CN1691165A

CN1691165A - Optical recording materials and optical recording media

Info

Publication number: CN1691165A
Application number: CN 200510066166
Authority: CN
Inventors: 田辺顺志; 门田敦志; 新海正博
Original assignee: TDK Corp
Current assignee: TDK Corp
Priority date: 2004-04-21
Filing date: 2005-04-21
Publication date: 2005-11-02
Anticipated expiration: 2025-04-21
Also published as: CN100361217C; JP2005305838A

Abstract

This optical recording material is used for an optical recording medium, which can record information by being irradiated with light and includes a cation represented by general formula (1a), wherein R1, R2, R3, R4, R5 and R6 independently and respectively represent a 1-4C alkyl group or the like, R<SP>7</SP>represents a hydrogen atom or the like, Q1 and Q2 independently and respectively represent an atomic group comprising a benzen ring or the like provided that at least one among R1, R2, R3 and R4 represents a group, which is not a methyl group, and a chelate compound of an azo compound and a metal under the condition that the containing percentage of the chelate compound is 10-70 mol% on the total amount of the cation and the chelate compound.

Description

Optical recording material and optical recording media

Technical field

The present invention relates to utilize illumination to come the optical recording media of recorded information, and the optical recording material that is used for this optical recording media.

Background technology

At present, extensively the optical recording media of popularizing has CD-R (appending type CD), DVD-R optical recordings such as (appending type DVD), but for making recording density higher, this record, reproduction light wavelength become shorter and shorter.For example, the current of record of CD-R, playback wavelength are 780nm, and the wavelength decreases of CD-R of future generation and DVD-R is to 635nm～680nm.Pigment up to the present known have used with the corresponding optical recording media of this short-wavelength light, is called as the pigments such as cyanines pigment that formed by azo-compound and metal chelate (opening flat 9-323478 communique with reference to the spy) of " containing metal azo cyanines pigment " at cyanines pigment (opening flat 11-34499 communique with reference to the spy).

Summary of the invention

Optical recording media is except that above-mentioned shortening wavelength, and also requirement can be corresponding to higher writing speed.For reaching high-speed, preferably use the higher pigment of sensitivity.Along with increasing of pigment sensitivity, might increase reproducing signal beating on time orientation.Then in further high speed after this, the degree that existing pigment is difficult to guarantee sensitivity and all fully satisfy the demand in the aspect of beating.

In view of the foregoing, the object of the present invention is to provide and to reach high sensitivity and can not increase the optical recording media of beating thereupon and be used for the optical recording material of this medium.

For addressing the above problem, the invention provides a kind of optical recording material, this optical recording material can be used for coming the optical recording media of recorded information by illumination, this optical recording material contains the kation shown in the general formula (1a) and azo-compound and metal chelate, total amount with kation and chelate is a benchmark, the containing than being 10～70 moles of % of chelate.

The present invention relates to come the optical recording media of recorded information by illumination, this optical recording media contains the kation shown in the general formula (1a) and azo-compound and metal chelate, total amount with kation and chelate is a benchmark, and the content ratio of chelate is 10～70 moles of %.

In the formula, R ¹And R ²The alkyl of independent separately expression carbon number 1～4 maybe can have substituent benzyl, or is connected to each other the base that forms 3～6 yuan of rings; R ³And R ⁴The alkyl of independent separately expression carbon number 1～4 maybe can have substituent benzyl, or is connected to each other the base that forms 3～6 yuan of rings; R ⁵And R ⁶The alkyl or aryl of independent separately expression carbon number 1～4; R ⁷Represent hydrogen atom, halogen atom, cyano group, can have the alkyl of substituent carbon number 1～4, maybe can have substituent aryl; Q ¹And Q ²Independent separately expression constitutes can have the former subgroup that substituent phenyl ring maybe can have substituent naphthalene nucleus; But R ¹, R ², R ³, R ⁴In at least 1 be not methyl.

The optical recording layer that possesses optical recording material of the present invention and optical recording media of the present invention, be that kation with above-mentioned ad hoc structure is as pigment, again with above-mentioned special ratios and the combination of above-mentioned chelate, like this, just form the high speed that to realize writing speed, but also has excellent sensitivity, the product of good stability.

Optical recording material of the present invention, the salt that forms by kation and balance anion thereof mix with chelate and obtain.In addition, the optical recording layer that optical recording media of the present invention possessed contain preferably that salt that kation and balance anion thereof form mixes with chelate and must potpourri.

This optical recording material and optical recording media are to get with simple mixing of two or more materials, so can make more efficiently.Mix like this and optical recording material and optical recording media contain above-mentioned cationic balance anion at least, and, also contain the balance cation of chelate sometimes.In the past, these balance anions and balance cation might be as the impurity of infringement optical recording material quality stability.But the inventor etc. have found in combinations thereof the technical scheme that is difficult to take place this defective in the optical recording material of the present invention of specific pigment and the optical recording media.

The invention still further relates to the optical recording material that is used for optical recording media that can be by the illumination recorded information, this optical recording material contains the compound shown in kation, azo-compound and metal chelate shown in the general formula (1b) and the general formula (2).

The present invention relates to have the optical recording media of recording layer, this recording layer contains compound shown in kation, azo-compound and the metal chelate shown in the general formula (1b), the general formula (2).

A ⁿ⁺-(X) _3+n?????(2)

In the formula, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶The alkyl that independent separately expression can have substituent carbon number 1～4 maybe can have substituent aryl; R ¹⁷Expression hydrogen atom, halogen atom, cyano group, the alkyl that can have a substituent carbon number 1～4 maybe can have substituent aryl; Q ¹¹And Q ¹²Independent separately expression constitutes the former subgroup that can have substituent aromatic rings; A represents nitrogen-atoms or phosphorus atoms; The alkyl that X represents hydrogen atom, can have a substituent carbon number 1～4 maybe can have substituent aryl; N is 0 or 1; And R ¹¹And R ¹²And R ¹³And R ¹⁴Can be to be connected to each other the base that forms ring texture, R ¹¹, R ¹², R ¹³And R ¹⁴In at least 1 be not methyl, with a plurality of X in a part can be identical also can be different.With at least 1 among a plurality of X in a part is that the alkyl that can have substituent carbon number 1～4 maybe can have substituent aryl.

The optical recording layer that possesses optical recording material of the present invention and optical recording media of the present invention is by making it to contain the pigment that kation shown in the formula (1b), azo-compound and metal chelate form, and with the combination of specific compound shown in the formula (2), and possess sufficient sensitivity, and fully suppress to beat.The present invention can reach the high writing speed that particularly is difficult to practicality for prior art also can fully satisfy sensitivity and the level of the requirement of beating.

In the prior art, if the recording layer of optical recording media contains the compound shown in the formula (2), just might cause sensitivity descend, in abutting connection with the problem such as rotten of the material of recording layer, so rather preferably do not contain these compounds in the recording layer.But discoveries such as the inventor contain the sensitivity that the compound shown in the formula (2) just can significantly improve pigment, and can fully suppress to beat in the system of the above-mentioned pigment that contains certain cationic.Although it is still indeterminate to show the mechanism of this effect, inventor's deduction, the compound shown in the formula (2) has consequently improved sensitivity by thermal decomposition of the above-mentioned pigment of some effect promotion under the situation of not following the significantly increase of beating.

The total number of carbon atoms of compound shown in the formula (2) is preferably below 20.In other words, add up to preferably below 20 with the carbon number that each X had in a part.In case the total number of carbon atoms surpasses 20, when cooperating these compounds, to compare when following with the total number of carbon atoms 20 with same mol ratio, the pigment concentration reduction in optical recording material or the recording layer is difficult to reach sufficient sensitivity.

In kation shown in the formula (1b), R ¹¹And R ¹²Expression separately independently the alkyl of carbon number 1～4 maybe can have the substituting group benzyl, or be connected to each other the base that forms 3～6 yuan of rings; R ¹³And R ¹⁴Expression separately independently the alkyl of carbon number 1～4 maybe can have substituent benzyl, or be connected to each other the base that forms 3～6 yuan of rings; R ¹⁵And R ¹⁶It is the alkyl or aryl of carbon number 1～4 independently separately; Q ¹¹And Q ¹²Expression independently can have the former subgroup that substituent phenyl ring maybe can have substituent naphthalene nucleus separately.The own sensitivity of kation with this ad hoc structure is just very high, by making up with compound shown in the above-mentioned formula (2), and can its sensitivity of compound raising.

The optical recording layer that possesses optical recording material of the present invention and optical recording media is except that mentioned component, also because of containing negative ion PF ₆ ^-Or SbF ₆ ^-, be easy to make the homogenizing rate to reach appropriate value.And in optical recording material and optical recording layer, at least a portion forms the salt as cationic balance anion shown in formula (1a) or the formula (1b) in these negative ion.

Description of drawings

Fig. 1 is a certain embodiment part sectioned view of the optical recording of optical recording media of the present invention.

Fig. 2 is a certain embodiment part sectioned view of the optical recording of optical recording media of the present invention.

Embodiment

Specify preferred implementation of the present invention below.But the present invention is not subject to following embodiment.

Optical recording material

Optical recording material of the present invention contains the kation shown in kation shown in the above-mentioned general formula (1a) (also being called the lush pigment kation of cyclonite 1a down) or the above-mentioned general formula (1b) (also being called cyclonite cyanines pigment kation 1b down), azo-compound and metal chelate.And the kation of formula (1a) and formula (1b) expression is the kation that belongs in the pigment that is called as cyclonite cyanines pigment.These cyclonite cyanines pigment kations and chelate also can play a role as the optical recording pigment separately separately, and in the present invention, are that it is used in combination.

In cyclonite cyanines pigment kation 1b, R ¹¹And R ¹²Be preferably separately independently that the alkyl of carbon number 1～4 maybe can have substituent benzyl, or be connected to each other the base that forms 3～6 yuan of rings; R ¹³And R ¹⁴Be preferably separately independently that the alkyl of carbon number 1～4 maybe can have substituent benzyl, or be connected to each other the base that forms 3～6 yuan of rings; R ¹⁵And R ¹⁶Be preferably separately the independently alkyl or aryl of carbon number 1～4; Q ¹¹And Q ¹²Be preferably and independently can have the former subgroup that substituent phenyl ring maybe can have substituent naphthalene nucleus separately.In other words, cyclonite cyanines pigment kation 1b is preferably and is and the same material of cyclonite cyanines pigment kation 1a.

R in the formula (1a) ¹, R ², R ³, R ⁴At least 1 be to have substituent benzyl, same, the R in the formula (1b) ¹¹, R ¹², R ¹³, R ¹⁴At least 1 be to have substituent benzyl.Because these substituting groups are to have substituent benzyl, suppress and sensitivity raising effect so can reach more significant beating.

R ⁷And R ¹⁷Be preferably hydrogen atom, halogen atom, cyano group, carbon number 1～4 alkyl, can have substituent phenyl, can have substituent benzyl.Wherein, be preferably R especially ⁷And R ¹⁷It is hydrogen atom.

The preferred concrete example of cyclonite cyanines pigment kation 1a and cyclonite cyanines pigment kation 1b can be enumerated material shown in the following table 1～table 6, and these materials can use separately or a plurality of combinations of substances is used.These cyclonite cyanines pigment kations can be synthesized into known method.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

During optical recording material contains usually and the balance anion of cyclonite cyanines pigment cationic charge, these balance anions can be enumerated for example ClO ₄ ^-, I ^-, BF ₄ ^-, PF ₆ ^-, SbF ₆ ^-Deng 1 valency negative ion.At chelate is under the anionic situation, also can form the salt of cyclonite cyanines pigment kation and chelate used as the cationic balance anion of cyclonite cyanines pigment.Wherein, optical recording material preferably contains PF at least ₆ ^-And SbF ₆ ^-At least one of them, be easy to reach best homogenizing rate this moment.

Homogenizing rate of the present invention is the value with formula " homogenizing rate C=(groove recording layer thickness DG (μ m)-convex region recording layer thickness DI (μ m))/groove depth A (μ m) " expression.By the optimization of homogenizing rate, reflectivity and degree of modulation reach well balanced, and reach good bouncing characteristic.The homogenizing rate C of DVD+R and DVD-R is preferably 0.1～0.4, and more preferably 0.2～0.3.The homogenizing rate is lower than at 0.1 o'clock, might not reach sufficient reflectivity and degree of modulation; And when the homogenizing rate is higher than 0.4, be easy to cause the degradation under increase, the reflectivity of beating.Because of containing negative ion PF in the optical recording material ₆ ^-And SbF ₆ ^-So, improved the flowability of the coating fluid that is used to form optical recording material.Improved thus by the coverage rate of convex region, can reduce the thickness difference of DG and DI to the recording layer of slot part.

Chelate is to have aromatic rings to replace the azo-compound of azo group and the metallo-chelate that metal-complexing forms.Being also referred to as azo is that pigment, azo are cyanines pigment etc.The azo-compound that constitutes these chelates can be enumerated the compound shown in for example following general formula (20).

Ar ¹-N＝N-Ar ²???????????????(20)

In the formula (20), Ar ¹And Ar ²Be the base that constitutes by identical or different aromatic rings, be wherein have at least one contain can with the substituent aromatic rings of metallic atom coordination, or contain can with the nitrogenous aromatic heterocycle of the nitrogen-atoms of metallic atom coordination.Can with the substituting group of metal-complexing and can be preferably placed at the nitrogen-atoms of metal-complexing with azo group can with the position (during phenyl ring, being the ortho position) of metal-complexing.

Constitute Ar ¹And Ar ²Aromatic rings can be monocycle, also can be condensed ring, many rings such as ring aggregate etc.This class aromatic rings can be enumerated phenyl ring, naphthalene nucleus, pyridine ring, thiazole ring, benzothiazole Huan, oxazole ring, benzoxazole ring, quinoline ring, imidazole ring, pyrazine ring, pyrrole ring etc.Wherein be preferably phenyl ring, pyridine ring, quinoline ring or thiazole ring especially.

Can enumerate with the substituting group of metallic atom coordination and contain the base that activates hydrogen.Contain the substituting group that activates hydrogen can enumerate-OH ,-SH ,-NH ₂,-COOH ,-CONH ₂,-SO ₂NH ₂,-SO ₃H ,-NHSO ₂CF ₃Deng, wherein be preferably especially-OH.

In addition, Ar ¹And Ar ²Except that above-mentioned, also can have other substituting group.Ar ¹And Ar ²The substituting group that is had can be identical also can be different.Not not simultaneously, Ar ¹Can have and be selected from least a in nitro, halogen atom (for example chlorine atom, bromine atoms etc.), carboxyl, sulfonyl, sulfamoyl, the alkyl (be preferably carbon number 1～4, be preferably methyl especially), Ar ²Can have and be selected from amino and (be preferably the dialkyl amido of the total number of carbon atoms 2～8; for example dimethylamino, diethylamino, methyl ethylamino, methyl-prop amino, dibutylamino, hydroxyethyl methylamino), alkoxy (is preferably carbon number 1～4; methoxyl for example), alkyl (is preferably carbon number 1～4; methyl more preferably), at least a in aryl (being preferably monocycle, for example phenyl, chlorphenyl etc.), carboxyl, the sulfonyl.And work as Ar ¹When being phenyl ring, be preferably the substituting group position or the contraposition between azo group that are had, more preferably in a position.

The metal (central metal) that constitutes chelate is preferably transition metal such as Co, Mn, Cr, Ti, V, Ni, Cu, Zn, Mo, W, Ru, Fe, Pd, Pt, Al.Or have a VO ²⁺, VO ³⁺, MoO ²⁺, MoO ³⁺, WO ³⁺Deng each acid ion of V, Mo, W, wherein be preferably VO especially ²⁺, VO ³⁺, Co, Ni or Cu.

Chelate usually with above-mentioned azo-compound as forming coordination bond between 2 teeth or 3 tooth ligands and the metal.And when azo-compound contained the substituting group of band activation hydrogen, usually, this activation hydrogen broke away from, and formed 2 teeth or 3 tooth ligands.

Chelate integral body sometimes is neutral, is negative ion or kation sometimes.When being negative ion, chelate forms salt usually with its balance cation.Its balance cation can be enumerated Na ⁺, Li ⁺, K ⁺Deng metal cation, ammonium, tetra-allkylammonium etc.Also can use the product that forms salt with above-mentioned cyclonite cyanines pigment kation as balance cation.

The concrete example of chelate can be enumerated the A1～A49 shown in table 7～table 12, and they can use separately, also can a plurality ofly be used in combination.In addition, in chelate shown in table 7～table 12, corresponding to 1 central metal element, coordination has 2 azo-compounds.And azo-compound and metallic element have two respectively in the table, then by 1: 1 mol ratio coordination; Represent then azo-compound being coordinated on the vanadium acetylacetonate of central metal with V=O.These chelates can be synthesized into (reference example is as, Gu Chuan, Anal.Chim.Acta., 140, p.289,1982 etc.) according to known method.

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

The ratio that contains of chelate is a benchmark with the total amount of cyclonite cyanines pigment kation and chelate, is 10～70 moles of %, and light stability is significantly improved.The effect that this light stability improves, any all can reach in using cyclonite cyanines pigment 1a or 1b, and when particularly using cyclonite cyanines pigment kation 1a, containing of chelate is proportional in above-mentioned scope the time, and the light stability effect is best.Containing of chelate is proportional preferably at 15～50 moles of %, more preferably at 20～30 moles of %.This mol ratio is during less than 10 moles of %, and the light stability inadequate trend that becomes in case surpass 70 moles of %, especially in the optical recording media of high-speed record, has the trend of beating and increasing.

The optical recording material that contains the cyclonite cyanines pigment kation of aforementioned proportion and chelate can obtain by mixing the method that chelate obtains potpourri in the salt that is synthesized at cyclonite cyanines pigment kation and balance anion thereof.When chelate when being anionic, also can obtain optical recording material by forming cyclonite cyanines pigment kation and the anionic salt of chelate (one-piece type salt).Perhaps also can make the coexistence of said mixture and one-piece type salt.Especially preferably modulate said mixture and obtain optical recording material, simple and efficient is high because of it, and pigment is selected the degree of freedom height.

Optical recording material preferably contains the compound shown at least a kind of formula (2) (also be called down and add compound).These the total number of carbon atoms that add compound are preferably below 20.When the total number of carbon atoms surpasses 20, when these add compounds with same mixed in molar ratio, to compare when following 20 with the total number of carbon atoms, the pigment concentration reduction because of optical recording material also has the trend that does not reach sufficient sensitivity.

And more preferably these to add in compounds with 3 or 4 among a plurality of X in a part be the alkyl of carbon number 1～4 because sensitivity at this moment etc. are good.

The ratio that contains that adds compound is a benchmark with the total amount of cyclonite cyanines pigment kation and this additive, is 0.5～50 mole of %.When this contains ratio and is lower than 0.5 mole of %, the sensitivity downward trend is arranged, when surpassing 50 moles of %, have impel reflection horizon that silver for example forms etc. on optical recording media with the rotten trend of other material of recording layer adjacency.

Adding compound is the phosphine compound shown in the ammonium compounds shown in the amines shown in for example following formula (3), following formula (4) or the formula (5), the following formula (6).These compounds can take the circumstances into consideration to use separately or a plurality of mixing is used.In following formula (3), (4), (5) and (6), X can have substituent alkyl maybe can have substituent aryl.

The amines of formula (3) expression can directly mix with other composition that constitutes optical recording material.And the phosphine compound of the ammonium compounds of formula (4) or (5) expression, formula (6) expression mixes with other composition that constitutes optical recording material with the state of the salt of its balance anion with formation usually.This balance anion can be enumerated the negative ion that is for example formed by above-mentioned azo-compound and metal chelate.Owing to contain this chelate in the optical recording material, can improve light stability (photostability) under the significantly reduced situation of sensitivity not following.

Add compound and specifically can enumerate the ammonium compounds of No.501～518 shown in amines, the No.401 shown in the table 14～406 and the table 15 of the No.301 shown in the table 13～306, the phosphine compound of the No.601 shown in the table 16～612.Wherein, add compound and preferably contain shown in No.301～305,401～403,501～503 that are selected from table 13～table 16,601～602 the chemical formula at least a in the compound.

Table 13

??No.	????????????????????X
??No.	????????????????????X			??301	??-CH ₃	??-CH ₃	??-CH ₃
??302	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??301	??-CH ₃	??-CH ₃	??-CH ₃
??302	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??303	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃
??304	??-(CH ₂) ₃CH ₃	??-(CH ₂) ₃CH ₃	??-(CH ₂) ₃CH ₃	??303	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃
??304	??-(CH ₂) ₃CH ₃	??-(CH ₂) ₃CH ₃	??-(CH ₂) ₃CH ₃	??305	??-CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃
??306	??-CH ₃	??-CH ₂CH ₃	??-CH ₃	??305	??-CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃

Table 14

??No.	???????????????????X
??No.	???????????????????X			??401	??-CH ₃	??-CH ₃	??-CH ₃
??402	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??401	??-CH ₃	??-CH ₃	??-CH ₃
??402	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??403	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃
??404	??-(CH ₂) ₃CH ₃	??-(CH ₂) ₃CH ₃	??-(CH ₂) ₃CH ₃	??403	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃
??404	??-(CH ₂) ₃CH ₃	??-(CH ₂) ₃CH ₃	??-(CH ₂) ₃CH ₃	??405	??-CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃
??406	??-CH ₃	??-CH ₂CH ₃	??-CH ₃	??405	??-CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃

Table 15

Table 16

??No.	???????????????????????????????????????X
??No.	???????????????????????????????????????X				??601	??-CH ₃	??-CH ₃	??-CH ₃	??-CH ₃
??602	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??601	??-CH ₃	??-CH ₃	??-CH ₃	??-CH ₃
??602	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??603	??-CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃
??604	??-CH ₃	??-(CH ₂) ₂CH ₃	??-CH ₃	??-CH ₃	??603	??-CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃	??-CH ₂CH ₃
??604	??-CH ₃	??-(CH ₂) ₂CH ₃	??-CH ₃	??-CH ₃	??605	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃
??606	??-CH ₃	??-CH ₃	??-(CH ₂) ₄CH ₃	??-CH ₃	??605	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂CH ₃
??606	??-CH ₃	??-CH ₃	??-(CH ₂) ₄CH ₃	??-CH ₃	??607	??-CH ₃	??-(CH ₂) ₂OH	??-(CH ₂) ₂OH	??-(CH ₂) ₂OH
??608	??-CH ₃	??-(CH ₂) ₂OH	??-CH ₃	??-CH ₃	??607	??-CH ₃	??-(CH ₂) ₂OH	??-(CH ₂) ₂OH	??-(CH ₂) ₂OH
??608	??-CH ₃	??-(CH ₂) ₂OH	??-CH ₃	??-CH ₃	??609	??-CH ₃	??-(CH ₂) ₄OH	??-(CH ₂) ₂CH ₃	??-CH ₃
??61O	??-CH ₂CH ₃	??-(CH ₂) ₄OH	??-CH ₂CH ₃	??-CH ₂CH ₃	??609	??-CH ₃	??-(CH ₂) ₄OH	??-(CH ₂) ₂CH ₃	??-CH ₃
??61O	??-CH ₂CH ₃	??-(CH ₂) ₄OH	??-CH ₂CH ₃	??-CH ₂CH ₃	??611	??-CH ₂CH ₃	??-(CH ₂) ₂OH	??-CH ₂CH ₃	??-CH ₂CH ₃
??612	??-(CH ₂) ₂CH ₃	??-(CH ₂) ₂OH	??-(CH ₂) ₂OH	??-(CH ₂) ₂OH	??611	??-CH ₂CH ₃	??-(CH ₂) ₂OH	??-CH ₂CH ₃	??-CH ₂CH ₃

For forming following optical recording media recording layer of the present invention, can use above-mentioned optical recording material as one sees fit.

Optical recording media

Fig. 1 is the part sectioned view of a certain preferred implementation of the optical recording of optical recording media of the present invention.Optical recording 1 shown in Figure 1 has order driving fit according to recording layer 3, reflection horizon 4, protective seam 5, adhesive phase 7, substrate 6 and is located at laminated structure on the substrate 2.Optical recording 1 is to append the type optical recording, and the short-wavelength light of available 630～685nm is realized record and reproduced.

Substrate

2 and 6 is respectively about diameter 64～200mm, and the pan of thickness 0.6mm carries out the record and the reproduction of the rear side (downside the figure) from substrate 2.For this reason, preferred substrate 2 at least is actually transparent concerning recording light and playback light, and particularly, the transmissivity of 2 pairs of recording light of preferable substrate and playback light is more than 88%.The material of this substrate 2 preferably satisfies the resin or the glass of the above-mentioned condition relevant with transmissivity, wherein, is preferably thermoplastic resins such as polycarbonate resin, acryl resin, amorphous polyolefin, TPX, polystyrene resin especially.In addition, the material of substrate 6 does not have special restriction, for example, can use the material the same with substrate 2.

In addition, form as the recess of following the tracks of with groove 23 on the recording layer 3 formation faces of substrate 2.Groove 23 is preferably the spiral fashion succeeding vat, is preferably its groove depth 80～250nm, groove width 200～500nm, slot pitch 600～1000nm.The groove that forms this spline structure can obtain good tracking signal under the situation that does not reduce the groove reflection levels.Can form groove 23 by with shaping substrates such as above-mentioned resin injection moulding 2 time, also can be by after making substrate 2, be formed with the resin bed of groove 23 with 2P method etc., as the composite base plate of substrate 2 and this resin bed.

Recording layer 3 uses the optical recording material of the invention described above to form.The mixed liquor that the optical recording material of the invention described above is dissolved in or is distributed in the solvent is coated on the substrate 2, just can wait formation recording layer 3 by removing to desolvate from film.The solvent of mixed liquor can be enumerated pure series solvent (comprising alkoxyl alcohol systems such as keto-alcohol system, ethylene glycol monoalkyl ether system), aliphatic hydrocarbon series solvent, ketone series solvent, ester series solvent, ether series solvent, aromatic series series solvent, halogenated alkane series solvent etc.Wherein, be preferably pure series solvent and aliphatic hydrocarbon series solvent.

The preferred alkoxyl alcohol of alcohol series solvent system, keto-alcohol system etc.The carbon number of preferred its alkoxy part of alkoxyl alcohol series solvent is 1～4, and the carbon number of alcohol moiety is preferably 1～5, more preferably 2～5, and preferred the total number of carbon atoms is 3～7.Specifically can adopt glycol monoethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (also claiming ethyl cellosolve, ethoxy ethanol), butyl cellosolve, 2-isopropoxy-ethylene glycol monoalkyl ethers such as 1-ethanol system (cellosolve) or 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-butanols, 3-methoxyl-1-butanols, 4-methoxyl-1-butanols, 1-ethoxy-2-propyl alcohol etc.Keto-alcohol system for example can enumerate acetol etc.Also can use 2,2,3, fluorinated alohols such as 3-tetrafluoropropanol.

The aliphatic hydrocarbon series solvent is preferably normal hexane, cyclohexane, methylcyclohexane, ethyl cyclohexane, cyclooctane, dimethyl cyclohexane, normal octane, isopropyl cyclohexane, tert-butyl group cyclohexane etc., wherein is preferably ethyl cyclohexane, dimethyl cyclohexane.

And the ketone series solvent can be enumerated cyclohexanone etc.

Alkoxyl alcohol series solvent such as preferred especially ethylene glycol monoalkyl ether system among the present invention, wherein preferred ethylene glycol monomethyl ether, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-butanols.Solvent can be used alone, and also can mix use more than 2 kinds.For example, preferably use the mixed solvent of ethylene glycol monomethyl ether and 1-methoxyl-2-propyl alcohol.

In addition, mixed liquor also can suitably add cementing agent, spreading agent, stabilizing agent etc. except that mentioned component.

The coating method of mixed liquor can be enumerated spin-coating method, gravure coating method, spraying process, dip coating etc., wherein preferred spin-coating method.

So the thickness of the recording layer 3 that forms is preferably 50～200nm.Particularly when 70～150nm, because of degree of modulation and reflectivity have fine balance, institute thinks more preferably.Outside this scope, reflectivity reduces, and the trend that is difficult to reproduce is arranged.And when the thickness of the recording layer 3 of the part of adjacent channels 23 when 200nm is above, the balance of degree of modulation and reflectivity has the trend of deterioration.

Recording layer 3 with respect to the attenuation coefficient (the imaginary part k of complex index of refraction) of recording light and playback light preferably 0～0.20.Attenuation coefficient surpasses 0.20, might not reach sufficient reflectivity.The refractive index of recording layer 3 (the real part n of complex index of refraction) is preferably more than 1.8.Refractive index is lower than at 1.8 o'clock, and the degree of modulation of signal has the trend that diminishes.The upper limit of refractive index does not have particular restriction, considers the situation that organic pigment is synthetic, is generally 2.6 degree.

The attenuation coefficient of recording layer 3 and refractive index can be tried to achieve according to following step.At first, the recording layer about 40～100nm is set on predetermined transparency carrier, makes testing sample, measure then, try to achieve attenuation coefficient and refractive index by the reflectivity of this testing sample substrate or the reflectivity that reflects by recording layer.At this moment, record reflectivity by direct reflection (about 5 °), also can record the sample transmissivity with record, playback wavelength.By these measured values, according to for example upright altogether pandect " optics ", the method for black great three, the 168～178 pages of records of stone is calculated attenuation coefficient and refractive index then.

On recording layer 3, driving fit is provided with reflection horizon 4 on the recording layer 3.Reflection horizon 4 can be made by using high-reflectivity metal or alloy to carry out evaporation, sputter etc.Metal or alloy can be enumerated gold (Au), copper (Cu), aluminium (Al), silver (Ag), AgCu etc.Reflection horizon 4 thickness of Xing Chenging are 10～300nm like this.

On reflection horizon 4, driving fit is provided with protective seam 5 on the reflection horizon 4.Protective seam 5 both can be that stratiform also can be lamellar.Protective seam 5 can be coated on the reflection horizon 4 by the coating fluid that will for example contain materials such as ultraviolet curable resin, again dry coating and getting as required.Can adopt spin-coating method, intaglio plate rubbing method, spraying process, dip coating etc. as one sees fit during coating.The thickness of the protective seam 5 of Xing Chenging is preferably 0.5～100 μ m like this.

In addition, on protective seam 5, be provided with the substrate 6 between protective seam 5 and adhesive phase 7.Substrate 6 can adopt material and the thickness same with substrate 2.Adhesive phase 7 can utilize with same material and the method for aftermentioned adhesive phase 50 and make.

When on optical recording 1, implementing record or tracking, be the pulse type irradiation from substrate 2 back sides and have the recording light of specific wavelength, the light reflectivity of irradiation portion is changed with above-mentioned composition.According to being provided with the optical recording 1 that contains as the recording layer 3 of the cyclonite cyanines pigment kation of pigment and chelate, but the long record of radiothermy, playback light be with record, the reproduction of high speed rotating implementation information, and record-playback characteristic (sensitivity and beat) is issued to well balanced state in high level.

In addition, in the above-described embodiment, the optical recording with 1 layer of recording layer 3 has been described, but also a plurality of recording layers can be set that each layer contains different pigments.Can realize recording of information, reproduction by many identical or different records of wavelength, playback light thus.At this moment, also can will be located at respectively on the light entrance face and opposite flank of recording layer with respect to the record of each wavelength, the semitransparent reflecting film that playback light is translucent.

The optical recording 1 that is obtained by said method can use two optical recordings 1 to fit mutually, or 1 optical recording 1 and different with 1 layer of structure of optical recording another optical recording are fitted, and makes the product of light entrance face (substrate 2 sides) for the outside etc.

Fig. 2 is the fragmentary cross-sectional view of other preferred implementation of the optical recording of above-mentioned fit-state.Optical recording 10 as shown in Figure 2 has the structure by the sequential laminating of substrate 12, recording layer 13, reflection horizon 14, protective seam 15, adhesive phase 50, protective seam 25, reflection horizon 24, recording layer 23 and substrate 22.That is, optical recording 10 is that two are fitted with the optical recording of spline structure with optical recording 1 shown in Figure 1, makes the structure that clips adhesive phase 50 between their each protective seam and be subtend.This optical recording 10 is the type that the appends digitized video dishes corresponding to the DVD specification, realizes record, reproduces with the short-wavelength light of wavelength 650～670nm.

Adhesive phase 50 uses bonding agents such as heat-fusible adhesive, ultraviolet-curing adhesive, heat-curing type adhesive, adhesion type bonding agent, by various correlation methods, and for example formation such as rolling method, silk screen print method, spin-coating method.Under the situation of DVD-R, consider the balance of operability, throughput rate, dish characteristic etc., preferably use ultraviolet-curing adhesive, form adhesive phase 50 with silk screen print method or spin-coating method, the thickness of adhesive phase 50 is preferably about 10～200 μ m.

Substrate 12 and 22, recording layer 13 and 23, reflection horizon 14 and 24, and protective seam 15 and 25 be to use with same material, the method for optical recording shown in Figure 1 to make.Substrate 12 and 22 thickness are respectively about 0.6mm.On the recording layer 23 formation faces of the recording layer 13 formation faces of substrate 12 and substrate 22, form groove 123 and 223 respectively.This groove 123 and 223 groove depth are 60～200nm, wide 200～500nm, slot pitch 60～1000nm.And the thickness of recording layer 13 and 23 preferably is respectively 50～300nm, and the complex index of refraction that is preferably with respect to 650nm light is n=1.8～2.6, k=0.00～0.10.

Embodiment

Enumerate embodiment below and Comparative Examples is described more specifically the present invention, but the present invention is not subject to following embodiment.

Embodiment 1

On the polycarbonate resin substrate of the pre-groove that the last on the one hand formation degree of depth is 0.16 μ m, wide 0.30 μ m, slot pitch 0.74 μ m, the cyclonite cyanines pigment and the chelate that will form with cyclonite cyanines pigment kation and its balance anion, the optical recording material that gets with combination and ratio hybrid modulation shown in the table 17, making its content is to be dissolved in 2 under the ratio of 1.0 weight %, 2,3, form mixed liquor in the 3-tetrafluoropropanol, be coated on the polycarbonate resin substrate the dry recording layer (thickness 130nm) that forms.Then, on this recording layer, form Ag reflection horizon (thickness 85nm), on the Ag reflection horizon, form the protective clear layer (thickness 5 μ m) that the ultraviolet hardening acryl resin forms again, obtain the laminated structure body with sputtering method.2 such laminated structure body and function bonding agents are fitted, it is inboard making their protective seams separately again, makes to have and the optical recording of optical recording 10 shown in Figure 2 with spline structure.With PF ₆ ^-For the cationic balance anion of cyclonite cyanines pigment, with Na ⁺Balance cation for chelate.

On the gained optical recording, with linear speed 3.5m/s (being equivalent to wait doubly speed) or 28.0m/s (being equivalent to 8 times of speed) tracer signal, be that the laser of 650nm is measured jitter values after the reproduction with linear speed 3.5m/s with wavelength then with the laser of wavelength 655nm.Lens openings NA is 0.6.Use the xenon lamp (the fast light machine of (strain) Shimadzu Seisakusho Ltd. system xenon lamp) of 80,000 Luxs,, to estimate its light stability again to postradiation optical recording mensuration jitter values also same as above to gained CD irradiation 40 hours (light exposure).Evaluation result is shown in table 17.

Embodiment 2～22 and comparative example 1～7

Optical recording material is except that the material that uses each combination shown in the table 17 and ratio to mix, with embodiment 1 the same making and the evaluation of carrying out optical recording.In addition, the No. that is used for the cyclonite cyanines pigment kation of optical recording material and chelate is respectively the material of No. and corresponding chemical structural formula thereof shown in table 1～table 6 and table 7～table 12.With PF ₆ ^-For the cationic balance anion of cyclonite cyanines pigment, with Na ⁺Balance cation for chelate.Have in the table 18 " ^*1 " or " ^*2 " salt (one-piece type salt) that example is expressed as follows described use cyclonite cyanines pigment kation and chelate is modulated into optical recording material.In addition, in comparative example 5,6,7, what use is that cyclonite cyanines pigment kation is the R in the formula (1a) ¹, R ², R ³, R ⁴All be the comparative compound A and the B that use following formula (7a) respectively or (7b) represent of methyl.Evaluation result comprehensively is shown in table 17 and the table 18.

In embodiment 19～22 and comparative example 6,7, with salt (mol ratio 1: 1) the light modulated recording materials of cyclonite cyanines pigment kation and the formation of chelate negative ion.For example, in embodiment 20, with 50 moles of % of salt (being that A3 is 25 moles of %), cyclonite cyanines pigment kation T26 and the PF of cyclonite cyanines pigment kation T26 and chelate A3 ₆ ^-The ratio of 50 moles of % of salt mix (adding up to 100 moles of %) light modulated recording materials, make optical recording and evaluation.

Table 17

	Cyclonite cyanines pigment	Chelate		[%] beats
				[%] beats				Linear velocity 3.5m/s		Linear velocity 28.0m/s
				Kation (No.)	Azo-compound (No.)	Contain proportional (mole %)	Before light exposes	Linear velocity 3.5m/s		Linear velocity 28.0m/s		Light exposes back (light stability)	After light exposes	Light exposes back (light stability)
	Embodiment 1	??T1	??A1	Kation (No.)	Azo-compound (No.)	Contain proportional (mole %)	Before light exposes	??40	??7.1	??7.8	??7.2	Light exposes back (light stability)	After light exposes	Light exposes back (light stability)	??7.5
Embodiment 2	Embodiment 1	??T1	??A1	??T2	??A14	??20	??6.5	??40	??7.1	??7.8	??7.2	??7.1	??6.9	??7.8	??7.5
Embodiment 2	Embodiment 3	??T5	??A18	??T2	??A14	??20	??6.5	??50	??7.2	??7.4	??7.6	??7.1	??6.9	??7.8	??8.0
Embodiment 4	Embodiment 3	??T5	??A18	??T7	??A13	??70	??7.9	??50	??7.2	??7.4	??7.6	??7.9	??7.6	??8.1	??8.0
Embodiment 4	Embodiment 5	??T9	??A32	??T7	??A13	??70	??7.9	??40	??7.2	??7.9	??7.9	??7.9	??7.6	??8.1	??8.0
Embodiment 6	Embodiment 5	??T9	??A32	??T11	??A35	??50	??7.1	??40	??7.2	??7.9	??7.9	??7.5	??6.8	??7.1	??8.0
Embodiment 6	Embodiment 7	??T12	??A24	??T11	??A35	??50	??7.1	??30	??6.7	??7.2	??7.1	??7.5	??6.8	??7.1	??7.6
Embodiment 8	Embodiment 7	??T12	??A24	??T21	??A9	??10	??6.7	??30	??6.7	??7.2	??7.1	??8.3	??7.0	??8.1	??7.6
Embodiment 8	Embodiment 9	??T22	??A11	??T21	??A9	??10	??6.7	??55	??7.4	??7.9	??6.9	??8.3	??7.0	??8.1	??7.1
Embodiment 10	Embodiment 9	??T22	??A11	??T24	??A17	??50	??7.0	??55	??7.4	??7.9	??6.9	??7.6	??7.1	??7.4	??7.1
Embodiment 10	Embodiment 11	??T26	??A27	??T24	??A17	??50	??7.0	??45	??7.2	??7.9	??7.3	??7.6	??7.1	??7.4	??7.9
Embodiment 12	Embodiment 11	??T26	??A27	??T32	??A23	??70	??7.6	??45	??7.2	??7.9	??7.3	??8.1	??8.1	??8.3	??7.9
Embodiment 12	Embodiment 13	??T35	??A21	??T32	??A23	??70	??7.6	??40	??7.2	??8.2	??7.5	??8.1	??8.1	??8.3	??7.5
Embodiment 14	Embodiment 13	??T35	??A21	??T46	??A16	??10	??7.1	??40	??7.2	??8.2	??7.5	??8.2	??7.1	??8.1	??7.5
Embodiment 14	Embodiment 15	??T49	??A22	??T46	??A16	??10	??7.1	??20	??7.0	??7.4	??6.9	??8.2	??7.1	??8.1	??7.4
Embodiment 16	Embodiment 15	??T49	??A22	??T51	??A4	??40	??7.4	??20	??7.0	??7.4	??6.9	??8.1	??7.5	??7.9	??7.4
Embodiment 16	Embodiment 17	??T53	??A3	??T51	??A4	??40	??7.4	??60	??7.2	??7.7	??7.4	??8.1	??7.5	??7.9	??7.5
Embodiment 18	Embodiment 17	??T53	??A3	??T63	??A7	??50	??7.1	??60	??7.2	??7.7	??7.4	??8.1	??7.4	??7.9	??7.5
Embodiment 18	Comparative example 1	??T1	??-	??T63	??A7	??50	??7.1	??-	??7.1	Can not measure	??6.7	??8.1	??7.4	??7.9	Can not measure
Comparative example 2	Comparative example 1	??T1	??-	??T1	??A15	??5	??7.4	??-	??7.1	Can not measure	??6.7	??15.2	??7.3	??15.1	Can not measure
Comparative example 2	Comparative example 3	??T1	??A1	??T1	??A15	??5	??7.4	??80	??8.0	??8.1	??9.5	??15.2	??7.3	??15.1	??9.9
Comparative example 4	Comparative example 3	??T1	??A1	??-	??A25	??100	??8.6	??80	??8.0	??8.1	??9.5	??8.8	??10.9	??11.2	??9.9
Comparative example 4	Comparative example 5	Comparative compound A	??A1	??-	??A25	??100	??8.6	??40	??8.1	??8.5	??9.1	??8.8	??10.9	??11.2	??9.2

Table 18

	Cyclonite cyanines pigment	Chelate		[%] beats
				[%] beats				Linear velocity 3.5m/s		Linear velocity 28.0m/s
				Kation (No.)	Azo-compound (No.)	Contain proportional (mole %)	Before light exposes	Linear velocity 3.5m/s		Linear velocity 28.0m/s		Light exposes back (light stability)	Before light exposes	Light exposes back (light stability)
	Embodiment 19	??T26 ^*1	??A3 ^*2	Kation (No.)	Azo-compound (No.)	Contain proportional (mole %)	Before light exposes	??50	??7.2	??7.6	??8.0	Light exposes back (light stability)	Before light exposes	Light exposes back (light stability)	??8.1
Embodiment 20	Embodiment 19	??T26 ^*1	??A3 ^*2	??T26 ^*1/T26	??A3 ^*2	??25	??7.0	??50	??7.2	??7.6	??8.0	??7.9	??7.1	??7.4	??8.1
Embodiment 20	Embodiment 21	??T26 ^*1/T53	??A3 ^*2	??T26 ^*1/T26	??A3 ^*2	??25	??7.0	??25	??7.2	??7.5	??6.9	??7.9	??7.1	??7.4	??7.6
Embodiment 22	Embodiment 21	??T26 ^*1/T53	??A3 ^*2	??T26 ^*1/T55	??A3 ^*2	??30	??7.2	??25	??7.2	??7.5	??6.9	??7.4	??6.8	??7.4	??7.6
Embodiment 22	Comparative example 6	Comparative compound B ^*1	??A3 ^*2	??T26 ^*1/T55	??A3 ^*2	??30	??7.2	??50	??8.1	??8.5	??14	??7.4	??6.8	??7.4	??14
Comparative example 7	Comparative example 6	Comparative compound B ^*1	??A3 ^*2	Comparative compound B ^*1	??A3 ^*2	??25	??8.7	??50	??8.1	??8.5	??14	??8.9	??9.4	??9.8	??14

* 1, * 2: salt (mol ratio 1: 1) the hybrid modulation optical recording material that cyclonite cyanines pigment and chelate are formed

Shown in table 17 and table 18, embodiment 1～22 compares with comparative example 1～7, also can be controlled at reduced levels with beating when high-speed record, and light stability is also fine.Therefore, can confirm, contain the cyclonite cyanines pigment kation 1a and the chelate of special ratios, just can obtain sensitivity good, beat and light stability also well optical recording material and optical recording media.

Embodiment 23

Go up to form the degree of depth on the one hand and be on the polycarbonate resin substrate of pre-groove of 0.16 μ m, wide 0.30 μ m, slot pitch 0.74 μ m, will be with cyclonite cyanines pigment kation and PF ₆ ^-Cyclonite cyanines pigment that forms and adjuvant are according to combined hybrid shown in the table 19, making containing of additive compound proportional all is that benchmark is the optical recording material that the ratio modulation of 10 weight % gets with optical recording material, making its content is to be dissolved in 2 under the ratio of 1.0 weight %, 2,3, form mixed liquor in the 3-tetrafluoropropanol, be coated on the polycarbonate resin substrate, the dry recording layer (thickness 130nm) that forms.Then, on this recording layer, form Ag reflection horizon (thickness 85nm), on the Ag reflection horizon, form the protective clear layer (thickness 5 μ m) that the ultraviolet hardening acryl resin forms again, obtain the laminated structure body with sputtering method.2 such laminated structure body and function bonding agents are fitted, it is inboard making their protective seams separately again, makes to have and the optical recording of optical recording 10 shown in Figure 2 with spline structure.In table 19, cyclonite cyanines pigment kation, add the material that compound and chelate No. are respectively No. and corresponding chemical structural formula thereof shown in table 1～table 6, table 13～table 16 and table 7～table 12.In addition, chelate forms and Na ⁺Or the cationic salt of interpolation compound, with these salt light modulated recording materials.

On the gained optical recording, with the 28.0m/s linear velocity tracer signal of (being equivalent to 8 times of speed), be the laser of 650nm with the linear velocity of 3.5m/s reproduce with wavelength then with the laser of wavelength 655nm, measure the suitableeest recording power P ₀With jitter values as the pigment sensitivity index.At this moment, lens openings NA is 0.60.Evaluation result is shown in table 19.

Embodiment 24～35 and comparative example 8～9

Optical recording material is except that the material that uses each combination shown in the table 19 and ratio to mix, with embodiment 1 the same making and the evaluation of carrying out optical recording.Evaluation result comprehensively is shown in table 19.In addition, in embodiment 26 and 27, chelate and Na ⁺Salt mix with other material, in embodiment 28～35, chelate and mix with other material as the ammonium compounds of adjuvant or the salt of phosphine compound is modulated into optical recording material respectively.In addition, in comparative example 8,9, use be that cyclonite cyanines pigment kation is the R in the above-mentioned formula (1b) ¹¹, R ¹², R ¹³, R ¹⁴It all is the comparative compound of formula (7a) expression of methyl.

Table 19

	Cyclonite cyanines pigment	Chelate		Add compound	??P ₀??[mW]	[%] beats
	Cyclonite cyanines pigment	Chelate					Kation (No.)	Azo-compound (No.)	Contain proportional (mole) ^*
	Embodiment 23	??T1	??-				Kation (No.)	Azo-compound (No.)	Contain proportional (mole) ^*	??-	??301	??39.5	??7.3
Embodiment 24	Embodiment 23	??T1	??-	??T7	??-	??-	??302	??41.4	??7.6	??-	??301	??39.5	??7.3
Embodiment 24	Embodiment 25	??T26	??-	??T7	??-	??-	??302	??41.4	??7.6	??-	??303	??38.3	??8.3
Embodiment 26	Embodiment 25	??T26	??-	??T21	??A17	??40	??304	??39.9	??7.2	??-	??303	??38.3	??8.3
Embodiment 26	Embodiment 27	??T39	??A28	??T21	??A17	??40	??304	??39.9	??7.2	??20	??305	??36.8	??7.3
Embodiment 28	Embodiment 27	??T39	??A28	??T11	??A3	??- ^**	??401	??40.2	??6.9	??20	??305	??36.8	??7.3
Embodiment 28	Embodiment 29	??T24	??A7	??T11	??A3	??- ^**	??401	??40.2	??6.9	??- ^**	??402	??39.8	??7.9
Embodiment 30	Embodiment 29	??T24	??A7	??T46	??A10	??- ^**	??403	??39.4	??8.1	??- ^**	??402	??39.8	??7.9
Embodiment 30	Embodiment 31	??T51	??A12	??T46	??A10	??- ^**	??403	??39.4	??8.1	??- ^**	??501	??42.1	??6.7
Embodiment 32	Embodiment 31	??T51	??A12	??T42	??A33	??- ^**	??502	??40.4	??8.2	??- ^**	??501	??42.1	??6.7
Embodiment 32	Embodiment 33	??T12	??A37	??T42	??A33	??- ^**	??502	??40.4	??8.2	??- ^**	??503	??37.6	??7.8
Embodiment 34	Embodiment 33	??T12	??A37	??T53	??A42	??- ^**	??601	??41.5	??7.4	??- ^**	??503	??37.6	??7.8
Embodiment 34	Embodiment 35	??T60	??A48	??T53	??A42	??- ^**	??601	??41.5	??7.4	??- ^**	??602	??38.7	??7.2
Comparative example 8	Embodiment 35	??T60	??A48	??T1	??-	??-	??-	??45.7	??7.7	??- ^**	??602	??38.7	??7.2
Comparative example 8	Comparative example 9	Comparative compound	??-	??T1	??-	??-	??-	??45.7	??7.7	??-	??301	??41.5	??9.7

*: the total amount benchmark of cyclonite cyanines pigment and chelate

*: as cooperating with the salt that adds compound

By shown in the table 19 as can be known, embodiment 23～35 compares with comparative example 8,9, demonstrates the excellent sensitivity (P that not following beats enlarges markedly ₀Little).Therefore, can confirm, contain cyclonite cyanines pigment kation 1b, above-mentioned interpolation compound and chelate, just can not followed the optical recording material of reaching very high sensitivity and the optical recording media of beating and significantly increasing.

According to the present invention, can access and not only have good sensitivity, and when writing speed is very high, beat and also good optical recording media of light stability, and the optical recording material that is used for this medium.In addition, according to the present invention, can access the optical recording media of reaching very high sensitivity that not following beats significantly increases and the optical recording material that is used for this optical recording media.

Claims

One kind be used for can recording light the optical recording material of optical recording media of irradiation information, it is characterized in that, described optical recording material contains the kation shown in the following formula (1a), with azo-compound and metal chelate, and the total amount with described kation and described chelate is a benchmark, containing of described chelate than being 10～70 moles of %

In the formula, R ¹And R ²The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ³And R ⁴The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ⁵And R ⁶The alkyl or aryl of 1～4 carbon atom of independent separately expression; R ⁷Expression hydrogen atom, halogen atom, cyano group, the alkyl that can contain substituent 1～4 carbon atom maybe can contain substituent aryl; Q ¹And Q ²Independent separately expression constitutes can contain the former subgroup that substituent phenyl ring maybe can contain substituent naphthalene nucleus, still, and R ¹, R ², R ³, R ⁴At least 1 be not methyl.
2. optical recording material as claimed in claim 1 is characterized in that, the salt that described optical recording material is formed by described kation and its balance anion mixes with above-mentioned chelate and obtains.
One kind be used for can recording light the optical recording material of optical recording media of irradiation information, it is characterized in that described optical recording material contains the kation shown in the following formula (1b), azo-compound and metal chelate, and compound shown in the following formula (2),

A ⁿ⁺-(X) _3+n?(2)

In the formula, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶The alkyl that independent separately expression can contain substituent 1～4 carbon atom maybe can contain substituent aryl; R ¹⁷Expression hydrogen atom, halogen atom, cyano group, the alkyl that can contain substituent 1～4 carbon atom maybe can contain substituent aryl; Q ¹¹And Q ¹²Independent separately expression constitutes the former subgroup that can contain substituent aromatic rings; A represents nitrogen-atoms or phosphorus atoms; X represents hydrogen atom, and the alkyl that can contain substituent 1～4 carbon atom maybe can contain substituent aryl; N represents 0 or 1, still, and R ¹¹With R ¹²And R ¹³With R ¹⁴, can be the ring texture that is connected to each other formation separately, R ¹¹, R ¹², R ¹³And R ¹⁴At least 1 be not methyl, both can be identical with a plurality of X in a part, also can be different, be that the alkyl that can contain substituent 1～4 carbon number maybe can contain substituent aryl with at least 1 among a plurality of X in a part.
4. optical recording material as claimed in claim 3 is characterized in that, the total number of carbon atoms of the described compound shown in the formula (2) is below 20.
5. optical recording material as claimed in claim 3 is characterized in that R ¹¹And R ¹²The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ¹³And R ¹⁴The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, and the base that is connected to each other 3～6 yuan of rings of formation; R ¹⁵And R ¹⁶Independently be the alkyl or aryl of 1～4 carbon number separately; Q ¹¹And Q ¹²Independent separately expression constitutes the former subgroup that the substituent phenyl ring that can contain maybe can contain substituent naphthalene nucleus.
6. optical recording material as claimed in claim 4 is characterized in that R ¹¹And R ¹²The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ¹³And R ¹⁴The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ¹⁵And R ¹⁶Independently be the alkyl or aryl of 1～4 carbon number separately; Q ¹¹And Q ¹²Independent separately expression constitutes the former subgroup that the substituent phenyl ring that can contain maybe can contain substituent naphthalene nucleus.
7. as each described optical recording material in the claim 3～6, it is characterized in that, contain PF ₆ ^-Or SbF ₆ ^-
8. but a recording light is shone the optical recording media of information, it is characterized in that, described optical recording media comprises: the recording layer that contains the kation shown in the following formula (1a) and azo-compound and metal chelate, and the total amount with described kation and described chelate is a benchmark, containing of described chelate than being 10～70 moles of %

In the formula, R ¹And R ²The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ³And R ⁴The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ⁵And R ⁶The alkyl or aryl of 1～4 carbon atom of independent separately expression; R ⁷Expression hydrogen atom, halogen atom, cyano group, the alkyl that can contain substituent 1～4 carbon atom maybe can contain substituent aryl; Q ¹And Q ²Independent separately expression constitutes can contain the former subgroup that substituent phenyl ring maybe can contain substituent naphthalene nucleus, still, and R ¹, R ², R ³, R ⁴At least 1 be not methyl.
9. optical recording media as claimed in claim 8 is characterized in that, described recording layer contains the salt that is formed by described kation and its balance anion and mixes the potpourri that obtains with described chelate.
10. but a recording light is shone the optical recording media of information, it is characterized in that described optical recording media comprises: contain the kation shown in the following formula (1b), and azo-compound and metal chelate, and the recording layer of compound shown in the following formula (2),

A ⁿ⁺-(X) _3+n??(2)

In the formula, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶The alkyl that independent separately expression can contain substituent 1～4 carbon atom maybe can contain substituent aryl; R ¹⁷Expression hydrogen atom, halogen atom, cyano group, the alkyl that can contain substituent 1～4 carbon atom maybe can contain substituent aryl; Q ¹¹And Q ¹²Independent separately expression constitutes the former subgroup that can contain substituent aromatic rings; A represents nitrogen-atoms or phosphorus atoms; X represents hydrogen atom, and the alkyl that can contain substituent 1～4 carbon atom maybe can contain substituent aryl; N represents 0 or 1, still, and R ¹¹With R ¹²And R ¹³With R ¹⁴, can be the ring texture that is connected to each other formation separately, R ¹¹, R ¹², R ¹³And R ¹⁴At least 1 be not methyl, both can be identical with a plurality of X in a part, also can be different, be that the alkyl that can contain substituent 1～4 carbon number maybe can contain substituent aryl with at least 1 among a plurality of X in a part.
11. optical recording media as claimed in claim 10 is characterized in that, the total number of carbon atoms of the described compound shown in the formula (2) is below 20.
12. optical recording media as claimed in claim 10 is characterized in that, R ¹¹And R ¹²The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ¹³And R ¹⁴The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, and the base that is connected to each other 3～6 yuan of rings of formation; R ¹⁵And R ¹⁶Independently be the alkyl or aryl of 1～4 carbon number separately; Q ¹¹And Q ¹²Independent separately expression constitutes the former subgroup that the substituent phenyl ring that can contain maybe can contain substituent naphthalene nucleus.
13. optical recording media as claimed in claim 11 is characterized in that, R ¹¹And R ¹²The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ¹³And R ¹⁴The alkyl of 1～4 carbon atom of independent separately expression maybe can contain substituent benzyl, perhaps is connected to each other the base of 3～6 yuan of rings of formation; R ¹⁵And R ¹⁶Independently be the alkyl or aryl of 1～4 carbon number separately; Q ¹¹And Q ¹²Independent separately expression constitutes the former subgroup that the substituent phenyl ring that can contain maybe can contain substituent naphthalene nucleus.
14. as each described optical recording media in the claim 10～13, it is characterized in that, contain PF ₆ ^-Or SbF ₆ ^-