ₁₁ is a substituted or unsubstituted aryl Represents a group,

Ring A and Ring B may have a substituent.

Description

Dimonium compound and its use {DIIMONIUM COMPOUNDS AND USE THEREOF}

The present invention relates to dimonium compounds having absorption in the near infrared region and the use thereof. In particular, the present invention relates to a dimonium compound, a near-infrared absorbing filter using the same, an optical recording medium, and a resin composition thereof, which are not poisons and are excellent in heat resistance, light resistance, solubility, and the like.

Conventionally, the dimonium compound as a near-infrared absorber is widely known (for example, refer patent documents 1-3), and is used widely in a near-infrared absorption filter, a heat insulation film, and sunglasses. However, among these compounds, it is excellent in heat resistance that a counter ion is a hex fluoride antimony acid ion, a hexa hexafluoride ion, etc., The compound of the hexafluoride antimonic acid ion was mainly used. However, since compounds containing antimony correspond to poisons, compounds that do not contain these metals have recently been desired in industrial fields in which use of heavy metals is regulated, particularly in the field of electrical materials. As a means to solve this problem, there is a method of using perchlorate ions, hexafluorophosphate ions, boron fluoride ions, etc. as counter ions, but these counter ions are insufficient in consideration of heat resistance and heat and moisture resistance. Moreover, although the compound using organic counterion, such as naphthalenedisulfonic acid, is also proposed (for example, refer patent document 2), since the molar extinction coefficient is low and the compound itself is lustrous, it cannot actually be used. It is also known to use trifluoromethanesulfonic acid ions, bis (trifluoromethane) sulfonic acid imides, and the like (see Patent Document 1, for example), but these cannot be said to have sufficient heat resistance and heat and humidity resistance. For example, see Patent Documents 4 and 5), still excellent materials are desired.

Patent Document 1: Japanese Patent Application Laid-Open No. 7-51555

Patent Document 2: Japanese Patent Application Laid-Open No. 10-316633

Patent Document 3: JP 43-25335

Patent Document 4: International Publication No. WO2004 / 068199

Patent Document 5: International Publication No. WO2004 / 048480

Disclosure of the Invention

Problems to be Solved by the Invention

The present invention has been carried out in view of such a situation, and an object of the present invention is to contain an antimony-free, near-infrared absorptive compound having excellent stability, particularly heat resistance, light resistance, and moist heat resistance, and excellent solubility using such a compound and its use. To provide an enlarged near-infrared absorption filter (particularly for plasma display panels), and to provide an optical recording medium and a resin composition excellent in resistance to weathering and the like.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnest effort in order to solve the above subjects, the present inventors discovered that the dimonium compound which has a specific structure solved the said subject, and completed this invention.

That is, the present invention relates to:

(1) Dimonium compound represented by following General formula (1):

In formula (1),

R ₁ to R ₈ are each independently an aliphatic hydrocarbon group which may have a hydrogen atom or a substituent, R ₉ to R ₁₀ are each independently an aliphatic hydrocarbon group which may have a halogen atom, and R ₁₁ is a substituted or unsubstituted aryl And

Ring A and Ring B may have a substituent.

(2) the dimonium compound according to the above (1), wherein R ₉ to R _{10 in} the formula (1) are aliphatic hydrocarbon groups having a fluorine atom;

(3) the dimonium compound according to the above (2), wherein R ₉ to R ₁₀ of the formula (1) are trifluoromethyl groups;

(4) the dimonium compound according to any one of the above (1) to (3), wherein R ₁₁ of the formula (1) is a pentafluorophenyl group;

(5) The dimonium compound according to any one of (1) to (4), wherein any one of R ₁ to R ₈ of the formula (1) is a linear or branched alkyl group,

(6) the dimonium compound according to the above (5), wherein all of R ₁ to R ₈ of the formula (1) are n-butyl groups or isobutyl groups;

(7) A resin composition comprising the dimonium compound according to any one of the above (1) to (6) and a resin,

(8) Near-infrared absorption filter which has a layer containing the dimonium compound in any one of said (1)-(6),

(9) A plasma display comprising the near infrared absorption filter according to (8) above, and

(10) An optical information recording medium comprising the dimonium compound according to any one of (1) to (6) in a recording layer.

Effects of the Invention

The near-infrared absorptive dimonium compound of the present invention does not contain antimony, arsenic, or the like and is not a poison, and thus has a high molar extinction coefficient of 90,000 or more, and is excellent in heat resistance, light resistance, and solubility. Moreover, compared with the conventional dimonium salt which has a hexafluorophosphate ion, a perchlorate ion, or a hexafluoride ion, it is especially excellent in heat resistance and heat and moisture resistance. The near-infrared absorption filter using the dimonium compound of this invention is a near-infrared absorption filter which does not contain antimony etc. and is extremely excellent in heat resistance, hardly induces reactions, such as decomposition | disassembly by heat, and coloring of a visible part is hardly confirmed. In view of such characteristics, the dimonium compound of the present invention can be suitably used for a near infrared absorbing filter or a near infrared absorbing film such as a heat insulating film and a sunglass, and is particularly suitable for a near infrared absorbing filter for a plasma display.

In addition, the optical information recording medium of the present invention can significantly improve the light resistance compared to the optical information recording medium containing the conventional dimonium compound. These dimonium compounds also have sufficient solubility and excellent processability in producing an optical information recording medium. Further, in the case where the compound is contained in the organic dye thin film corresponding to the recording layer of the optical information recording medium, for example, an optical information recording medium having remarkably improved durability and light stability in repeated reproduction can be provided.

Implement the invention  Best form for

The dimonium compound of the present invention is a salt having a dimonium cation and two arylbis (alkylsulfonyl) carbonyl anions as counter ions and is represented by the above formula (1).

In formula (1), R ₁ to R ₈ each independently represent an aliphatic hydrocarbon group which may have a hydrogen atom or a substituent. Aliphatic hydrocarbon group means a group excluding one hydrogen atom from saturated and unsaturated linear, branched and cyclic aliphatic hydrocarbons. The carbon number is usually 1 to 36, preferably those having 1 to 20 carbon atoms.

Specific examples of the saturated aliphatic hydrocarbon group or unsaturated aliphatic hydrocarbon group having no substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n- Pentyl group, isopentyl group, tert-pentyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, cyclopentyl group, cyclohexyl group, vinyl group, aryl group, propenyl group, butenyl group, pente Neyl group, hexenyl group, hexadienyl group, isopropenyl group, iso hexenyl group, cyclohexenyl group, cyclopentadienyl group, ethynyl group, propynyl group, pentynyl group, hexynyl group, isohexynyl group, cyclohexynyl group Etc. can be mentioned. Preferred among them are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group and tert-pentyl group C1-C5 straight, branched, saturated aliphatic hydrocarbon groups or unsaturated groups such as vinyl, aryl, propenyl, pentynyl, isopentinyl, tert-pentynyl, vinyl, aryl, propenyl and pentynyl groups Fatty hydrocarbon group etc. are mentioned.

In the present invention, it is preferable that at least one of R ₁ to R ₈ is a straight chain or branched (C1-C6) alkyl group, and at least one of R ₁ to R ₈ is a straight chain (C1-C3) alkyl group, and R ₁ It is preferable that at least 1 of -R <_8> is a branched alkyl group, in particular, R <_1> -R <_8> is the alkyl group which is branched at the whole terminal. R ₁ ~ R ₈ R standing by is a group which is branched from all terminal ₁ ~ R ₈ all are iso-butyl group is especially preferred.

Substituents according to aliphatic hydrocarbon groups having a substituent include, for example, halogen atoms (e.g., F, Cl, Br), hydroxyl groups, alkoxy groups (e.g., methoxy groups, ethoxy, isobutoxy groups, etc.), alkoxyalkoxy groups (e.g., methoxy Ethoxy groups, etc.), aryl groups (e.g., phenyl groups, naphthyl groups, such aryl groups may also have substituents), aryloxy groups (e.g., phenoxy groups, etc.), acyloxy groups (e.g., acetyloxy groups, The aryloxy group including the butyloxy group, hexyloxy group, benzoyloxy group, and the benzoyloxy group may further have a substituent, an amino group, an alkyl substituted amino group (e.g., methylamino group, dimethylamino group, etc.) ), Cyano group, nitro group, carboxyl group, carbonamide group, alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), acyl group, acylamide group (e.g. acetamide group, etc.), sulfonamide group (e.g. , Methanesulfonamide groups, etc.), sulfo groups Can be mentioned. Among these substituents, a halogen atom, cyano group, nitro group, hydroxyl group, carboxyl group, carbonamide group, alkoxycarbonyl group, acyl group, aryl group or alkoxy group is preferable.

These substituents may be present independently of each other, for example, an unsubstituted linear alkyl group and a cyano substituted alkyl group substituted with one amino group, an unsubstituted branched alkyl group and a cyano substituted alkyl group substituted, an unsubstituted The linear alkyl group or the unsubstituted branched alkyl group may be substituted.

Specific examples of the aliphatic hydrocarbon group having a substituent include cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2-cyanopropyl group, 4-cyanobutyl group, 3-cyanobutyl group, 2-cya Cyano-substituted (C1-C6) alkyl groups such as nobutyl group, 5-cyanopentyl group, 4-cyanopentyl group, 3-cyanopentyl group, 2-cyanopentyl group, 3,4-dicyanobutyl group, methoxy Alkoxy such as ethyl group, ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, 5-methoxypentyl group Substituted (C1-C6) alkyl group, trifluoromethyl group, monofluoromethyl group, pentafluoroethyl group, tetrafluoroethyl group, trifluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluorobutylethyl group Fluorinated (C1-C8) alkyl groups such as perfluorohexyl group, perfluorohexylethyl group, perfluorooctyl group, and perfluorooctylethyl group The can.

In formula (1), R ₉ to R ₁₀ represent an aliphatic hydrocarbon which may have a halogen atom independently of each other. Examples of the aliphatic hydrocarbon group include saturated and unsaturated linear, branched, and cyclic alkyl groups, and the carbon number is preferably 1 to 36, more preferably a saturated straight chain alkyl group which may have a substituent. And 1-4 carbon atoms are the most preferable. As the halogen atom, fluorine, chlorine, bromine and iodine atoms are preferred, fluorine, chlorine and bromine atoms are preferred, and fluorine atoms are most preferred. Specifically, for example, R ₉ to R ₁₀ each independently represent a methyl group, trifluoromethyl group, difluoromethyl group, monofluoromethyl group, dichloromethyl group, monochloromethyl group, dibromomethyl group, difluorochloromethyl group, and ethyl group. Pentafluoroethyl group, tetrafluoroethyl group, trifluoroethyl group, trifluorochloroethyl group, difluoroethyl group, monofluoroethyl group, trifluoroiodoethyl group, propyl group, heptafluoropropyl group, hexa Fluoropropyl group, pentafluoropropyl group, tetrafluoropropyl group, trifluoropropyl group, difluoropropyl group, monofluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluoro Unsaturated, such as saturated straight chain alkyl groups, such as an octyl group and a perfluorooctyl ethyl group, an aryl group, a tetrafluoroaryl group, a trifluorovinyl group, and a perfluoro butyl vinyl group Branched alkyl groups such as alkyl groups, isopropyl groups, pentafluoroisopropyl groups, heptafluoroisopropyl groups, perfluoro-3-methylbutyl groups, perfluoro-3-methylhexyl groups, and cyclohexyl groups A cyclic alkyl group etc. are mentioned, It is preferable that R <_9> -R <_10> is the same. In addition, R ₉ and R ₁₀ may be bonded to form a cyclic alkyl group.

It is preferable that R ₉ to R ₁₀ are all an aliphatic hydrocarbon group having a fluorine atom, and specific examples thereof include trifluoromethyl group, difluoromethyl group, monofluoromethyl group, pentafluoroethyl group, tetrafluoroethyl group, and trifluoroethyl group. , Difluoroethyl group, heptafluoropropyl group, hexafluoropropyl group, pentafluoropropyl group, tetrafluoropropyl group, trifluoropropyl group, perfluorobutyl group, etc. are preferable. Trifluoromethyl group, difluoromethyl group, pentafluoroethyl group, trifluoroethyl group, heptafluoropropyl group, tetrafluoropropyl group, perfluorobutyl group and the like, and are preferably trifluoromethyl group. The alkyl moiety is straight chain unless specifically defined in each of the above groups.

R ₁₁ represents a substituted or unsubstituted aryl group, and specific examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a kmenyl group, a mesityl group, a xylyl group and a 4- (trifluoromethyl) phenyl group, 2,4,6- (tri Fluoromethyl) phenyl group, pentafluorophenyl group, 4- (pentafluorophenyl) -2,3,5,6-tetrafluorophenyl group, etc. are mentioned. Preferably, 4- (trifluoromethyl) phenyl group, 2,4,6- (trifluoromethyl) phenyl group, pentafluorophenyl group, 4- (pentafluorophenyl) -2,3, which are electron-withdrawing aryl groups, 5,6-tetrafluorophenyl group is mentioned, Especially preferably, it is a pentafluorophenyl group.

In Formula (1), Ring A and Ring B may each have 1 to 4 substituents in addition to the 1,4-position. As a substituent which can couple | bond, a halogen atom, a hydroxyl group, a lower alkoxy group, a cyano group, a lower alkyl group is mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. As an alkoxy group, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group, are mentioned, for example, As a lower alkyl group, C1-C5 alkyl groups, such as a methyl group and an ethyl group, are mentioned, for example. It is preferable that Ring A and Ring B both have no substituent or are substituted with a halogen atom (especially a chlorine atom, bromine atom, fluorine atom), a methyl group or a cyano group.

In the case where the ring B has a substituent, the four B rings are all the same, or the position of the substituent is preferably the m-position to the nitrogen atom bonded to the phenylene diamine skeleton of the A ring. Moreover, it is preferable that ring A and B do not have a substituent other than a 1, 4-position.

The dimonium compound represented by General formula (1) of this invention can be obtained by the method according to the method of patent document 3, for example. That is, the following general formula (4) obtained by reducing the product obtained by wool-reacting p-phenylenediamine and 1-chloro-4-nitrobenzene

(4)

(4)

The compound represented by is 30 to 160 ° C in an organic solvent, preferably in a water-soluble polar solvent such as DMF (dimethylformamide), DMI (dimethylimidazolidinone) or NMP (N-methylpyrrolidone). Preferably, at 50 to 140 ° C., a halogen compound corresponding to the desired R ₁ to R ₈ (e.g., nC ₄ H ₉ Br when R ₁ to R ₈ is nC ₄ H ₉ ) is reacted with all substituents (R ₁ to R ₈ ) The same compound (henceforth a full substituent) (formula (2)) can be obtained. In addition, when synthesize | combining the compound of General formula (2) other than the compound whose all R <_1> -R <_8> is the same substituent (for example, the precursor of the compound of following compound number 19), a predetermined mole number (4 mol per 1 mol of said Formula (4)) The number of moles required to introduce the n-butyl group to 4 of R ₁ to R ₈ by reacting with the reagent (nC ₄ H ₉ Br) and then to introduce the remaining substituent (isobutyl group) (amino body of formula (4) Compounds of formula (2) can be synthesized by reacting with 4 moles per mole of the corresponding reagent (iso-C ₄ H ₉ Br). Arbitrary compounds other than the whole substituent can be obtained by the method similar to the manufacturing method of the compound of illustrated number 19.

(2)

(2)

The compound synthesized above is oxidizing agent (e.g., silver salt) in an organic solvent, preferably in a water-soluble polar solvent such as DMF, DMI, NMP, etc., from 0 to 100 ° C, preferably from 5 to 70 ° C, ) 2 equivalents is added to carry out the oxidation reaction. The compound synthesized above is oxidized with an acetic acid such as silver acetate or silver perchlorate, and then the reaction product is added with an acid or salt of the anion of formula (3) to the reaction solution. The dimonium compound represented by can be synthesized.

(3)

(3)

Next, the specific example of the dimonium compound of this invention represented by General formula (1) is shown in Table 1. In the table, with respect to R ₁ to R ₈ , i represents a branched chain such as "iso-" and Ph represents a phenyl group. With respect to the rings A and B, when unsubstituted except 1,4-position is unsubstituted, "4H" is indicated, and the substitution position is a position with respect to the nitrogen atom bonded to the phenylenediamine skeleton of the A ring. In addition, with respect to R ₁ to R ₈ , when R ₁ to R ₈ are all n-butyl groups, the abbreviation is referred to as “4 (nC ₄ H ₉ , nC ₄ H ₉ )”, and for example, one iso-pentyl group and the other is Is an n-butyl group, i.e., if one of the combinations of the 4 groups of substituents contains an iso-pentyl group and the remaining 3 groups are all n-butyl groups, "3 (nC ₄ H ₉ , nC ₄ H ₉ ) (nC ₄ H ₉ , iC ₅ H ₁₁ ). Cy also means cyclo. Moreover, the alkyl part of C3 or more in R <_9> -R <_10> is all linear. In R ₁₁ , X represents a pentafluorophenyl group, Y represents a 4- (pentafluorophenyl) -2,3,5,6-tetrafluorophenyl group, and Z represents a 2,4,6- (trifluoro) group. Romethyl) phenyl group.

The resin composition of this invention contains resin and the dimonium compound of this invention represented by General formula (1).

Specific examples of the resin that can be used include addition polymers of polyvinyl compounds such as polyethylene, polystyrene, polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, and polyvinyl fluoride, polymethacrylic acid, and polymethacryl. Krylic acid esters, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene fluoride, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate Vinyl compounds such as copolymers or copolymers of fluorine-based compounds, resins containing fluorine such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, polyamides such as nylon 6 and nylon 66, and poly Mead, polyurethane, polypeptide, polyethylene terephthalate And the like can be given of polyester, polycarbonates, polyethers, epoxy resins such as polyoxymethylene, polyvinyl alcohol, polyvinyl butyral and the like.

Although it does not specifically limit as a method of manufacturing the resin composition of this invention, For example, the following well-known method itself can be used.

(1) a method of kneading and heating molding the dimonium compound of the present invention in a resin to produce a resin plate or film,

(2) a method of producing a resin plate or film by cast polymerization of the dimonium compound of the present invention with a resin monomer or a prepolymer of a resin monomer in the presence of a polymerization catalyst,

(3) a method of preparing a coating material containing the resin composition of the present invention and coating it on a transparent resin plate, a transparent film, or a transparent glass plate,

(4) It is the method of manufacturing the combined resin plate, the combined resin film, or the combined glass plate using the resin composition containing the dimonium compound of this invention, and adhesive resin.

Although the processing temperature, film forming (resin engraving) conditions, etc. differ somewhat as a manufacturing method of said (1), the dimonium compound of this invention is normally added to the powder or pellet of a base resin, and is 150- The method of heating to 350 degreeC, making it melt | dissolving, and shape | molding, and manufacturing a resin plate, or the method of film-forming (resin engraving) by an extruder can be used. The addition amount of the dimonium compound of the present invention varies depending on the thickness, absorption strength, visible light transmittance, etc. of the resin plate or film to be produced, but is usually 0.01 to 30% by weight, preferably 0.03 to 15% by weight, based on the weight of the base resin. Used.

In the method of (2), the compound and the resin monomer or the prepolymer of the resin monomer are injected into the mold in the presence of a polymerization catalyst, reacted and cured or flowed into the mold to solidify until it becomes a cured product in the mold. Mold. Many resins can be molded by this method, and specific examples of the resin which can employ such a method include acrylic resins, diethylene glycol bis (arylcarbonate) resins, epoxy resins, phenolformaldehyde resins, polytilbene resins, and silicone resins. Etc. can be mentioned. Especially, the casting method by the bulk polymerization of methyl acrylate which can obtain the acrylate excellent in hardness, heat resistance, and chemical resistance is preferable.

A well-known radical thermal polymerization initiator can be used as a polymerization catalyst, For example, Azo compounds, such as peroxides, such as a benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, and azobisisobutyronitrile, are mentioned. have. The amount used is generally 0.01 to 5% by weight based on the total amount of the mixture. The heating temperature according to thermal polymerization is 40-200 degreeC normally, and polymerization time is about 30 minutes-about 8 hours normally. Moreover, the method of photopolymerizing by adding a photoinitiator or a sensitizer other than thermal polymerization can also be employ | adopted.

As a method of said (3), the dimonium compound of this invention is melt | dissolved in binder resin and an organic solvent, and the coating method is carried out, The compound is made to disperse | distribute and disperse | distribute the compound in presence of resin, and to make it an aqueous coating material. As such, the method of dissolving the dimonium compound of the present invention in a binder resin and an organic solvent to form a paint includes, for example, an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, and a polyvinyl resin. , An aliphatic polyolefin resin, an aromatic polyolefin resin, a polyvinyl alcohol resin, a polyvinyl modified resin, or the like or a copolymer resin thereof can be used as the binder.

As the solvent, a solvent of halogen, alcohol, ketone, ester, aliphatic hydrocarbon, aromatic hydrocarbon, ether solvent, or a mixture thereof can be used. The concentration of the dimonium compound of the present invention varies depending on the thickness, absorption strength and visible light transmittance of the coating to be produced, but is generally 0.1 to 30% by weight relative to the binder resin.

The near-infrared absorption filter can be obtained by coating with a spin coater, a bar coater, a roll coater, a spray, etc. on the transparent resin film, the transparent resin plate, transparent glass, etc. using the coating material produced in this way.

As the resin for the adhesive in the method of the above (4), a known transparent adhesive for the combined glass such as a polyvinyl butyral adhesive for a resin such as silicone, urethane, acrylic or the like, or a combined glass, an ethylene-vinyl acetate adhesive, etc. Can be used. Bonding transparent resin plates, resin plates and resin films, resin plates and glasses, resin films, resin films and glasses, or glasses using an adhesive obtained by adding 0.1 to 30% by weight of the dimonium compound of the present invention To make a filter.

When kneading and mixing by each method, the usual additives used for resin molding, such as a ultraviolet absorber and a plasticizer, can be added.

Next, the near-infrared absorption filter of this invention is demonstrated.

The near-infrared absorption filter of this invention may be provided with the resin layer containing the dimonium compound of this invention on a base material, or the layer itself consists of a resin composition (or hardened | cured material thereof) containing a near-infrared absorption compound. good. The substrate is generally not particularly limited as long as it can be used in a near infrared absorption filter. Usually, a substrate made of a resin is used. Although the thickness of the layer containing the dimonium compound of this invention is about 0.1 micrometer-about 10 mm normally, it determines suitably according to the objectives, such as a near-infrared cut rate. Moreover, content of the dimonium compound of this invention can also be suitably determined according to the target near-infrared cut rate. As resin which can be used, the same resin as a resin composition is mentioned, When shape | molding with a resin plate or a resin film, it is preferable that transparency is as high as possible. As a method of producing a near-infrared absorption filter, the method similar to manufacture of the said resin composition is mentioned.

Although the near-infrared absorption filter of this invention may contain only the dimonium compound of General formula (1) of this invention as a near-infrared absorption compound, it may also use 2 or more types of dimonium compounds of this invention together, These compounds and this invention You may produce by using together a near-infrared absorption compound other than the dimonium compound of this. As another near-infrared absorption compound which can be used together, a phthalocyanine pigment | dye, a cyanine pigment | dye, a dithiol nickel complex, etc. are mentioned, for example. Examples of near-infrared absorbing compounds of inorganic metals that can be used in combination include copper compounds such as metal copper or copper sulfide and copper oxide, metal mixtures containing zinc oxide as a main component, tungsten compounds, ITO and ATO.

Moreover, in order to change the color tone of a filter, you may add the pigment | dye (coloring dye) which has absorption in a visible region in the range which does not impair the effect of this invention. Moreover, the filter containing only coloring pigment | dye can be produced, and the near-infrared absorption filter of this invention can also be bonded later.

When such a near-infrared absorption filter is used for the front panel of a plasma display, the higher the transmittance of visible light is, the better, at least 40% or more, preferably 50% or more is required. The cut region of the near infrared ray is preferably 750 to 1200 nm, more preferably 800 to 1000 nm, and the average transmittance of the near infrared ray in the region is 50% or less, more preferably 30% or less, even more preferably 20% or less. Especially preferably, it becomes 10% or less.

The near-infrared absorption filter of this invention is not limited to the use like the front plate of a display, It can be used also for the filter and film which need to cut infrared rays, such as a heat insulation film, an optical product, sunglass, etc.

The near-infrared absorption filter of the present invention is an excellent near-infrared absorption filter having a very high transmittance in the visible light region, containing no antimony or arsenic, and being environmentally superior, and broadly absorbing the near infrared region. Moreover, it is excellent in stability compared with the near-infrared absorption filter containing perchlorate ion, hexafluorophosphate ion, and boron fluoride ion which does not contain the conventional antimony. It also has sufficient solubility and excellent processability. In particular, the near-infrared absorption filter of the present invention is very excellent in heat resistance, heat-and-moisture resistance, and light resistance, and hardly causes a reaction such as decomposition by heat, so that a near-infrared absorption filter with little coloration of visible parts can be obtained. Since it has such a characteristic, it can be used suitably for a near-infrared absorption filter or a near-infrared absorption film, such as a heat insulation film and sunglass, and is especially suitable for a near-infrared absorption filter for plasma displays.

In particular, the optical information recording medium of the present invention will be described.

An optical information recording medium of the present invention is characterized by having a recording layer on a substrate, wherein the recording layer contains the dimonium compound of the present invention. This recording layer may be comprised only with a dimonium compound, and may be mixed and contained with various additives, such as a binder. In this case, information is recorded by the dimonium compound of the present invention.

In addition, the light resistance of the optical information recording medium can be improved by containing the dimonium compound of the present invention and a mixture containing other organic dyes in the recording layer of the optical information recording medium on which information is recorded by the organic dyes. have. As such organic pigments provided for recording information in such optical information recording media, for example, cyanine dyes, scarylium pigments, inaniline crab dyes, phthalocyanine dyes, azo dyes, merocyanine dyes, and polymethine dyes. And naphthoquinone dyes and pyryllium dyes.

In such a method, the dimonium compound of the present invention is usually used in an amount of 0.01 to 10 mol, preferably 0.03 to 3 mol, with respect to 1 mol of these organic dyes.

The optical information recording medium of the present invention is provided with a dimonium compound of the present invention and a recording layer containing other dyes as desired on the substrate, and a reflective layer and a protective layer are provided as necessary. As a board | substrate, a well-known thing can be used arbitrarily. A glass plate, a metal plate, a plastic plate, or a film is mentioned, for example, As a plastic for manufacturing these, an acrylic resin, a polycarbonate resin, methacryl resin, a polysulfone resin, a polyimide resin, an amorphous polyolefin resin, a polyester resin, a polypropylene resin Etc. can be mentioned. As a shape of a board | substrate, various things, such as a disk form, a card form, a sheet form, and a roll film form, are mentioned.

Guides may be formed on glass or plastic substrates to facilitate tracking during recording. A glass binder or an undercoat layer such as an inorganic oxide or an inorganic sulfide may be provided on the glass or plastic substrate, and the undercoat layer is preferably lower in thermal conductivity than the substrate.

In the optical information recording medium of the present invention, the recording layer is, for example, the dimonium compound of the present invention and more preferably, the dimonium compound of the present invention and other organic dyes are known in organic solvents such as tetrafluoropropanol (TFP). , Octafluoropentanol (OFP), diacetone alcohol, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, dichloroethane, isoboron, cyclohexanone, etc. The solution can be obtained by applying onto a substrate with a spin coater, bar coater, roll coater or the like. As another method, it can also be obtained by the vacuum vapor deposition method, the sputtering method, the doctor blade method, the casting method, or the dipping method which immerses a board | substrate in solution. As the binder, acrylic resins, urethane resins, epoxy resins and the like can be used.

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.

The optical information recording medium of the present invention can be provided with a lower layer under the recording layer and a protective layer on the recording layer, if necessary, and a reflective layer can be provided between the recording layer and the protective layer. When providing a reflection layer, a reflection layer is comprised from gold, silver, copper, aluminum, etc., Preferably, metal of gold, silver, or aluminum, These metals may be used independently and may be used as 2 or more types of alloys. This layer is formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like. The thickness of such a reflection layer is 0.02-2 micrometers normally. The protective layer provided on the reflective layer is usually formed by applying an ultraviolet curable resin by spin coating and then irradiating ultraviolet rays to cure the coating film. In addition, an epoxy resin, an acrylic resin, a silicone resin, a urethane resin, etc. are also used for the molding material of a protective layer. The thickness of such a protective film is 0.01-100 micrometers normally.

In the optical information recording medium of the present invention, the recording of information or the formation of an image is carried out through a substrate by a high energy beam on a focused spot such as a laser, for example, a semiconductor laser, a helium neon laser, a He-Cd laser, a YAG laser, an Ar laser, or the like. Or by irradiating the recording layer from the substrate and the reflection side, and reading out information or an image by irradiating a low-power laser beam to determine the difference between the amount of reflected light or the amount of transmitted light between the fit portion and the portion where the fit is not formed. By detecting it.

The dimonium compound of the present invention has a maximum absorption wavelength of 900 nm or more and a molar extinction coefficient of tens of thousands to hundreds of thousands. Moreover, from the result of stability tests, such as heat resistance, light resistance, and heat and humidity resistance, it can be used as an infrared absorber which has less discoloration compared to the conventional thing, excellent stability, sufficient solvent solubility from a solubility test, and a processability.

The near-infrared absorption filter using the dimonium compound of this invention is high in solubility, excellent workability, and excellent stability, such as heat resistance, moisture-heat resistance, and the like compared with the near-infrared absorption filter using the conventional dimonium compound. In particular, it is a near-infrared absorption filter which is excellent in heat resistance, heat-and-moisture resistance, and light resistance in which reactions, such as decomposition, hardly occur in these stability tests and coloring of visible parts hardly occur. Since it has such a characteristic, it can be used suitably as a near-infrared absorption filter or a near-infrared absorption film, such as a heat insulation film and sunglasses, for example, and is especially suitable for the near-infrared absorption filter for plasma displays.

The optical information recording medium of the present invention is excellent in light stability as compared to the optical information recording medium made of a conventional dimonium compound. In addition, the dimonium compound of the present invention has sufficient solubility and excellent processability in producing an optical information recording medium. Further, for example, when the organic dye thin film corresponding to the recording layer of the optical information recording medium contains these compounds as a light stabilizer, it is possible to provide an optical information recording medium with remarkably improved durability and light stability when repeatedly reproduced.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. In the examples, "part" and "%" are by weight unless otherwise specified.

Example 1 (Synthesis Example 1)

(Synthesis of Compound of Number 1 in Table 1)

1 part of N, N, N ', N'- tetrakis (p-di (n-butyl) aminophenyl) -p-phenylenediamine is added to 20 parts of DMF, and it melt | dissolves at 60 degreeC, and 1- [bis 1 part of (trifluoromethanesulfonyl) methyl] -2,3,4,5,6-pentafluorobenzene was added. Next, 0.4 part of silver nitric acid dissolved in 10 parts of DMF was added, and it stirred for 30 minutes by heating. After insoluble fractions were filtered, water and methanol were added to the reaction solution, and the precipitated crystals were filtered out, washed with methanol, and washed with water to obtain 0.9 part of the compound of No. 1.

λmax 1103 nm (dichloromethane)

Molar extinction coefficient (ε) 107,000

Melting point 202-208 ℃

Example 2 (Synthesis Example 2)

(Synthesis of Compound of Number 2 in Table 1)

1 part of N, N, N ', N'- tetrakis (p-di (iso-butyl) aminophenyl) -p-phenylenediamine is added to 20 parts of DMF, and it melt | dissolves at 60 degreeC, and 1- [bis 1 part of (trifluoromethanesulfonyl) methyl] -2,3,4,5,6-pentafluorobenzene was added. Next, 0.4 part of silver nitric acid dissolved in 15 parts of DMF was added, and it stirred for 60 minutes by heating. After insoluble fractions were filtered, water was added to the reaction solution. The precipitated crystals were filtered, washed with methanol, washed with water and dried to obtain 1.3 parts of the compound of No. 2.

λmax 1108 nm (dichloromethane)

Molar extinction coefficient (ε) 108,000

Melting Point 186-191 ℃

Other compounds can also be synthesized in the same manner as in Synthesis Example 1 by oxidizing a corresponding phenyldiamine derivative with an oxidizing agent in the presence of a corresponding anion or by oxidizing with an oxidizing agent and reacting with a corresponding anion.

Example 3 (Near Infrared Absorption Filter and Thermal Stability Test)

1.2 parts of the dimonium compounds obtained in Example 1 were dissolved in 18.8 parts of MEK (methyl ethyl ketone). 80 parts of resin liquids which added and melt | dissolved 25 parts of acrylic resin (Mitsubishi Rayon Co., Ltd., diamond BR-80) in MEK 75 parts were melt | dissolved in this solution, and the coating solution was obtained. This was apply | coated to a polyester film so that it might become thickness 2-4 micrometers, and it dried at 80 degreeC, and obtained the near-infrared absorption filter of this invention.

The obtained near-infrared absorption filter was left to stand in 100 degreeC oven for 250 hours, and the heat stability test was done. Before and after the test, the filter was measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-3150), and the pigment residual ratio was evaluated by the change in absorbance at the maximum absorption wavelength. Moreover, L ^* value (brightness), a ^* value, and b ^* value (chromaticity) were measured with the said spectrophotometer, and stability evaluation was performed from the change of b ^* value. The results are shown in Table 2-1 and Table 2-2.

Comparative Examples 1 and 2

Hexafluorinated antimonate of N, N, N ', N'-tetrakis {p-di (n-butyl) aminophenyl} phenylenedimonium as dimonium compound (Comparative Example 1, compound number 21) , Bis (trifluoromethanesulfonyl) imide salt of N, N, N ', N'-tetrakis {p-di (n-butyl) aminophenyl} phenylenedimonium (Comparative Example 2, compound number 22 A filter was produced and evaluated in the same manner as in Example 3 except for the use of the same), and the results are shown in Table 2-1 and Table 2-2.

As is apparent from Tables 2-1 and 2-2, the near-infrared absorption filter containing the dimonium compound of the present invention has a high pigment residual ratio and a small change in b ^* value for the comparative test under high temperature conditions. The physical properties are considered to be excellent.

Example 4 (Near Infrared Absorption Filter and Moisture Heat Stability Test)

The near-infrared absorption filter obtained in the same manner as in Example 3 was allowed to stand in a thermo-hygrostat for 250 hours under a condition of 85 ° C. and 85% RH, and then subjected to a heat and humidity resistance test. Before and after the experiment, the filter was measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-3150), and the pigment residual ratio was evaluated from the change in absorbance at the maximum absorption wavelength. Moreover, L ^* value (brightness), a ^* value, and b ^* value (chromaticity) were measured with the said spectrophotometer, and stability evaluation was performed from the change of b ^* value. The results are shown in Table 3-1 and Table 3-2.

Comparative Examples 3 to 4

Hexafluorinated antimonate of N, N, N ', N'-tetrakis {p-di (n-butyl) aminophenyl} phenylenedimonium as dimonium compound (Comparative Example 3, Compound No. 21), N Bis (trifluoromethanesulfonyl) imide salt of (N, N ', N'-tetrakis {p-di (n-butyl) aminophenyl} phenylenedimonium) (Comparative Example 4, Compound No. 22) A filter was prepared and evaluated in the same manner as in Example 4 except for the use, and the results are shown in Tables 3-1 and 3-2.

As is apparent from Tables 3-1 and 3-2, the near-infrared absorption filter containing the dimonium compound of the present invention has a high pigment residual ratio with respect to the comparative sample and high temperature and high humidity in that the change in b ^* value is small. It turns out that resistance under conditions is excellent.

Claims (10)

Dimonium compound represented by following General formula (1):

(One) In formula (1), R ₁ to R ₈ are each independently an aliphatic hydrocarbon group which may have a hydrogen atom or a substituent, R ₉ to R ₁₀ are each independently an aliphatic hydrocarbon group which may have a halogen atom, and R ₁₁ is a substituted or unsubstituted aryl And Ring A and Ring B may have a substituent. The dimonium compound according to claim 1, wherein R ₉ to R _{10 in} formula (1) are aliphatic hydrocarbon groups having a fluorine atom. The dimonium compound according to claim 2, wherein R ₉ to R _{10 in} formula (1) are trifluoromethyl groups. The dimonium compound according to any one of claims 1 to 3, wherein R _{11 in} formula (1) is a pentafluorophenyl group. The dimonium compound according to any one of claims 1 to 4, wherein any one of R ₁ to R ₈ of formula (1) is one linear or branched alkyl group. The dimonium compound according to any one of claims 1 to 4, wherein all of R ₁ to R ₈ in formula (1) are n-butyl groups or isobutyl groups. The dimonium compound and resin of any one of Claims 1-6 are contained, The resin composition characterized by the above-mentioned. The near-infrared absorption filter which has a layer containing the dimonium compound in any one of Claims 1-6. The near-infrared absorption filter of Claim 8 was provided, The plasma display characterized by the above-mentioned. An optical information recording medium comprising the dimonium compound according to any one of claims 1 to 6 in a recording layer.