CN101189133A - Optical information recording medium and method for recording information - Google Patents

Abstract

There is provided an optical information-recording medium, comprising a recording layer capable of recording of information by irradiation of a laser beam having a wavelength of 440 nm or less on or above a substrate, the recording layer comprising a dye having two or more independent dye moieties in the molecule that are bound to each other in a manner other than by forming a conjugated bond to the dye moieties, and a method of recording information, comprising recording information by irradiating a laser beam having a wavelength of 440 nm or less on or above the optical information-recording medium according to the present invention described above.

Description

Optical data recording medium and information recording method

The cross reference of related application

The disclosure of Japanese patent application 2006-071707,2005-190319 is combined in this with its full content by reference.

Technical field

The present invention relates to allow by using the optical data recording medium and the method for recording information of laser beam record and Copy Info.The present invention be more particularly directed to be suitable for by using wavelength to carry out the heating mode optical data recording medium and the information recording method of information record as 440nm or shorter laser beam.

Can only be known by laser beam irradiation recorded information optical data recording medium (CD) once.The such CD that is commonly referred to one-time write CD (so-called CD-R) has typical structure, wherein will include the recording layer of organic dye, the reflection layer and the resin protective layer of metals like gold is formed on the transparent disk substrate in proper order with this.Come recorded information on CD-R by go up the laser beam (usually, wavelength is near the laser beam the 780nm) of irradiation in the near infrared region to CD-R.Recording layer by irradiation zone in, light is absorbed, and cause the part of temperature to raise, and this has changed its physics and chemical property (for example, the generation of pit).Because these physics and chemical change, optical property is changed, and can recorded information.Also by carry out read (the duplicating) of information with laser beam irradiation with wavelength identical with the wavelength of recording laser bundle.Information is the reflectivity difference reflex system between the unaltered zone of optical property (not recording areas) of the zone (recording areas) that changed of the optical property by the detection record layer and recording layer.

Recently, network such as internet and definition TV become more and more universal rapidly.The universal increase that has also caused effective more recording image information on cost is used huge storage capacity recording medium demand of HDTV (high-definition television).Although above-mentioned CD-R and the one-time write DVD (so-called DVD-R) that allows to carry out high density recording by use visible laser bundle (630 to 680nm) have made them oneself occupy a tiny space as the huge storage capacity recording medium to a certain extent, also do not tackle the enough big recording capacity of tomorrow requirement.After deliberation have more high record density and bigger recording capacity and use and have than DVD-R with the wavelength of the laser beam CD of short wavelength's laser beam more, and for example, use the optical recording commercialization of wavelength as the what is called " blue light pattern " of the blue laser of 405nm.

Disclose by being 530nm or shorter laser irradiation organic dyestuff recording layer with wavelength, thereby recorded the information on the optical record medium that comprises this recording layer, and from the described method that comprises the optical record medium playback of information of recording layer.These methods specifically propose: comprise the CD of recording layer with blue (wavelength of 430nm or 488nm) or bluish-green (wavelength of 515nm) laser irradiation, described recording layer comprises dyestuff as porphyrin compound, azo dyes, metallized azo dye, quinolinone dyestuff, cyclonite cyanine dye, dicyano ethenylphenyl skeleton dyestuff, coumarin compound, phthalocyanine dye and naphthalene phthalocyanine compound.In addition, disclose by being that 550nm or shorter laser irradiation have the method that the CD of the recording layer that comprises oxonol dye comes recorded information and playback of information with wavelength.Referring to for example, Japanese Patent Application Publication (JP-A) 2001-287460,2001-287465,2001-253171,2001-39034,2000-318313,2000-318312,2000-280621,2000-280620,2000-263939,2000-222772,2000-222771,2000-218940,2000-158818,2000-149320,2000-108513,2000-113504,2002-301870 and 2001-287465; United States Patent (USP) 2002-76648A1; JP-A 2003-94828 and 2001-71638.

Yet,, use the CD of known dye still not to be in the level that satisfies about the record property requirements according to the inventor's research.In addition, use the CD of one of the oxonol dye be disclosed among the JP-A 2001-71638 also unsatisfactory in practice, because the optics of the oxonol dye that uses in this patent application storage property is lower.Alternatively, the optics storage property that is described in the oxonols among the JP-A 2004-188968 is abundant, does not allow by using wavelength to come the dyestuff of information record as 440nm or shorter laser but wherein describe.

Summary of the invention

The present invention considers above situation and carries out, and a kind of optical record medium and method for recording information are provided.

A first aspect of the present invention provides a kind of optical data recording medium, described optical data recording medium comprises to be provided at pass through irradiation that wavelength is 440nm or shorter laser beam and recording layer that can recorded information on the substrate or above substrate, wherein said recording layer comprises the dyestuff that has two or more individual dye parts in the molecule, and described two or more individual dye parts are to mutually combine except that forming conjugated bonds to the mode the described dyestuff part.

It is a kind of by being 440nm or shorter laser beam irradiation with wavelength on according to the optical data recording medium of first aspect and method for recording information that a second aspect of the present invention provides.

Implement best mode of the present invention

(1) optical data recording medium

Optical data recording medium according to the present invention is to have the optical data recording medium that is provided at the recording layer on the substrate or above substrate, described recording layer can be the irradiation of 440nm or shorter laser beam and recorded information by wavelength, wherein this recording layer comprises the dyestuff that has two or more individual dye parts in the molecule, and described two or more individual dye parts are to mutually combine except that forming conjugated bonds to the mode the described dyestuff part.Dyestuff is partly represented to have from wherein having removed hydrogen atom and can being bonded to the group of the dye structure of another compound.

Below, will describe in detail according to optical data recording medium of the present invention.When concrete part was called as " group " in the present invention, unless stipulate in addition, this group can be by maybe can't help one or more substituting groups (until maximum possible) replacement.

For example, " alkyl " is meant and replaces or unsubstituted alkyl.In addition, the substituting group on compound of the present invention can be any substituting group, and is irrelevant with its substituted again situation.In addition, in the present invention, when concrete zone is called as " ring ", or when " group " comprises " ring ", unless stipulate that in addition described ring can be monocycle or condensed ring, and can be that replace or unsubstituted.For example, " aryl " can be phenyl or naphthyl, or the phenyl that replaces.

Above dyestuff preferably has the structure by following formula (1) expression.In following formula (1), Dye ¹¹, Dye ¹²And Dye ^2kIndependent separately expression dyestuff part.To by Dye ¹¹, Dye ¹²Or Dye ^2kThe dyestuff of expression partly is not specifically limited, and their example comprises the part of following dyestuff, for example: cyanine dye, styryl dye, merocyanine dyes, phthalocyanine dye, oxonols (oxonol) dyestuff, azo dyes, azomethine dyes, side's (squalium) dyestuff and metal chelate dye.By Dye ¹¹, Dye ¹²Or Dye ^2kThe dyestuff part of expression is preferably the part of following dyestuff especially: cyanine dye, merocyanine dyes, oxonol dye, phthalocyanine dye or metal chelate dye.By Dye ¹¹, Dye ¹²And Dye ^2kThe dyestuff part of expression is the part of cyanine dye, merocyanine dyes or oxonol dye more preferably, and most preferably is the part of cyanine dye or oxonol dye.By Dye ¹¹, Dye ¹²And Dye ^2kThe dyestuff part of expression can be identical or different mutually, but be preferably identical mutually.L ¹¹And L ^2kRepresent divalent linker separately, described divalent linker does not form pi-conjugated key with the dyestuff part that is attached on it; N is 0 to 10 integer; K is 0 to n integer; Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge.

Formula (1)

When by Dye ¹¹, Dye ¹²Or Dye ^2kWhen the dyestuff of expression partly was the cyanine dye part, this cyanine dye was preferably the cyanine dye by following formula (2) expression.

Formula (2)

In formula (2), Za ¹And Za ²Expression forms the atomic group of 5-or 6 member heterocyclic ring containing nitrogens separately, and this nitrogen heterocyclic ring can condense with phenyl ring, benzofuran ring, pyridine ring, pyrrole ring, indole ring or thiphene ring etc.

Ra ¹And Ra ²Represent hydrogen atom separately, replacement or unsubstituted alkyl (preferably have 1 to 20 carbon atom, methyl for example, ethyl, n-pro-pyl, isopropyl, normal-butyl, n-pentyl, benzyl, 3-sulfo group propyl group, 4 sulfo group butyl, 3-methyl-3-sulfo group propyl group, 2 '-sulfo group benzyl, carboxymethyl or 5-carboxylic amyl group), replacement or unsubstituted alkenyl (preferably have 2 to 20 carbon atoms, vinyl for example, pi-allyl), replacement or unsubstituted aryl (preferably have 6 to 20 carbon atoms, phenyl for example, the 2-chlorphenyl, the 4-anisyl, 3-aminomethyl phenyl or 1-naphthyl), replacement or unsubstituted heterocyclic group (preferably have 1 to 20 carbon atom, for example pyridine radicals, thienyl, furyl, thiazolyl, imidazole radicals, pyrazolyl, pyrrolidinyl, piperidino or morpholino); Preferred hydrogen atom, replacement or unsubstituted alkyl, or replacement or unsubstituted sulfo group alkyl; And more preferably replace or unsubstituted alkyl, or replacement or unsubstituted sulfo group alkyl.Ma ¹To Ma ⁷Independent separately expression can substituted methine; and substituent favourable example comprise have 1 to 20 carbon atom alkyl (for example; methyl; ethyl and isopropyl); halogen atom (chlorine for example; bromine; iodine and fluorine); nitro; alkoxyl (for example methoxyl group and ethyoxyl) with 1 to 20 carbon atom; aryl (for example phenyl and 2-naphthyl) with 6 to 26 carbon atoms; heterocyclic group (for example 2-pyridine radicals and 3-pyridine radicals) with 0 to 20 carbon atom; aryloxy group with 6 to 20 carbon atoms (for example; phenoxy group; 1-naphthoxy and 2-naphthoxy); acylamino-(for example acetylamino and benzamido) with 1 to 20 carbon atom; carbamoyl (for example N, N-dimethylamino formamido group) with 1 to 20 carbon atom; sulfo group; hydroxyl; carboxyl; alkylthio group (for example methyl mercapto) with 1 to 20 carbon atom; cyano group etc.Described group can be bonded on another methine that forms ring, or is bonded on the auxochrome that forms ring.

Ma ¹To Ma ⁷Be preferably replace or the methyl substituted methine of unsubstituted, ethyl separately.Na ¹And na ²Be 0 or 1, and be preferably 0.Ka ¹Be 0 to 3 integer, be preferably 0 to 2 integer, and more preferably 0.Work as ka ¹Be 2 when above, Ma ³And Ma ⁴Can be identical or different mutually.Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge.

In formula (2), Za ¹, Za ², Ra ¹, Ra ²And Ma ¹To Ma ⁷In any one can be bonded to the linking group L of the dyestuff part that forms the formula (1) removed its hydrogen atom ¹¹Or L ^2k

When by Dye ¹¹, Dye ¹²Or Dye ^2kWhen the dyestuff of expression partly was the merocyanine dyes part, this merocyanine dyes was preferably the merocyanine dyes by following formula (3) expression.

Formula (3)

In formula (3), Za ³Expression forms the atomic group of 5-or 6 member heterocyclic ring containing nitrogens, and this nitrogen heterocyclic ring can condense with phenyl ring, benzofuran ring, pyridine ring, pyrrole ring, indole ring or thiphene ring etc.Za ⁴Expression forms the atomic group of acid core.Ra ³Expression hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted alkenyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic group (example that it is favourable and Ra ¹And Ra ²Example identical).Ma ⁸To Ma ¹¹Represent methine (example that it is favourable and Ma independently of one another ¹To Ma ⁷Example identical).Na ³Be 0 or 1.Ka ²Be 0 to 3 integer, and be preferably 0 to 2 integer.Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge.Work as ka ²Be 2 when above, Ma ¹⁰And Ma ¹¹Can be identical or different mutually.In formula (3), Za ³, Za ⁴, Ra ³And Ma ⁸To Ma ¹¹In any one can be bonded to the linking group L of the dyestuff part that forms the formula (1) removed its hydrogen atom ¹¹Or L ^2k

When by Dye ¹¹, Dye ¹²Or Dye ^2kWhen the dyestuff of expression partly is the oxonol dye part, this dyestuff part will be described below.Oxonol dye according to the present invention is defined as having the polymethin dyes of anionic dye.Based on the viewpoint of record character, what be particularly conducive to use is the oxonol dye of being represented by following formula (I).

Formula (I)

In formula (I), A, B, C and D represent electron withdraw group separately; " A and B " or " C and D " can mutually combine and form ring; And when group did not mutually combine, total Hammett σ p value of total Hammett σ p value of group A and B and group C and D was respectively more than 0.6.R represents the substituting group on the methine carbon; M is 0 to 3 integer; N is 0 to 2m+1 integer; When n was integer more than 2, a plurality of radicals R can be identical or different mutually, maybe can mutually combine to form ring; Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge.

The different a plurality of tautomerides of symbol that comprise the anion position point by the compound of formula (I) expression, and especially when among A, B, C and the D any one during by-CO-E (E represents substituting group) expression, this compound is expressed by place anionic charge on its oxygen atom usually.For example when D be-during CO-E, this compound is generally expressed by following formula (II), and the compound in the formula (II) also comprises in the compound of formula (I).

Formula (II)

Identical in the definition of A, B, C, R, m, n, Q and y in the following formula (II) and the formula (I).

Below, the oxonol dye by following formula (I) expression will be described.In formula (I), A, B, C and D represent electron withdraw group separately; A and B or C and D can mutually combine and form ring; And when group did not mutually combine, total Hammett σ p value of total Hammett σ p value of group A and B and group C and D was respectively more than 0.6.A, B, C and D can be identical or different mutually.The Hammett substituent constant σ p value of the electron withdraw group of being represented by A, B, C or D is preferred independently in 0.30 to 0.85 scope, and more preferably in 0.35 to 0.80 scope.

Hammett substituent constant σ p value (below, be called σ p value) be described in for example Chem.Rev.91, in 165 (1991) lists of references that reach wherein, and the σ p value that does not have therein to describe can be estimated according to the method for describing therein.When A and B (or C and D) mutually combine when forming ring, the σ p value of A (C) is meant-A-B-H (C-D-H) the σ p value of group, and the σ p value of B (D) is meant-B-A-H (D-C-H) the σ p value of group.Under these circumstances, σ p value is different mutually, because bonding direction difference between the two.

The typical favourable example of electron withdraw group comprises cyano group, nitro, acyl group (acetyl group for example with 1 to 10 carbon atom, propiono, bytyry, valeryl, benzoyl), alkoxy carbonyl group (methoxycarbonyl group for example with 2 to 12 carbon atoms, carbethoxyl group, the different third oxygen carbonyl, butoxy carbonyl and the last of the ten Heavenly stems oxygen carbonyl), aryloxy carbonyl (for example carbobenzoxy) with 7 to 11 carbon atoms, carbamoyl (methylamino formoxyl for example with 1 to 10 carbon atom, ethylamino formoxyl and phenyl amino formoxyl), alkyl sulphonyl (for example mesyl) with 1 to 10 carbon atom, aryl sulfonyl (for example benzenesulfonyl) with 6 to 10 carbon atoms, alkoxyl sulfonyl (for example methoxyl group sulfonyl) with 1 to 10 carbon atom, sulfamoyl (for example ethyl sulfamoyl and phenyl sulfamoyl base) with 1 to 10 carbon atom, alkyl sulfinyl (for example first sulfinyl and second sulfinyl) with 1 to 10 carbon atom, aryl sulfinyl (for example benzene sulfinyl) with 6 to 10 carbon atoms, alkyl sulfhydryl (for example first sulfenyl and second sulfenyl) with 1 to 10 carbon atom, aryl sulfenyl (for example benzene sulfenyl) with 6 to 10 carbon atoms, halogen atom, alkynyl (for example acetenyl) with 2 to 10 carbon atoms, diamides base (for example diacetylamino) with 2 to 10 carbon atoms, phosphoryl, carboxyl, and 5-or 6 yuan of heterocyclic groups (2-[4-morpholinodithio base for example, the 2-benzoxazolyl, the 3-pyridine radicals, 5-(1H)-tetrazole radical and 4-pyrimidine radicals); And be preferably cyano group, alkoxy carbonyl group, alkyl sulphonyl and aryl sulfonyl.

In formula (I), the substituent example of being represented by R on the methine carbon comprises as follows: linearity or cyclic alkyl (methyl with 1 to 20 carbon atom, ethyl, n-pro-pyl, isopropyl and normal-butyl), has the replacement of 6 to 18 carbon atoms or unsubstituted aryl (phenyl for example, chlorophenyl, anisyl, toluyl groups, 2,4-two tertiary pentyls and 1-naphthyl), alkenyl (for example vinyl and 2-methyl ethylene), alkynyl (acetenyl for example, 2-methylacetylenyl and 2-phenylacetylene base), halogen atom (F for example, Cl, Br and I), cyano group, hydroxyl, carbonyl, acyl group (acetyl group for example, benzoyl, salicyl and valeryl), alkoxyl (methoxyl group for example, butoxy and cyclohexyloxy), aryloxy group (for example phenoxy group and 1-naphthoxy), alkylthio group (methyl mercapto for example, butylthio, benzylthio and 3-methoxy propyl sulfenyl), arylthio (for example thiophenyl and 4-chlorobenzene sulfenyl), alkyl sulphonyl (for example mesyl and fourth sulfonyl), aryl sulfonyl (for example benzenesulfonyl and p-toluenesulfonyl), carbamoyl with 1 to 10 carbon atom, acylamino-with 1 to 10 carbon atom, imino group with 2 to 12 carbon atoms, acyloxy with 2 to 10 carbon atoms, alkoxy carbonyl group with 2 to 10 carbon atoms, and heterocyclic group (comprising: aromatic heterocycle, for example pyridine radicals, thienyl, furyl, thiazolyl, imidazole radicals and pyrazolyl; And aliphatic heterocycle, for example pyrrolidine ring, piperidine ring, morpholine ring, pyranoid ring, thiapyran ring, diox ring and dithiolane).

The favourable example of substituent R comprises: halogen atom, have 1 to 8 carbon atom linearity or cyclic alkyl, have 6 to 10 carbon atoms aryl, have 1 to 8 carbon atom alkoxyl, have the aryloxy group of 6 to 10 carbon atoms, and heterocyclic group with 3 to 10 carbon atoms; Particularly preferably be the chlorine atom, have 1 to 4 carbon atom alkyl (for example methyl, ethyl and isopropyl), phenyl, have alkoxyl (for example methoxyl group and ethyoxyl), the phenoxy group of 1 to 4 carbon atom, and nitrogen heterocyclic ring group (for example 4-pyridine radicals, benzoxazole-2-base and benzothiazole-2-yl) with 4 to 8 carbon atoms.

N is 0 to 2m+1 integer, and when n was integer more than 2, a plurality of radicals R can be identical or different mutually, and can mutually combine and form ring.Thereby the number of ring is preferably 4 to 8, is preferably 5 or 6 especially, and the atom that constitutes ring is preferably carbon and oxygen or nitrogen, and is preferably carbon especially.

A, B, C, D and R can further have substituting group, and this substituent example comprises those unit price substituting groups that are used for the group that the R by formula (I) represents.

Being used for the dyestuff of CD, based on the viewpoint of thermal decomposition, A and B or C and D preferably mutually combine and form ring, and the example of ring comprises following (A-1 to A-66): in following example, Ra, Rb and Rc independently represent hydrogen atom or substituting group separately.

In above ring, the ring of representing by A-2, A-8, A-9, A-10, A-13, A-14, A-16, A-17, A-36, A-39, A-42, A-54, A-57, A-59, A-61, A-65 and A-66 preferably.The ring of representing by A-2, A-9, A-10, A-13, A-17, A-42, A-54, A-57, A-59, A-61, A-65 and A-66 more preferably.The ring of representing by A-13, A-17, A-54, A-57, A-59, A-61, A-65 and A-66 most preferably.

The substituting group of being represented by Ra, Rb and Rc is identical with the substituting group of being represented by R respectively.Ra, Rb and Rc can mutually combine to form carbocyclic ring or heterocycle.The example of carbocyclic ring comprises saturated or undersaturated 4-to 7 yuan of carbocyclic ring, for example cyclohexyl ring, cyclopenta ring, cyclohexene ring and phenyl ring.The example of heterocycle comprises saturated or undersaturated 4-to 7 yuan of heterocycle, for example piperidine ring, piperazine ring, morpholine ring, oxolane ring, furan nucleus, thiphene ring, pyridine ring and pyrazine ring.These carbocyclic rings and heterocycle can further be substituted.The group that can further replace is with identical for those groups of the substituting group institute example of being represented by R.

In formula (I), m is 0 to 3 integer, and the absorbing wavelength of oxonol dye depends on the value of m and marked change.Need design consideration to be used to write down the oscillation wavelength of the laser that duplicates and have the dyestuff of optimum absorb wavelength, thereby in this, the selection of m value is important.When the center oscillation wavelength that is used to write down the laser that duplicates was 780nm (CD-R record semiconductor laser), the m in the formula (I) was preferably 2 or 3; When the center oscillation wavelength was 635nm or 650nm (DVD-R record semiconductor laser), m was preferably 1 or 2; And when the center oscillation wavelength was 550nm or shorter (for example, the center oscillation wavelength is the royal purple semiconductor laser of 405nm), m was preferably 0 or 1.

Can mutually combine at an arbitrary position by the oxonols chromophore of formula (I) expression and to form polymer, and under these circumstances, the unit can be identical or different mutually, and for example can be bonded to polymer chain: polystyrene, polymethacrylates, polyvinyl alcohol or cellulose.

In formula (I), any linking group L that can be bonded to the dyestuff part that forms the formula (1) of having removed its hydrogen atom of A, B, C, D and R ¹¹Or L ^2k

The representative instance of cyanine dye, merocyanine dyes and oxonol dye is included in F.M.Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds, John Wiley﹠amp; Sons, New York, London, the dyestuff described in 1964.

Methine dyes is preferably by formula (2-1), (2-2), (2-3), (2-4) and any represented oxonol dye (2-5).

Formula (2-1)

Formula (2-2)

Formula (2-3)

Formula (2-4)

Formula (2-5)

In formula (2-1), (2-2), (2-3), (2-4) with (2-5), R is illustrated in the substituting group on the methine carbon; M represents 0 to 1 integer; N represents 0 to 2m+1 integer; When n was integer more than 2, a plurality of radicals R can be identical or different mutually, maybe can mutually combine to form ring; Za ⁵And Za ⁶Expression forms the atomic group of acid core separately; L ¹¹, Q and the definition of y and the L in the formula (I) ¹¹, Q is identical with y; Y represents-O-,-NR ¹-and-CR ²R ³-in any; R ¹To R ⁹Independent separately expression hydrogen atom or substituting group; Z represents to replace or unsubstituted alkylidene; And x represents 1 or 2.G represents oxygen atom or sulphur atom, the preferred oxygen atom.

To by R ¹To R ⁹The substituting group of expression is not specifically limited, and the example comprises those substituting groups of being represented by the R in the formula (I), and the preferable range of the example is identical equally.Z represents to replace or unsubstituted alkylidene.The favourable example of alkylidene comprises: replaces or unsubstituted methylene, replacement or unsubstituted ethylidene, and replacement or unsubstituted propylidene; Its preferred example comprises and replacing or unsubstituted methylene and replacement or unsubstituted ethylidene; And more preferably replace again or unsubstituted methylene.

Formula (2-1), (2-2), (2-3), (2-4) and (2-5) in m be preferably 0.

Be included in have in the dyestuff by formula (1) expression by following formula (5-1), (5-2), (5-3), (5-4) or (5-5) optical data recording medium of the dyestuff of the structure of expression be preferred.

Formula (5-1)

Formula (5-2)

Formula (5-3)

Formula (5-4)

Formula (5-5)

The definition of R, Z, Y, Q, y and x in the definition of R, Z, Y, Q, y and x among formula (5-1), (5-2), (5-3), (5-4) and (5-5) and the formula (2-1) to (2-5) is identical.R ¹To R ⁹Independent separately expression hydrogen atom or substituting group; And G represents oxygen atom or sulphur atom.

Za ¹, Za ²And Za ³Example comprise: (for example have 3 to 25 carbon atom De oxazoles nuclear, 2-3-Jia Ji oxazolyl, 2-3-Yi Ji oxazolyl, 2-3,4-Er Yi Ji oxazolyl, 2-3-Jia base benzoxazolyl, 2-3-ethyl benzoxazolyl, 2-3-sulfoethyl benzoxazolyl, 2-3-sulfopropyl benzoxazolyl, 2-3-methylmercaptoethyl benzoxazolyl, 2-3-methoxy ethyl benzoxazolyl, 2-3-sulphur butyl benzoxazolyl, 2-3-methyl-β-Nai Bing oxazolyls, 2-3-methyl-α-Nai Bing oxazolyls, 2-3-sulfopropyl-β-Nai Bing oxazolyls, 2-3-sulfopropyl-β-Nai Bing oxazolyls, 2-3-(3-naphthoxy ethyl) benzoxazolyl, 2-3,5-benzoxazole dimethyl base, 2-6-chloro-3-Jia base benzoxazolyl, 2-5-bromo-3-Jia base benzoxazolyl, 2-3-ethyl-5-methoxyl group benzo oxazolyl, 2-5-phenyl-3-sulfopropyl benzoxazolyl, 2-5-(4-bromophenyl)-3-sulphur butyl benzoxazolyl and 2-3-dimethyl-5,6-diformazan sulfenyl benzoxazolyl); Thiazole nucleus with 3 to 25 carbon atoms (for example, 2-3-methylthiazol base, 2-3-ethyl thiazole base, 2-3-sulfopropyl thiazolyl, 2-3-sulfo group butyl thiazolyl, 2-3,4-dimethylthiazole base, 2-3,4,4-trimethylthiazole base, 2-3-carboxyethyl thiazolyl, 2-3-methylbenzothiazole base, 2-3-ethylo benzene benzothiazolyl, 2-3-butyl benzene benzothiazolyl, 2-3-sulfopropyl benzothiazolyl, 2-3-sulphur butyl benzene benzothiazolyl, 2-3-methyl-β-naphthothiazoles base, 2-3-sulfopropyl-γ-naphthothiazoles base, 2-3-(1-naphthoxy ethyl) benzothiazolyl, 2-3,5-dimethyl-benzothiazole base, 2-6-chloro-3-methylbenzothiazole base, 2-6-iodo-3-ethylo benzene benzothiazolyl, 2-5-bromo-3-methylbenzothiazole base, 2-3-ethyl-5-methoxybenzene benzothiazolyl, 2-5-phenyl-3-sulfopropyl benzothiazolyl, 2-5-(4-bromophenyl)-3-sulphur butyl benzene benzothiazolyl and 2-3-dimethyl-5,6-diformazan sulfenyl benzothiazolyl); Imidazole nucleus (for example, 2-1,3-diethyl imidazole radicals, 2-1 with 3 to 25 carbon atoms, 3-methylimidazole base, 2-1-tolimidazole base, 2-1,3,4-triethyl group imidazole radicals, 2-1,3-diethyl benzo imidazole radicals, 2-1,3,5-trimethyl benzo imidazole radicals, 2-6-chloro-1,3-dimethylbenzimidazole base, 2-5,6-two chloro-1,3-diethyl benzo imidazole radicals and 2-1,3-two sulfopropyls-5-cyano group-6-chloro-benzimidazole base); Indolenine nuclear (for example 3,3-dimethyl indolenine) with 10 to 30 carbon atoms; Quinoline nuclei with 9 to 25 carbon atoms (for example, 2-1-methylquinoline base, 2-1-ethyl quinolyl, 2-1-methyl-6-chloro quinolyl, 2-1,3-diethyl quinolyl, 2-1-methyl-6-methyl mercapto quinolyl, 2-1-sulfopropyl quinolyl, 4-1-methylquinoline base, 4-1-sulfoethyl quinolyl, 4-1-methyl-7-chloro quinolyl, 4-1,8-diethyl quinolyl, 4-1-methyl-6-methyl mercapto quinolyl and 4-1-sulfopropyl quinolyl); Selenazole nucleus (for example 2-3-methyl benzo selenazoles base) with 3 to 25 carbon atoms; With the pyridine nucleus with 5 to 25 carbon atoms (for example 2-pyridine radicals), and thiazoline He, oxazoline is examined, selenazoline is examined, tellurium azoles quinoline is examined, the tellurium azoles is examined, benzo tellurium azoles is examined, imidazoline is examined, imidazo [4, examine, thiadiazoles is examined, tetrazolium is examined and pyrimidine is examined by 5-quinoxaline] He, oxadiazole.

These can further be substituted, and substituent favourable example comprises: alkyl (methyl for example, ethyl and propyl group), halogen atom (chlorine for example, bromine, iodine and fluorine), nitro, alkoxyl (for example methoxyl group and ethyoxyl), aryl (for example phenyl), heterocyclic group (2-pyridine radicals for example, the 3-pyridine radicals, 1-pyrrole radicals and 2-thienyl), aryloxy group (for example phenoxy group), acylamino-(for example acetylamino and benzamido), carbamoyl (for example N, N-dimethylamino formamido group), sulfo group, sulfoamido (for example Methanesulfomide), sulfamoyl (for example N-methyl sulfamoyl), hydroxyl, carboxyl, alkylthio group (for example methyl mercapto) and cyano group; And preferably azoles nuclear, imidazole nucleus and thiazole nucleus.These heterocycles can further condense with another ring.The example of the ring that can condense with it comprises: phenyl ring, benzofuran ring, pyridine ring, pyrrole ring, indole ring and thiphene ring etc.

Za ⁴, Za ⁵And Za ⁶Expression is used to form the needed atomic group of acid core separately, and is defined in the The Theory of the Photographic Process of James work, and the 4th edition, McMillan is in 1977, the 198 pages.Its instantiation comprises the nuclear of following compound: the 2-pyrazolin-5-one, pyrazolidine-3, the 5-diketone, imidazoline-5-ketone, hydantoins, 2-or 4-thiohydantoin, 2-Ya An Ji oxazole pyridine-4-ketone (2-iminooxazorigin-4-one), 2-oxazoline-5-ketone, 2-Liu oxazolines-2, the 4-diketone, different rhodanine, rhodanine, indenes-1, the 3-diketone, thiophene-3-ketone, thiophene-3-ketone-1, the 1-dioxide, Indolin-2-one, indoline-3-ketone, 2-oxo indazole, 5,7-dioxo-6,7-thiazoline also [3,2-a] pyrimidine, 3,4-dihydro-isoquinoline-4-ketone, 1,3-diox-4, the 6-diketone, barbituric acid, the 2-thiobarbituric acid, cumarin-2, the 4-diketone, indazole quinoline-2-ketone, pyrido [1,2-a] pyrimidine-1, the 3-diketone, pyrazolo [1,5-b] quinolinone, Pyrazolopyridine ketone, 3-dicyano methylene (dicyanomethylidenyl)-3-phenyl propionitrile, oxa-tetrahydrothiophenone dioxide (oxathiolanonedioxide) or Michaelis acid (Meldrum ' s acid); And preferably 2-pyrazolin-5-one, barbituric acid, 2-thiobarbituric acid, oxa-tetrahydrothiophenone dioxide, Michaelis acid and pyrazolidine-3, the 5-diketone.

In formula (1), L ¹¹And L ^2kIndependent separately expression divalent linker, and except that it be attached to chromophore on it and do not form the Pi-conjugated systems, it is not specifically limited, and its favourable example comprises: alkylidene (has 1 to 20 carbon atom, methylene for example, ethylidene, propylidene, butylidene and pentylidene), arlydene (has 6 to 26 carbon atoms, for example phenylene and naphthylene), alkylene group (has 2 to 20 carbon atoms, for example ethenylidene and allylidene), alkynylene (having 2 to 20 carbon atoms, for example ethynylene and inferior propinyl), inferior Metallocenyl (metallocenylene groups) (for example ferrocene),-CO-N (R ¹⁰¹)-,-CO-O-,-SO ₂-N (R ¹⁰²)-,-SO ₂-O-,-N (R ¹⁰³)-CO-N (R ¹⁰⁴)-,-SO ₂-,-SO-,-S-,-O-,-CO-,-N (R ¹⁰⁵)-, and has 0 to 100 or still less, preferred carbon atom more than 1 and below 20, and the linking group with one or more inferior heteroaryls (heterylene groups) (has 1 to 26 carbon atom, for example the 6-chloro-1,3,5-triaxyl-2,4-two base and pyrimidines-2,4-two bases).Above R ¹⁰¹, R ¹⁰², R ¹⁰³, R ¹⁰⁴And R ¹⁰⁵Independent separately expression hydrogen atom, replacement or unsubstituted alkyl perhaps replace or unsubstituted aryl.In addition, above by L ¹¹Or L ^2kOne or more linking groups of expression may reside between two chromophores that are attached on it, and this a plurality of linking groups (preferred two) can mutually combine and form to encircle.L ¹¹And L ^2kBe preferably the ring that forms by (preferred ethylidene) combination of two alkylidenes separately.Especially, its more preferably 5-or 6 yuan of ring (preferred cyclohexyl) again.

In formula (1), n represents 0 to 10 integer, preferred 0 to 5 integer, more preferably 0 to 3 integer, and preferred especially 0 to 2 integer.

In formula (1), the integer that k represents more than 0 and n is following.For example, when n was 2, k was 0,1 or 2 integer; And Dye ^2kAnd L ^2kIndependent separately expression Dye ²⁰, Dye ²¹Or Dye ²²Chromophore and L ²⁰, L ²¹Or L ²²Linking group.When n is integer more than 2, a plurality of group Dye ^2kCan be identical or different mutually.When n represents integer more than 2, a plurality of group L ^2kAlso can be identical or different mutually.

In formula (1), Q represents to be used for the ion with electric charge; And y represents to be used for and the number of the needed ion of electric charge.It depends on the substituting group of compound, and no matter this compound is cation or anion, perhaps has clean ionic charge.The ion of being represented by Q in formula (1) and (3) to (5) can be represented cation and anion according to the corresponding electric charge of dye molecule, and when dye molecule did not carry electric charge, Q did not exist.Ionic charge to the ion represented by Q is not specifically limited, and can be the ion of inorganic or organic compound.The ion of being represented by Q can be unit price or multivalence.The cationic example of being represented by Q comprises: metal cation such as sodium ion and potassium ion, and ion such as quaternary ammonium ion, oxonium ion, sulfonium cation, Phosphonium ion, plasma selenium and iodide ion.On the other hand, the anionic example of being represented by Q comprises: halide anion such as chlorion, bromide ion and fluorine ion; Heteropoly acid ion such as sulfate ion, phosphate anion and bis phosphoric acid radical ion (biphosphateion); Organic multivalent anions such as succinate ion, maleate ion, fumarate ion and aromatics disulfonic acid radical ion; And tetrafluoroborate ion and hexafluorophosphoricacid acid ions.

The cation of being represented by Q is preferably ion, and quaternary ammonium ion more preferably.Among quaternary ammonium ion, particularly preferably be by 4 of the formula (I-4) of JP-A 2000-52658 expression 4 '-bipyridine cation and be disclosed in 4 among the JP-A 2002-59652,4 '-bipyridine cation.

The anion of being represented by Q is preferably tetrafluoroborate ion, hexafluorophosphoricacid acid ions or organic multivalent anions, more preferably divalence or trivalent organic anion such as naphthalenedisulfonic acid salt derivative.Among divalence or trivalent organic anion, particularly preferably be the naphthalenedisulfonic acid anion that is disclosed among the JP-A 10-226170.

Among dyestuff by formula (1) expression, have by following formula (2-1), (2-2), (2-3), (2-4) or (2-5) dyestuff of the structure of expression be preferred.

Formula (2-1)

Formula (2-2)

Formula (2-3)

Formula (2-4)

Formula (2-5)

Will be in following description by formula (2-1), (2-2) and (2-3) dyestuff of expression.Y represents-O-,-NR ¹-and-CR ²R ³In any.Y is preferably-O-or-CR ²R ³, and more preferably-O-.

R ¹To R ⁹Independent separately expression hydrogen atom or substituting group.To by R ¹To R ⁹The substituting group of expression is not specifically limited, and the example comprises those substituting groups of being represented by R in the formula (I), and its preferred embodiment is also identical.

Z represents to replace or unsubstituted alkylidene.The favourable example of alkylidene comprises: replaces or unsubstituted methylene, replacement or unsubstituted ethylidene, and replacement or unsubstituted propylidene; Preferred example comprises: replace or unsubstituted methylene and replacement or unsubstituted ethylidene; And preferred again example comprises replacement or unsubstituted methylene.

X represents 1 or 2, is preferably 2.

G represents oxygen atom or sulphur atom, is preferably oxygen atom.

With following formula (2-1), (2-2), (2-3), (2-4) with (2-5), R is illustrated in the substituting group on the methine carbon; M represents 0 to 1 integer; N represents 0 to 2m+1 integer; When n was integer more than 2, a plurality of radicals R can be identical or different mutually, perhaps can mutually combine to form ring; Za ⁵And Za ⁶Expression forms the atomic group of acid core separately; L ¹¹, Q and the definition of y and the L in the formula (1) ¹¹, Q is identical with y.

By formula (2-1), (2-2), (2-3), (2-4) with (2-5) among the structure of expression, preferably wherein m is 0 dyestuff.

Above by formula (2-1), (2-2), (2-3), (2-4) with (2-5) in the dyestuff of expression, based on the viewpoint of photostability and good degradability, have by following formula (5-1), (5-2), (5-3), (5-4) or (5-5) dyestuff of the structure of expression be most preferred.

Formula (5-1)

Formula (5-2)

Formula (5-3)

Formula (5-4)

Formula (5-5)

In formula (5-1), (5-2), (5-3), (5-4) with (5-5), R1 to R9, R, x, Y, Z, Q, y and G and formula (2-1), (2-2), (2-3), (2-4) and (2-5) in R1 to R9, R, x, Y, Z, Q, y and G identical.

Below, will list typical preferred example (S-1 to S-27), but the invention is not restricted to this according to the compound by formula (1) and (2) expression of the present invention.

(S-1)

(S-2)

(S-3)

(S-4)

(S-5)

(S-6)

(S-7)

(S-8)

(S-18)

(S-19)

(S-20)

(S-21)

(S-22)

The typical compound that helps using in the present invention is shown in down in the tabulation 1.

Table 1

By can using separately or with the combination of two or more of formula (1) expression according to dye composition of the present invention.Alternatively, can be used in combination with other dye composition according to dye composition of the present invention.

In the recording layer of information recording carrier of the present invention,, can comprise various anti-decolourants in order to strengthen the light resistance of recording layer.

As anti-decolourant, can use organic oxidizing agent and singlet oxygen quencher.As organic oxidizing agent, can use the compound that is described among the JP-A 10-151861.As singlet oxygen quencher, can use those singlet oxygen quenchers that are described in the open patent specification as is known.The instantiation of this singlet oxygen quencher comprises the singlet oxygen quencher that is described in the following content: JP-A58-175693,59-81194,60-18387,60-19586,60-19587,60-35054,60-36190,60-36191,60-44554,60-44555,60-44389,60-44390,60-54892,60-47069,63-209995,4-25492, Japanese Patent Application Publication (JP-B) 1-38680 and 6-26028; Deutsche Bundespatent 350399; And Nippon Kagaku Kaishi, October (1992), the 1141st page.Other preferred embodiment of singlet oxygen quencher comprises the compound by following general formula (II) expression.

Formula (II)

R wherein ²¹Expression can have substituent alkyl, and Q ^-The expression anion.

In general formula (II), R ²¹Be generally and have 1 to 8 carbon atom and can have substituent alkyl, and be preferably unsubstituted alkyl with 1 to 6 carbon atom.Substituent example for alkyl comprises: halogen atom (for example; F and Cl), alkoxyl (for example; methoxyl group and ethyoxyl), alkylthio group (for example; methyl mercapto and ethylmercapto group), acyl group (for example; acetyl group and propiono), acyloxy (for example, acetoxyl group and propionyloxy), hydroxyl, alkoxy carbonyl group (for example, methoxycarbonyl group and carbethoxyl group), alkenyl (for example; vinyl) and aryl (for example, phenyl and naphthyl).Preferably halogen atom, alkoxyl, alkylthio group and alkoxy carbonyl group.Q ^-Anionic preferred embodiment comprises ClO ₄ ^-, AsF ₆ ^-, BF ₄ ^-And SbF ₆ ^-

(example of compound number II-1～II-8) is shown in the following table 2 by the compound of general formula (II) expression.

Table 2

Amount with respect to dyestuff, the use amount of anti-decolourant such as singlet oxygen quencher is usually in the scope of 0.1 to 50 quality %, preferably in the scope of 0.5 to 45 quality %, more preferably in the scope of 3 to 40 quality %, and in the scope particularly preferably in 5 to 25 quality %.

The form of＜optical data recording medium 〉

Aspect of the present invention in (1), optical data recording medium according to the present invention is preferably contain dyestuff one-time write recording layer and the thickness that have with this order on thickness is 0.7 to 2mm substrate be 0.01 to 0.5mm tectal optical data recording medium; And aspect in (2), it preferably has the optical data recording medium that dyestuff one-time write recording layer and thickness are 0.1 to 1.0mm protectiveness substrate that contains with this order on thickness is 0.7 to 2mm substrate.Aspect above in (1), be formed on pre-groove on the substrate and preferably have 50 to 500nm track pitch, 25 to 250nm groove width and 5 to 150nm groove depth; And aspect above in (2), be formed on pre-groove on the substrate and preferably have 200 to 600nm track pitch, 50 to 300nm groove width, 30 to 200nm groove depth and 10 to 50nm the amplitude of oscillation.

The optical data recording medium of aspect (1) has substrate, one-time write recording layer and cover layer at least, and will describe these part and parcels at first one by one.

[according to the substrate of aspect (1)]

Will with have whole pre-grooves (guide groove) of the shape of the track pitch in following scope, groove width (half breadth), groove depth and the amplitude of oscillation be formed on basically favourable aspect on the substrate of (1).Form pre-groove and be in order to give substrate the packing density higher, and, be particularly advantageous for example will be during as the medium compatible with royal purple laser according to optical data recording medium of the present invention than the packing density of CD-R or DVD-R.

Pre-groove track pitch is preferably in 50 to 500nm scope, and the upper limit is preferably below the 420nm, more preferably below the 370nm, and more more preferably below the 330nm.Lower limit is preferably more than the 100nm, more preferably more than the 200nm, and more more preferably more than the 260nm.Track pitch less than 50nm may cause being difficult to accurately forming pre-groove, produce cross-interference issue, and may cause the problem that packing density reduces above the track pitch of 500nm.

Pre-well width (half breadth) is preferably in 25 to 250nm scope, and its upper limit is preferably below the 200nm, more preferably below the 170nm, and more more preferably below the 150nm.Its lower limit is preferably more than the 50nm, more preferably more than the 80nm, and more more preferably more than the 100nm.The transfer printing deficiency that may cause the groove between shaping period less than the pre-well width of 25nm, and be increased in the error rate (error rate) during the record, and the hole (pit) that the pre-well width that surpasses 250nm causes forming is widened, is caused and crosstalk and modulate (modulation) deficiency during writing down.

Pre-groove depth is preferably in 5 to 150nm scope, and its upper limit is preferably below the 100nm, more preferably below the 70nm, and more more preferably below the 50nm.Its lower limit is preferably more than the 10nm, more preferably more than the 20nm, and more more preferably more than the 28nm.Pre-groove depth less than 5nm may cause record modulation (recording modulation) deficiency, and reduces reflectance significantly above the pre-groove depth of 150nm.

The upper limit at the angle of pre-groove is preferably below 80 °, more preferably below 70 °, more more preferably below 60 °, and is preferably especially below 50 °.In addition, the lower limit at the angle of pre-groove is preferably more than 20 °, more preferably more than 30 °, and more more preferably more than 40 °.

May cause tracking error signal amplitude deficiency less than 20 ° pre-groove angles, the pre-groove angle that surpasses 80 ° then causes difficult forming.

As the substrate among the present invention, can at random select and use the various materials that in existing optical data recording medium, are used as backing material.

The instantiation of this material comprises: glass; Merlon; Acrylic resin such as polymethyl methacrylate; Vinyl chloride-based resin such as polyvinyl chloride and vinyl chloride copolymer; Epoxy resin; Amorphous polyolefin; Polyester; And metal such as aluminium, and if desired, can use the combination in they two or more.

Among above-mentioned material, based on moisture resistance, dimensional stability and viewpoint cheaply, preferred thermoplastic resin such as amorphous polyolefin and Merlon, and Merlon is particularly preferred.

In the situation of using such resin, can make substrate by injection molding way.

What need is that the thickness of substrate is in 0.7 to 2mm scope.Preferred it in 0.9 to 1.6mm scope, and more preferably in 1.0 to 1.3mm scope.

On the surface of a side of the following optical reflecting layer of substrate arrangement,, be preferably formed priming coat in order to improve flatness and to increase bonding force.

The example of the material of priming coat comprises: polymer, for example polymethyl methacrylate, acrylate-methacrylate copolymer, styrene-maleic anhydride copolymers, polyvinyl alcohol, N hydroxymethyl acrylamide, styrene-ethylene base toluene copolymer, chlorosulfonated polyethylene, celluloid, polyvinyl chloride, chloridized polyolefin, polyester, polyimides, vinyl acetate-vinyl chloride copolymer, vinyl-vinyl acetate copolymer, polyethylene, polypropylene and Merlon; And surface modifier, for example silane coupler.

Priming coat can form by the following method: prepare coating solution in the appropriate solvent by above-mentioned material is dissolved or is dispersed in, rely on coating process such as spin-coating method, dip coating or squeezing and coating method that coating solution is coated on the surface of substrate subsequently.Usually, the film thickness of priming coat is in the scope of 0.05 to 20 μ m, and is and preferred in the scope of 0.01 to 10 μ m.

[according to the one-time write recording layer of aspect (1)]

The favourable one-time write recording layer of aspect (1) prepares by the following method: by with dyestuff (the above-mentioned dyestuff that has two or more individual dye part in molecule, and this dyestuff partly mutually combines, and do not have above-mentioned conjugated bonds) and adhesive and other be dissolved in together in the suitable solvent, with the preparation coating solution; And form coated film by coating coating solution on substrate or following reflection layer; And dry this coated film.In this, the one-time write recording layer can be individual layer or multilayer.Under the situation of the one-time write recording layer with multilayer configuration, this recording layer can form by carrying out repeatedly application step.

The concentration of dyestuff is usually in the scope of 0.01 to 15 quality %, preferably in the scope of 0.1 to 10 quality %, more preferably in the scope of 0.5 to 5 quality %, and most preferably in the scope of 0.5 to 3 quality % in the coating solution.

Coating solution comprises with the example of solvent: ester, for example butyl acetate, ethyl lactate and cellosolve acetate; Ketone, for example methyl ethyl ketone, cyclohexanone and methyl second butyl ketone; Chlorinated hydrocabon, carrene, 1 for example, 2-dichloroethanes and chloroform; Acid amides, for example dimethyl formamide; Hydrocarbon, for example hexahydrotoluene; Ether, for example oxolane, ether He diox; Alcohol, for example ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol and diacetone alcohol; Fluorated solvent, for example 2,2,3, the 3-tetrafluoropropanol; And glycol ether, for example glycol monomethyl methyl ether, ethylene glycol monomethyl ether and propylene glycol monomethyl ether.

Consider the dissolubility of employed dyestuff, above-mentioned solvent can be separately or is used with their two or more combination.In addition, can in coating solution, add various additive such as antioxidant, UV absorbent, plasticizer and lubricant according to purpose.

As coating process, that can enumerate has: spraying process, spin-coating method, infusion process, rolling method, cutter are coated with method, coating weight control roll method and silk screen print method.

When coating, the temperature of coating solution is preferably in 23 to 50 degrees centigrade scope, more preferably in 24 to 40 degrees centigrade scope, among this, in 23 to 50 degrees centigrade scope.

On groove (ledge on the substrate), the thickness of the one-time write recording layer of Xing Chenging is preferably below the 300nm like this, more preferably below the 250nm, more preferably below the 200nm, and is preferably below the 180nm especially.Its lower limit is preferably more than the 30nm, more preferably more than the 50nm, more preferably more than the 70nm, and is preferably more than the 90nm especially.

In addition, on platform (land) (recess on the substrate), the thickness of one-time write recording layer is preferably below the 400nm, more preferably below the 300nm, and further more preferably below the 250nm.Its lower limit is preferably more than the 70nm, more preferably more than the 90nm, and further more preferably more than the 110nm.

Again in addition, the ratio at the thickness of the one-time write recording layer on the platform is preferably more than 0.4, more preferably more than 0.5, further more preferably more than 0.6, and is preferably more than 0.7 especially at the thickness of the one-time write recording layer on the groove.Its upper limit is preferably less than 1, more preferably below 0.9, more preferably below 0.85, and is preferably below 0.8 especially.

Comprise the situation of adhesive at coating solution, the example of adhesive comprises: natural organic polymer, for example gelatin, cellulose derivative, glucan, rosin and rubber; And synthetic organic polymer, for example, hydrocarbon resins such as polyethylene, polypropylene, polystyrene and polyisobutene, vinylite such as polyvinyl chloride, poly-inclined to one side vinylidene chloride and polyvinyl chloride-polyvinyl acetate ester copolymer, acrylic resin such as PMA and polymethyl methacrylate; And the initial condensation product of thermosetting resin, for example polyvinyl alcohol, haloflex, epoxy resin, butyral resin, rubber derivative and phenolic resins.In the situation that adhesive uses as the material of recording layer simultaneously, the use amount of adhesive is usually in 0.01 to 50 times scope of the amount (mass ratio) of dyestuff, and preferably in 0.1 to 5 times scope of the amount (mass ratio) of dyestuff.

[according to the cover layer of aspect (1)]

On above-mentioned one-time write recording layer or following barrier layer, by adhesive or tackifier and the cover layer of the preferred aspect of bonding basis (1).As long as use the film of making from material transparent, the cover layer that uses among the present invention be not specifically limited.Yet, can preferably use Merlon; Acrylic resin such as polymethyl methacrylate; Vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer; Epoxy resin; Amorphous polyolefin; Polyester; And cellulose triacetate.In these, can preferably use Merlon or cellulose triacetate.

" transparent " is meant that for writing down and duplicating the transmittance of using up be more than 80%.

In cover layer,, can comprise various additives as long as do not hinder effect of the present invention.For example, it is the UV absorbent that 400nm or shorter light cut off that cover layer can comprise wavelength, and/or is the dyestuff that 500nm or longer light cut off with wavelength.

In addition, as tectal Surface Physical character, in two-dimentional roughness parameter and three-dimensional roughness parameter, surface roughness preferably all is below the 5nm.

Based on the viewpoint of the collection power (collecting power) of the light of use in writing down and duplicating, tectal birefringence is preferably below the 10nm.

Write down and duplicate and the Wavelength of Laser and the NA of irradiation according to being used to, tectal thickness suitably is provided.Yet in the present invention, it is in 0.01 to 0.5mm scope, and more preferably in 0.05 to 0.12mm scope.

Total thickness of the layer of being made by cover layer and adhesive or tackifier layer is preferably in 0.09 to 0.11mm scope, and more preferably in 0.095 to 0.105mm scope.

Produce defective in order when making optical data recording medium, to suppress light incident surface, on tectal light incident surface, can arrange protective layer (hard conating).

As being used for bonding tectal adhesive, can preferably using for example UV curable resin, EB curable resin and thermosetting resin, and can especially preferably use the UV curable resin.

At the UV curable resin as under the situation of adhesive, can from distributor with UV curable resin former state or by the UV curable resin is dissolved in appropriate solvent such as methyl ethyl ketone with ethyl acetate on the surface of coating solution supply that prepare on the barrier layer.For the optical data recording medium warpage that suppresses to make, the UV curable resin that constitutes adhesive layer preferably has little cure shrinkage speed.As the example of such UV curable resin, that can enumerate has: such as by Dainippon Inkand Chemicals, and the UV curable resin of the commodity that Incorporated makes SD-640 by name.

Preferably, for example, on the adhesive surface that the coating of the adhesive of scheduled volume is made by the barrier layer; Arrange cover layer thereon; Rely on to be spin-coated on subsequently and sprawl adhesive between adhesive layer and the cover layer equably; Again subsequently can cure adhesive.

The thickness of the adhesive layer of being made by such adhesive is preferably in the scope of 0.1 to 100 μ m, more preferably in the scope of 0.5 to 50 μ m, and further more preferably in the scope of 10 to 30 μ m.

As being used for bonding tectal tackifier, can use acrylic compounds, rubber-based and silica-based tackifier.Yet, based on the viewpoint of the transparency and durability, preferably acrylic compounds tackifier.As such acrylic compounds tackifier, that can preferably use has: the acrylic compounds tackifier, wherein with acrylic acid-2-ethyl caproite or n-butyl acrylate as its key component, in order to increase cohesive force, copolymerization short chain alkyl acrylate or alkyl methacrylate such as methyl acrylate, ethyl acrylate and methyl methacrylate, with acrylic acid, methacrylic acid, acrylamide derivative, maleic acid, hydroxy-ethyl acrylate and glycidyl acrylate, they all can be used as the crosslinking points with crosslinking agent.Mixed proportion and kind by suitably regulating key component, short chain component and increasing the component of crosslinking points can change glass transition temperature (Tg) and crosslink density.

As the crosslinking agent that uses with tackifier, that can enumerate has: isocyanates based cross-linker for example.The example of such isocyanates based cross-linker comprises: isocyanates, trichloro-ethylene vulcabond, 4 for example, 4 '-'-diphenylmethane diisocyanate, 1, hexamethylene-diisocyanate, XDI, naphthylene-1,5-vulcabond, ortho-aminotoluene isocyanates, IPDI and triphenylmethane triisocyanate; Or the product of isocyanates and polyalcohol; Or by the PIC of the condensation prepared of isocyanates.The example that is purchased product of isocyanates comprises trade name: Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR and Millionate HTL, produced by Nippon Polyurethane Industry Co.Ltd.; Trade name: Takenate D-102, Takenate D-110N, Takenate D-200 and Takenate D-202, by Takeda Chemical Industries Co., Ltd. produces; And trade name: Desmodule L, Desmodule IL, Desmodule N and Desmodule HL, by Sumitomo Bayer Co., Ltd. produces.

Be coated on equably after the adhesive surface of making by the cover layer of arranging on barrier layer and its at tackifier, can solidify tackifier scheduled volume; Perhaps be coated in advance on the cover layer forming the tackifier coated film, and after this coated film is laminated to adhesive surface, can solidify tackifier at tackifier with scheduled volume.

In addition, as cover layer, can use the bonding film that is purchased that is furnished with the tackifier layer on it in advance.

The thickness of the tackifier layer of being made by tackifier is preferably in the scope of 0.1 to 100 μ m, more preferably in the scope of 0.5 to 50 μ m, and further more preferably in the scope of 10 to 30 μ m.

[according to other layer of aspect (1)]

Except that above-mentioned indispensable layer, only otherwise damage effect of the present invention, can have other optional layer according to the optical data recording medium of preferred aspect (1).As optional layer, that for example can enumerate has: have at substrate back (with the opposite face of face that forms the one-time write recording layer) and go up the mark layer that needs image that forms; Contain the mark layer that needs image; Be arranged in the reflection layer (following) between substrate and the one-time write recording layer; Be arranged in the barrier layer (following) between one-time write layer and the cover layer; And be arranged in boundary layer between reflection layer and the one-time write recording layer.This mark layer forms by using UV curable resin, thermosetting resin and heated drying resin (thermal dry resins).

All indispensable layer and optional layer can be individual layers, maybe can have sandwich construction.

[according to the reflection layer of aspect (1)]

In the present invention, in order to increase reflectance, perhaps in order to give the function of improving record and duplicating character, preferred arrangements reflection layer between substrate and one-time write recording layer to laser.

Reflection layer can have the light reflective material of high reflectance to laser and forms on substrate by vacuum evaporation, sputter or ion plating.

The layer thickness of reflection layer is usually in 10 to 300mm scope, and is and preferred in 50 to 200mm scope.

In addition, reflectance is preferably more than 70%.

The example of the light reflective material that reflectance is high comprises metal and metalloid such as Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn and Bi, or stainless steel.Light reflective material can be used separately, perhaps with their two or more be used in combination, perhaps can also use as their alloy.In these, Cr, Ni, Pt, Cu, Ag, Au, Al and stainless steel are preferred.Particularly preferably, Au, Ag, Al or their alloy can be used, and most preferably, Au, Ag or their alloy can be used.

[formation in barrier layer (intermediate layer)]

In the present invention, preferably between one-time write recording layer and cover layer, form the barrier layer.

Barrier layer disposed is for the bin stability that increases the disposable recording layer, increases cohesive, control reflectance and control thermal conductivity between one-time write recording layer and the cover layer.

To the material that is used for the barrier layer without limits, as long as these materials are can transmission to be used to the light that writes down and duplicate, and can show that above materials with function gets final product.For example, usually, the low material of the permeability of gas and water preferably, and be dielectric.

Particularly, the material of being made by nitride, oxide, carbide and the sulfide of Zn, Si, Ti, Te, Sn, Mo and Ge is preferred.Among these, ZnS, MoO ₂, GeO ₂, TeO, SiO ₂, TiO ₂, ZnO, ZnS-SiO ₂, SnO ₂And ZnO-Ga ₂O ₃Be preferred, and ZnS-SiO ₂, SnO ₂And ZnO-Ga ₂O ₃Be preferred.

The barrier layer can also form by vacuum diaphragm forming method such as vacuum evaporation, DC sputter, RF sputter or ion plating.Among these, the preferred sputtering method that is to use, and can further more preferably use the RF sputter.

According to the thickness on barrier layer of the present invention preferably in 1 to 200nm scope, more preferably in 2 to 100nm scope, and further more preferably in 3 to 50nm scope.

Below, the optical data recording medium of favourable aspect (2) will be described.The optical data recording medium of aspect (2) is the optical data recording medium with laminate layers structure, and the representative instance of this layer structure is as follows:

(1) ground floor structure, it has one-time write recording layer, reflection layer and the adhesive layer that forms in the following order on substrate, and the protectiveness substrate that forms on adhesive layer again.

(2) second layer structure, it has one-time write recording layer, reflection layer, protective layer and the adhesive layer that forms in the following order on substrate, and the protectiveness substrate that forms on adhesive layer again.

(3) three-deckers, it has one-time write recording layer, reflection layer, protective layer, adhesive layer and the protective layer that forms in the following order on substrate, and the protectiveness substrate that forms on protective layer again.

(4) four-layer structures, it has one-time write recording layer, reflection layer, protective layer, adhesive layer, protective layer and the reflection layer that forms in the following order on substrate, and the protectiveness substrate that forms on reflection layer again.

(5) layer 5 structure, it has one-time write recording layer, reflection layer, adhesive layer and the reflection layer that forms in the following order on substrate, and the protectiveness substrate that forms on reflection layer again.

Layer structure (1) to (5) only be illustration, and a layer structure is not limited to above-mentioned these structures, and the order that can change some layers maybe can be removed it.The one-time write recording layer can also be formed on the surface of protectiveness substrate side, and under these circumstances, has obtained the optical data recording medium that permission is write down and duplicated from the two sides.In addition, each layer can be that individual layer maybe can comprise multilayer.Below the medium that will have on substrate the one-time write recording layer, reflection layer, adhesive layer and the protectiveness substrate that form in the following order by employing is described as an example according to optical data recording medium of the present invention.

[according to the substrate of aspect (2)]

Basically form to have all pre-grooves (guide groove) of the shape of the track pitch in following scope, groove width (half breadth), groove depth and the amplitude of oscillation on the substrate of (2) aspect favourable.For example when will be according to optical data recording medium of the present invention during as the medium compatible with royal purple laser, it be particularly advantageous being used to give the pre-groove that substrate forms than the higher packing density of the packing density of CD-R or DVD-R.

Pre-groove track pitch is preferably in 200 to 600nm scope, and the upper limit is preferably below the 500nm, more preferably below the 450nm, and more more preferably below the 430nm.Lower limit is preferably more than the 300nm, more preferably more than the 330nm, and more more preferably more than the 370nm.May make less than the track pitch of 200nm to be difficult to accurately form pre-groove, cause the problem of crosstalking, and may cause the problem of packing density deterioration greater than the track pitch of 600nm.

Pre-well width (half breadth) is preferably in 50 to 300nm scope, and the upper limit is preferably below the 250nm, more preferably below the 200nm, and more more preferably below the 180nm.Lower limit is preferably more than the 100nm, more preferably more than the 120nm, and more more preferably more than the 140nm.May cause the transfer printing deficiency of the groove between shaping period less than the pre-well width of 50nm, and be increased in the error rate during the record, and cause the hole of formation during writing down to widen, cause and crosstalk and undermodulation above the pre-well width of 300nm.

Pre-groove depth is preferably in 30 to 200nm scope, and its upper limit is preferably below the 170nm, more preferably below the 140nm, and more more preferably below the 120nm.Its lower limit is preferably more than the 40nm, more preferably more than the 50nm, and more more preferably more than the 60nm.Pre-groove depth less than 30nm may cause writing down undermodulation, and reduces reflectance significantly above the pre-groove depth of 200nm.

Any one of various materials that is used for the substrate of conventional optical data recording medium can be used for preparation help aspect the substrate of (2) use, because it is suitably to select, and its representative instance and favourable example are identical with favourable example with the described representative instance of substrate in aspect (1).The thickness of substrate should be in 0.1 to 1.0mm scope, preferably in 0.2 to 0.8mm scope, and more preferably in 0.3 to 0.7mm scope.

Priming coat is preferably formed on the surface of one-time write recording layer side of substrate, improving flatness and bonding strength, and the typical case of the material of priming coat, coating process and layer thickness and favourable example are identical with layer thickness with the described material of priming coat, coating process for aspect (1).

[according to the one-time write recording layer of aspect (2)]

The details of the one-time write recording layer of aspect (2) is identical with the details of the one-time write recording layer of aspect (1).

[according to the reflection layer of aspect (2)]

Aspect favourable, in (2), sometimes reflection layer is formed on the one-time write recording layer, duplicates character with reflectance and the record that improves laser beam.The details of the reflection layer of aspect (2) is identical with the details of the reflection layer of aspect (1).

[according to the adhesive layer of aspect (2)]

The adhesive layer of favourable aspect (2) is the random layer that forms in order to improve bonding between reflection layer and protectiveness substrate.Adhesive layer is preferably the photocurable resin with material, and particularly has the light-cured resin that is used to prevent coil the low cure shrinkage of warpage.

The example of light-cured resin comprises such as by Dainippon Ink and Chemicals, the UV-curable resin (UV-curing adhesive) of the commodity that Inc. produces SD-640 by name and SD-347 etc.In order to provide sufficient elasticity to layer, the thickness of adhesive layer is preferably in the scope of 1 to 1000 μ m.

[according to the protectiveness substrate of aspect (2)]

Can be with identical shaped and the protectiveness substrate (false substrate (dummy substrate)) of the material identical materials that is used for above-mentioned substrate as favourable aspect (2).The thickness of protectiveness substrate should be in 0.1 to 1.0mm scope, preferably in 0.2 to 0.8mm scope, and more more preferably in 0.3 to 0.7mm scope.

[according to the protective layer of aspect (2)]

The optical data recording medium of favourable aspect (2) depends on that its layer structure can have the protective layer that is used for physics and chemoproection reflection layer, one-time write recording layer etc.The example of material for protective layer comprises: inorganic material, for example ZnS, ZnS-SiO ₂, SiO, SiO ₂, MgF ₂, SnO ₂And Si ₃N ₄And organic material, for example thermoplastic resin, thermosetting resin and UV-curable resin.Protective layer can for example prepare by bonding film, and described film prepares by plastic resin (plastic resin) and adhesive are expressed on the reflection layer.Alternatively, it can form by other method such as vacuum moulding machine, sputter or coating.

When protective layer is made by thermoplastic resin or thermosetting resin, this protective layer can by with resin dissolves in The suitable solvent with the preparation coating solution, and coating and dry this coating solution form.When using the UV-curable resin, protective layer can be by being dissolved in it in the The suitable solvent with the preparation coating solution, being coated with this coating solution and forming by UV irradiation hardening coated film.According to its application, can be in addition with the coating solution of various additives as antistatic additive, antioxidant and UV absorbent add.The thickness of protective layer is usually in the scope of 0.1 μ m to 1mm.

[according to other layer of aspect (2)]

Aspect in the optical data recording medium of (2), as long as do not hinder effect of the present invention, outside the upper strata, can also comprise other optional layer.The details of other optional layer is identical with the details of other layer of aspect (1).

[2] optical information recording method:

Optical information recording method according to the present invention is by using the optical data recording medium in favourable aspect (1) or (2) to carry out, for example as follows: at first, to write down with light beam such as semiconductor laser irradiation on optical data recording medium, simultaneously from aspect under the situation of (1) cover layer one side or from aspect substrate one side under the situation of (2) with constant linear velocity (0.5 to 10m/ second) or CAV rotation.It seems, along with light irradiation because the temperature of the regional area of light absorption and rising recording layer, thereby cause its physics or chemical property to change (for example, pit forms), information is recorded.

In the present invention, the semiconductor laser of oscillation wavelength in 390 to 440nm (preferred 400 to 410nm) scope is used as recording light.The example of preferred light source comprises the royal purple semiconductor laser of oscillation wavelength in 390 to 415nm scopes, and the center oscillation wavelength is the royal purple SHG laser instrument of 425nm, and described center oscillation wavelength is by using optical waveguide elements that the wavelength of branch center oscillation wavelength as the infrared semiconductor laser of 850nm obtained.According to packing density, the royal purple semiconductor laser of oscillation wavelength in 390 to 415nm scopes is particularly preferred.By with cover layer one side and substrate from aspect (2) the one side irradiation medium of semiconductor laser from aspect (1), simultaneously with constant linear velocity rotating media same as described above, and detection of reflected light, information that can playback.

Comprise and have two or more in the molecule and make it possible to carry out the high density recording of information as 440nm or shorter laser beam and duplicate, and help its optical stability by the irradiation wavelength using of the recording layer of the dyestuff of the individual dye that do not have to mutually combine under the situation of conjugated bonds part.Possible is owing to reduced the association of the dyestuff of per unit volume.

Preferably following first at least one aspect to the eight aspect is applied to according to optical data recording medium of the present invention.

(1) first aspect, wherein dyestuff has the structure by following formula (1) expression.

Formula (1)

(in the formula (1), Dye ¹¹, Dye ¹²And Dye ^2kRepresent the dyestuff part separately; L ¹¹And L ^2kRepresent divalent linker separately, described divalent linker does not form pi-conjugated key with the dyestuff part that is attached on it; N is more than 0 and 10 following integers; K is 0 to n integer; When n is integer more than 2, a plurality of group Dye ^2kCan be identical or different mutually; When n is integer more than 2, a plurality of group L ^2kCan be identical or different mutually; Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge).

Dyestuff with structure of being represented by formula (1) has reduced the association of the dyestuff of per unit volume, and has improved the light robustness.

(2) second aspect, wherein dyestuff partly is the oxonol dye part.

The polymer dyestuff is insoluble in the solvent usually, yet by the dyestuff part as oxonols, dyestuff can be dissolvable in water in the fluorinated alohol more.

(3) third aspect, wherein dyestuff is by following formula (2-1), (2-2), (2-3), (2-4) or (2-5) expression.

Formula (2-1)

Formula (2-2)

Formula (2-3)

Formula (2-4)

Formula (2-5)

(following formula (2-1), (2-2), (2-3), (2-4) and (2-5) in, R is illustrated in the substituting group on the methine carbon; M is 0 to 1 integer; N is 0 to 2m+1 integer; When n was integer more than 2, a plurality of radicals R can be identical or different mutually, maybe can mutually combine to form ring; Za ⁵And Za ⁶Expression forms the atomic group of acid core separately; L ¹¹, Q and the definition of y and the L in the formula (1) ¹¹, Q is identical with y; Y represents-O-,-NR ¹-and-CR ²R ³-in any; R ¹To R ⁹Independent separately expression hydrogen atom or substituting group; Z represents to replace or unsubstituted alkylidene; And x is 1 or 2.G represents oxygen atom or sulphur atom, the preferred oxygen atom).

The dyestuff degradability of expression is good by formula (2-1), (2-2), (2-3), (2-4) with (2-5), thereby has allowed favourable record.

(4) fourth aspect, its Chinese style (2-1), (2-2), (2-3), (2-4) or (2-5) in m be 0.When m was 0, it was the better photostability of photostability of the dyestuff more than 1 that dyestuff has than m wherein.May be because when m was 0, conjugated chain spatially mixed more, thereby had suppressed the infiltration of singlet oxygen.

(5) the 5th aspects, wherein dyestuff is by following formula (5-1), (5-2), (5-3), (5-4) or (5-5) oxonol dye of expression.

Formula (5-1)

Formula (5-2)

Formula (5-3)

Formula (5-4)

Formula (5-5)

(following formula (5-1), (5-2), (5-3), (5-4) and (5-5) in, R, Z, Y, Q and y are identical with R, Z, Y, Q and y in the formula (2-1) to (2-5); R ¹To R ⁹Independent separately expression hydrogen atom or substituting group; And G represents oxygen atom or sulphur atom).

The dyestuff degradability of expression is good by formula (5-1), (5-2), (5-3), (5-4) or (5-5), has allowed favourable record.

(6) the 6th aspects wherein except that recording layer, also form the reflection layer that is made of metal.During information reproduction, the existence of reflection layer has effectively improved reflectance.

(7) the 7th aspects wherein except that recording layer, also form protective layer.The existence of protective layer is the various layers of protection effectively.

(8) eight aspect, wherein substrate is to have the transparent disk substrate that the magnetic track pitch that forms on its surface is 50 to 600nm pre-groove, and recording layer is formed on the surface of pre-groove one side of substrate.In such configuration, can carry out the high density recording of information more reliably.

It is the information recording method that 440nm or shorter laser beam come recorded information by irradiation wavelength on according to the optical data recording medium of the invention described above that the present invention also provides a kind of.Information recording method according to the present invention has advantageously allowed the high density recording of information according to the optical data recording medium of the invention described above and has duplicated by using.

Embodiment

Below, will the exemplary synthetic method of some compounds among the embodiment be described.Can prepare other compound (S-2 to S-4, S-6 to S-22 and S-24 to S-27) similarly.

[synthetic embodiment 1]

Synthesizing of above compound (S-1): according to synthetic this compound of following scheme (A).

" compound 2 " of 2.84g is dissolved in the N of 50ml, in N '-dimethyl formamide, solution is cooled to 0 ℃ then, agitating solution simultaneously adds the triethylamine of 8.34ml, then to " compound 1 " that wherein add 5.86g.After 4 hours, add the Tetrabutylammonium bromide of 8.00g 0 ℃ of reaction, stirred subsequently 1 hour.Reaction solution is poured in the water of 300ml, and filters to obtain white crystal.With the crystal that the ethyl acetate washing obtains, obtain the compound (S-1) of 6.06g.

Measure structure by NMR. ¹H NMR (DMSO-d ⁶): d:0.95 (t, 24H), 1.31 (m, 16H), 1.4 to 1.9 (m, 20H), 2.05 (s, 8H), 3.15 (t, 16H) and 7.89 (s, 2H).

[synthetic embodiment 2]

Synthesizing of above compound (S-5): according to synthetic this compound of following scheme (B).

" compound 2 " of 2.84g is dissolved in the N of 50ml, in N '-dimethyl formamide, solution is cooled to 0 ℃ then, agitating solution simultaneously adds the triethylamine of 8.34ml, then to " compound 3 " that wherein add 6.12g.After 4 hours, add the Tetrabutylammonium bromide of 7.00g 0 ℃ of reaction, stirred subsequently 1 hour.Reaction solution is poured in the water of 300ml, and filters to obtain white crystal.With the crystal that ethyl acetate-methanol wash obtains, obtain the compound (S-5) of 8.00g.

Measure structure by NMR. ¹H NMR (DMSO-d ⁶): d:0.95 (t, 24H), 1.31 (m, 16H), 1.5 to 2.5 (m, 28H), 3.15 (t, 16H) and 7.92 (s, 2H).

[synthetic embodiment 3]

Synthesizing of above compound S-23: according to synthetic this compound of following scheme (C) to (D).

" compound 4 " of 0.29g and " compound 2 " of 0.29g are joined in the ethanol of 5ml, and the while agitating solution is to the triethylamine that wherein adds 0.57g.After at room temperature reacting 4 hours, filter the crystallization that generates, obtain " compound 5 " of 0.24g.

0.24g " compound 5 " joined in the dimethyl formamide of 2.5ml, then to " compound 6 " that wherein add 0.27g, to react 1 hour at 50 ℃.After this, solution is cooled to room temperature, then to the methyl alcohol that wherein adds 40ml to generate crystal.Filter the compound (S-23) that the crystal that generates obtains 0.31g.

Measure structure by NMR. ¹H NMR (DMSO-d ⁶): d:2.0 (s, 8H), 3.65 (s, 6H), 7.2 to 7.8 (m, 14H), 7.9 (s, 2H), 8.15 (s, 2H), 9.0 (d, 4H), 9.7 (d, 4H) and 10.75 (s, 2H).

[synthesizing of comparative compound (H-1)]

According to synthetic this compound of following scheme (E).

" compound 3 " of 4.15g and " compound 7 " of 2.50g are dissolved in the acetonitrile of 40ml, dropwise add the acetic anhydride of 1.28ml subsequently, dropwise add the triethylamine of 1.90ml then, then solution is refluxed under condition of stirring.React after 2 hours, add the Tetrabutylammonium bromide of 7.00g, and mixture was stirred 1 hour.The ethyl acetate that adds 300ml in reaction solution, and filtering solution obtain white crystal.Obtain the compound (H-1) of 5.33g with the crystal of ethyl acetate washing generation.

Measure structure by NMR. ¹H NMR (CDCl ₃): d:0.95 (t, 12H), 1.31 (m, 16H), 1.55 to 2.7 (m, 20H), 3.22 (t, 8H) and 8.21 (s, 2H).

[embodiment 1 to 4]

The preparation of＜optical data recording medium 〉

(preparation of substrate)

Prepare the polycarbonate resin substrate by injection moulding, described polycarbonate resin substrate has the thickness of 1.1mm, the external diameter of 120mm and the internal diameter of 15mm, and have the pre-groove of spiral (track pitch: 320nm; Groove width: width on the groove (on-groove width) 120nm; Groove depth: 35nm; Angle of groove inclination: 65 °; The amplitude of oscillation: 20nm).By laser cutting (351nm) pressing mold (stamper) that uses in the injection moulding is carried out mastering (mastering).

(formation of reflection layer)

In Ar gas atmosphere, by using the trade name of making by Unaxis: Cube, rely on the DC sputter, forming film thickness on substrate is APC reflection layer (the Ag:98.1 quality % of 100nm; Pd:0.9 quality %; With Cu:1.0 quality %) as vacuum deposited layer.The film thickness of reflection layer is controlled by sputtering time.

(formation of one-time write recording layer)

With every kind of compound in the tables 1 of 2 grams: (S-1), (S-4), (S-5) and (S-23) be added to 2,2,3 of 100ml, the 3-tetrafluoropropanol is with dissolving, thereby prepares the coating solution that contains dyestuff.Under the condition of 23 degrees centigrade and 50%RH, what rely on that spin-coating method will prepare contains the dye-coating solution coat on reflection layer, and wherein revolution changes in 300 to 400rpm scopes.Then, it was stored 1 hour with 50%RH at 23 degrees centigrade, form one-time write recording layer (on groove, have the thickness of 120nm, and have the thickness of 170nm at platform).

After forming the one-time write recording layer, in the stove of cleaning, carry out annealing in process.Substrate is supported on the stacked vertically bar (stack pole) that separates with spacer, and carried out annealing in process 1 hour at 80 degrees centigrade.

(formation on barrier layer)

After this, in Ar gas atmosphere,, rely on the RF sputter, on the one-time write recording layer, form the thickness of 5nm and by ZnO-Ga by using the trade name of making by Unaxis: Cube ₂O ₃(ZnO: Ga ₂O ₃=7: 3 (by mass ratioes)) barrier layer of making.

(tectal bonding)

As cover layer, adopt internal diameter with 15mm, the external diameter of 120mm, and on one surface, used the polycarbonate membrane (trade name: Teijin Pure Ace of tackifier; Thickness: 80 μ m), the summation of the thickness of control tackifier layer and polycarbonate membrane is so that it is 100 μ m.

Then, cover layer is being arranged on the barrier layer, is making the barrier layer, suppressing bonding cover layer by using press members, with bonding with after the tackifier layer can contact.

(comparative example 1 to 4)

Remove and to use comparative compound (A) to (D) to replace compound (S-1) respectively by following chemical formulation, (S-4), (S-5) and (S-23), with just in time same mode preparation dish with embodiment 1 to 4.

Comparative compound A (representative instance of describing among the JP-A11-58758 (b))

Comparative compound B (representative instance of describing among the JP-A11-58758 (c))

Comparative compound C (representative instance of describing among the JP-A 2001-71638 (32))

Comparative compound D (representative instance of describing among the JP-A 2001-71638 (34))

Prepare the optical data recording medium of embodiment 1 to 4 and comparative example 1 to 4 thus.

The evaluation of＜optical data recording medium 〉

The evaluation of-C/N ratio (carrier-to-noise ratio)

Under condition, having recording/copying checking machine (the inspectingmachine) (trade name: DDU1000 that 403-nm laser instrument and NA are 0.85 wave detector in the linear velocity of the clock frequency of 66MHz and 5.28m/s; Make by Pulstec Industrial Co.Ltd.) in, record and when duplicating 0.16-μ m signal (2T), measure the C/N of each optical data recording medium for preparing than (after record) by spectroanalysis instrument (TR4171 is made by AdvantestCorporation).The results are shown in the table 3.At the enterprising line item of groove to estimate.So record output (recording output) is 5.2mW, and reproducing power (reproduction power) is 0.3mW.

[embodiment 5 to 8]

The preparation of＜optical data recording medium 〉

(preparation of substrate)

The injection moulding substrate that preparation is become by polycarbonate resin, described substrate has the thickness of 0.6mm, the external diameter of 120mm and the internal diameter of 15mm, and the pre-groove of spiral (track pitch: 400nm; Groove width: 170nm; Groove depth: 100nm; Groove angle: 65 °; The amplitude of oscillation: 20nm).By using laser cutting (351nm) pressing mold that uses in the injection moulding is carried out mastering.

(formation of one-time write recording layer)

With every kind of compound in the tables 1 of 2 grams: (S-1), (S-4), (S-5) and (S-23) be added to 2,2,3 of 100ml, the 3-tetrafluoropropanol is with dissolving, thereby prepares the coating solution that contains dyestuff.Under the condition of 23 degrees centigrade and 50%RH, what rely on that spin-coating method will prepare contains the dye-coating solution coat on substrate, and wherein revolution changes in 300 to 400 rpm scopes.Then, it was stored 1 hour with 50%RH at 23 degrees centigrade, form one-time write recording layer (on groove, have the thickness of 120nm, and have the thickness of 170nm at platform).

After forming the one-time write recording layer, in the stove of cleaning, carry out annealing in process.Substrate is supported on the stacked vertically bar that separates with spacer, and carried out annealing in process 1 hour at 80 degrees centigrade.

(formation of reflection layer)

In Ar gas atmosphere, by using the trade name of making by Unaxis: Cube, rely on the DC sputter, forming film thickness on the one-time write recording layer is APC reflection layer (the Ag:98.1 quality % of 100nm; Pd:0.9 quality %; And Cu:1.0 quality %) as vacuum deposited layer.The film thickness of reflection layer is controlled by sputtering time.

(protectiveness substrate bonding)

By spin coating with uv curing resin (SD640; make by Dainippon Ink and Chemicals) be coated on the reflection layer; the protectiveness substrate that to be made by Merlon is not (except that forming pre-groove then; identical with above substrate) thereon bonding, and solidify by ultraviolet irradiation.The thickness of the adhesive layer of the uv curing resin in the optical data recording medium of preparation is 25 μ m.

(comparative example 5 to 8)

Except that use comparative compound (A) to (D) by above chemical formulation replace respectively compound (S-1), (S-4), (S-5) and (S-23), with just in time same mode preparation dish with embodiment 5 to 8.

Thus, prepare the optical data recording medium of embodiment 5 to 8 and comparative example 5 to 8.

The evaluation of＜optical data recording medium 〉

The evaluation of-C/N ratio (carrier-to-noise ratio):

Under condition, having the recording/copying checking machine (trade name: DDU1000 that 405-nm laser instrument and NA are 0.65 wave detector in the linear velocity of the clock frequency of 64.8MHz and 6.61m/s; Make by Pulstec Industrial) in, record and when duplicating 0.204-μ m signal (2T), measure the C/N of each optical data recording medium for preparing than (after record) by spectroanalysis instrument (TR4171 is made by Advantest Corporation).The results are shown in the table 3.In evaluation,, record is remained on the groove by using according to optical information recording method of the present invention.So record is output as 12mW, and reproducing power is 0.5mW.The results are shown in the table 3.The above C/N of 25dB shows that than (after record) reproducing signals intensity is fully big, and record character is favourable.

[table 3]

Result in the above table 3 shows, the reproducing signals intensity (reproduction signal intensity) with optical data recording medium (embodiment 1 to 8) of the recording layer that contains the dyestuff that has two or more individual dye parts that do not mutually combine by conjugated bonds in molecule is better than the reproducing signals intensity of the optical data recording medium that obtains in comparative example 1 to 8.In addition, optical data recording medium (I) to (IV) is to use compound (S-28), (S-29), (S-30) or (S-31) respectively, prepares in the mode identical with embodiment 5.In addition, be clear that these optical data recording mediums are also good aspect reproducing signals intensity.

The effect of＜optics storage property 〉

[preparation of glass substrate]

With the compound in the table 1 (S-1) and (S-5) and comparative compound (H-1) and (H-2) in every kind of compound join 2,2,3 of 1ml with the amount of 20mg, the 3-tetrafluoropropanol is with dissolving, thus preparation contains the coating solution of dyestuff.Under the condition of 23 degrees centigrade and 50%RH, what rely on that spin-coating method will prepare contains the dye-coating solution coat on glass substrate, and wherein revolution changes in 300 to 400rpm scopes.The compound (I-8) of compound (H-2) for describing among the JP-A 2001-52293, this compound is according to the preparation of the method among the embodiment wherein.

[evaluation of light fastness]

Then, under the condition of covering, with glass substrate room temperature storage 1 day.After this, the glass substrate that has been coated with dyestuff is arranged on the Merry-Go-Round type light resistance test machine (being made according to the client by EAGLEENGINEERING Inc.), and use with optical filter (H-A-50 in the distance of distance light source 8 cm, make by HOYA) xenon lamp (XL-500D-O 500W is made by USHIO DISCHARGE LAMPS) carry out light irradiation.Then by using UV-1600 (trade name: make) to measure trap by SHIMADZU.

Compound (S-1) and trap (S-5) and comparative compound (H-1) and trap (H-2) are compared.To be shown in over time in the following table 4 according to the trap of above mensuration.

[table 4]

	H-2	H-1	S-1	S-5
					After 0 hour	100％	100％	100％	100％
After 24 hours	81.20％	72.00％	93.10％	85.30％
					After 48 hours	67.60％	24.10％	87.20％	75.40％

Result in the table 4 discloses, compound (S-1) and (S-5) have frequently than compound (H-1) and (H-2) longer optics storage property.

With compound (H-2) as standard, when finishing in 48 hours, remaining dye composition has shown the comparison that shows as in the table 5, when compound (H-1) with compound (S-1) or (S-5) is compared, and discovery compound (S-1) or (S-5) be that photostability exceeds 3 times good dyestuff.This has proved serviceability of the present invention.

[table 5]

(H-1/H-2)	(H-2/H-2)	(S-1/H-2)	(S-5/H-2)
				0.356	1	1.29	1.12

More than all results show, by using the dyestuff in molecule, have two or more individual dye parts that do not mutually combine by conjugated bonds, can obtain helping writing down the optical data recording medium of character and storage property.Because have than the used Wavelength of Laser of CD-R and DVD-R more during short wavelength's laser in use, favourable like this effect can be obtained, therefore a kind of more highdensity information recording carrier and a kind of record of this information recording carrier and method of duplicating used can be provided.

According to aspects of the present invention, provide a kind of optical data recording medium and a kind of on optical data recording medium method for recording information, it is that 440nm or shorter laser beam carry out the high density recording of information and duplicate that described optical data recording medium has advantageously allowed by the irradiation wavelength, and light to store property good.

Whole announcements, patent application and the technical standard mentioned in this specification all are incorporated into this by reference, to as representing that particularly and individually the announcement that each is independent, patent application or technical standard are by reference and in conjunction with identical degree.

Claims (according to the modification of the 19th of treaty)

1. (correction) a kind of optical data recording medium, it can be the recording layer that 440nm or shorter laser beam come recorded information by the irradiation wavelength on the substrate or above substrate that described optical data recording medium is included in, described recording layer comprises the dyestuff that has two or more individual dye parts in the molecule, described two or more individual dye parts are to mutually combine to the mode the described dyestuff part except that forming conjugated bonds, and wherein said dyestuff partly is the oxonol dye part.

2. (correction) according to the described optical data recording medium of claim 1, and wherein said dyestuff has the structure by following formula (1) expression:

Formula (1)

Wherein in formula (1), Dye ¹¹, Dye ¹²And Dye ^2kRepresent the oxonol dye part separately; L ¹¹And L ^2kRepresent divalent linker separately, described divalent linker does not form pi-conjugated key with the dyestuff part that is attached on it; N is 0 to 10 integer; K is 0 to n integer; When n is integer more than 2, a plurality of group Dye ^2kCan be identical or different mutually; When n is integer more than 2, a plurality of group L ^2kCan be identical or different mutually; Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge.

3. (deletion)

4. according to the described optical data recording medium of claim 1, wherein said dyestuff is by following formula (2-1), (2-2), (2-3), (2-4) or (2-5) dyestuff of expression:

Formula (2-1)

Formula (2-2)

Formula (2-3)

Formula (2-4)

Formula (2-5)

Wherein at following formula (2-1), (2-2), (2-3), (2-4) or (2-5), R represents the substituting group on the methine carbon; M is 0 to 1 integer; N is 0 to 2m+1 integer; When n was integer more than 2, a plurality of R can be identical or different mutually, maybe can mutually combine to form ring; Za ⁵And Za ⁶Expression forms the atomic group of acid core separately; L ¹¹Represent divalent linker separately, described divalent linker does not form pi-conjugated key with the dyestuff part that is attached on it; Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge; Y represents-O-,-NR ¹-or-CR ²R ³-in any; R ¹To R ⁹Independent separately expression hydrogen atom or substituting group; Z represents to replace or unsubstituted alkylidene; And x is 1 or 2; G represents oxygen atom or sulphur atom.

5. according to the described optical data recording medium of claim 4, its Chinese style (2-1), (2-2), (2-3), (2-4) and (2-5) in m be 0.

6. according to the described optical data recording medium of claim 5, wherein said dyestuff is by following formula (5-1), (5-2), (5-3), (5-4) or (5-5) dyestuff of expression:

Formula (5-1)

Formula (5-2)

Formula (5-3)

Formula (5-4)

Formula (5-5)

Wherein at following formula (5-1), (5-2), (5-3), (5-4) with (5-5), R represents the substituting group on the methine carbon; Q represents to be used for the ion with electric charge; Y is used for and the number of the needed ion of electric charge; Y is-O-,-NR ¹-and-CR ²R ³-in any; Z represents to replace or unsubstituted alkylidene; X is 1 or 2; And R ¹To R ⁹Independent separately expression hydrogen atom or substituting group; And G represents oxygen atom or sulphur atom.

7. according to the described optical data recording medium of claim 1, described optical data recording medium also comprises the reflection layer that is made of metal except that described recording layer.

8. according to the described optical data recording medium of claim 1, described optical data recording medium also comprises protective layer except that described recording layer.

9. according to the described optical data recording medium of claim 1, wherein said substrate is the transparent disk substrate, described transparent disk substrate has be formed on it lip-deep, and to have track pitch be 50 to 600nm pre-groove, and described recording layer is formed on described substrate on the surface on pre-groove one side.

10. method for recording information, described method for recording information comprises that with wavelength be 440nm or shorter laser beam irradiation recorded information on optical data recording medium, described optical data recording medium has recording layer on the substrate or above substrate, described recording layer comprises the dyestuff that has two or more individual dye parts in the molecule, and described two or more individual dye parts are to mutually combine except that forming conjugated bonds to the mode the described dyestuff part.

Claims (10)

1. optical data recording medium, it can be the recording layer that 440nm or shorter laser beam come recorded information by the irradiation wavelength on the substrate or above substrate that described optical data recording medium is included in, described recording layer comprises the dyestuff that has two or more individual dye parts in the molecule, and described two or more individual dye parts are to mutually combine except that forming conjugated bonds to the mode the described dyestuff part.

2. according to the described optical data recording medium of claim 1, wherein said dyestuff has the structure by following formula (1) expression:

Formula (1)

Wherein in formula (1), Dye ¹¹, Dye ¹²And Dye ^2kRepresent the dyestuff part separately; L ¹¹And L ^2kRepresent divalent linker separately, described divalent linker does not form pi-conjugated key with the dyestuff part that is attached on it; N is 0 to 10 integer; K is 0 to n integer; When n is integer more than 2, a plurality of group Dye ^2kCan be identical or different mutually; When n is integer more than 2, a plurality of group L ^2kCan be identical or different mutually; Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge.

3. according to claim 1 or 2 described optical data recording mediums, wherein said dyestuff partly is the oxonol dye part.

4. according to the described optical data recording medium of claim 1, wherein said dyestuff is by following formula (2-1), (2-2), (2-3), (2-4) or (2-5) dyestuff of expression:

Formula (2-1)

Formula (2-2)

Formula (2-3)

Formula (2-4)

Formula (2-5)

Wherein at following formula (2-1), (2-2), (2-3), (2-4) or (2-5), R represents the substituting group on the methine carbon; M is 0 to 1 integer; N is 0 to 2m+1 integer; When n was integer more than 2, a plurality of R can be identical or different mutually, maybe can mutually combine to form ring; Za ⁵And Za ⁶Expression forms the atomic group of acid core separately; L ¹¹Represent divalent linker separately, described divalent linker does not form pi-conjugated key with the dyestuff part that is attached on it; Q represents to be used for the ion with electric charge; And y is used for and the number of the needed ion of electric charge; Y represents-O-,-NR ¹-or-CR ²R ³-in any; R ¹To R ⁹Independent separately expression hydrogen atom or substituting group; Z represents to replace or unsubstituted alkylidene; And x is 1 or 2; G represents oxygen atom or sulphur atom.

5. according to the described optical data recording medium of claim 4, its Chinese style (2-1), (2-2), (2-3), (2-4) and (2-5) in m be 0.

6. according to the described optical data recording medium of claim 5, wherein said dyestuff is by following formula (5-1), (5-2), (5-3), (5-4) or (5-5) dyestuff of expression:

Formula (5-1)

Formula (5-2)

Formula (5-3)

Formula (5-4)

Formula (5-5)

Wherein at following formula (5-1), (5-2), (5-3), (5-4) with (5-5), R represents the substituting group on the methine carbon; Q represents to be used for the ion with electric charge; Y is used for and the number of the needed ion of electric charge; Y is-O-,-NR ¹-and-CR ²R ³-in any; Z represents to replace or unsubstituted alkylidene; X is 1 or 2; And R ¹To R ⁹Independent separately expression hydrogen atom or substituting group; And G represents oxygen atom or sulphur atom.

7. according to the described optical data recording medium of claim 1, described optical data recording medium also comprises the reflection layer that is made of metal except that described recording layer.

8. according to the described optical data recording medium of claim 1, described optical data recording medium also comprises protective layer except that described recording layer.

9. according to the described optical data recording medium of claim 1, wherein said substrate is the transparent disk substrate, described transparent disk substrate has be formed on it lip-deep, and to have track pitch be 50 to 600nm pre-groove, and described recording layer is formed on described substrate on the surface on pre-groove one side.

10. method for recording information, described method for recording information comprises that with wavelength be 440nm or shorter laser beam irradiation recorded information on optical data recording medium, described optical data recording medium has recording layer on the substrate or above substrate, described recording layer comprises the dyestuff that has two or more individual dye parts in the molecule, and described two or more individual dye parts are to mutually combine except that forming conjugated bonds to the mode the described dyestuff part.