JP4912010B2 - COMPOUND HAVING DIOXINONE STRUCTURE, AND OPTICAL FILTER AND OPTICAL RECORDING MATERIAL USING THE COMPOUND - Google Patents

Description

  The present invention relates to a compound having a novel dioxinone structure (hereinafter referred to as a dioxinone compound), an optical filter and an optical recording material using the dioxinone compound. The dioxinone compound is useful as an optical element. The dioxinone compound is particularly useful as an ultraviolet absorber to be contained in an optical filter for an image display device, and has a wavelength in the visible and near-infrared regions and has a high density optical recording by a low energy laser or the like. And an optical recording material used for an optical recording medium capable of reproduction.

  Optical recording media are generally widespread because they have excellent characteristics such as a large recording capacity and non-contact recording or reproduction. In a write-once optical disk such as WORM, CD-R, and DVD-R, the laser is focused on a small area of the optical recording layer, and recording is performed by changing the properties of the optical recording layer, and reflection between the recorded portion and the unrecorded portion is performed. Reproduction is performed by the difference in the amount of light.

  At present, in the above optical disk, the wavelength of the semiconductor laser used for recording and reproduction is 750 to 830 nm for CD-R and 620 to 690 nm for DVD-R. However, in order to realize further increase in capacity, the wavelength is short. An optical disk using a wavelength laser has been studied. For example, an optical disk using light having a wavelength of 380 to 420 nm as recording light is being studied.

  In an optical recording medium for a short wavelength laser, various compounds are used for forming an optical recording layer. For example, Patent Document 1 reports an azo compound, Patent Document 2 reports a porphyrin compound, and Patent Document 3 reports a metal complex of a triazole compound. However, these compounds are not always suitable for the absorption wavelength characteristics as optical recording materials used for forming an optical recording layer.

  In addition, in an optical filter for an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), a fluorescent display tube, a field emission display, A compound that absorbs light having a wavelength of 300 to 390 nm is used as an ultraviolet absorber.

  As an optical filter using the above-described ultraviolet absorber, for example, Patent Document 4 reports an organic EL display element filter containing an ultraviolet absorber and blocking light of 200 to 410 nm. However, the ultraviolet absorber used in the organic EL display element filter does not necessarily match the absorption wavelength characteristic as an ultraviolet absorber for an optical filter.

JP 2004-209771 A JP 2004-58365 A JP 2004-174838 A JP 2004-102223 A

  Accordingly, an object of the present invention is to provide a compound having optical characteristics suitable for an optical element used for an optical filter for an image display device and an optical recording material using a short wavelength laser beam.

  As a result of repeated studies, the present inventor has found that a specific compound having a dioxinone structure has an absorption wavelength characteristic that satisfies the above optical element, and has reached the present invention.

  The present invention has been made on the basis of the above knowledge, and a dioxinone compound represented by the following general formula (I), an optical filter containing the dioxinone compound, and an optical recording layer formed on a substrate. The present invention provides an optical recording material containing the dioxinone compound, which is used as a material for forming the optical recording layer in an optical recording medium.

（式中、Ａは下記 [化２] に示す（イ）〜（ヘ）の群から選ばれる構造を表し、Ｒ¹ 及びＲ² はそれぞれ独立に、水素原子、置換基を有してもよい炭素原子数１〜１０のアルキル基、置換基を有してもよい炭素原子数１〜１０のアルコキシ基、置換基を有してもよい炭素原子数６〜３０のアリール基、置換基を有してもよい炭素原子数６〜３０のアリールオキシ基又は置換基を有してもよい炭素原子数６〜３０のアリールアルキル基を表し、ｎは１〜４の整数を表す。）

(In the formula, A represents a structure selected from the group of (a) to (f) shown in the following [Chemical Formula 2], and R ¹ and R ² may each independently have a hydrogen atom or a substituent. It has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent. An aryloxy group having 6 to 30 carbon atoms which may be substituted or an arylalkyl group having 6 to 30 carbon atoms which may have a substituent, and n represents an integer of 1 to 4).

（式中、Ｒ³ 及びＲ⁴ はそれぞれ独立に、水素原子、置換基を有してもよい炭素原子数１〜１０のアルキル基、置換基を有してもよい炭素原子数１〜１０のアルコキシ基、置換基を有してもよい炭素原子数６〜３０のアリール基、置換基を有してもよい炭素原子数６〜３０のアリールオキシ基、置換基を有してもよい炭素原子数６〜３０のアリールアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアミノ基、ハロゲン原子、シアノ基、ヒドロキシル基、ニトロ基又は下記一般式（α）で表される基を表し、Ｒ⁶ 〜Ｒ¹⁴は各々独立に水素原子又は炭素原子数１〜４のアルキル基を表し、該アルキル基中のメチレン基は−Ｏ−又は−ＣＯ−で置換されていてもよく、Ｚ¹ は、直接結合又は置換基を有してもよい炭素原子数１〜８のアルキレン基を表し、該アルキレン基中のメチレン基は−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ₂ −、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で置換されていてもよく、Ｚ² は直接結合又は置換基を有してもよい炭素原子数１〜８のアルキレン基を表し、該アルキレン基中のメチレン基は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂ −、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で置換されていてもよく、Ｘ¹ は、酸素原子、硫黄原子、セレン原子又は−ＮＲ⁵ −を表し、Ｘ² は、窒素原子又は＝ＣＲ⁵ を表し、Ｒ⁵ は水素原子、置換基を有してもよい炭素原子数１〜１０のアルキル基、置換基を有してもよい炭素原子数１〜１０のアルコキシ基、置換基を有してもよい炭素原子数２〜１０のアルケニル基、置換基を有してもよい炭素原子数６〜３０のアリール基、置換基を有してもよい炭素原子数６〜３０のアリールオキシ基、置換基を有してもよい炭素原子数６〜３０のアリールアルキル基、置換基を有してもよい複素環基又はハロゲン原子を表し、Ｍ¹ はＦｅ、Ｃｏ、Ｎｉ、Ｔｉ、Ｃｕ、Ｚｎ、Ｚｒ、Ｃｒ、Ｍｏ、Ｏｓ、Ｍｎ、Ｒｕ、Ｓｎ、Ｐｄ、Ｒｈ、Ｐｔ又はＩｒを表し、ｍ、ｐ、ｑ、ｔはそれぞれ独立に１〜４の整数を表し、ｒ、ｂ、ｃはそれぞれ独立に１〜３の整数を表し、ｓは１〜５の整数を表し、ａは１又は２を表す。）

(In the formula, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group having 1 to 10 carbon atoms which may have a substituent. An alkoxy group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an aryloxy group having 6 to 30 carbon atoms which may have a substituent, and a carbon atom which may have a substituent An arylalkyl group of formula 6 to 30, a heterocyclic group which may have a substituent, an amino group which may have a substituent, a halogen atom, a cyano group, a hydroxyl group, a nitro group, or the following general formula (α) R ^{6 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the methylene group in the alkyl group is substituted with —O— or —CO—. even if well, Z ¹ is the number direct bond or an optionally substituted carbon atoms from 1 to 8 It represents an alkylene group, a methylene group in the alkylene group -CO -, - COO -, - OCO -, - O -, - S -, - SO 2 -, - NH -, - CONH -, - NHCO-, -N = CH- or -CH = CH- may be substituted with, Z ² represents a direct bond or an optionally substituted alkylene group having 1 to 8 carbon atoms, in the alkylene radical A methylene group is —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, —CONH—, —NHCO—, —N═CH— or —CH═CH. X ¹ represents an oxygen atom, a sulfur atom, a selenium atom or —NR ⁵ —, X ² represents a nitrogen atom or ═CR ⁵ , R ⁵ represents a hydrogen atom or a substituent. An alkyl group having 1 to 10 carbon atoms which may have a substituent, and an alkyl group having 1 to 10 carbon atoms which may have a substituent. Lucoxy group, alkenyl group having 2 to 10 carbon atoms which may have a substituent, aryl group having 6 to 30 carbon atoms which may have a substituent, and the number of carbon atoms which may have a substituent Represents an aryloxy group having 6 to 30 carbon atoms, an arylalkyl group having 6 to 30 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent or a halogen atom, and M ¹ represents Fe, Co , Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, Pt, or Ir, m, p, q, and t are each independently an integer of 1 to 4. And r, b and c each independently represent an integer of 1 to 3, s represents an integer of 1 to 5, and a represents 1 or 2.

（式中、Ｒ¹⁵〜Ｒ²³は各々独立に水素原子又は炭素原子数１〜４のアルキル基を表し、該アルキル基中のメチレン基は−Ｏ−又は−ＣＯ−で置換されていてもよく、Ｚ³ は、直接結合又は置換基を有してもよい炭素原子数１〜８のアルキレン基を表し、該アルキレン基中のメチレン基は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂ −、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で置換されていてもよく、Ｍ² はＦｅ、Ｃｏ、Ｎｉ、Ｔｉ、Ｃｕ、Ｚｎ、Ｚｒ、Ｃｒ、Ｍｏ、Ｏｓ、Ｍｎ、Ｒｕ、Ｓｎ、Ｐｄ、Ｒｈ、Ｐｔ又はＩｒを表す。）

(Wherein R ^{15 to} R ²³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the methylene group in the alkyl group may be substituted with —O— or —CO—). , Z ³ represents an alkylene group having 1 to 8 carbon atoms which may have a direct bond or a substituent, and the methylene group in the alkylene group is —O—, —S—, —CO—, —COO. -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - N = CH- or -CH = CH- may be substituted by, M ² is Fe, Co, Ni , Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, Pt or Ir.)

  The present invention can provide a novel dioxinone compound suitable as an optical element such as an ultraviolet absorber contained in an optical filter or an optical recording agent contained in an optical recording material. In addition, an optical filter using the dioxinone compound is suitable as an optical filter for an image display device, and an optical recording material containing the dioxinone compound emits a low molecule at the time of decomposition and thus has low animal heat resistance and thermal interference. In addition, since the decomposition point is low, the sensitivity is high, which is suitable for forming an optical recording layer of an optical recording medium.

  Hereinafter, the dioxinone compound of the present invention, and an optical filter and an optical recording material containing the dioxinone compound will be described in detail based on preferred embodiments.

First, the dioxinone compound of the present invention will be described.
Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the general formula (I) include methyl, ethyl, propyl, isopropyl, butyl, second Butyl, tertiary butyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, etc. Examples of the alkoxy group having 1 to 10 carbon atoms include methyloxy, ethyloxy, isopropyloxy, propyloxy, butyloxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and the like. Examples of the aryl group having 6 to 30 carbon atoms include phenyl, Examples of the aryloxy group having 6 to 30 carbon atoms include phenoxy and naphthyloxy. Examples of the arylalkyl group having 6 to 30 carbon atoms include benzyl, phenethyl, diphenylmethyl, and triphenyl. And methyl, styryl, cinnamyl and the like.

Examples of the heterocyclic group represented by R ³ , R ⁴ and R ⁵ in the general formula (I) include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, Triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl, etc., and halogen atoms include fluorine, chlorine, bromine, iodine and the like.

Examples of the amino group which may have a substituent represented by R ³ and R ⁴ in the general formula (I) include amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, Dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, Carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino Etc.

Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ⁵ in the general formula (I) include vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl and 3-butenyl. 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricocenyl and the like.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ represented by the above alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, an arylalkyl group having 6 to 30 carbon atoms, a heterocyclic group represented by R ³ , R ⁴ and R ⁵ , and an amino group represented by R ³ and R ⁴ In addition, any of the alkenyl groups having 2 to 10 carbon atoms represented by R ⁵ may have a substituent. Examples of the substituent include the following. In addition, R < ¹ > -R < ⁵ > is group containing carbon atoms, such as said C1-C10 alkyl group, and those groups contain a carbon atom among the following substituents. When it has a substituent, the number of carbon atoms of the entire R ^{1 to} R ⁵ including the substituent satisfies the specified range.
Examples of the substituent include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, and 3-hexyl. , Alkyl groups such as cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl Methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, hex Alkoxy groups such as tiloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, Dibutylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, etc. Alkylthio group; vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl , Alkenyl groups such as 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricosenyl; arylalkyls such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl Groups; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio; pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, Benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, Benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxy Heterocyclic groups such as oxazolidin-3-yl; halogen atoms such as fluorine, chlorine, bromine, iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoro Acyl groups such as methylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acetyloxy, benzoylo An acyloxy group such as amino; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino; 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino , Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbo Substituted amino groups such as ruamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl Group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group and the like, and these groups may be further substituted. Moreover, the carboxyl group and the sulfo group may form a salt.

The alkyl group having 1 to 4 carbon atoms represented by R ^{6 to} R ¹⁴ in the general formula (I) and the alkyl having 1 to 4 carbon atoms represented by R ^{15 to} R ²³ in the general formula (α). Examples of the group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, etc. Examples of the group in which the methylene group in the alkyl group is substituted with -O- include methoxy, ethoxy , Propyloxy, isopropyloxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl and the like. Examples of the group in which the methylene group in the alkyl group is substituted with -CO- include acetyl, 1-carbonylethyl, acetylmethyl 1-carbonylpropyl, 2-oxobutyl, 2-acetylethyl, 1-carbonylisopropyl and the like.

Examples of the alkylene group having 1 to 8 carbon atoms represented by Z ¹ and Z ² in the general formula (I) and the alkylene group having 1 to 8 carbon atoms represented by Z ³ in the general formula (α) include , Methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, ethane-1,1-diyl, propane-2,2-diyl, ethenylene, propenylene, etc. Can be mentioned.
Examples of the group in which the methylene group in the alkyl group is substituted with -CO- include -CO-, 1-oxoethylene, 1-oxopropylene, 2-oxopropylene, 1-oxobutylene, 2-oxobutylene, 2- Examples of the group in which the methylene group in the alkylene group is substituted with -COO- include -COO-, methylenecarbonyloxy, ethylenecarbonyloxy, and the like. Examples of the group in which the methylene group is substituted with -OCO- include -OCO-, methyleneoxycarbonyl, ethyleneoxycarbonyl and the like, and the group in which the methylene group in the alkyl group is substituted with -O- -O-, methyleneoxy, ethyleneoxy, propyleneoxy, isopropyleneoxy, methyleneoxymethylene, methyl As the group in which the methylene group in the alkyl group is substituted with -S-, -S-, methylenethio, ethylenethio, propylenethio, isopropylenethio, methylenethiomethylene, methylenethioethylene, etc. can be mentioned a methylene group in the alkylene group is the -SO ₂ - groups which are substituted with, -SO ₂ -, methylene sulfonyl, sulfonyl ethylene and the like, a methylene group in the alkylene group -NH- Examples of the group substituted with —NH—, aminomethylene, ethyleneamino, etc. include —CONH—, methylenecarbonylamino, carbonyl as the group in which the methylene group in the alkylene group is substituted with —CONH—. Aminoethylene and the like, and a group in which the methylene group in the alkylene group is substituted with -NHCO-. -NHCO-, methyleneaminocarbonyl, aminocarbonylethylene and the like are mentioned. As the group in which the methylene group in the alkylene group is substituted with -N = CH-, -N = CH-, iminomethylene, ethyleneimino Examples of the group in which the methylene group in the alkylene group is substituted with —CH═CH— include ethenylene, propenylene and the like. When the methylene group in the alkylene group is replaced with a group containing carbon atoms such as -CO- or -COO-, the total number of carbon atoms including -CO- or -COO- is there.

Preferable examples of the dioxinone compound of the present invention include those represented by any one of the following general formulas (II) to (V).
The dioxinone compound represented by the following general formula (II) has a structure in which n is 1 and A is represented by the above (a) in the above general formula (I).
In the dioxinone compound represented by the following general formula (III), in the above general formula (I), n is 1, A is a structure represented by the above (d), and in the above (d), X ¹ is a sulfur atom, X ² is ═CR ⁵ —, and R ⁵ is a hydrogen atom.
The dioxinone compound represented by the following general formula (IV) has a structure in which n is 2 and A is represented by the above (a) in the above general formula (I).
The dioxinone compound represented by the following general formula (V) has a structure in which n is 1 and A is represented by the above (f) in the above general formula (I).

（式中、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、ｍ及びｐは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , m and p are the same as those in the general formula (I).)

（式中、Ｒ¹ 、Ｒ² 、Ｒ³ 及びａは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , R ³ and a are the same as those in the general formula (I).)

（式中、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、ｍ及びｐは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , m and p are the same as those in the general formula (I).)

（式中、Ｒ¹ 、Ｒ² 、Ｒ⁶ 、Ｒ⁷ 、Ｒ⁸ 、Ｒ⁹ 、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｚ² 及びＭ¹ は、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , Z ² and M ¹ are the above-mentioned general formula (I) Is the same.)

In the general formulas (I) to (V), R ¹ is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, particularly a methyl group; R ² has a substituent. Preferred is an alkyl group having 1 to 10 carbon atoms, particularly a methyl group; R ³ is preferably a hydrogen atom; R ⁴ is preferably a hydrogen atom; n is preferably 1 or 2.

  Therefore, specific examples of the dioxinone compound of the present invention include the following compound No. 1-22.

  The production method of the dioxinone compound of the present invention represented by the above general formula (I) is not particularly limited and can be obtained by a method using a known general reaction. For example, the dioxinone compound in which n = 1 As a production method in the case of obtaining the above, a synthesis method such as the route shown in the following [Chemical Formula 11] can be mentioned. In addition, compounds other than n can be synthesized according to the route shown in the following [Chemical Formula 11].

（式中、Ａ，Ｒ¹ 及びＲ² は、上記一般式（Ｉ）と同じであり、Ｒ⁶ 及びＲ⁷ はそれぞれ独立に、アルキル基又はアリール基を表す。）

(In the formula, A, R ¹ and R ² are the same as those in the general formula (I), and R ⁶ and R ⁷ each independently represents an alkyl group or an aryl group.)

The dioxinone compound of the present invention is useful as an optical element that exhibits a function by absorbing light having a specific wavelength, particularly 320 to 420 nm. Examples of the optical element include an ultraviolet absorbent contained in an optical filter and an optical recording agent used for forming an optical recording layer of an optical recording medium such as an optical disk.
In addition to the optical element, the dioxinone compound of the present invention can also be used for synthetic intermediates such as pharmaceuticals, agricultural chemicals, fragrances and dyes, or various functional materials.

Next, the optical filter of the present invention will be described.
The optical filter of the present invention contains the dioxinone compound of the present invention. The dioxinone compound of the present invention has an absorption maximum wavelength at 340 to 390 nm, and can absorb and block ultraviolet rays of 410 nm or less and part of visible light, so that the optical system of the present invention containing the dioxinone compound of the present invention. The filter is particularly suitable as an optical filter for an image display device used for improving the quality of a display image. The optical filter of the present invention can be used not only for image display devices but also for various uses such as analysis devices, semiconductor device manufacturing, astronomical observation, optical communication, and spectacle lenses.

  The optical filter of the present invention is usually disposed in front of the display. For example, the optical filter of the present invention may be directly attached to the surface of the display. When a front plate is provided in front of the display, the optical filter is attached to the front side (outside) or back side (display side) of the front plate. May be.

  A typical configuration of the optical filter of the present invention includes a transparent support provided with various layers such as an undercoat layer, an antireflection layer, a hard coat layer, and a lubricating layer as necessary. Examples of the method for incorporating the optical filter of the present invention with optional components such as the dioxinone compound of the present invention, dye compounds other than the dioxinone compound of the present invention, and various stabilizers in the optical filter of the present invention include (1) (2) A method of coating a transparent support or any desired layer, (3) A pressure-sensitive adhesive layer provided between any two adjacent members selected from the transparent support and any desired layer, or an optical filter In a pressure-sensitive adhesive layer provided as the outermost layer for adhering to a display, (4) a method of providing a light-absorbing layer containing a light-absorbing agent such as the dioxynon compound of the present invention separately from any arbitrary layer, etc. Is mentioned.

In the optical filter of the present invention, the amount of Jiokishinon compounds of the invention, per unit area of the optical filter, typically 1 to 1000 mg / m ^2, preferably 5 to 100 mg / m ^2, the use of less than 1 mg / m ² In the amount, the light absorption effect cannot be sufficiently exhibited, and when it is used in excess of 1000 mg / m ² , the color of the filter may become too strong and the display quality may be deteriorated. There is also a risk that the brightness will decrease.

The dioxinone compound of the present invention is usually used in the following manner in order to bring the amount used into the above-mentioned range per unit area of the optical filter. For example, when an optical filter containing the dioxinone compound of the present invention is produced in the pressure-sensitive adhesive layer, the dioxynone compound of the present invention is preferably added in an amount of 0.001 to 0.00. A solvent such as 05 parts by mass and methyl ethyl ketone is preferably added in an amount of 40 to 500 parts by mass to prepare a varnish, and this varnish is applied to a transparent support such as a PET film subjected to an easy adhesion treatment, and then cured to obtain a thick varnish. An optical filter having an adhesive layer (cured film) of 0.1 to 10 microns is obtained.

As a method of including the dioxinone compound of the present invention and an optional component in the optical filter of the present invention, when any of the above methods (1) to (4) is employed, the blending ratio of each component is the above blending ratio. Just follow.

  Examples of the material for the transparent support include inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamides; polycarbonates; polyethylenes Polyesters such as terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene Polyolefins such as polypropylene and polymethylpentene; acrylic resins such as polymethyl methacrylate; polycarbonates; ; Polyether sulfone; polyether ketone; polyetherimides; polyoxyethylene, and polymer materials such as norbornene resins. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, and more preferably 1% or less. The refractive index is preferably 1.45 to 1.70. The thickness of the transparent support is preferably 0.1 to 200 μm.

  In these transparent supports, an infrared absorber, inorganic fine particles, etc. can be added, and various surface treatments can be applied to the transparent support.

  Examples of the inorganic fine particles include layered clay minerals, silicon dioxide, titanium dioxide, barium sulfate, and calcium carbonate.

  Examples of the various surface treatments include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. It is done.

  The undercoat layer is a layer used between the transparent support and the light absorption layer when a light absorption layer containing a light absorber is provided. The undercoat layer is formed as a layer containing a polymer having a glass transition temperature of −60 to 60 ° C., a layer having a rough surface on the light absorption layer side, or a layer containing a polymer having affinity with the polymer of the light absorption layer. To do. In addition, the undercoat layer is provided on the surface of the transparent support on which the light absorption layer is not provided, thereby improving the adhesive force between the transparent support and the layer provided thereon (for example, an antireflection layer or a hard coat layer). It may be provided in order to improve the affinity between the optical filter and the adhesive for bonding the optical filter and the image display device. The thickness of the undercoat layer is preferably 2 nm to 20 μm, more preferably 5 nm to 5 μm, further preferably 20 nm to 2 μm, still more preferably 50 nm to 1 μm, and most preferably 80 nm to 300 nm. The undercoat layer containing a polymer having a glass transition temperature of −60 to 60 ° C. adheres the transparent support and the filter layer due to the tackiness of the polymer. Polymers having a glass transition temperature of −60 to 60 ° C. are exemplified by polymerization of vinyl chloride, vinylidene chloride, vinyl acetate, butadiene, neoprene, styrene, chloroprene, acrylic ester, methacrylic ester, acrylonitrile or methyl vinyl ether, or a copolymer thereof. It can be obtained by polymerization. The glass transition temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, further preferably 30 ° C. or lower, further preferably 25 ° C. or lower, and further preferably 20 ° C. or lower. Most preferred. The elastic modulus at 25 ° C. of the undercoat layer is preferably 1 to 1000 MPa, more preferably 5 to 800 MPa, and most preferably 10 to 500 MPa. The undercoat layer having a rough surface on the light absorption layer side forms a light absorption layer on the rough surface, thereby bonding the transparent support and the light absorption layer. The undercoat layer having a rough surface on the light absorption layer side can be easily formed by applying a polymer latex. The average particle size of the latex is preferably 0.02 to 3 μm, and more preferably 0.05 to 1 μm. Examples of the polymer having an affinity for the binder polymer of the light absorption layer include acrylic resin, cellulose derivative, gelatin, casein, starch, polyvinyl alcohol, soluble nylon, and polymer latex. The optical filter of the present invention may be provided with two or more undercoat layers. In the undercoat layer, a solvent for swelling the transparent support, a matting agent, a surfactant, an antistatic agent, a coating aid, a hardening agent, and the like may be added.

  In the antireflection layer, a low refractive index layer is essential. The refractive index of the low refractive index layer is lower than the refractive index of the transparent support. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, and more preferably 1.30 to 1.50. The thickness of the low refractive index layer is preferably 50 to 400 nm, and more preferably 50 to 200 nm. The low refractive index layer is a layer made of a fluorine-containing polymer having a low refractive index (Japanese Patent Laid-Open Nos. 57-34526, 3-130103, 6-115023, 8-313702, and 7- 168004), a layer obtained by a sol-gel method (described in JP-A-5-208811, JP-A-6-299091, and JP-A-7-168003), or a layer containing fine particles (Japanese Patent Publication No. 60). -59250, JP-A-5-13021, JP-A-6-56478, JP-A-7-92306, and JP-A-9-288201). In the layer containing fine particles, voids can be formed in the low refractive index layer as microvoids between the fine particles or within the fine particles. The layer containing fine particles preferably has a porosity of 3 to 50% by volume, and more preferably has a porosity of 5 to 35% by volume.

  In order to prevent reflection in a wide wavelength region, in the antireflection layer, in addition to the low refractive index layer, a layer having a high refractive index (medium / high refractive index layer) is preferably laminated. The refractive index of the high refractive index layer is preferably 1.65 to 2.40, and more preferably 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.50 to 1.90, and more preferably 1.55 to 1.70. The thickness of the middle / high refractive index layer is preferably 5 nm to 100 μm, more preferably 10 nm to 10 μm, and most preferably 30 nm to 1 μm. The haze of the middle / high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The middle / high refractive index layer can be formed using a polymer binder having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having a halogen atom other than fluorine as a substituent also have a high refractive index. You may use the polymer formed by the polymerization reaction of the monomer which introduce | transduced the double bond and enabled radical hardening.

  In order to obtain a higher refractive index, inorganic fine particles may be dispersed in the polymer binder. The refractive index of the inorganic fine particles is preferably 1.80 to 2.80. The inorganic fine particles are preferably formed from a metal oxide or sulfide. Examples of the metal oxide or sulfide include titanium oxide (for example, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Among these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The inorganic fine particles are mainly composed of oxides or sulfides of these metals, and can further contain other elements. The main component means a component having the largest content (% by weight) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. An inorganic material that is film-forming and can be dispersed in a solvent, or is itself a liquid, such as alkoxides of various elements, salts of organic acids, coordination compounds bonded to coordination compounds (eg chelate compounds), active inorganics A medium / high refractive index layer can also be formed using a polymer.

  An antiglare function (function of preventing incident scenery from being transferred to the film surface by scattering incident light on the surface) can be imparted to the surface of the antireflection layer. For example, it has an anti-glare function by forming fine irregularities on the surface of the transparent film and forming an antireflection layer on the surface, or by forming irregularities on the surface with an embossing roll after forming the antireflection layer. An antireflection layer can be obtained. An antireflection layer having an antiglare function generally has a haze of 3 to 30%.

  The hard coat layer has a height higher than the hardness of the transparent support. The hard coat layer preferably contains a crosslinked polymer. The hard coat layer can be formed using an acrylic, urethane, or epoxy polymer, oligomer, or monomer (for example, an ultraviolet curable resin). A hard coat layer can also be formed from a silica-based material.

  A lubricating layer may be formed on the surface of the antireflection layer (low refractive index layer). The lubricating layer has a function of imparting slipperiness to the surface of the low refractive index layer and improving scratch resistance. The lubricating layer can be formed using polyorganosiloxane (for example, silicon oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or derivative thereof. The thickness of the lubricating layer is preferably 2 to 20 nm.

  In the case where a light absorption layer is provided separately from the above-described layers, the dioxinone compound of the present invention can be used as it is, and a binder can also be used. Examples of the binder include natural polymer materials such as gelatin, casein, starch, cellulose derivatives, and alginic acid, or polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene, and polycarbonate. Synthetic polymer materials such as polyamide, polyurethane, polyester and polyurea are used.

  The undercoat layer, antireflection layer, hard coat layer, lubricating layer, light absorption layer, pressure-sensitive adhesive layer and the like can be formed by a general coating method. As a coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, an extrusion coating method using a hopper (described in US Pat. No. 2,681,294), etc. Is mentioned. Two or more layers may be formed by simultaneous application. Regarding the simultaneous application method, for example, US Pat. No. 2,761,791, US Pat. No. 2,941,898, US Pat. No. 3,508,947, US Pat. No. 3,526,528 and Yuji Harasaki “Coating Engineering”, page 253 (1973 Asakura Shoten) Issued).

Next, the optical recording material of the present invention will be described.
The optical recording material of the present invention contains the above dioxinone compound and is used for forming an optical recording layer of an optical recording medium, and is applied to various optical recording media according to the light absorption characteristics of the contained dioxynon compound. can do. Among the optical recording materials of the present invention, the optical recording material particularly suitable for an optical disk for a short wavelength laser having a wavelength of 380 nm to 420 nm is that the dioxinone compound contained has a maximum absorption wavelength λmax of 320 to 320 in light absorption characteristics in a solution state. It is in the range of 420 nm. The absorption intensity is preferably 1.0 × 10 ⁴ or more because ε at λmax is less than 1.0 × 10 ⁴ because the recording sensitivity may be lowered. Measurement of λmax and ε in the solution state of the dioxinone compound can be performed by selecting the concentration of the sample solution, the solvent used for the measurement, and the like according to a conventional method.

  The method for forming the optical recording layer of the optical recording medium using the optical recording material of the present invention containing the above dioxinone compound is not particularly limited. In general, lower alcohols such as methanol and ethanol; ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and butyl diglycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, ethyl acetate, Esters such as butyl acetate and methoxyethyl acetate; acrylic acid esters such as ethyl acrylate and butyl acrylate; fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol; benzene, toluene, xylene and the like Hydrocarbons: Optical recording of the present invention, which is a solution in which the dioxinone compound of the present invention and, if necessary, various compounds described below are dissolved in an organic solvent such as chlorinated hydrocarbons such as methylene dichloride, dichloroethane, and chloroform Fee, on a substrate, a wet coating method is applied by spin-coating, spraying, dipping, vapor deposition, sputtering, and the like. When using the said organic solvent, it is preferable that the usage-amount is made into the quantity from which content of the said dioxynon compound in the optical recording material of this invention will be 0.1-10 mass%.

  The optical recording layer is formed as a thin film, and the thickness is usually 0.001 to 10 μm, preferably 0.01 to 5 μm.

  Further, the content of the dioxinone compound of the present invention in the optical recording material of the present invention is preferably 10 to 100% by mass in the solid content contained in the optical recording material of the present invention. The optical recording layer is preferably formed so as to contain 50 to 100% by mass of the dioxynon compound represented by the general formula (I) in the optical recording layer. In order to form a layer, the optical recording material of the present invention contains 50 to 100% by mass of the dioxynone compound represented by the general formula (I) based on the solid content contained in the optical recording material of the present invention. Is more preferable.

  In addition to the dioxinone compound of the present invention, the optical recording material of the present invention includes, as necessary, a cyanine compound, an azo compound, a phthalocyanine compound, an oxonol compound, a squarylium compound, an indole compound, a styryl compound, a porphine. Compounds, azulenium compounds, croconic methine compounds, pyrylium compounds, thiopyrylium compounds, triarylmethane compounds, diphenylmethane compounds, tetrahydrocholine compounds, indophenol compounds, anthraquinone compounds, naphthoquinone compounds, xanthenes Compounds commonly used in optical recording layers, such as polyethylene compounds, thiazine compounds, acridine compounds, oxazine compounds, spiropyran compounds, fluorene compounds, rhodamine compounds; , Polyester, polystyrene, polycarbonate and other resins; surfactants; antistatic agents; lubricants; flame retardants; radical scavengers such as hindered amines; pit formation accelerators such as ferrocene derivatives; dispersants; antioxidants; You may contain a light fastness imparting agent. Furthermore, the optical recording material of the present invention may contain an aromatic nitroso compound, an aminium compound, an iminium compound, a biiminium compound, a transition metal chelate compound, etc. as a quencher such as singlet oxygen. Also good. In the optical recording material of the present invention, these various compounds are used in an amount ranging from 0 to 50% by mass in the solid content contained in the optical recording material of the present invention.

  The material of the substrate on which such an optical recording layer is provided is not particularly limited as long as it is substantially transparent to writing (recording) light and reading (reproducing) light. For example, polymethyl methacrylate, A resin such as polyethylene terephthalate or polycarbonate, glass or the like is used. Moreover, the shape can use arbitrary shapes, such as a tape, a drum, a belt, a disk, according to a use.

  On the optical recording layer, a reflective film can be formed by vapor deposition or sputtering using gold, silver, aluminum, copper, etc., or a protective layer can be formed by acrylic resin, ultraviolet curable resin, or the like. It can also be formed.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited by the following examples.

Example 1 Compound No. 1 Synthesis of 1 Into a nitrogen-substituted reaction flask was added 0.75 g (2.00 mmol) of [(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl) methyl] diphenyl phosphate ester and tetrahydrofuran. (THF) 5 ml was charged, and (1,8-diazabicyclo [5.4.0] undes-7-ene (DBU) 0.45 ml (2.86 mmol) was added dropwise at room temperature, followed by stirring at room temperature for 20 minutes. A solution prepared by dissolving 0.15 g (1.43 mmol) in 5 ml of THF was added dropwise at room temperature, followed by stirring at room temperature for 18 hours, the solvent was distilled off from the reaction solution, and column chromatography (silica gel, ethyl acetate: n-hexane = 1). : 3) to obtain a pale yellow transparent oily substance, the obtained pale yellow transparent oily substance was E-form and Z-form 1: 0.7 (former: later ) Was an isomer mixture containing a ratio of.
0.16 g (0.69 mmol) of the obtained isomer mixture and 10 ml of benzene were mixed, 46.1 mg (182 mmol) of iodine was added, and the mixture was stirred at room temperature for 2 days. 30 ml of saturated aqueous sodium thiosulfate solution and 30 ml of ethyl acetate were added to separate the oil layer, and the oil layer was dried over anhydrous magnesium sulfate. After filtration and evaporation of the solvent, the residue was purified by column chromatography (silica gel, ethyl acetate: n-hexane = 1: 3) to give compound No. 1 as a pale yellow solid. 0.15 g (yield 93.7%) of 1 was obtained. The obtained pale yellow solid was the target compound No. 1 was confirmed by the following analysis results. The obtained Compound No. The analysis results for 1 are shown below.

(1) ¹ H-NMR (ppm, CDCl ₃ solvent)
1.78 (s; 6H), 5.44 (s; 1H), 6.55 (d; 1H; J = 15.9 Hz), 7.31 (d; 1H; J = 15.9 Hz), 7. 34-7.40 (m; 3H), 7.45-7.55 (m; 2H)
(2) IR absorption (cm ^-1 )
2999, 1718, 1634, 1591, 1382, 1374, 1279, 1197, 1017, 975, 903, 815, 757, 692
(3) UV absorption measurement (chloroform solvent)
λmax; 345.0 nm, ε; 1.86 × 10 ⁴ (concentration 6.68 × 10 ⁻⁶ mol / l)
(4) Decomposition temperature (TG-DTA: 100 ml / min in nitrogen stream, temperature increase of 10 ° C / min)
Melting point: 81.2 ° C
First mass decrease starting point: 143.3 ° C
Second mass decrease starting point: 331.2 ° C

Example 2 Compound No. Synthesis of 2 To a nitrogen-substituted reaction flask, [(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl) methyl] diphenyl phosphate 4.19 g (11.2 mmol) and 56 ml of THF were added. Then, DBU 2.44 ml (16.0 mmol) was added dropwise at room temperature, and the mixture was stirred at room temperature for 30 minutes. A solution obtained by dissolving 0.90 g (8.00 mmol) of 2-thiophenaldehyde in 57 ml of THF was added dropwise at room temperature, and the mixture was stirred at room temperature for 22 hours. The solvent was distilled off from the reaction solution, and purification was performed by column chromatography (silica gel, ethyl acetate: n-hexane = 1: 4) to obtain a light yellow transparent oily substance. The obtained pale yellow transparent oily substance was an isomer mixture containing E form and Z form at a ratio of 1: 1.6 (former: latter).
1.33 g (5.62 mmol) of the obtained isomer mixture and 100 ml of benzene were mixed, 0.5 g (1.97 mmol) of iodine was added, and the mixture was stirred at room temperature for 15 hours. Further, 1.6 g (6.30 mmol) of iodine was added and stirred at room temperature for 3 days. A saturated aqueous sodium thiosulfate solution (100 ml) and ethyl acetate (100 ml) were added to separate the oil layer, and the oil layer was dried over anhydrous magnesium sulfate. After filtration and evaporation of the solvent, the residue was purified by column chromatography (silica gel, ethyl acetate: n-hexane = 1: 4) to give compound No. 1 as a pale yellow transparent oil. 1.15 g (yield: 86.4%) of 2 was obtained. The obtained pale yellow transparent oily substance was Compound No. 2 was confirmed by the following analysis results. The obtained Compound No. The analysis results for 2 are shown below.

(1) ¹ H-NMR (ppm, CDCl ₃ solvent)
1.75 (s; 6H), 5.39 (s; 1H), 6.33 (d; 1H; J = 15.6 Hz), 7.06 (dd; 1H; J = 5.1, 3.7 Hz) ), 7.22 (d; 1H; J = 3.7 Hz), 7.38 (d; 1H; J = 5.1), 7.41 (d; 1H; J = 15.6)
(2) IR absorption (cm ^-1 )
2997, 1718, 1625, 1388, 1272, 1249, 1202, 1018, 959, 707
(3) UV absorption measurement (chloroform solvent)
λmax; 347.5 nm, ε; 3.00 × 10 ⁴ (concentration 2.07 × 10 ⁻⁵ mol / l)
(4) Decomposition temperature (TG-DTA: 100 ml / min in nitrogen stream, temperature increase of 10 ° C / min)
First mass decrease starting point: 131.7 ° C
Second mass decrease starting point; 288.2 ° C

Example 3 Compound no. 4 Synthesis of ((2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl) methyl] diphenyl phosphate 1.0 g (2.67 mmol) and 14 ml of THF in a nitrogen-substituted reaction flask Then, 0.6 ml (3.96 mmol) of DBU was added dropwise at room temperature, and the mixture was stirred at room temperature for 30 minutes. A solution prepared by dissolving 0.13 g (0.97 mmol) of 1,4-benzenedialdehyde in 13 ml of THF was dropped at room temperature and stirred at room temperature for 18 hours. The solvent was distilled off from the reaction solution, and purification was performed by column chromatography (silica gel, ethyl acetate: n-hexane = 1: 3) to obtain a yellow solid. The obtained yellow solid was an isomer mixture containing E form and Z form at a ratio of 1: 1.2 (the former: the latter).
0.11 g (0.24 mmol) of the obtained isomer mixture, 20 ml of benzene and 30 ml of acetonitrile were mixed, 0.69 g (2.71 mmol) of iodine was added, and the mixture was stirred at room temperature for 2 days. To the reaction solution, 30 ml of a saturated aqueous sodium thiosulfate solution and 30 ml of ethyl acetate were added to separate the oil layer, and the oil layer was dried over anhydrous magnesium sulfate. After filtration and evaporation of the solvent, the product was washed with 10 ml of ethyl acetate to give compound No. 1 as a pale yellow solid. 4 (yield 45.4%) was obtained. The obtained pale yellow solid was the target compound No. 4 was confirmed by the following analysis results. The obtained Compound No. The analysis results for 4 are shown below.

(1) ¹ H-NMR (ppm, CDCl ₃ solvent)
1.78 (s; 12H), 5.47 (s; 2H), 6.59 (d; 2H; J = 15.9 Hz), 7.29 (d; 2H; J = 16.1 Hz), 7. 53 (s; 4H)
(2) IR absorption (cm ^-1 )
3032, 1718, 1632, 1589, 1381, 1271, 1250, 1201, 1020, 980, 901, 830
(3) UV absorption measurement (chloroform solvent)
λmax; 373.0 m, ε; 6.32 × 10 ⁴ (concentration 3.18 × 10 ⁻⁶ mol / l)
(4) Decomposition temperature (TG-DTA: 100 ml / min in nitrogen stream, temperature increase of 10 ° C / min)
Mass decrease start point: 105.5 ° C

Example 4 Compound no. Synthesis of 20 To a nitrogen-substituted reaction flask, 0.76 g (2.03 mmol) of [(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl) methyl] diphenyl phosphate and 10 ml of THF was added. Then, DBU 0.44 g (2.90 mmol) was added dropwise at room temperature, and the mixture was stirred at room temperature for 30 minutes. A solution prepared by dissolving 0.31 g (1.45 mmol) of ferrocenealdehyde in 10 ml of THF was added dropwise at room temperature, and the mixture was stirred at room temperature for 22 hours. The solvent was distilled off from the reaction solution, and purification was performed by column chromatography (silica gel, ethyl acetate: n-hexane = 1: 10) to obtain a pale yellow oil. The obtained pale yellow oil was an isomer mixture containing E-form and Z-form in a ratio of 1: 1.96 (former: latter).
To 0.68 g (2.00 mmol) of the obtained isomer mixture, 10 ml of benzene and 194 mg (0.76 mmol) of iodine were added, and the mixture was stirred at room temperature for 3 days. To the reaction solution, 30 ml of a saturated aqueous sodium thiosulfate solution and 30 ml of ethyl acetate were added to separate the oil layer, and the oil layer was dried over anhydrous magnesium sulfate. After filtration and evaporation of the solvent, the residue was purified by column chromatography (silica gel, ethyl acetate: n-hexane = 1: 4) to obtain compound No. 1 as a red solid. 44.2 mg (9.0% yield) of 20 was obtained. The obtained red solid was the target compound No. It was confirmed by the following analysis result that it was 20. The obtained Compound No. The analysis results for 20 are shown below.

(1) ¹ H-NMR (ppm, CDCl ₃ solvent)
1.76 (s; 6H), 4.17 (s; 5H), 4.44 (s; 2H), 4.49 (s; 2H), 5.29 (s; 1H), 6.12 (d 1H, J = 15.4 Hz), 7.15 (d; 1H, J = 15.4 Hz)
(2) IR absorption (cm ^-1 )
1708, 1626, 1381, 1275, 1252, 1205, 1022, 963
(3) UV absorption measurement (chloroform solvent)
λmax; 331.0 m, ε; 2.63 × 10 ⁴ (concentration 7.48 × 10 ⁻⁶ mol / l)
(4) Decomposition temperature (TG-DTA: 100 ml / min in nitrogen stream, temperature increase of 10 ° C / min)
Melting point: 84.3 ° C
Mass decrease starting point: 138.6 ° C

[Example 5] Manufacture of optical filter including pressure-sensitive adhesive layer After preparing a pressure-sensitive adhesive solution with the following composition, and applying the pressure-sensitive adhesive solution to a 188 μm-thick PET film subjected to easy adhesion treatment using bar coater # 9 And dried at 100 ° C. for 10 minutes to obtain an optical filter having an adhesive layer having a thickness of about 10 μm on the PET film. The optical filter was measured with an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation, and λmax was 348.5 nm.

(Combination)
Compound No. 2 2.0mg
Acrylic adhesive (DB5541: manufactured by Diabond) 20g
80g of methyl ethyl ketone

[Example 6] Manufacture of optical filter A UV varnish was prepared with the following composition, applied to an easily adhered PET film having a thickness of 188 µm with a bar coater # 9, and then dried at 100 ° C for 10 minutes. I let you. Then, 100 mJ of ultraviolet rays were irradiated with a high-pressure mercury lamp with an infrared cut film filter to obtain an optical filter having a film layer with a cured film thickness of about 5 μm on the PET film. The optical filter was measured with an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation, and λmax was 369 nm.

(Combination)
Adekaoptomer KRX-571-65 100g
(Asahi Denka Kogyo's UV curable resin, resin content 80% by mass)
Compound No. 4 2.0mg
Methyl ethyl ketone 60g

Example 7 Production of optical recording material and optical recording medium and evaluation of optical recording medium Compound No. 1 obtained in Example 2 above was used. 2 with compound no. An optical recording material was obtained as a 2,2,3,3-tetrafluoropropanol solution by dissolving in 2,2,3,3-tetrafluoropropanol so that the concentration of 2 was 1.0% by mass. Titanium chelate compound (T-50: manufactured by Nippon Soda Co., Ltd.) is applied, hydrolyzed, and the above optical recording material is applied by spin coating onto a 12 cm diameter polycarbonate disk substrate provided with a base layer (0.01 μm). Then, an optical recording layer having a thickness of 100 nm was formed to obtain an optical recording medium. With respect to this optical recording medium, when the absorption UV spectrum of the thin film and the UV spectrum of the reflected light with an incident angle of 5 ° were measured, the absorption λmax was 348.5 nm and the reflected light λmax was 396.5 nm.

[Example 8] Production of optical recording material and optical recording medium and evaluation of optical recording medium Compound No. 1 obtained in Example 2 above was used. Instead of the compound No. 2 obtained in Example 3 above, An optical recording medium was obtained in the same manner as in Example 7 except that 4 was used. With respect to this optical recording medium, when the absorption UV spectrum of the thin film and the UV spectrum of the reflected light with an incident angle of 5 ° were measured, the absorption λmax was 369 nm and the reflected light λmax was 430 nm.

Example 9 Production of Optical Recording Material and Optical Recording Medium and Evaluation of Optical Recording Medium Compound No. 1 obtained in Example 2 above was used. In place of Compound No. 2 obtained in Example 4 above, An optical recording medium was obtained in the same manner as in Example 7 except that 20 was used. The optical recording medium was irradiated with light of 55000 lux for 100 hours, and the residual absorbance after irradiation with respect to the absorbance at λmax of the UV absorption spectrum before irradiation was measured at λmax of the UV absorption spectrum before irradiation. %Met.

The optical filter using the dioxinone compound of the present invention has an absorption maximum at a specific wavelength (340 to 390 nm) (Examples 5 and 6), and the dioxinone compound of the present invention is used as an ultraviolet absorber for an optical filter. It was confirmed that it was suitable.
An optical recording medium having an optical recording layer formed of the optical recording material of the present invention containing the dioxinone compound of the present invention has an absorption maximum of reflected light at a specific wavelength (340 to 430 nm) ( Examples 7 and 8). In the reproduction mode of an optical recording medium represented by an optical disc, the presence or absence of recording is detected by the difference in the amount of laser wavelength with respect to the reflected light reflected from the optical recording medium. In the absorption spectrum, it is preferable to have a higher absorption intensity near the wavelength of the laser beam. Therefore, the optical recording material of the present invention containing the dioxinone compound of the present invention is suitable as an optical recording material used for forming an optical recording layer of an optical recording medium using a laser beam of 405 nm such as an optical disk for a short wavelength laser.

Claims (5)

A compound having a dioxynone structure represented by the following general formula (IV) .

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ and R ⁴ represent a hydrogen atom, and m + p is 4. ) A compound having a dioxinone structure represented by the following general formula (V) .

( Wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ^{6 to} R ¹⁴ represent a hydrogen atom, Z ² represents a direct bond, M ¹ Represents Fe .) An optical filter comprising the compound having a dioxinone structure according to claim 1 or 2, or a compound having a dioxynone structure represented by the following general formula (II) or the following general formula (III) .

(In the formula, R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ and R ⁴ represent a hydrogen atom, and m + p is 5. )

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom, and a is 3. ) The optical filter according to claim 3 , which is used for an image display device. The compound having a dioxynon structure according to claim 1 or 2 or the general formula (II) according to claim 3, which is used as a material for forming the optical recording layer in an optical recording medium having an optical recording layer formed on a substrate. Alternatively , an optical recording material containing a compound having a dioxinone structure represented by the general formula (III) .