CN101322189A - Optical information recording medium, method for visible information recording, method for use of mixture and mixture - Google Patents

Optical information recording medium, method for visible information recording, method for use of mixture and mixture Download PDF

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CN101322189A
CN101322189A CNA2006800449480A CN200680044948A CN101322189A CN 101322189 A CN101322189 A CN 101322189A CN A2006800449480 A CNA2006800449480 A CN A2006800449480A CN 200680044948 A CN200680044948 A CN 200680044948A CN 101322189 A CN101322189 A CN 101322189A
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visual information
substrate
recording medium
information recording
recording layer
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今村清文
柴田路宏
新居一巳
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Fujifilm Corp
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Abstract

This invention provides an optical information recording medium (10A) that can record information by laser beam (38) irradiation. The optical information recording medium (10A) comprises a visible information recording layer (24) on which visible information is to be recorded. The visible information recording layer (24) contains a coloring matter, and at least one metal atom selected from the group consisting of Na, Mg, K, and Ca. The coloring matter is at least one material selected from the group consisting of oxonol coloring matter, cyanine coloring matter, azo coloring matter, phthalocyanine coloring matter, and pyrromethene coloring matter.

Description

Optical data recording medium, the method for preparing optical data recording medium, the method for visual information record, the application and the potpourri of potpourri
Technical field
The present invention relates to have the optical data recording medium of the visual information recording layer that can write down visual information, be used for preparing the method for (manufacturing) described optical data recording medium, the visible information recording (method that is used for the visual information record) that is used for record visual information on described optical data recording medium, use the method (application of potpourri) and the described potpourri of the potpourri that forms described visual information recording layer.
Background technology
The optical data recording medium (CD) that can use laser beam only to write down once above is known so far.Such CD comprises write-once type CD (so-called CD-R) and write-once type digital multi-purpose disk (so-called DVD-R).
CD comprises: label can be adhered to lip-deep those CDs, described label is positioned in and is used for the opposite side of recording surface of recording musical data etc. in the above, wherein can be with visual information (image), be included in the music title of the music data that writes down on the recording surface, and/or other title of the data of difference record, be printed on the label.Such CD is following manufacturing.Promptly in advance title etc. is printed on the circular label paper, and label paper is adhered on the surface of settling on the side opposite with the recording surface of CD by printer etc.
On the other hand, studied wherein by laser beam irradiation is formed the system of label to CD, this system is different from the aforesaid system on the optical disc surface (referring to, for example, patent document 1) that wherein label paper adhered to.
Propose: can in CD, form the visual information recording layer, wherein with dyestuff as the material of visual information recording layer (referring to, for example, patent document 2, patent document 3 and patent document 4).In addition, a kind of optical data recording medium has also been proposed so far, this optical data recording medium has by lamination in succession and contains the visual information recording layer of phthalide-Ji leuco dye and the structure that colorable laser beam transmission layer constitutes, described colorable laser beam transmission layer have tone with respect to the part that on the visual information recording layer, writes down (drafting part) become the complementary color relation tone (referring to, for example, patent document 5).According to this technology,, can use laser beam clearly to write down visual information in a side of label surface by for example the electronic information that is writing down on the medium not being produced under the situation of any heat affecting with low output irradiation laser bundle.
In the CD that has the visual information recording layer as mentioned above, necessary is by with forming the substrate of visual information recording layer above painted the giving, advantageously to improve change color.
On the other hand, from the viewpoint of technology, when using colored substrate, the problem of appearance is: the situation during with the use transparency carrier is compared, and must export control to laser beam.
Especially, as under the situation of the CD described in the patent document 5 with conventional visual information recording layer, form colorable laser beam transmission layer, described colorable laser beam transmission layer has the tone that becomes the complementary color relation on the visual information recording layer with respect to the tone of the part that writes down (drafting part).Therefore, force some restrictions for the color that can use.In addition, when writing visual information, monitor is exported control to laser beam before must using, and makes and can write with suitable power.
The conventional CD that wherein forms based on the visual information recording layer of the use of dyestuff also comprises other problem, so that after forming label, it is not enough that light permanance and/or heat durability become.
Patent document 1: Japanese publication is announced 11-066617
Patent document 2: Japanese publication is announced 2000-113516
Patent document 3: Japanese publication is announced 2001-283464
Patent document 4: Japanese publication is announced 2000-173096
Patent document 5: Japanese publication is announced 2004-246981
Summary of the invention
The present invention considers that above-mentioned general issues carries out.One object of the present invention is to provide a kind of optical data recording medium that is equipped with the visual information recording layer, wherein can use laser beam to form label, and wherein visual information has excellent light permanance and/or heat durability.One object of the present invention also is to provide a kind of potpourri that is used to form the visual information recording layer, and the method for using described potpourri.
Another object of the present invention is to provide a kind of optical data recording medium and a kind of method that is used to prepare described optical data recording medium, even wherein with colored substrate with thereon can be on label surface during the optical data recording medium of drawing image, also the output control of laser beam can be suppressed to minimum.
A further object of the present invention is to provide a kind of method that is used to write down visual information, wherein the necessary hardware resource that is used for record cell can be minimized, and makes the general user use this record cell can easily write down visual information.
According to a first aspect of the invention, a kind of optical data recording medium is provided, it can pass through irradiation laser beam recording information, described optical data recording medium comprises: the visual information recording layer, to write down visual information on it, wherein said visual information recording layer contains dyestuff and at least a metallic atom, and described metallic atom is selected from: Na, Mg, K and Ca.
In this optical data recording medium, owing to contain at least a Na of being selected from the visual information recording layer, Mg, the fact of the metallic atom among K and the Ca, visual information have excellent light permanance and heat durability.Not exclusively know for the reason that why obtains above-mentioned effect.But the inventor has carried out following supposition.
Particularly, after the enterprising line item of visual information recording layer, dye density writes down the zone of visual information therein and does not wherein write down between the zone of visual information different.Especially, do not write down the zone of visual information therein, dye density is low.When the exposure of optical data recording medium being carried out over a long time, write down the zone of visual information therein and wherein do not write down and tend to occur deterioration at the interface between the zone of visual information.But think: because in a first aspect of the present invention, comprising of metallic atom makes such deterioration obtain inhibition, so be improved for the permanance of light and/or for the permanance of heat.
As mentioned above, according to a first aspect of the invention, can use laser beam to form label.Therefore, can provide the optical data recording medium that is equipped with the visual information recording layer, wherein visual information has excellent light permanance and heat durability.
In a first aspect of the present invention, dyestuff can be to be selected from least a in the following dyestuff: oxonols (oxonol) dyestuff, cyanine dye, azo dyes, phthalocyanine dye and pyrroles's methylene (pyrromethene) dyestuff.
In a first aspect of the present invention, with respect to the described dyestuff of 1kg, preferably with 0.1 to 100g ratio, more preferably with 1 to 50g ratio and more preferably contain described metallic atom again with 1 to 10g ratio.If content surpasses the upper limit, then be difficult to write down satisfactorily visual information, reason is in the visual information recording layer crystallization to take place.If content is lower than lower limit, tend to deficiency for the permanance of light and heat.In addition, more preferably lower limit is 0.5g again, and in the case, this moment, higher limit was preferably 50g, and 10g more preferably.
Have again, when aspect the content ratio of metallic atom, considering, preferably in the visual information recording layer, comprise metallic atom, and more preferably be limited to 0.001 weight % under it with 0.001 to 1 weight % scope.
In this manual, under the situation of any above-mentioned standard,,, the content of metallic atom is not particularly limited as long as obtain effect of the present invention although indicated higher limit and lower limit.
In a first aspect of the present invention, dyestuff can also contain the cyclonite cyanine dye and have the phthalocyanine dye of central metal Cu.
In the case, with respect to the content of 50g, preferably with 0.1 to 10g ratio and more preferably contain described metallic atom with 1 to 5g ratio as the Cu of described central metal.
In a first aspect of the present invention, optical data recording medium comprises first substrate, the recording layer that on first substrate, forms, first reflection horizon that on recording layer, forms, the adhesive phase that on first reflection horizon, forms, second reflection horizon that on adhesive phase, forms, second substrate that is formed the visual information recording layer on second reflection horizon and forms at the visual information recording layer.
In a first aspect of the present invention, dyestuff can be an oxonol dye, and it has the structure by following general formula (1-1) expression:
Figure A20068004494800091
In the general formula (1-1), Za 25, Za 26Independence and the atomic group that is respectively the formation acid core, and Ma 27, Ma 28, Ma 29Independently replace or unsubstituted methine with being respectively.Ka 23Be illustrated in the integer in 0 to 3 scope.During Q represents to be used for and the monovalent cation of electric charge.At Ka 23When being a plurality of, a plurality of Ma 27, Ma 28Can be identical mutually, or different mutually.It is also preferred that to use the dyestuff that has wherein by general formula (1-1) expression be by linking group or connect the dyestuff of the structure that base connects.
In a first aspect of the present invention, dyestuff can be an oxonol dye, and it has the structure by following general formula (1-2) expression:
Figure A20068004494800101
In the general formula (1-2), Za 21, Za 22, Za 23, Za 24Independent and the atomic group of expression with acid core respectively, and Ma 21, Ma 22, Ma 23, Ma 24, Ma 25, Ma 26Independently and respectively represent to replace or unsubstituted methine.L represents divalent linker, and this divalent linker does not form pi-conjugated system with two keys.Ka 21, Ka 22Independently with the integer that is illustrated respectively in 0 to 3 scope.During Q represents to be used for and the monovalent cation of electric charge.Alternatively, 2Q represents bivalent cation.At Ka 21, Ka 22When being a plurality of, a plurality of Ma 21, Ma 22, Ma 25, Ma 26Can be identical mutually, or different mutually.
In a first aspect of the present invention, dyestuff can be the cyanine dye by general formula (2-1) expression:
Figure A20068004494800111
In the general formula (2-1), Za 21, Za 22Independently with the atomic group of representing to form heterocycle or heterocyclic ring respectively.Ma 21, Ma 22, Ma 23Independently and respectively represent to replace or unsubstituted methine.Ka2 is illustrated in the integer in 0 to 3 scope.At ka2 is 2 or when bigger, a plurality of Ma 21, Ma 22Can be identical mutually, or different mutually.R 101, R 102Independently and respectively represent substituting group.During Q2 represents to be used for and the ion of electric charge.During y2 represents and the needed number of electric charge.
In a first aspect of the present invention, dyestuff can be the cyanine dye by following general formula (2-2) expression:
In the general formula (2-2), Za 31, Za 32Independently with the atomic group of representing to form carbocyclic ring or heterocycle respectively.R 1a, R 2aIndependently and respectively represent substituting group.R 121, R 122, R 123, R 124, R 125, R 126, R 127Independently and respectively represent hydrogen atom or substituting group.Ka3 is illustrated in the integer in 0 to 3 scope.At ka3 is 2 or when bigger, a plurality of R 121, R 122Can be identical mutually, or different mutually.During Q3 represents to be used for and the ion of electric charge.During y3 represents and the needed number of electric charge.
In a first aspect of the present invention, dyestuff can be the azo dyes by following general formula (3-1) expression:
A-N＝N-B ...(3-1)
In the general formula (3-1), A represents the univalent perssad derived from the colour coupler composition, and B represents the univalent perssad derived from diazo salt.
In a first aspect of the present invention, dyestuff can be the azo dyes by following general formula (3-2) expression:
Figure A20068004494800121
In the general formula (3-2), A 1, B 2Independently and respectively represent to form replacement or unsubstituted aromatic hydrocarbon ring, or the atomic group of replacement or unsubstituted aromatic heterocycle.G represents to have the univalent perssad that carries out coordination ability for metallic ion.
In a first aspect of the present invention, dyestuff can be the phthalocyanine dye by following general formula (4-1) expression.
Figure A20068004494800131
In the general formula (4-1), R α 1To R α 8, R β 1To R β 8The expression hydrogen atom; halogen atom; nitro; nitro, formoxyl, carboxyl; sulfo group; carbon number is 1 to 20 alkyl, and carbon number is 6 to 14 aryl, and carbon number is 7 to 15 aralkyl; carbon number is 1 to 10 heterocyclic radical; carbon number is 1 to 20 alkoxy, and carbon number is 6 to 14 aryloxy group, and carbon number is 2 to 21 acyl group; carbon number is 1 to 20 alkyl sulphonyl; carbon number is 6 to 20 aryl sulfonyl, and carbon number is 1 to 25 carbamyl, and carbon number is 0 to 32 sulfamoyl; carbon number is 2 to 21 alkoxy carbonyl group; carbon number is 7 to 15 aryloxy carbonyl, and carbon number is 2 to 21 acyl amino, and carbon number is that 1 to 20 sulfuryl amino and carbon number are 0 to 36 amino.M represents two hydrogen atoms, metal, and metal oxide, or have the metal of part.
In a first aspect of the present invention, dyestuff can be the pyrroles's methylene dye by general formula (5-1) expression.
Figure A20068004494800141
In the general formula (5-1), A represents by metal M and the chelate ring that formed by pyrroles's methylene compound of following general formula (5-2) expression, and B represents to form and have nitrogen-atoms, oxygen atom, and/or the chelate ring of sulphur atom with M.A and B can be identical mutually, or different mutually.
Figure A20068004494800142
In the general formula (5-2), Ya represents N or CR A3R A1, R A2, R A3, R A4, R A5, R A6, R A7Expression hydrogen atom or substituting group.R A1And R A2, R A2And R A3, R A5And R A6, and R A6And R A7Can be respectively in conjunction with forming aromatic ring or heterocycle.Described ring can have substituting group.In addition, aromatic ring or heterocycle can condense with described ring.
Below, as the result who deeply and carefully studies about the problems referred to above, the inventor thereby find a kind of optical data recording medium and a kind of method that is used to prepare this optical data recording medium, on described optical data recording medium, can be on its label surface drawing image, and wherein: on the basis of the output of the laser beam when drawing, regulate dyestuff and/or the content of pigment in substrate in the step process by forming, even use colored substrate also the output control of laser beam can be suppressed to minimum at substrate.
Promptly, according to a second aspect of the invention, a kind of optical data recording medium is provided, described optical data recording medium includes chromogen substrate, with the visual information recording layer that is formed on the described colored substrate, and on described visual information recording layer, by laser beam record visual information, wherein form so described colored substrate: on the output basis of described laser beam, be adjusted in the dyestuff that contains in the described substrate and/or the addition of pigment.
According to a third aspect of the invention we, a kind of optical data recording medium is provided, described optical data recording medium comprises coloured first substrate, be formed on described first substrate and the top visual information recording layer that passes through first laser beam record visual information, second transparency carrier, with be formed on described second substrate and the top data record layer that passes through the second laser beam record data, wherein form first substrate like this: on the output basis of described first laser beam, be adjusted in the dyestuff that contains in described first substrate and/or the addition of pigment.
In addition, according to a forth aspect of the invention, a kind of optical data recording medium is provided, described optical data recording medium comprises coloured first substrate, be formed on first substrate and the top visual information recording layer that passes through first laser beam record visual information, second transparency carrier, with be formed on second substrate and the top data record layer that passes through the second laser beam record data, wherein in described first substrate-side, arrangement is used to control the first laser beam control area of first laser beam, and the described first laser beam control area comprises the laser power control information that is used to control laser power corresponding to the colouring information of coloured first substrate.
In this case, the pre-pit that comprises laser power control information can be formed, prefabricated groove, or coding pattern (bar code etc.) in the laser beam control area.
At first substrate is under the situation of colored substrate, exists wherein by first substrate to absorb the situation that first laser beam and wherein given laser power do not reach the visual information recording layer.In the case, must laser power be set, make that it is difficult carrying out such setting by driver by driver.But, among the present invention, on first substrate, settle the first laser beam control area that is used to control first laser beam.Owing to comprise laser power control information in the first laser beam control area, described laser power control information is corresponding to the colouring information control laser power of coloured first substrate, even when first substrate is colored substrate, as the such information of drive access and based on it the result of laser power is set, the laser power that needs arrives the visual information recording layer, so the visual information of enough contrasts is recorded.
According to a fifth aspect of the invention, a kind of method that is used to prepare optical data recording medium is provided, described optical data recording medium includes chromogen substrate and visual information recording layer, described visual information recording layer is formed on the described substrate, and wherein can write down visual information at the visual information recording layer by laser beam from substrate-side irradiation, this method comprises: substrate forms step, be used for forming described colored substrate by the dyestuff that contains at described substrate in the basic adjusted of described laser beam output and/or the addition of pigment; Form step with recording layer: on described substrate, form described visual information recording layer.
According to a sixth aspect of the invention, a kind of method that is used to prepare optical data recording medium is provided, described optical data recording medium comprises: coloured first substrate, be formed on the visual information recording layer on described first substrate, second transparency carrier, with the data record layer that is formed on described second substrate, wherein can write down visual information at described visual information recording layer by laser beam from the described first substrate-side irradiation, and can by from the laser beam of the described second substrate-side irradiation at described data record layer identifying recording layer, described method comprises: substrate forms step: the dyestuff that contains in described first substrate by the basic adjusted in described laser beam output and/or the addition of pigment form described first substrate; First recording layer forms step: form described visual information recording layer on described first substrate; Form step with second recording layer: on described second substrate, form described data record layer.
In aspect of the present invention second to the 6th, even colored substrate is used for optical data recording medium, wherein can be on label surface drawing image, also the output control of laser beam can be suppressed to minimum.In addition, can use shades of colour.Therefore, can respond the needs that wherein need the change color that increases fully.
Aspect the of the present invention the 3rd, the 4th and the 6th, when data record layer was the recording layer that forms by the coating dyestuff, the dyestuff that can be used for data record layer was as the dyestuff that contains at the visual information recording layer.
Below, according to a seventh aspect of the invention, provide a kind of on the visual information recording layer of the optical data recording medium that defines in any one to the third aspect as the present invention first method of record visual information, wherein this method comprises and will be used for the laser beam used as record visual information on described visual information recording layer in the same laser beam of described data record layer identifying recording layer.
Thereby, the necessary hardware resource of record cell is minimized, and the general user can use such record cell easily to write down visual information.
Below, according to an eighth aspect of the invention, a kind of method that potpourri is used to form the optical data recording medium with visual information recording layer is provided, on described optical data recording medium, can pass through irradiation laser beam recording information, and wherein can on described visual information recording layer, write down visual information, described method comprises: the described visual information recording layer that described potpourri is used for described optical data recording medium, wherein said potpourri is made up of dyestuff and at least a metallic atom, described metallic atom is selected from: Na, Mg, K and Ca.
Therefore, can provide a kind of optical data recording medium, on described visual information recording layer, can form label by using laser beam, and wherein visual information have excellent light permanance and heat durability with visual information recording layer.
Below, according to a ninth aspect of the invention, a kind of potpourri is provided, and it is used to form the visual information recording layer of optical data recording medium, on described visual information recording layer, can pass through irradiation laser beam recording information, and wherein can write down visual information on described visual information recording layer, wherein said potpourri is made up of dyestuff and at least a metallic atom, and described metallic atom is selected from: Na, Mg, K and Ca.
Therefore, can provide a kind of optical data recording medium, on described visual information recording layer, can form label by using laser beam, and wherein visual information have excellent light permanance and heat durability with visual information recording layer.
As explained above, in the method for optical data recording medium according to the present invention and potpourri and use potpourri, can use laser beam on the visual information recording layer, to write down visual information, wherein provide the visual information recording layer dividually with data record layer to the excellent in te pins of durability of light and heat.In addition, can form visual information with high-contrast.That is, can provide a kind of optical data recording medium that is equipped with the visual information recording layer, wherein can form label, and wherein visual information have excellent light permanance and heat durability by using laser beam.
In the method that is used for writing down visual information according to the present invention, the necessary hardware resource that is used for record cell can be minimized, make the general user use this record cell can easily write down visual information.
In optical data recording medium according to the present invention and the method that is used for preparing optical data recording medium, can be on label surface during the optical data recording medium of drawing image even colored substrate is used for wherein, also the output control of laser beam can be suppressed to minimum.In addition, can use shades of colour.Therefore, can respond the needs that wherein need the change color that increases fully.
The accompanying drawing summary
Fig. 1 is the sectional view that illustrates the structure of optical data recording medium according to an embodiment of the invention in diagram under the situation of part abridged;
Fig. 2 is the planimetric map according to the optical data recording medium of first modification;
Fig. 3 is the planimetric map according to the optical data recording medium of second modification;
Fig. 4 is the sectional view that illustrates under the situation of part abridged according to the optical data recording medium of second modification;
Fig. 5 is the sectional view of the structure of diagram first optical data recording medium under the situation of part abridged;
Fig. 6 is the sectional view of the structure of diagram second optical data recording medium under the situation of part abridged;
Fig. 7 is first substrate of diagram second optical data recording medium under the situation of part abridged, and the sectional view of data record layer, first reflection horizon and first protective seam;
Fig. 8 is the colored substrate of diagram second optical data recording medium under the situation of part abridged, and the sectional view of visual information recording layer, second reflection horizon and second protective seam;
Fig. 9 is the table of diagram according to the painted example of L*a*b* colour system, and described example is used for the colored substrate of second optical data recording medium;
Figure 10 is the calcspar of the illustrative steps of the diagram method that is used to prepare second optical data recording medium;
Figure 11 is the table of the color of the color combination of colored substrate of examples shown and visual information recording layer;
Figure 12 is the key diagram that shows the track of the laser beam that is used to form image irradiation;
Figure 13 shows the enlarged drawing of laser beam at the track of the part of the thick line of Figure 12 drafting;
Figure 14 is the table of explanation according to the evaluation of the optical data recording medium contrast of embodiment 1 to 4;
Figure 15 A is explanation drives the drafting condition under the situation of records appraisal image a table;
Figure 15 B is the table of the spectrophotometric measuring condition of explanation;
Figure 16 is the table of explanation CIE standard spectrum luminescence efficiency; With
Figure 17 is the formula of explanation based on indication contrast evaluation index, the table of contrast evaluation criterion.
Implement best mode of the present invention
Below with reference to relating to according to method, the potpourri of the present invention of optical data recording medium of the present invention, the method for preparing optical data recording medium, record visual information and using Fig. 1 to 17 of exemplary of the method for this potpourri to make an explanation.
As shown in fig. 1, the basic structure of optical data recording medium according to an embodiment of the invention comprises: data carrier part 12 and visual information recording medium segment 14.Data carrier part 12 comprises: transparent first substrate 16 is formed on the data record layer 18 on first substrate 16 and is formed on first reflection horizon 20 on the data record layer 18.Visual information recording medium segment 14 comprises: transparent second substrate 22 is formed on the visual information recording layer 24 on second substrate 22 and is formed on second reflection horizon 26 on the visual information recording layer 24.In addition, data carrier part 12 and visual information recording medium segment 14 is stacked together by adhesive phase 28, win reflection horizon 20 and second reflection horizon 26 are faced with each other.
Data record layer 18 can pass through laser record data (pit information) in the above, and described laser is from for example first substrate, 16 side irradiation.
Visual information recording layer 24 can pass through laser log visual information (image and literal), and described laser is from for example second substrate, 22 side irradiation.
And, on optical data recording medium 10, pre-pit district 30 is assigned to a part of surface (forming the surfaces on visual information recording layer 24 1 sides) of second substrate 22, wherein at least one pre-pit 32 and preferred a plurality of pre-pit 32 is formed in the pre-pit district 30.
As the information of indicating by the combination of pre-pit 32, can consider to relate to the various information of optical data recording medium 10, whether for example indicate optical data recording medium 10 are identifying informations of comprising the optical data recording medium 10 of visual information recording layer 24, the laser beam output when on visual information recording layer 24, drawing visual information (for example, laser power) information, relates to the information of spot diameter, perhaps relate to the information etc. of the contrast of visual information that will be drawn.Therefore, by detecting pre-pit 32, easily whether detection optical information recording carrier 10 is the optical data recording mediums 10 that comprise visual information recording layer 24.In addition, when on visual information recording layer 24, drawing visual information, can draw visual information in best laser output (optimal laser power), and can under the situation of high performance characteristic, write down visual information.Except above-mentioned information, as can providing manufacturer's information etc. by the out of Memory of the combination of pre-pit 32 indication.
Position as in the described surface that pre-pit district 30 is distributed in second substrate 22 is not particularly limited it.For example, as according to as shown in the optical data recording medium 10a of first variation example of Fig. 2, pre-pit district 30 can be formed into than the drafting district 34 more close inside circumferences that form by visual information recording layer 2.By the existence of pre-pit district 30 at inside circumference, because pre-pit 32 is not filled by dye composition, the advantage of generation is: detect the light echo from pre-pit 32 easily.But, in order in pre-pit district 30, not form visual information recording layer 24, need and draw the blank that has between interior week in district 34 to a certain degree at the most peripheral in pre-pit district 30.
Certainly, consider drafting district 34 is remained wide as far as possible, as shown in fig. 1, pre-pit district 30 and draw district 34 and can overlap each other.More specifically, can be formed on the pre-pit 32 to the part of major general's visual information recording layer 24.In the case, because the formation position of visual information recording layer 24 can more freely be set, so improved yield in manufacturing processes.
As shown in Fig. 1 and Fig. 2, under the situation of the inside circumference that pre-pit district 30 is placed in second substrate 22, preferably pre-pit district 30 is placed in second substrate, 22 center radius are 21 to 24mm scope.
Second substrate 22 that can use pressing mold as follows manufacturing has above-mentioned pre-pit 32.Pressing mold has the pattern of recesses that forms therein, and purpose is to form pre-pit 32.In these patterns, the average height of its protuberance is preferably 150 to 400nm.By using described pressing mold, can make above-mentioned optical data recording medium 10 in good efficiencies ground.
Method as making pressing mold can adopt the method that is suitable for making pressing mold, and this method is identical with the method that is generally used for making CD-ROM basically.Particularly, can develop thereon etc. by on original glass plate, forming photoresist film, splash-proofing sputtering metal such as nickel etc. then, and carry out electroforming process, make pressing mold.
Replace pre-pit district 30, also can use the prefabricated groove district that wherein forms prefabricated groove.Alternatively, replace pre-pit district 30, can adopt train of impulses cutting area (burst cuttingarea) (BCA), wherein write down the bar code pattern that forms by pattern of recesses.In the case, according to prefabricated groove or bar code pattern, whether indication optical data recording medium 10 can be provided be the identifying information that comprises the optical data recording medium 10 of visual information recording layer 24, the laser beam output when on visual information recording layer 24, drawing visual information (for example, laser power) information, relates to the information of spot diameter and relate to the information etc. of the contrast of visual information that will be drawn.
Structure as for above-mentioned optical data recording medium 10 is not particularly limited it, as long as it comprises and is equipped with the structure that can draw the visual information recording layer 24 of visual information by the irradiation laser bundle thereon.Particularly, but can use any in read-only type, write-once type or the rewriting type etc.In these types, preferred write-once type.In addition,, can use inversion of phases, magneto-optical, dye-type etc. as for record format with being not particularly limited, but in these types, the preferred coloring agent type.
Especially, the optical data recording medium shown in Fig. 1 10 comprises: at data record layer 18 on first substrate 16 and the visual information recording layer 24 on second substrate 22.Owing to the fact that these layers are provided with stacked version, the application of preferred DVD structure (except that DVD, comprising DVD-R, DVD-RW and HD-DVD etc.).
Stratification as for optical data recording medium 10 arranges that the layer in Fig. 1 for example, can provide down array structure arranging:
(1) shown in back (referring to Fig. 5), first kind of layer arranged and is configured to: form data record layer 18 in succession on first substrate 16, first reflection horizon 20 and adhesive phase 28 then, will comprise that second substrate 22 of visual information recording layer 24 is laminated on the adhesive phase 28.
(2) although not shown; second kind of layer arranged and is configured to: form data record layer 18, the first reflection horizon 20 in succession on first substrate 16, protective seam and adhesive phase 28; then, second substrate 22 that will comprise visual information recording layer 24 is laminated on the adhesive phase 28.
(3) although not shown, the third layer layout is configured to: form data record layer 18, the first reflection horizon 20 on first substrate 16 in succession; first protective seam; the adhesive phase 28 and second protective seam then, will comprise that second substrate 22 of visual information recording layer 24 is formed on second protective seam.
(4) although not shown; the 4th kind of layer arranged and is configured to: form data record layer 18 in succession on first substrate 16; first reflection horizon 20; first protective seam; adhesive phase 28; second protective seam and the 3rd protective seam then, will comprise that second substrate 22 of visual information recording layer 24 is formed on the 3rd protective seam.
(5) the 5th kinds of layers are arranged and are configured to: form data record layer 18, the first reflection horizon 20 on first substrate 16 in succession, the adhesive phase 28 and second reflection horizon 26 then, will comprise that second substrate 22 of visual information recording layer 24 is formed on second reflection horizon 26.This layer is arranged and is arranged substantially the same with the layer shown in Fig. 1.
(6) shown in back (referring to Fig. 6); the 6th kind of layer arranged and is configured to: form data record layer 18 in succession on first substrate 16; first reflection horizon 20 and first protective seam; and on the other hand; on second substrate 22, form visual information recording layer 24 in succession; second reflection horizon 26 and second protective seam, then, that first protective seam and second protective seam is laminated together via adhesive phase 28.
Layer shown in aforesaid Fig. 1 is arranged and layer arranges that (1) to (6) only is to describe by the mode of example.Arrange that at above-mentioned layer what can also allow is exchange sequence not only, and exchanges its parts a kind of or several given.Even omit its one or more parts (not comprising visual information recording layer 24), also do not go wrong.In addition, for every kind of layer, can allow to constitute by one or more layers.
In addition, as the variation example of optical data recording medium 10, can provide the structure shown in Fig. 3 and 4.Note, in Fig. 4, omitted data record layer 18 (with reference to figure 1).
Have the structure substantially the same according to the optical data recording medium 10b shown in Fig. 3 and 4 of second variation example with the structure of above-mentioned optical data recording medium 10.But its difference is: form print zone 36 on the inside circumference of second substrate, 22 first type surfaces.In addition, pre-pit district 30 is not overlapping with drafting district 34, obtains wherein arranging successively from neighboring to the inside circumference of second substrate 22 drawing district 34, the structure of pre-pit district 30 and print zone 36.
Can will for example print on it or the cover plate (coversheet) of the bar code of impressing pastes on the print zone 36.Can be by printing or impress on the cover board bar code recognition ProductName, fabricator's name, laser power etc.Form print zone 36 by the inside circumference at second substrate 22, the inside circumference of sealing optical data recording medium 10b makes the effect of the visually-perceptible that can improve the user.
Below, will explain two instantiations that comprise according to the basic structure of the optical data recording medium 10 of the present embodiment with reference to figure 5 to 11.
At first, as shown in Figure 5, according to the optical data recording medium of first embodiment (below be called " the first optical data recording medium 10A ") is a kind of optical data recording medium, on described optical data recording medium, can be by irradiation laser bundle 38 recorded informations, and described visual information recording layer 24 has the visual information recording layer 24 that can write down visual information on it.
As shown in Figure 6, have visual information recording layer 24 according to the optical data recording medium of second embodiment (below be called " the second optical data recording medium 10B "), wherein write down visual information at visual information recording layer 24 by laser beam 38 from colored substrate 22a one side irradiation by making second substrate, the 22 painted substrates that form (being designated hereinafter simply as " colored substrate 22a ") and on colored substrate 22a, forming.
As shown in Fig. 5 and 6, the first optical data recording medium 10A and the second optical data recording medium 10B have wherein data carrier part 12 and the visual information recording medium segment 14 help structure bonded to each other by adhesive phase 28.
As shown in Figure 5, the data carrier part 12 of the first optical data recording medium 10A comprises: first substrate 16 is formed with prefabricated groove 40 on the surface of described first substrate 16.Along protruding/concave portion, form data record layer 18 at first substrate, 16 lip-deep prefabricated grooves 40.On data record layer 18, form first reflection horizon 20.
As shown in Figure 5, the visual information recording medium segment 14 of the first optical data recording medium 10A comprises second substrate 22 with flat surfaces.On the surface of second substrate 22, form visual information recording layer 24.On visual information recording layer 24, form second reflection horizon 26.
With data carrier part 12 and visual information recording medium segment 14 when bonded to each other, as shown in Figure 5, relative with second reflection horizon 26 of formation on second substrate 22 in first reflection horizon 20 that forms on first substrate 16.In addition, data carrier part 12 and visual information recording medium segment 14 is bonded to each other, and meanwhile adhesive phase 28 is inserted between data carrier part 12 and the visual information recording medium segment 14.Thereby, construct the first optical data recording medium 10A by this way.
By laser beam 38 from first substrate, 16 1 side irradiation, can be at data record layer 18 identifying recording layers (pit information).
On the other hand, as shown in Figure 7, the data carrier part 12 of the second optical data recording medium 10B comprises first substrate 16, is formed with prefabricated groove 40 on the surface of described first substrate 16.Along protruding/concave portion, form data record layer 18 at first substrate, 16 lip-deep prefabricated grooves 40.On data record layer 18, form first reflection horizon 20, and on first reflection horizon 20, form first protective seam 42.
As shown in Figure 8, the visual information recording medium segment 14 of the second optical data recording medium 10B comprises the colored substrate 22a with flat surfaces.On colored substrate 22a, form visual information recording layer 24.On visual information recording layer 24, form second reflection horizon 26, and on second reflection horizon 26, form second protective seam 44.
With data carrier part 12 and visual information recording medium segment 14 when bonded to each other, as shown in Figure 6, first protective seam 42 that forms on first substrate 16 is relative with second protective seam 44 that forms on colored substrate 22a.In addition, data carrier part 12 and visual information recording medium segment 14 is bonded to each other, and meanwhile adhesive phase 28 is inserted between data carrier part 12 and the visual information recording medium segment 14.Therefore, construct the second optical data recording medium 10B by this way.
Especially, because the second optical data recording medium 10B adopts colored substrate 22a, as the information that obtains by detection pre-pit 32 or BCA, can provide the laser power control information corresponding to the colouring information of colored substrate 22a, purpose is to make that the visual information of record realizes favourable contrast on visual information recording layer 24.
Under the situation that adopts colored substrate 22a, there is the situation that does not wherein reach visual information recording layer 24 by colored substrate 22a absorption laser beam 38 and wherein given laser power.In the case, although must laser power be set by driver, it is difficult carrying out such setting by driver.But, adopt the second optical data recording medium 10B, settle the pre-pit district 30 (referring to Fig. 1) that is used to control laser beam 38 in the side of colored substrate 22a.Because pre-pit district 30 is included in the laser power control information that is used to control laser power corresponding to the colouring information of colored substrate 22a wherein, even when adopting colored substrate 22a, as the such information of drive access and based on it the result of laser power is set, the laser power that needs arrives visual information recording layer 24, so the visual information of enough contrasts can be recorded.
The visual information recording layer 24 that comprises in each at the first optical data recording medium 10A and the second optical data recording medium 10B contains dyestuff and at least a metallic atom, and described metallic atom is selected from: Na, Mg, K and Ca.
Dyestuff can be to be selected from least a in the following dyestuff: oxonol dye, cyanine dye, azo dyes, phthalocyanine dye and pyrroles's methylene dye.Preferably the absorptance with respect to laser beam is not less than 0.05 dyestuff.Dyestuff can use individually, or alternatively, can be used in combination two or more dyestuffs.
Among the first optical data recording medium 10A and the second optical data recording medium 10B, with respect to the dyestuff of 1kg, preferably with 0.1 to 100g ratio, more preferably with 1 to 50g ratio and more preferably contain metallic atom again with 1 to 10g ratio.If this ratio surpasses the upper limit, at visual information recording layer 14 crystallization appears.Therefore, be difficult to write down satisfactorily visual information thereon.On the other hand, if this ratio less than lower limit, its light permanance and/or heat durability become not enough.
In the first optical data recording medium 10A and the second optical data recording medium 10B, also suitable is: contain cyclonite cyanine dye and the phthalocyanine dye with central metal Cu in dyestuff.In the case, preferably with respect to the content of 50g as the Cu of central metal, the ratio with 0.1 to 10g and more preferably contain metallic atom with 1 to 5g ratio.
Below, will be referred to each layer, first substrate, 16, the second substrates 22 and colored substrate 22a, make an explanation.
[visual information recording layer 24]
As mentioned above, the first optical data recording medium 10A has visual information recording layer 24, described visual information recording layer 24 contains the principal ingredient dyestuff, wherein is different from data record layer 18 (preferably on apparent surface's a side) and settles visual information recording layer 24.The phrase of this paper " contains the principal ingredient dyestuff " and be meant that with respect to all solids content that contains, the content of dyestuff is not less than the fact of 50% (preferably being not less than 80%) in visual information recording layer 24.
The first optical data recording medium 10A and second optical data recording medium 10B visual information recording layer 24 separately contain dyestuff and at least a metallic atom, and described metallic atom is selected from: Na, Mg, K and Ca.
Because underlying cause, with respect to the dyestuff of 1kg, the ratio with 0.1 to 100g is preferably with 1 to 50g ratio and more preferably contain metallic atom with 1 to 10g ratio.Have ground,, crystallization occurs at visual information recording layer 14 if this ratio surpasses the upper limit.Therefore, be difficult to write down satisfactorily visual information.On the other hand, if this ratio less than lower limit, light permanance and/or heat durability are not enough.
When the dyestuff that will contain the cyclonite cyanine dye and have the phthalocyanine dye of central metal Cu is used for described dyestuff, preferably with respect to the content of 50g as the Cu of central metal, the ratio with 0.1 to 10g and more preferably contain metallic atom with 1 to 5g ratio.
Any visual information (image or literal) that can recording user is wished on visual information recording layer 24 comprises for example literal, figure and pattern.Visual information can comprise, for example, coils name, content information, and the content breviary, relational pattern, pattern is as design, copyright information, record date, recording method and record format.
For visual information recording layer 24 enough be, can be with this sample loading mode recorded information that can visual identity information, as literal, image and pattern.In this embodiment, preferably use and in 400 to 850nm optical wavelength range, have absorption maximum and have with respect to the laser beam of using be not less than 0.05 dyestuff of absorptance of (preferably be not less than 0.1 and be not more than 1.0).
The instantiation of dyestuff comprises: cyanine dye, imidazo quinoxaline-radical dye, pyrans-Ji and sulfo-pyranose dyestuff, azulenes-radical dye, side-radical dye, azo dyes, metal complex-radical dye (the phthalocyanine dye that contains Ni, Cr etc., the coupling metal chelating dye, pyrroles's methylene metal chelating dye), naphthoquinones-radical dye, anthraquinone-radical dye, indophenols-radical dye, indoles and aniline-radical dye, triphenyl methane-radical dye, merocyanine-radical dye, oxonols-radical dye, ammonium-radical dye, and ultraviolet absorber.Operable special preferred coloring agent is cyanine-radical dye according to the present invention, phthalocyanine-radical dye, azo dyes (comprising metal chelating dye), merocyanine-radical dye, oxonols-radical dye, and ultraviolet absorber.
By changing the length of dyestuff conjugated system, can obtain the dyestuff of the wavelength of the recording laser bundle 38 that is suitable for using in each case.When the laser beam 38 that with wavelength is 750 to 850nm writes down, for example, preferred wherein its methine chain length is 5 to 7 dyestuff under the situation of using cyanine dye and/or merocyanine dyes, and preferred wherein its methine chain length is 7 to 9 dyestuff under the situation of using oxonols-radical dye.
On the other hand, when the laser beam 38 that with wavelength is 600 to 700nm writes down, for example, preferred wherein its methine chain length is 3 to 5 dyestuff under the situation of using cyanine dye and/or merocyanine dyes, and preferred wherein its methine chain length is 5 to 7 dyestuff under the situation of using oxonols-radical dye.
When the laser beam 38 that with wavelength is 350 to 450nm writes down, can also use ultraviolet absorber and near ultraviolet absorbing agent.But, preferably in the wavelength zone of laser beam 38, demonstrate the dyestuff as mentioned above of additional absorption.Also preferably using methine length is that 1 cyanine dye and methine length are 1 oxonol dye.
Preferred dye combinations comprises respectively: the combination of oxonols and cyanine dye, the combination of oxonols and azo dyes, the combination of oxonol dye and another kind of oxonol dye, the combination of oxonols and phthalocyanine dye, the combination of oxonols and pyrroles's methylene dye, the combination of cyanine dye and another kind of cyanine dye, the combination of cyanine and azo dyes, the combination of cyanine and phthalocyanine dye, the combination of cyanine and pyrroles's methylene dye, the combination of azo and phthalocyanine dye, the combination of the combination of azo and pyrroles's methylene dye and phthalocyanine and pyrroles's methylene dye.
When the combination dyestuff, the content ratio between the dyestuff (quality ratio) is preferably 99: 1 to 1: 99, more preferably 95: 5 to 30: 70 and more preferably 90: 10 to 40: 60 again.
To explain oxonol dye now.Oxonol dye is that wherein oxonol dye preferably has the dyestuff of straight or branched acid core or ring-type acid core by the compound of following general formula (ch-1) expression, and wherein the quantity of methine is preferably 5 to 7.In the general formula (ch-1), n is preferably 1 to 4 integer.A plurality of R can form one or more rings.More preferably, use the oxonol dye of representing by general formula recited above (1-1).More preferably, use the dyestuff of representing by general formula (1-2).Again more preferably, use the dyestuff of general formula (ch-8) expression as described later.Can also use general formula (ch-2) as described later, (ch-3), (ch-4), (ch-5) with the dyestuff of (ch-6) representing.
Figure A20068004494800271
R: hydrogen or substituting group, n: be not less than 0 integer.
Can also comprise by the examples for compounds of general formula (ch-8) expression as described later by the compound of following general formula (ch-2) expression.
Figure A20068004494800281
In general formula (ch-2), R 11, R 12, R 13, R 14Independent and represent any in following respectively: hydrogen atom, replace or unsubstituted alkyl, replace or unsubstituted aryl and replacement or unsubstituted heterocyclic.R 21, R 22, R 3Represent any in following: hydrogen atom; replace or unsubstituted alkyl, replace or unsubstituted alkoxy, replace or unsubstituted aryl; replace or unsubstituted aryloxy group; replace or unsubstituted heterocyclic halogen atom, carboxyl; replace or unsubstituted alkoxy carbonyl group; cyano group replaces or unsubstituted acyl, replaces or unsubstituted carbamyl; amino; the amino that replaces, sulfo group, hydroxyl; nitro; replace or the unsubstituted alkyl sulfuryl amino, replace or unsubstituted arlysulfonylamino, replace or unsubstituted carbamyl amino; replace or the unsubstituted alkyl sulfonyl; replace or unsubstituted aryl sulfonyl, replace or the unsubstituted alkyl sulfinyl, replace or unsubstituted aryl sulfonyl kia and replacement or unsubstituted sulfamoyl.M represents to be not less than 0 integer.When m is not less than 2, a plurality of R 3Can be identical mutually, or different mutually.Z X+Expression kation and x represent to be not less than 1 integer.
In the general formula (ch-2), R 11, R 12, R 13, R 14Independent and represent any in following respectively: hydrogen atom, replace or unsubstituted alkyl, replace or unsubstituted aryl and replacement or unsubstituted heterocyclic.By R 11, R 12, R 13, R 14The replacement of expression or unsubstituted alkyl can be 1 to 20 alkyl example by carbon number.Work as R 11, R 12, R 13, R 14When representing alkyl respectively, they can be bonded to each other, to form carbocyclic ring or heterocycle.By R 11, R 12, R 13, R 14It is 1 to 8 straight or branched alkyl that the alkyl of expression is preferably carbon number, or naphthenic base, and more preferably carbon number is 1 to 5 alkyl, and carbon number is 1 to 8 naphthenic base, wherein R 11And R 12And R 13And R 14Being bonded to each other forms ring respectively, or the carbon number that replaces is 1 to 20 alkyl.
In general formula (ch-2) by R 11, R 12, R 13, R 14The replacement of expression or unsubstituted aryl can be 6 to 20 aryl example by carbon number.By R 11, R 12, R 13, R 14It is 6 to 10 aryl that the aryl of expression is preferably carbon number.
In general formula (ch-2) by R 11, R 12, R 13, R 14The replacement or the unsubstituted heterocyclic of expression are by carbon atom, nitrogen-atoms, oxygen atom, and/or the saturated or unsaturated heterocyclic radical of the 5-unit of sulphur atom formation or 6-unit.What can also allow is to use its benzo cyclic condensation and the material that obtains.By R 11, R 12, R 13, R 14The replacement of expression or unsubstituted heterocyclic preferably carbon number are 6 to 10 replacement or unsubstituted heterocyclic.
In general formula (ch-2) by R 11, R 12, R 13, R 14The replacement or the unsubstituted alkyl of expression, replacement or unsubstituted aryl and replacement or unsubstituted heterocyclic are by substituting group S example described below.
The substituting group of being represented by S comprises: carbon number is 1 to 20 alkyl; carbon number is 7 to 20 aralkyl; carbon number is 1 to 8 alkoxy; carbon number is 6 to 20 aryl; carbon number is 6 to 20 aryloxy group, heterocyclic radical, halogen atom; carboxyl; carbon number is 2 to 10 alkoxy carbonyl group, and cyano group, carbon number are 2 to 10 acyl group; carbon number is 1 to 10 carbamyl; amino, carbon number are 1 to 20 substituted-amino, sulfo group; hydroxyl; nitro, carbon number are 1 to 10 alkyl sulfonyl-amino, and carbon number is 1 to 10 carbamyl amino; carbon number is 1 to 10 sulfonyl, and carbon number is that 1 to 10 sulfinyl and carbon number are 0 to 10 sulfamoyl.Under the situation of carboxyl and sulfo group, these materials can adopt the form of salt.
R in the general formula (ch-2) 21, R 22, R 3Independent and represent any in following respectively: hydrogen atom; replace or unsubstituted alkyl; replace or unsubstituted alkoxy; replace or unsubstituted aryl, replace or unsubstituted aryloxy group, replace or unsubstituted heterocyclic; halogen atom; carboxyl replaces or unsubstituted alkoxy carbonyl group cyano group; replace or unsubstituted acyl; replace or unsubstituted carbamyl amino, the amino of replacement; sulfo group; hydroxyl, nitro replaces or the unsubstituted alkyl sulfuryl amino; replace or unsubstituted carbamyl amino; replace or the unsubstituted alkyl sulfonyl, replace or unsubstituted aryl sulfonyl, replace or unsubstituted sulfinyl and replacement or unsubstituted sulfamoyl.As for R 21, R 22, R 3The material that will be used for this is preferably hydrogen atom, carbon number is 1 to 20 replacement or unsubstituted alkyl, carbon number is 2 to 20 replacement or unsubstituted heterocyclic, carbon number is 1 to 20 replacement or unsubstituted alkoxy, and carbon number is 6 to 20 replacement or unsubstituted aryl and halogen atom.More preferably, the material that will be used for this is a hydrogen atom, and carbon number is 1 to 10 replacement or unsubstituted alkyl, and carbon number is 1 to 10 replacement or unsubstituted alkoxy, and carbon number is 2 to 10 replacement or unsubstituted heterocyclic and halogen atom.Again more preferably, the material that will be used for this is any of following groups: hydrogen atom, carbon number are 1 to 5 replacement or unsubstituted alkyl, and carbon number is 1 to 5 unsubstituted alkoxy, carbon number is 2 to 6 replacement or unsubstituted heterocyclic, and halogen atom.R 21, R 22, R 3Can further contain substituting group.Such substituting group is by substituting group S example recited above.
Preferably m is 0, and R 21And R 22It all is hydrogen atom.Further preferably m is 1, and R 21, R 22, R 3It all is hydrogen atom.
The integer that in the general formula (ch-2), m represents to be not less than 0 integer, preferred 0 to 5 (be not less than 0 and be not more than 5), more preferably 0 to 3 integer and more preferably 0 to 2 integer again.
In the general formula (ch-2), be not less than at 2 o'clock at m, a plurality of R 3Can be identical mutually, or different mutually, wherein a plurality of R 3Independently and respectively represent hydrogen atom or its aforesaid substituting group.
In the general formula (ch-2), Z X+The expression kation, and x represents to be not less than 1 integer.
By Z X+The kation of expression is preferably quaternary ammonium ion, and more preferably announce 4 of general formula (I-4) expression described in the 2000-52658 as Japanese publication, 4 '-bipyridine cation and as Japanese publication announce 2002-59652 disclosed 4,4 '-bipyridine cation.In the general formula (ch-2), x is preferably 1 or 2.
Under the situation of oxonol dye, the preferred compound that uses by aforesaid general formula (1-1) expression.
Below, with the following above-mentioned general formula (1-1) of explaining in further detail.In the general formula (1-1), Za 25, Za 26Independent and be respectively the atomic group that is used for forming acid core.This acid core with in above-mentioned general formula (1-2) by Za 21, Za 22, Za 23, Za 24Those acid core synonyms that form.Its instantiation is also identical or suitable.By Za 25, Za 26The acid core that forms is preferably 2,3-dihydro-1,3-indenes diketone, pyrazolone, pyrazoline diketone and Bendioxide bithiophene ketone.Especially, pyrazolone most preferably.
Ma 27, Ma 28, Ma 29Independently replace or unsubstituted methine itself and the Ma that represents by general formula (1-2) with being respectively 21, Ma 22, Ma 23, Ma 24, Ma 25, Ma 26Synonym.Instantiation is also identical or suitable with preferred embodiment.Ma 27, Ma 28, Ma 29Be preferably unsubstituted methine.
Ka 23Be illustrated in integer in 0 to 3 scope.Ka 23With the Ka in the general formula (1-2) 21, Ka 22Synonym.Under any circumstance, Ka 23Be preferably 2.During Q represents to be used for and the monovalent cation of electric charge.
At Ka 23When being a plurality of, a plurality of Ma 27, Ma 28, Ma 29Can be identical mutually, or different mutually.
Dyestuff with structure of being represented by above-mentioned general formula (1-1) (ch-4), (ch-5) and (ch-6) is represented preferably by general formula (ch-3).
General formula (ch-3), (ch-4), (ch-5) and (ch-6) in, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 32, R 33, R 34, R 41, R 42, R 43, R 44Independent and be respectively hydrogen atom or substituting group.Ma 27, Ma 28, Ma 29Independently replace or unsubstituted methine with being respectively.Ka 23Be illustrated in the integer in 0 to 3 scope.During Q represents to be used for and the monovalent cation of electric charge.At Ka 21, Ka 22When being a plurality of, a plurality of Ma 27, Ma 28Can be identical mutually, or different mutually.
General formula (ch-3), (ch-4), (ch-5) and (ch-6) in, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 32, R 33(in some cases, these are called " R ") independently and respectively represents hydrogen atom or substituting group.Substituent example can comprise halogen atom; replace or unsubstituted alkyl; replace or unsubstituted thiazolinyl; replace or unsubstituted alkynyl; replace or unsubstituted aryl; replace or unsubstituted heterocyclic; cyano group; hydroxyl; nitro; carboxyl; replace or unsubstituted alkoxy; replace or unsubstituted aryloxy group; replace or unsubstituted siloxy; replace or unsubstituted heterocyclic oxy group; replace or unsubstituted acyloxy; replace or unsubstituted carbamyl oxygen base; replace or unsubstituted alkoxy carbonyl oxygen base; replace or unsubstituted aryloxy group carbonyl oxygen base; replace or unsubstituted amino, replace or unsubstituted acyl amino, replace or unsubstituted amino carbonyl amino; replace or unsubstituted alkoxycarbonyl amido; replace or unsubstituted aryloxy carbonyl amino, replace or unsubstituted sulfamoyl amino replacement or unsubstituted alkyl and arlysulfonylamino; replace or unsubstituted sulfydryl; replace or unsubstituted alkylthio group, replace or unsubstituted arylthio, replace or unsubstituted heterocycle sulfenyl; replace or unsubstituted sulfamoyl; sulfo group, replacement or unsubstituted alkyl and aryl sulfonyl kia, replacement or unsubstituted alkyl and aryl sulfonyl; replace or unsubstituted acyl; replace or unsubstituted aryloxy carbonyl, replace or unsubstituted alkoxy carbonyl group, replace or unsubstituted carbamyl; replace or unsubstituted aryl and heterocycle azo base; replace or unsubstituted imide, replace or unsubstituted phosphino-, replace or unsubstituted phosphono; replace or unsubstituted phosphono oxygen base, replace or unsubstituted phosphono amino and replacement or unsubstituted silicyl.
Most preferably, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28Be hydrogen atom.
As for R 31, R 34, R 41, R 42, R 43, R 44, example the substituting group identical with those substituting groups of R arranged.But, preferably select hydrogen atom, replace or unsubstituted alkyl, or replacement or unsubstituted aryl.Especially, more preferably, should select to replace or unsubstituted aryl.
Ma 27, Ma 28, Ma 29Independent and be respectively and replace or unsubstituted methine, the Ma of itself and above-mentioned general formula (1-1) 27, Ma 28, Ma 29Synonym.It is also identical or suitable with preferred embodiment that it has an example.Ka 23Independently with the integer that is illustrated respectively in 0 to 3 scope.Ka 23Be preferably 2.During Q represents to be used for and the monovalent cation of electric charge.At Ka 23When being a plurality of, a plurality of Ma 27, Ma 28Can be identical mutually, or different mutually.
Dyestuff with structure of being represented by general formula (1-1) is preferably the dyestuff that has by the structure of following general formula (ch-7) expression.
Figure A20068004494800341
To the compound with structure of being represented by general formula (ch-7) at length be made an explanation now.
In the general formula (ch-7), R 51, R 52, R 53, R 54, R 55, R 56, R 57, R 58, R 59, R 60Independently and respectively represent hydrogen atom or substituting group.Under substituent situation, the preferred selection replaces or unsubstituted alkyl, replaces or unsubstituted alkoxy, and halogen atom replaces or unsubstituted carbamyl, or replacement or unsubstituted acyl amino.Especially, preferred its whole substituting groups of selecting wherein all are the compound of hydrogen and R wherein 51, R 53, R 55, R 56, R 58, R 60That replaced by halogen atom and R 52, R 54, R 57, R 59It is the compound of hydrogen atom.R 61, R 67The expression hydrogen atom replaces or unsubstituted alkyl, replaces or unsubstituted aryl; cyano group replaces or unsubstituted carbamyl, replaces or unsubstituted alkoxy; replace or unsubstituted alkoxy carbonyl group, replace or unsubstituted aryloxy carbonyl, or replacement or unsubstituted acyl amino.Especially, preferably replace or unsubstituted alkoxy carbonyl group, and more preferably unsubstituted again alkoxy carbonyl group.
R 62, R 63, R 64, R 56, R 66Independently and respectively represent hydrogen atom, replace or unsubstituted alkyl, replace or unsubstituted aryl, replace or unsubstituted acyl amino, or replacement or unsubstituted heterocyclic.R preferably 62, R 63, R 65, R 66It all is hydrogen atom.R preferably 64Be hydrogen atom or replacement or unsubstituted aryl.
R 71, R 72, R 73, R 74, R 75, R 76, R 77, R 78, R 79, R 80, R 81, R 82, R 83, R 84, R 85, R 86, R 87, R 88Independently and respectively represent hydrogen atom or substituting group.Under substituent situation, the preferred selection replaces or unsubstituted alkyl, replaces or unsubstituted aryl hydroxyl, or replacement or unsubstituted acyl amino.R preferably 71, R 72, R 75, R 76, R 77, R 80It all is hydrogen atom.R preferably 73, R 78It is respectively hydroxyl.R preferably 74, R 79It is respectively phenyl.
R preferably 81, R 82, R 83, R 84, R 85, R 86, R 87, R 88It all is hydrogen atom.
Then, below will at length make an explanation to dyestuff with structure of representing by above-mentioned general formula (1-2).
In the general formula (1-2), Za 21, Za 22, Za 23, Za 24Independently with the atomic group of representing to form acid core respectively.The example is described in " The Theory of the Photographic Process ", the 4th edition, is edited Macmillan, 1977, the 198 pages by James.Specifically, there is the following nuclear of example respectively: for example, pyrazoles-5-ketone (can be substituted), pyrazolidine-3, the 5-diketone, imidazoline-5-ketone, hydantoins, 2-or 4-thio-hydantoin, 2-Ya An Ji oxazolidine-4-ketone, 2-oxazoline-5-ketone, 2-Liu oxazolines-2,4-diketone, different rhodanine, rhodanine, thiophene-3-ketone, thiophene-3-ketone-1, the 1-dioxide, 3,3-dioxo [1,3] oxygen thia penta ring (oxathiolane)-5-ketone, Indolin-2-one, indoline-3-ketone, 2-oxo indazole, 5,7-dioxo-6,7-thiazoline be [3,2-a] pyrimidine also, and 3,4-difluoro isoquinoline-4-ketone, 1,3-diox-4, the 6-diketone is (for example, Meldrum ' s acid), barbiturates, 2-thiobarbituricacid, cumarin-2, the 4-diketone, indazole quinoline (indazoline)-2-ketone, pyrido [1,2-a] pyrimidine-1, the 3-diketone, pyrazolo [1,5-b] quinazolinone, Pyrazolopyridine ketone and 5-unit or 6-unit carbocyclic ring (for example, hexane-1, the 3-diketone, pentane-1,3-diketone, 1,2-dihydroindene-1,3-diketone).In the middle of these, pyrazoles-5-ketone preferably, pyrazolidine-3,5-diketone, barbiturates, 2-thiobarbituricacid, 1,3-diox-4,6-diketone and 3,3-dioxo [1,3] oxygen thia penta ring-5-ketone.
Za 21, Za 22, Za 23, Za 24Can be substituted respectively.In the case, most preferably 1,3-diox-4,6-diketone.
The substituent example that is used for replacing acid core comprises: halogen atom, alkyl (comprising naphthenic base and bicyclic alkyl), thiazolinyl (comprising cycloalkenyl group and bicyclic alkenyl), alkynyl; aryl, heterocyclic radical, cyano group; hydroxyl, nitro, carboxyl; alkoxy, aryloxy group, siloxy; heterocyclic oxy group, acyloxy, carbamyl oxygen base; alkoxy carbonyl oxygen base, aryloxy group carbonyl oxygen base, amino (comprising anilino-); acyl amino, amino carbonyl amino, alkoxycarbonyl amido; aryloxy carbonyl amino, sulfamoyl amino, alkyl and arlysulfonylamino; sulfydryl, alkylthio group, arylthio; the heterocycle sulfenyl, sulfamoyl, sulfo group; alkyl and aryl sulfonyl kia, alkyl and aryl sulfonyl, acyl group; aryloxy carbonyl, alkoxy carbonyl group, carbamyl; aryl and heterocycle azo base, imide, phosphino-; phosphono, phosphono oxygen base, phosphono amino and silicyl.Especially, preferably selecting carbon number is 1 to 20 replacement or unsubstituted alkyl, or carbon number is 6 to 20 replacement or unsubstituted aryl.
As for acid core, preferably select unsubstituted those acid core, be those acid core that 1 to 20 replacement or unsubstituted alkyl replace by carbon number, or be those acid core that 6 to 20 replacement or unsubstituted aryl replace by carbon number.
By Za 21, Za 22, Za 23, Za 24The acid core that forms is preferably 2,3-dihydro-1,3-indenes diketone, pyrazolone, pyrazoline diketone and Bendioxide bithiophene ketone.Especially, pyrazolone most preferably.
Ma 21, Ma 22, Ma 23, Ma 24, Ma 25, Ma 26Independently replace or unsubstituted methine with being respectively.Substituting group preferably includes, for example, carbon number be 1 to 20 alkyl (for example; methyl, ethyl and isopropyl), halogen atom is (for example; chlorine, bromine, iodine; and fluorine), carbon number is 1 to 20 alkoxy (for example, methoxyl; ethoxy and isopropoxy), carbon number is 6 to 26 aryl (for example, phenyl and 2-naphthyl); carbon number is 0 to 20 heterocyclic radical (for example, 2-pyridine radicals and 3-pyridine radicals), carbon number be 6 to 20 aryloxy group (for example; phenoxy group, 1-naphthoxy and 2-naphthoxy), carbon number be 1 to 20 acyl amino (for example; acetyl-amino and benzoyl-amido); carbon number is 1 to 20 carbamyl (for example, N, N-formyl-dimethylamino); sulfo group; hydroxyl, carboxyl, carbon number be 1 to 20 alkylthio group (for example; and cyano group methyl mercapto).This group can be incorporated on another methine to form ring structure.This group can be incorporated into by Za 21, Za 22, Za 23, Za 24On any atomic group of expression, to form ring structure.
Ma 21, Ma 22, Ma 23, Ma 24, Ma 25, Ma 26Independent and be preferably unsubstituted methine respectively and by ethyl, any in the methine that methyl and/or phenyl replace.Ma most preferably 21, Ma 22, Ma 23, Ma 24, Ma 25, Ma 26It is unsubstituted methine.
L represents divalent linker, and it is with not forming pi-conjugated system with two keys.Divalent linker is not particularly limited, still between the chromophore that their connect therein, does not form outside the fact the pi-conjugated system.But, L represents that preferably carbon number is to be not less than 0 and be not more than 100 and preferably be not less than 1 and be not more than 20 linking group, it is by making up one or more formations in the following group: (carbon number is 1 to 20 to alkylidene, for example, methylene, ethylidene, propylidene, butylidene and pentylidene), (carbon number is 6 to 26 to arlydene, for example, phenylene and naphthylene), alkenylene (carbon number is 2 to 20, for example, and ethenylidene and allylidene), (carbon number is 2 to 20 to alkynylene, for example, ethynylene and alkynylene) ,-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/or inferior heterocyclic radical (carbon number is 1 to 26, for example, and 6-chloro-1,3,5-triazolyl-2,4-two base and pyrimidines-2,4-two bases).Above-mentioned R 101, R 102, R 103, R 104, R 105Independent and represent any in following respectively: hydrogen atom, replacement or unsubstituted alkyl and replacement or unsubstituted aryl.One or more perhaps a plurality of linking groups of being represented by L may reside between two chromophories of their connections.A plurality of (preferred two) linking group can be connected to form ring.
Preferably, as for L, respectively two alkylidenes (preferred ethylidene) are encircled in conjunction with forming.Especially, more preferably form 5-unit or 6-unit ring (preferred cyclohexyl ring).
In the general formula (1-2), Ka 21And Ka 22Independent and be illustrated respectively in integer in 0 to 3 scope.
At Ka 21, Ka 22When being a plurality of, a plurality of Ma 21, Ma 22, Ma 25, Ma 26Can be identical mutually, or different mutually.
Preferred Ka 21And Ka 22All be 2.
During Q represents to be used for and the monovalent cation of electric charge.Therefore, 2Q represents bivalent cation.The ion of being represented by Q is not particularly limited.Ion can be made up of mineral compound, or ion can be made up of organic compound.The kation of being represented by Q comprises, for example, metallic ion such as sodion and potassium ion and ion such as quaternary ammonium ion, oxonium ion, sulfonium cation ， Phosphonium ion,
Figure A20068004494800371
Ion, and iodide ion.
The kation of being represented by Q is preferably ion, more preferably quaternary ammonium ion.Particularly preferred quaternary ammonium ion be as announce in Japanese publication 4,4 of general formula (I-4) expression described in the 2000-52658 '-bipyridine cation and Japanese publication announce disclosed 4,4 among the 2002-59652 '-bipyridine cation.Two cationic compounds as 4,4 '-situation of bipyridine cation under, Q accounts for 1/2 (two cationic compounds).
Preferably, in above-mentioned general formula (1-2), by Za 21, Za 22, Za 23, Za 24The acid core that forms is independent and be respectively pyrazoles-5-ketone, pyrazolidine-3,5-diketone, barbiturates, 2-thiobarbituricacid, 1,3-diox-4,6-diketone and 3,3-dioxo [1,3] oxygen thia penta ring-5-ketone, they are unsubstituted, and they are that 1 to 20 replacement or unsubstituted alkyl replace by carbon number, or they are that 6 to 20 replacement or unsubstituted aryl replace by carbon number.Ma 21, Ma 22, Ma 23, Ma 24, Ma 25, Ma 26Independent and be respectively unsubstituted methine or the methine that replaced by ethyl, methyl or phenyl in any.5-unit or the 6-unit ring of L shaped one-tenth by forming in conjunction with two alkylidenes (preferred ethylidene).Ka 21, Ka 22All be 2.In addition, the kation of representing by 2Q be as announce in Japanese publication 4,4 of general formula (I-4) expression described in the 2000-52658 '-bipyridine cation and announce in Japanese publication disclosed 4,4 among the 2002-59652 '-bipyridine cation.In dyestuff by general formula (1-2) expression, the preferred dyestuff of selecting by following general formula (ch-8) expression.
Figure A20068004494800391
In the general formula (ch-8), R 1, R 2Independently and respectively represent hydrogen atom, replace or unsubstituted alkyl, or replacement or unsubstituted aryl.R 3, R 4, R 5Independent and be respectively hydrogen atom or its substituting group.R 1, R 2Can be bonded to each other and form ring.A plurality of R 6Independently and respectively represent hydrogen atom, replace or unsubstituted alkyl, or replacement or unsubstituted aryl.L 1It is divalent linker.Two R 6Can be in conjunction with forming divalent linker.N, m independence and the integer that is illustrated respectively in 0 to 2 scope.During Q represents to be used for and the monovalent cation of electric charge.At n, when m is a plurality of value, a plurality of R 3, R 4Can be identical mutually, or different mutually.
To explain general formula (ch-8) in detail below.R 1, R 2Independently and respectively represent hydrogen atom, replace or unsubstituted alkyl, or replacement or unsubstituted aryl.R 1, R 2The formation ring structure can be bonded to each other.Preferably, R 1, R 2Independently replace or unsubstituted alkyl with being respectively.More preferably, R 1, R 2Be unsubstituted alkyl, it has 1 to 6 carbon number separately, and they are different mutually.R 3, R 4, R 5The group of independently and respectively representing hydrogen atom or replacement.Preferably, R 3, R 4, R 5Be hydrogen atom, replace or unsubstituted alkyl, replace or unsubstituted aryl, or replacement or unsubstituted heterocyclic.More preferably, R 3, R 4, R 5Be hydrogen atom, ethyl, methyl, or phenyl.R most preferably 3, R 4, R 5It all is hydrogen atom.R 6Be hydrogen atom, replace or unsubstituted alkyl, or replacement or unsubstituted aryl.Especially, two R preferably 6The formation divalent linker is bonded to each other.L 1It is divalent linker.Preferably, L 1Be to replace or unsubstituted alkylidene.As for L 1And R 6, most preferably ring structure is by L 1With two on R 6Form.In the case, ring structure is preferably 5-unit or 6-unit ring (more preferably 6-unit ring).N, m independence and the integer that is illustrated respectively in 0 to 2 scope.Preferred n and m are 2.During Q represents to be used for and the monovalent cation of electric charge.Therefore, 2Q represents bivalent cation.At n, when m is a plurality of, a plurality of R 3, R 4Can be identical mutually, or different mutually.
Can synthesize general oxonol dye by the condensation reaction between corresponding methylene compound and the methine source (that is, being used for methine is incorporated into the compound of methine dyes).For the details of such compound, can be respectively with reference to the instructions of following patent: Japanese patent publication 39-22069,43-3504,52-38056,54-38129,55-10059, and 58-35544, Japanese publication is announced 49-99620,52-92716,59-16834,63-316853, and 64-40827, BrP 1133986 and United States Patent (USP) 3,247,127,4,042,397,4,181,225,5,213,956 and 5,260,179.Such compound also is described in Japanese publication respectively and announces 63-209995,10-309871 and 2002-249674.
In addition, the method that is used for synthetic dimorphism oxonol dye is disclosed in European patent EP 1424691A2.
Below, also can be used for described dyestuff as cyanine dye by above-mentioned general formula (2-1) expression.
In the general formula (2-1), Ma 21, Ma 22, Ma 23Independently and respectively represent to replace or unsubstituted methine.R 1, R 2Independently and respectively represent substituting group.But preferred the selection replaces or unsubstituted alkyl, replaces or unsubstituted aryl, replaces or unsubstituted thiazolinyl, replace or unsubstituted alkynyl, or replacement or unsubstituted heterocyclic.Above-mentioned group can further be substituted.R 101, R 102Be preferably and replace or unsubstituted alkyl, more preferably, carbon number be 1 to 8 replacement or unsubstituted alkyl and more more preferably carbon number be 1 to 8 unsubstituted alkyl.R 101, R 102Can be different mutually, or identical mutually.But, preferred R 101And R 102Identical mutually.Ka2 is illustrated in the integer in 0 to 3 scope.Be not less than at 2 o'clock at ka2, a plurality of Ma 21And Ma 22Can be identical mutually, or different mutually.
During Q2 represents to be used for and the ion of electric charge, and y2 represent in and the number of electric charge needs.Represent negative ion by the ion that Q2 represents, depend on the electric charge of corresponding dye molecule.To the ion represented by Q2 without limits, and the ion that can form by mineral compound or the ion of forming by organic compound.The electric charge of the ion of being represented by Q2 can be monovalence or multivalence.
During y2 represents and the number of electric charge needs.When Q2 is dianion, and if y2 be 1/2, think that so Q2y2 is univalent anion as a whole.
Below, also can be used for described dyestuff as dyestuff by above-mentioned general formula (2-2) expression.
In the general formula (2-2), R 121, R 122, R 123Be hydrogen atom or substituting group.R 124, R 125, R 126, R 127Also be hydrogen atom or substituting group.This substituting group and R 1a, R 2aSynonym, and its preferred embodiment is also suitable.R 1a, R 2aWith the R in the above-mentioned general formula (2-1) 101, R 102Synonym, and its preferred embodiment is also suitable.Ka2 synonym in ka3 and the general formula (2-1), and its preferred embodiment is also suitable.
During Q3 represents to be used for and the ion of electric charge and y3 represent in and the number of electric charge needs.Represent negative ion by the ion that Q3 represents, depend on the electric charge of corresponding dye molecule.To the ion represented by Q3 without limits, and the ion that can form by mineral compound or the ion of forming by organic compound.The electric charge of the ion of being represented by Q3 can be monovalence or multivalence.The ion of being represented by Q3 comprises, for example, and halide anion such as chlorion, bromide ion, and fluorine ion, heteropoly acid ion such as sulfate ion, phosphate ion, and phosphoric acid hydrogen radical ion, organic multivalent anions such as succinic acid ion, maleic acid ion, the fumaric acid ion, with aromatics disulfonic acid ion, tetrafluoro boric acid ion and hexafluorophosphoric acid ion.
During y3 represents and the number of electric charge needs.Y2 synonym in y3 and the general formula (2-1).When Q3 is dianion, and if y3 be 1/2, think that so Q3y3 is univalent anion as a whole.
For use in this embodiment by the general formula (2-1) or (2-2) cyanine dye of expression, Ma 21, Ma 22, Ma 23Be preferably unsubstituted methine, R 101, R 102Independent and to be preferably carbon number respectively be 1 to 8 unsubstituted alkyl, R 124, R 125, R 126, R 127Independently replace or unsubstituted alkyl with being respectively, Ka3 is preferably 1 or 2, and Q3 is preferably inorganic or organic anion, and y3 is preferably 1.Most preferably satisfy the dyestuff of whole preferred features as mentioned above.
Instantiation should be with reference to about having the cyanine compound by the structure of general formula (2-1) expression, and described cyanine compound is used for the first optical data recording medium 10A and the second optical data recording medium 10B.Be to be understood that and the invention is not restricted to described instantiation.
General cyanine dye is described in " Cyanine Dyes and Related Compounds ", JohnWiley ﹠amp; Sons, New York, London, in 1964 with serial issue, " The Chemistryof Heterocyclic Compounds ".
In embodiment of the present invention, consider the optical characteristics of amorphous film, cyanine dye (the preferably dye composition of being represented by above-mentioned general formula (2-1)) has following feature.Particularly, the coefficient n of the complex refractive index of recording laser wavelength (real part: refractive index), k (imaginary part: extinction coefficient) preferably satisfy expression formula 1.50≤n≤3.0 and 0.9≤k≤3.00.More preferably coefficient satisfies expression formula 1.50≤n≤2.00 and 0.90≤k≤2.00.More preferably coefficient satisfies expression formula 1.60≤n≤1.90 and 1.20≤k≤1.50 again.
Preferred heat decomposition temperature is in 100 ℃ to 350 ℃ scopes.More preferably heat decomposition temperature should be in 150 ℃ to 300 ℃ scopes.More preferably heat decomposition temperature should be in 200 ℃ to 300 ℃ scopes again.
Below, can also be with azo dyes as described dyestuff.Synthesize azo dyes by compound (colour coupler compound) reaction that makes aryl or heteroaryl diazo salt (diazo composition) and have an acid hydrogen atom, purpose is to prepare dyestuff by carrying out azo coupling with diazo salt.Operable in this embodiment azo dyes preferably has the structure by above-mentioned general formula (3-1) expression.
In the formula, A represents the residue of compound (colour coupler compound), and promptly derived from the univalent perssad of colour coupler composition, it comprises acid hydrogen atom, to prepare dyestuff by carrying out azo coupling with diazo salt.A is preferably and replaces or unsubstituted aryl, or carbon number is 1 to 20 and contains the 5-unit heterocyclic radical of nitrogen-atoms, or carbon number is 2 to 20 and contains the 6-unit heterocyclic radical of nitrogen-atoms.
Have by the dyestuff of the structure of above-mentioned general formula (3-1) expression preferably by the dyestuff of general formula (3-2) expression.
In dyestuff with structure of representing by general formula (3-2), A 1Expression is used for forming with the carbon atom that connects the atomic group of aromatic hydrocarbon ring or aromatic heterocycle.By A 1The ring that forms preferably has substituent aromatic hydrocarbon ring (preferably having substituent phenyl ring), carbon number is 1 to 20 and contains the 5-unit heterocycle of nitrogen-atoms, or carbon number is 2 to 20 and contains the 6-unit heterocycle of nitrogen-atoms and the substituting group aromatic hydrocarbon ring (preferably having substituent phenyl ring) that more preferably has.
By substituent A or A 1Below the example of the structure that forms is shown in:
Figure A20068004494800431
R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22Independently and respectively represent hydrogen atom or its substituting group.
In above-mentioned ring structure, preferably by formula (ch-9), (ch-10) with those ring structures of (ch-11) representing.
In the above-mentioned general formula, R 11, R 13Be preferably carbon number and be 1 to 20 replacement or unsubstituted alkyl, carbon number is 6 to 20 replacement or unsubstituted aryl, cyano group, carbon number are 1 to 20 replacement or unsubstituted alkoxy carbonyl group, or carbon number is 2 to 20 replacement or unsubstituted amino carbonyl.R 14Be preferably cyano group, carbon number is 1 to 20 replacement or unsubstituted alkoxy carbonyl group, and carbon number is 6 to 20 replacement or unsubstituted aryloxy group, or carbon number is 2 to 20 replacement or unsubstituted amino carbonyl.R 15For carbon number is 1 to 20 replacement or unsubstituted alkyl, carbon number is 6 to 20 aryl, or carbon number is 1 to 20 replacement or unsubstituted amino carbonyl amino.
Preferably, R 13Be cyano group, R 14For carbon number is 1 to 20 alkoxy carbonyl group, and R 15For carbon number is 1 to 20 replacement or unsubstituted alkyl, or carbon number is 6 to 20 replacement or unsubstituted aryl.
B represents univalent perssad, and described univalent perssad is derived from diazo salt, and it is preferably and replaces or unsubstituted aryl, or replacement or unsubstituted heterocyclic.In other words, B is the diazonium composition.The diazonium composition is to be converted into substituting group and to be incorporated into diazo-compounds (diazo salt) by having amino heterogeneous ring compound or benzene derivative, carries out the part-structure of diazo coupling simultaneously with colour coupler.This notion is used in the azo dyes of being everlasting.In other words, the diazonium composition is the heterogeneous ring compound that can carry out the amino-replacement of diazo reaction, or the substituting group that obtains by the amino of removing benzene derivative, so that univalent perssad to be provided.B is preferably by B 2The ring that forms.B 2Expression is used for forming the atomic group of replacement or unsubstituted aromatic hydrocarbon ring or replacement or unsubstituted aromatic heterocycle.By B 2The ring of expression preferably has substituent aromatic hydrocarbon ring (preferably having substituent phenyl ring), and carbon number is 1 to 20 and contains the 5-unit heterocycle of nitrogen-atoms, or carbon number is 2 to 20 and contains the 6-unit heterocycle of nitrogen-atoms.More preferably, by B 2The ring of expression is that carbon number is 1 to 20 and contains the 5-unit heterocycle of nitrogen-atoms, or carbon number is 2 to 20 and contains the 6-unit heterocycle of nitrogen-atoms, and to be more preferably carbon number again be 1 to 20 and contain the 5-unit heterocycle of nitrogen-atoms.
The example of monovalence heterocycle A and B can be by any one example in following (ch-23) to (ch-47).
Figure A20068004494800451
Figure A20068004494800461
In the superincumbent general formula, R 21To R 50Independently and respectively represent hydrogen atom or its substituting group.
B, c are the integers in 0 to 6 scope.
A, p, q, r are the integers in 0 to 4 scope.
D, e, f, g, t, u are the integers in 0 to 3 scope.
H, i, j, k, l, o are the integers in 0 to 2 scope.
Be not less than at 2 o'clock at a to u, plural by R 21To R 50The substituting group of expression can be identical mutually, or different mutually.
About structure B, preferably descend array structure (ch-48) to (ch-60).
Figure A20068004494800471
In the above-mentioned general formula, R 11, R 12, R 13, R 14, R 15, R 61To R 66, R 71, R 72Independently and respectively represent hydrogen atom or its substituting group.Substituent example with relate to described those substituting groups of the explanation of R identical.
The G of general formula (3-2) represents to have the univalent perssad with the ability of metallic ion coordination.The example of G comprises: hydroxyl, carboxyl, amino (comprising alkyl amino); acyl amino, amino carbonyl amino, alkoxycarbonyl amido; aryloxy carbonyl amino, sulfamoyl amino, alkyl or aryl sulfuryl amino; sulfydryl, sulfamoyl, sulfo group; alkyl and aryl sulfonyl kia; carbamyl, aryl and heterocycle azo base, phosphino-and phosphono.Preferably, G is an alkyl sulfonyl-amino.
Azo dyes compounds according to this embodiment also is preferably selected from: have with the ability of metallic ion coordination to form the compound of azo-metal chelate dye.Especially, this chelating dyes has excellent light permanance, and this is preferred.The metallic ion that is used for metal chelating dye is preferably selected from: Ni, Cu, Zn, Al, Ti, Fe, B, Cr and Co.Especially, preferred Ni, Co and Al.
When forming chelate structure, if part is not enough with respect to central metal, make to form stable complex unsuccessfully, so also preferably the molecule different with the dyestuff of above-mentioned general formula (3-1) added as part, so that the stable chelated dyestuff to be provided.Separately the part that adds is preferably the compound that contains nitrogen, oxygen and/or sulphur atom.Especially, preferably use amines (comprising aniline) and contain the heterogeneous ring compound of at least one nitrogen-atoms.Most preferably using carbon number is 3 to 20 5-unit or 6-unit amines.
The method that is used for synthetic azo dyes is described in Japanese publication respectively and announces 3-268994,3-61088, and 7-161069,7-251567,10-204070,11-12483,11-166125,2001-199169 is among 2001-152040 and the 2002-114922.
In embodiment of the present invention, consider the optical characteristics of amorphous film, dye composition has following feature.Particularly, the coefficient n of the complex refractive index of recording laser wavelength (real part: refractive index), k (imaginary part: extinction coefficient) preferably satisfy expression formula 2.0≤n≤3.0 and 0.00≤k≤0.20.More preferably coefficient satisfies expression formula 2.1≤n≤2.7 and 0.00≤k≤0.10.More preferably coefficient satisfies expression formula 2.15≤n≤2.50 and 0.00≤k≤0.05 again.
In the azo dyes compounds according to embodiment of the present invention, preferred heat decomposition temperature is in 100 ℃ to 350 ℃ scopes.More preferably heat decomposition temperature should be in 150 ℃ to 300 ℃ scopes.Again more preferably heat decomposition temperature in 200 ℃ to 300 ℃ scopes.
Below, can be with phthalocyanine dye as described dyestuff.Such phthalocyanine dye is preferably represented by above-mentioned general formula (4-1).
In the general formula (4-1), R α 1To R α 8And R β 1To R β 8Independently and respectively represent hydrogen atom; halogen atom; cyano group; nitro, formoxyl, carboxyl; sulfo group; carbon number is 1 to 20 alkyl, and carbon number is 6 to 14 aryl, and carbon number is 7 to 15 aralkyl; carbon number is 1 to 10 heterocyclic radical; carbon number is 1 to 20 alkoxy, and carbon number is 6 to 14 aryloxy group, and carbon number is 2 to 21 acyl group; carbon number is 1 to 20 alkyl sulphonyl; carbon number is 6 to 20 aryl sulfonyl, and carbon number is 1 to 25 carbamyl, and carbon number is 0 to 32 sulfamoyl; carbon number is 2 to 21 alkoxy carbonyl group; carbon number is 7 to 15 aryloxy carbonyl, and carbon number is 2 to 21 acyl amino, and carbon number is that 1 to 20 sulfuryl amino and carbon number are 0 to 36 amino.M represents two hydrogen atoms, metal, and metal oxide, or have the metal of part.
In the general formula (4-1), preferred all R α 1To R α 8Be not hydrogen atom simultaneously.In addition, R preferably α 1And R α 2In any one, R α 3And R α 4In any one, R α 5And R α 6In any one, and R α 7And R α 8In any one, that is, always have 4 substituting groups simultaneously for hydrogen atom.Especially, in the case, preferred R β 1To R β 8All be hydrogen atom simultaneously.
In the general formula (4-1), R α 1To R α 8And R β 1To R β 8Preferred embodiment can comprise hydrogen atom, halogen atom, carboxyl; sulfo group; carbon number is 1 to 16 alkyl, and carbon number is 6 to 10 aryl, and carbon number is 1 to 16 alkoxy; carbon number is 6 to 10 aryloxy group; carbon number is 1 to 16 sulfonyl, and carbon number is 2 to 20 sulfamoyl, and carbon number is 2 to 17 alkoxy carbonyl group; carbon number is 7 to 11 aryloxy carbonyl, and carbon number is that 2 to 18 acyl amino and carbon number are 1 to 18 sulfuryl amino.More preferably; example comprises hydrogen atom, halogen atom, carboxyl; sulfo group; carbon number is 1 to 16 alkoxy, and carbon number is 6 to 10 aryloxy group, and carbon number is 1 to 14 alkyl sulphonyl; carbon number is 6 to 14 aryl sulfonyl; carbon number is 2 to 16 sulfamoyl, and carbon number is 2 to 13 alkoxy carbonyl group, and carbon number is that 2 to 14 acyl amino and carbon number are 1 to 14 sulfuryl amino.Again more preferably, R α 1To R α 8Example be hydrogen atom, halogen atom, sulfo group; carbon number is 8 to 16 alkoxy, and carbon number is 1 to 12 sulfonyl, and carbon number is 1 to 12 sulfamoyl; carbon number is that 2 to 12 acyl amino and carbon number are 1 to 12 sulfuryl amino, and R β 1To R β 8Example be hydrogen atom or halogen atom.Again more preferably, R α 1To R α 8In at least one be sulfo group, carbon number is 1 to 10 sulfonyl, or carbon number is 1 to 10 sulfamoyl, and R β 1To R β 8In each all be hydrogen atom.
In the general formula (4-1), R α 1To R α 8And R β 1To R β 8May further include substituting group.Substituent example like this can be for as follows.Especially; example is: carbon number be 1 to 20 straight chain or naphthenic base (for example; methyl; ethyl; isopropyl and cyclohexyl); carbon number be 6 to 18 aryl (for example; phenyl; chlorphenyl; 2; 4-two-uncle aminophenyl and 1-naphthyl); carbon number be 7 to 18 aralkyl (for example; benzyl and anisyl); carbon number be 2 to 20 thiazolinyl for example; vinyl and 2-methyl ethylene); carbon number be 2 to 20 alkynyl (for example; ethinyl; 2-methylacetylenyl and 2-phenylacetylene base); halogen atom (for example; F; Cl, Br and I), cyano group; hydroxyl; carboxyl, carbon number are 2 to 20 acyl group (for example, acetyl group; benzoyl; salicyl and valeryl), carbon number is 1 to 20 alkoxy (for example, methoxyl; butoxy and cyclohexyloxy); carbon number is 6 to 20 aryloxy group (for example, phenoxy group, 1-naphthoxy and toluyl groups); carbon number be 1 to 20 alkylthio group (for example; methyl mercapto, butylthio, benzylthio and 3-methoxy propyl sulfenyl); carbon number be 6 to 20 arylthio (for example; thiophenyl and 4-chlorobenzene sulfenyl), carbon number is 1 to 20 alkyl sulphonyl (for example, mesyl and fourth sulfonyl); carbon number be 6 to 20 aryl sulfonyl (for example; benzenesulfonyl and p-toluenesulfonyl), carbon number is 1 to 17 carbamyl (for example, unsubstituted carbamyl; the methylamino formoxyl; ethylamino formoxyl, normal-butyl carbamyl and formyl-dimethylamino), carbon number be 1 to 16 amide group (for example; acetamido and benzamido); carbon number is 2 to 10 acyloxy (for example, acetoxyl group and benzoyloxy), carbon number be 2 to 10 alkoxy carbonyl group (for example; methoxycarbonyl group and carbethoxyl group); (for example, aromatic heterocyclic radical is as pyridine radicals with 5-unit or 6-unit heterocyclic radical; thienyl; furyl, thiazolyl, imidazole radicals and pyrazolyl; and heterocyclic radical such as pyrrolidine cyclic group; the piperidines cyclic group, morpholine cyclic group, pyrans cyclic group; thiapyran cyclic group ， Er Evil cyclic group and dithiolane base).
In the general formula (4-1), can be used for R α 1To R α 8And R β 1To R β 8Substituting group preferably: carbon number is 1 to 16 straight chain or naphthenic base; carbon number is 6 to 14 aryl; carbon number is 7 to 15 aralkyl; carbon number is 1 to 16 alkoxy; carbon number is 6 to 14 aryloxy group; halogen atom, carbon number are 2 to 17 alkoxy carbonyl group, and carbon number is that 1 to 10 carbamyl and carbon number are 1 to 10 amide group.Especially; more preferably; available substituting group is that carbon number is 1 to 10 straight chain or naphthenic base; carbon number is 7 to 13 aralkyl, and carbon number is 6 to 10 aryl, and carbon number is 1 to 10 alkoxy; carbon number is 6 to 10 aryloxy group; chlorine atom, carbon number are 2 to 11 alkoxy carbonyl group, and carbon number is that 1 to 7 carbamyl and carbon number are 1 to 8 amide group.Again more preferably, as substituting group can be that carbon number is 1 to 8 straight chain or naphthenic base, carbon number is 7 to 11 aralkyl, carbon number is 1 to 8 alkoxy, carbon number is 3 to 9 alkoxy carbonyl group, phenyl and chlorine atom.Again more preferably, as substituting group can be that carbon number is 1 to 6 alkoxy.
In the general formula (4-1), M is preferably metal.Especially, more preferably, M can be a zinc, magnesium, copper, nickel, or palladium.Again more preferably, M should be copper or nickel, and most preferably is copper.
Operable in embodiments of the invention phthalocyanine derivates can be synthetic according to the method for describing in following document for example or relating to or any other similar method: " Phthalocyanine-Chemistry and Function " (the 1st to 62 page), the IPC distribution, by Shirai and Kobayashi work, with " Phthalocyanine-Properties and Applications " (the 1st to 54 page), the VCH distribution is by C.C.Leznoff and A.B.P.Lever work.
Below, can be with pyrroles's methylene dye as described dyestuff.Pyrroles's methylene metal chelate compound that pyrroles's methylene dye is preferably represented by following general formula (ch-61).
Figure A20068004494800511
In the general formula (ch-61), A represents by metal M and the chelate ring that formed by pyrroles's methylene compound of following general formula (ch-62) expression, and B represents to form and have a nitrogen-atoms, the chelate ring of oxygen atom and/or sulphur atom with M.A and B can be identical mutually, or different mutually.
Figure A20068004494800512
In the general formula (ch-62), Ya represents N or CR A3R A1, R A2, R A3, R A4, R A5, R A6And R A7Expression hydrogen atom or its substituting group.R A1And R A2, R A2And R A3, R A5And R A6, and R A6And R A7Can be respectively in conjunction with forming aromatic ring or heterocycle.This ring can have substituting group.In addition, aromatic ring or heterocycle and this ring can be condensed.
In the general formula (ch-62), R A1, R A2, R A3, R A4, R A5, R A6, and R A7Independently and respectively represent hydrogen atom or substituting group, and preferably, halogen atom; nitro, cyano group, hydroxyl; carboxyl, sulfonic group, carbon number are 1 to 20 alkyl; aryl, heteroaryl, carbon number are 2 to 20 thiazolinyl; aralkyl, alkoxy, hydroxy alkoxy base; the alkoxy alkoxy, alkylthio group alkoxy, aryloxy group; heteroaryloxy, alkyl amino alkoxy, dialkyl amido alkoxy; carbon number is 2 to 20 thiazolinyl oxygen base, alkylthio group, alkylthio alkyl; arylthio, heteroarylthio, alkyl sulphonyl; aryl sulfonyl, heteroarylsulfonyl, alkyl sulphonyl alkyl; amino; alkyl amino, dialkyl amido, hydroxy alkyl amino; two (hydroxy alkyl) amino; alkoxyalkyl amino, two (alkoxyalkyl) amino, arylamino; ammonia diaryl base; heteroaryl amino, two heteroaryl aminos, alkyl-carbonyl-amino; aryl-amino-carbonyl; haloalkyl, aminoalkyl, alkyl amino alkyl; dialkyl aminoalkyl; the hydroxy alkyl aminoalkyl, two (hydroxy alkyl) aminoalkyl, alkoxyalkyl aminoalkyl; two (alkoxyalkyl) aminoalkyl; hydroxy alkyl, alkoxyalkyl, alkyl-carbonyl alkyl; aryl alkyl carbonyl; amino carbonyl, alkyl amino-carbonyl, dialkyl amino carbonyl; the hydroxy alkyl amino carbonyl; two (hydroxy alkyl) amino carbonyl, alkoxyalkyl amino carbonyl, two (alkoxyalkyl) amino carbonyl; aromatic yl aminocarbonyl; acyl group, alkoxy carbonyl group, aryloxy carbonyl; carbon number is 2 to 20 thiazolinyl oxygen carbonyl; the alkoxy carbonyl group alkoxy carbonyl group, alkyl-carbonyl alkoxy carbonyl group, or aralkoxycarbonyl.R A1And R A2, R A2And R A3, R A5And R A6, and R A6And R A7Can be in conjunction with forming aromatic ring or heterocycle, it can comprise substituting group.
For pyrroles's methylene dye, available those comprise pyrroles's methylene dye of for example describing respectively in following patent document: Japanese publication is announced 10-226172,10-162430,10-287819,11-43491,11-92479,11-92682,11-165465,11-227332,11-227333,11-255774,11-256056,11-256057,11-302551,11-302253,2000-48406,2000-260064,2002-212456,2002-154271,2002-155076,2002-211136,2002-363437,2003-64274,2003-73574,2003-140300,2003-182219,2003-286415,2003-266947,2004-66459,2004-114394, and 2004-122585, and international publication (WO) 03/082593A1.Those pyrroles's methylene dyes of describing in above-mentioned patent documentation also can be used for instantiation and be used for the method for synthetic this dyestuff.
The first optical data recording medium 10A is not particularly limited, and condition is that dyestuff is placed in the visual information recording layer 24 (and preferably also in data record layer 18).But, when the first optical data recording medium 10A is applied to CD-R, preferred following layout.Particularly, to contain the data record layer 18 of dyestuff as mentioned above, first reflection horizon 20, adhesive phase 28, second reflection horizon 26, to be placed in thickness in proper order be 1.2 ± 0.2mm and wherein be formed with on transparent disk first substrate 16 of prefabricated groove 40 (referring to Fig. 1) that track pitch is 1.4 to 1.8 μ m with this to contain the visual information recording layer 24 of dyestuff as mentioned above and second substrate 22.When the first optical data recording medium 10A is applied to DVD-R, preferably adopt following two kinds of patterns.
(1) optical data recording medium comprises two duplexers, and each duplexer has that to be placed in thickness be 0.6 ± 0.1mm and wherein be formed with the data record layer 18 and the reflection layer of dyestuff as mentioned above of containing on transparent disk first substrate 16 of prefabricated groove that track pitch is 0.6 to 0.9 μ m.Two duplexers are engaged with each other, make data record layer 18 be placed in the inboard respectively, wherein thickness is 1.2 ± 0.2mm, and visual information recording layer 24 is positioned in first substrate 16 at least one.
(2) optical data recording medium comprises duplexer and transparent disk protective substrate; described duplexer has that to be placed in thickness be 0.6 ± 0.1mm and wherein be formed with the data record layer 18 and the reflection layer of dyestuff as mentioned above of containing on transparent disk first substrate 16 of prefabricated groove that track pitch is 0.6 to 0.9 μ m, and described transparent disk protective substrate has the identical shape of shape with plate-like first substrate 16 of duplexer.Duplexer and protective substrate are engaged with each other, make data record layer 18 be positioned in the inboard, wherein thickness is 1.2 ± 0.2mm, and visual information recording layer 24 is positioned at least one substrate.DVD-R type optical data recording medium can also have the layout of wherein further settling protective seam on reflection layer.
Similarly, the second optical data recording medium 10B is not particularly limited, condition is that dyestuff is positioned in (preferably also in data record layer 18) in the visual information recording layer 24.But, when the second optical data recording medium 10B is applied to CD-R, preferred following layout.Particularly; to comprise the data record layer 18 of dyestuff as mentioned above; first reflection horizon 20; first protective seam 42; adhesive phase 28; second protective seam, 44, the second reflection horizon 26, to be placed in thickness in proper order be 1.2 ± 0.2mm and wherein be formed with on first substrate 16 of prefabricated groove 40 (referring to Fig. 2) that track pitch is 1.4 to 1.8 μ m with this to contain the visual information recording layer 24 of dyestuff as mentioned above and colored substrate 22a.When the second optical data recording medium 10B is applied to DVD-R, preferably adopt following two kinds of patterns.
(1) optical data recording medium comprises two duplexers, and each duplexer has that to be placed in thickness be 0.6 ± 0.1mm and wherein be formed with the data record layer 18 and the reflection layer of dyestuff as mentioned above of containing on plate-like first substrate 16 of prefabricated groove that track pitch is 0.6 to 0.9 μ m.Two duplexers are engaged with each other, make data record layer 18 be placed in the inboard respectively, wherein thickness is 1.2 ± 0.2mm, and visual information recording layer 24 is positioned in first substrate 16 at least one.
(2) optical data recording medium comprises duplexer and transparent disk protective substrate; described duplexer has that to be placed in thickness be 0.6 ± 0.1mm and wherein be formed with the data record layer 18 and the reflection layer of dyestuff as mentioned above of containing on first substrate 16 of prefabricated groove that track pitch is 0.6 to 0.9 μ m, and described transparent disk protective substrate has the identical shape of shape with plate-like first substrate 16 of duplexer.Duplexer and protective substrate are engaged with each other, make data record layer 18 be positioned in the inboard, wherein thickness is 1.2 ± 0.2mm, and visual information recording layer 24 is positioned at least one substrate.DVD-R type optical data recording medium can also have the layout of wherein further settling protective seam on reflection layer.
On visual information recording layer 24 visual information of record comprise any can be by the image of visual identity, it comprise can visual identity information such as literal (sequence), pattern and figure.Word message for example comprises, be used for specifying the information of authorized user, be used for specifying the information of term of life, be used for specifying the information of access times, about the information of rent, be used for specifying the information of resolution, be used for the information of designated layer, be used for the information of designated user, about copyright owner's information, information about number of copies, about the information of manufacturer, about the information of date of manufacture and/or date of sale, about the commission agent or the seller's information, about using the information of tricks, be used for the information of designated area, be used for the information of appointed language, be used for specifying the information of use-pattern, about the information of product user with about the information of access times.
Can form visual information recording layer 24, make aforesaid dyestuff be dissolved in the solvent with the preparation coating fluid, and the coating coating fluid.As for solvent, can use and the identical solvent of solvent that is used to prepare data record layer 18 usefulness coating solutions as hereinafter described.About for example other adjuvant and coating process, can carry out described program in the same manner with the program that is used for recording layer as hereinafter described.
The layer thickness of visual information recording layer 24 is preferably 0.01 to 200 μ m, 0.05 to 100 μ m more preferably, and 0.1 to 50 μ m more preferably again.
Visual information recording layer 24 is preferably 1/100 to 100/1 with the thickness ratio of data record layer 18, and more preferably 1/10 to 10/1.
[data record layer 18]
Data record layer 18 be on it record coding information (information encoded) as the layer of digital information, it for example comprise following those: write-once type (preferred coloring agent write-once type), inversion of phases and magneto-optical.Although be not particularly limited, preferably use those data record layers of dye-type.
The instantiation of the dyestuff that contains in dye-type data record layer 18 for example can comprise, cyanine dye, oxonol dye, metal complex-radical dye, azo dyes and phthalocyanine dye.
The preferred use respectively announced 4-74690,8-127174,11-53758,11-334204,11-334205,11-334206,11-334207,2000-43423, the dyestuff described in 2000-108513 and the 2000-158818 in Japanese publication.
Forming data record layer 18 makes: recorded matter such as above-mentioned dyestuff are dissolved in the The suitable solvent with bonding agent etc., prepare coating fluid thus, then, coating fluid is coated on the substrate, formation is filmed, and is then dry.The concentration of recorded matter in coating fluid 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 more more preferably in the scope of 0.5 to 3 quality %.
Can form data record layer 18 by the method that comprises for example vapour deposition, sputter, CVD and solvent coating.But, when preparation data record layer 18, preferably use the solvent coating.In this program, can carry out following method.Particularly, for example, the preparation coating fluid makes if desired, and except aforesaid dyestuff etc., quencher and bonding agent also are dissolved in the solvent.Subsequently, coating fluid is coated on the surface of first substrate 16, films to form thereon, then dry.
Coating process can be by following method example: spraying process, and spin-coating method, dip coating, rolling method, cutter is coated with method, and doctor roll side is coated with method, and silk screen print method.Data record layer 18 can form individual layer or form with multilayer.The layer thickness of data record layer 18 is usually in 10 to 500nm scope, preferably in 15 to 300nm scope, and more preferably in 20 to 150nm scope.
Various anti-stripping agents can be included in the data record layer 18, to improve the photostability of data record layer 18.Usually, singlet oxygen quencher is used as anti-stripping agent.Anti-stripping agent so has been described in the various known publication files, in patent specification, and can be used to singlet oxygen quencher.
The instantiation that constitutes the material of inversion of phases data record layer 18 can comprise, for example, Sb-Te alloy, Ge-Sb-Te alloy, the Pd-Ge-Sb-Te alloy, the Nb-Ge-Sb-Te alloy, Pd-Nb-Ge-Sb-Te alloy, Pt-Ge-Sb-Te alloy, the Co-Ge-Sb-Te alloy, In-Sb-Te alloy, Ag-In-Sb-Te alloy, Ag-V-In-Sb-Te alloy and Ag-Ge-In-Sb-Te alloy.
The layer thickness of inversion of phases data record layer 18 is preferably 10 to 50nm, and more preferably 15 to 30nm.
For example, can form above-mentioned inversion of phases data record layer 18 by gas phase membrane deposition process such as vacuum vapor deposition method or sputtering method.
Can be according to common method for quantitatively determining, the content of the metallic atom that the material of the above-mentioned visual information recording layer 24 of measurement formation contains.
For example,, use atomic absorption unit (AA240FS that makes by Varian) by flame analysis method or absolute calibration curve method, can quantitative measurement metallic atom Na, the content of K.By flame analysis method or absolute calibration curve method, also can quantitative measurement metallic atom Mg, the content of Ca.Following pre-service also is available.Particularly, from sample, collect the 2g sample powder, and with HNO 3Join in the sample powder, to carry out many ripples ashing treatment (multiwave ashing process).Then, sample is washed out in water, with the sample solution of preparation 50ml.Then, measure the metallic atom content of the sample solution that obtains by above-mentioned method for quantitatively determining.
Even after preparing the first optical data recording medium 10A or the second optical data recording medium 10B, also can by collection material from visual information recording layer 24, measure the content of metallic atom by the method identical with those above-mentioned methods.
[first substrate 16]
Can at random select first substrate 16 of the first optical data recording medium 10A and first substrate 16 of the second optical data recording medium 10B from conventional optical data recording medium, being used as in the various materials of substrate so far.
The material that is used for first substrate 16 for example can comprise, glass, acrylic resin such as polycarbonate and polymethylmethacrylate, vinyl chloride-Ji resin such as Polyvinylchloride and vinyl chloride copolymer, epoxy resin, amorphous polyolefin, and polyester.If desired, above-mentioned material can be used in combination.
Above-mentioned material can be used for first substrate 16 with rigid form or with the form of film.In above-mentioned material, consider its moisture-proof, dimensional stability and price, preferably use polycarbonate.
First substrate 16 thickness separately is preferably 0.1 to 1.2mm, and more preferably 0.2 to 1.1mm.
Can provide that (that is, forming the face side of prefabricated groove 40 on it) goes up and settle undercoat on the surface of data record layer 18 sides at first substrate 16 on it, purpose is to improve flatness and adhesion, and avoids the variation of data record layer 18 quality.
[20, the second reflection horizon 26, first reflection horizon]
In some cases, 20 arrangements of first reflection horizon are adjacent with data record layer 18, and purpose is to improve the reflectivity in the information reproduction process.In some cases, also second reflection horizon 26 is settled adjacently with visual information recording layer 24, purpose is to write the satisfied focusing that obtains laser beam 38 in the process of visual information on visual information recording layer 24.
Light reflecting material as first reflection horizon 20 and second reflection horizon, 26 usefulness materials is the material that has high reflectance with respect to laser beam 38.The example of such light reflecting material comprises stainless steel, semimetal and metal 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.Material can use separately as mentioned above, or alternatively, can make up or uses two or more above-mentioned substances with the form of alloy.By carrying out for example vapour deposition, sputter or ion plating, can form first reflection horizon 20 and second reflection horizon 26 on separately at data record layer 18 and visual information recording layer 24 with above-mentioned reflecting material.First reflection horizon 20 and second reflection horizon 26 layer thickness separately are usually in 10 to 300nm scope, and be and preferred in 50 to 200nm scope.
[adhesive phase 28]
Form adhesive phase 28, to guarantee the tight contact between data carrier part 12 and the visual information recording medium segment 14.
Preferably, light-cured resin is used for construction adhesive layer 28.Especially, the preferred wherein little resin of degree of shrinkage in solidification process that uses is with any warpage of avoiding coiling.Above-mentioned light-cured resin can be by UV curable resin (UV curing adhesive) as " SD-640 " and " SD-347 " example by the preparation of Dainippon Ink andChemicals company limited.In order to improve elasticity, the thickness of adhesive phase 28 is preferably in the scope of 1 to 1,000 μ m, more preferably in the scope of 5 to 500 μ m, and more more preferably in the scope of 10 to 100 μ m.
[second substrate 22]
The material identical in quality of the quality and first substrate 16 can be used as second substrate 22 (protective substrate).
[colored substrate 22a]
Be configured with chromogen substrate 22a (protective substrate), in the material identical in quality of the quality and first substrate 16, to contain dyestuff and/or pigment.
In the case, preferably in output (default output: on the basis laser power the present embodiment) from the laser beam 38 of colored substrate 22a side direction visual information recording layer 24 irradiation, by being adjusted in the dyestuff that contains among the colored substrate 22a and/or the addition of pigment, make colored substrate 22a.
For colored substrate 22a, can adopt in the L*a*b* colour system, to limit painted by 1 to 8 expression of the expression formula among Fig. 9.
Be used to make the method for colored substrate 22a, the method that promptly is used for painted this substrate comprises: wherein with a certain amount of method by dye composition or pigment are mixed with uncoloured pellet with the pellet that is called " masterbatch " of high concentration (dense concentration) preparation, wherein directly and the method for mixed with resin and wherein on substrate, be mounted with the method for chromatograph with dyestuff such as dye composition or pigment.
The dyestuff that directly mixes or be used for masterbatch or nonferrous layer with baseplate material for example can comprise cyanine-radical dye, side-radical dye, azo-radical dye, naphthoquinones-radical dye, anthraquinone-radical dye, porphyrin-radical dye, tetraazatetradecane porphyrin-radical dye, acridine-radical dye, acridone-radical dye ， oxazine-radical dye, pyrroles's methylene-radical dye, spiral shell-radical dye, ferrocene-radical dye, fluorenes-radical dye, fulgide-radical dye, the imidazo-5-yl-dyestuff, thiazole-radical dye ， perylene (pyrilene)-radical dye, azophenlyene-radical dye, phenothiazine-radical dye, polyenoid-radical dye, indol-1-yl-dyestuff, aniline-radical dye, quinophthalones (quinophthalone)-radical dye phenoxazine-radical dye, diphenylamine-radical dye, cumarin-radical dye, quinolone (carbostyryl)-radical dye, 1,2-talan-radical dye, and fluorescein (fluorein)-radical dye.Above-mentioned dyestuff can use separately, or alternatively, can use above-mentioned dyestuff in the mode of mixing.When being used to visual information recording layer 24, for directly mix or be used for the dye selection dyestuff of masterbatch or nonferrous layer with baseplate material, described dyestuff does not have absorption peak near the absorption peak of the dyestuff that is used for visual information recording layer 24.
[first protective seam 42 and second protective seam 44]
In some cases; first protective seam 42 is provided; purpose is at physics and chemically protects first reflection horizon 20 and data record layer 18, and provides second protective seam 44, purpose to be at physics and chemically protect second reflection horizon 26 and visual information recording layer 24.
Preparing under the situation of optical data recording medium with the form suitable with DVD-R type optical data recording medium; promptly; two substrates (comprising wherein a layout that forms first substrate 16 in two substrates) are being laminated to each other; being provided at simultaneously under the situation of two data recording layers 18 of its positioned inside, is not to necessarily require to form first protective seam 42 and second protective seam 44.
As mentioned above, the first optical data recording medium 10A and the second optical data recording medium 10B can be applied to so-called read-only type optical data recording medium, it has the recording section of recorded information (pit) therein, wherein can enough laser beam 38 Copy Infos.
[method that is used for the second optical data recording medium 10B]
Then, with reference to Figure 10, will make an explanation especially for the method for preparing the second optical data recording medium 10B to being used to prepare the method for optical data recording medium according to embodiments of the present invention.
At first, in the step S1 shown in Figure 10, make first pressing mold that is used to prepare first substrate 16.In this program,,, produce first pressing mold that has recessed/convex portion on the surface by motherboard is optionally applied etching for first pressing mold is provided.For example, make first pressing mold, make, motherboard is carried out the mastering of high precision by with DUV (wavelength is no more than the deep UV (ultraviolet light) of 330nm) laser or EB (electron beam) cutting.
In this program, mastering is applied to motherboard, to make first pressing mold, make and passing through to use as finally prepd first pressing mold, carry out injection moulding or extrusion molding with resin material, when forming first substrate 16, can on the surface of first substrate 16, form prefabricated groove 40.
Then, in the step S2 shown in Figure 10, by with comprising that the resin material with polycarbonate of first pressing mold for example carries out injection moulding, produces first substrate 16.In this program, the recessed/convex portion of first pressing mold is transferred on the surface of first substrate 16, to form prefabricated groove 40.
In above-mentioned example,, make first substrate 16 by carrying out extrusion molding or injection moulding with resin material such as polycarbonate.But, in order to form prefabricated groove 40, also can describe respectively as the back, on the surface of first substrate 16, form the prefabricated groove layer with flat surfaces.
As for the material of prefabricated groove layer, can make the potpourri of the monomer (or oligomer) of using up poly-initiating agent and at least a acrylic acid monoesters, diester, three esters and four esters.As for first substrate 16, for example, following therein formation prefabricated groove layer.Particularly, the liquid mixture of being made up of acrylate and the poly-initiating agent of light as mentioned above is coated on first pressing mold.In addition, first substrate 16 is placed on the coating liquid layer, then via first substrate 16 or via the first pressing mold irradiation ultraviolet ray.Therefore, coating is solidified, to fix first substrate 16 and the coating.Subsequently, first substrate 16 is peeled off from first pressing mold.Therefore, can obtain to comprise first substrate 16 of prefabricated groove layer, described prefabricated groove layer is formed with prefabricated groove 40 in its surface.
Subsequently, in the step S3 shown in Figure 10, with 16 coolings of first substrate, the dyestuff that will will change into data record layer 18 then later on is coated on the surface of first substrate 16.For example, preparation wherein contains the coating fluid (dye-coating liquid) of dyestuff.By spin coating method dye-coating liquid is coated on the surface that is formed with prefabricated groove 40 of first substrate 16.
Then, in the step S4 shown in Figure 10, carry out annealing in process, with the dried dye coating fluid.Annealing in process was for example carried out 3 hours 80 ℃ temperature.Thus, by annealing in process, dye-coating liquid is changed into data record layer 18.
Then, in the step S5 shown in Figure 10, for example, on the surface of data record layer 18, form first reflection horizon 20 by sputtering method.
Then, in the step S6 shown in Figure 10, on the surface in first reflection horizon 20, form first protective seam 42.For example, the UV curable resin can be dissolved in the The suitable solvent,, apply coating fluid then with the preparation coating fluid, and by irradiation UV light-cured resin.Thereby, formed first protective seam 42 by this way.In this stage, finished data carrier part 12.
On the other hand, in the step S101 shown in Figure 10, make second pressing mold that is used to make colored substrate 22a.In this program, make second pressing mold, make: on the part surface of colored substrate 22a, for example, by using as finally prepd second pressing mold, when carrying out injection moulding and be formed with chromogen substrate 22a with resin material, the perimeter surface side forms pre-pit 32 within it.
Then, in the step S102 shown in Figure 10, the dyestuff that adjusting will contain in colored substrate 22a and/or the addition of pigment.
Particularly, among the step S102a, on the basis of the predetermined thickness of colored substrate 22a, determine the distribution character of the absorptance of laser beam 38, it is corresponding to the amount of dyestuff that will be added into and/or pigment.As for distribution character, for example, according to the increase of the amount of the dyestuff that is added, absorptance increases with about proportional relation.This relation is set up too for pigment.Certainly, dyestuff and pigment are being added fashionable in the mode of mixing, the ratio when adding dyestuff and pigment respectively obtains the wherein reformed characteristic of proportionate relationship.
In addition, in step S102b,, in visual information recording layer 24 can write the scope of visual information, determine the scope (that is the effective range of absorptance) of absorptance with the power of the laser beam 12 that will use.
Among the step S102c, the dyestuff of determining to comprise in definite scope of absorptance, add and/or the scope of pigment are with the dyestuff determining to comprise in this scope, add and/or the amount of pigment.
In this stage, when the content of dyestuff of in aforesaid step S102c, having determined to be added and/or pigment, in next step S103, to determine the aforesaid dyestuff of amount and/or pigment and for example basic material is (for example, polycarbonate) powdery granule blend is so that provide coloured pellet with for example extruder.
In the step S104 shown in Figure 10, there is coloured pellet of dyestuff and/or pigment to carry out injection moulding or extrusion molding blend, to make colored substrate 22a with respect to second pressing mold.In this program, make and form colored substrate 22a (referring to Fig. 8) in it on the perimeter surface side with pre-pit 32.
Subsequently, in the step S105 shown in Figure 10,, then, the dyestuff that will change into visual information recording layer 24 subsequently is coated on the surface of colored substrate 22a colored substrate 22a cooling.For example, preparation wherein contains the coating fluid (dye-coating liquid) of dyestuff, and by spin coating method dye-coating liquid is coated on the surface of smooth colored substrate 22a.
Then, in the step S106 shown in Figure 10, carry out annealing in process, with the dried dye coating fluid.Annealing in process was for example carried out 3 hours 80 ℃ temperature.As the result of annealing in process, dye-coating liquid is changed into visual information recording layer 24.
Then, in the step S107 shown in Figure 10, for example,, on the surface of visual information recording layer 24, form second reflection horizon 26 by sputtering method.
Then, in the step S108 shown in Figure 10, on the surface in second reflection horizon 26, form second protective seam 44.For example, the UV curable resin is dissolved in the The suitable solvent,, applies coating fluid then with the preparation coating fluid, and by irradiation UV light-cured resin, to form second protective seam 44.In this stage, finished visual information recording medium segment 14.
Then, in the step S201 shown in Figure 10, that data carrier part 12 and visual information recording medium segment 14 is bonded to each other.In this program, will be toward each other at first protective seam 42 that forms on the data carrier part 12 and second protective seam 44 that on visual information recording medium segment 14, forms.Under adhesive phase 28 is inserted in situation between data carrier part 12 and the visual information recording medium segment 14, that data carrier part 12 and visual information recording medium segment 14 is bonded to each other.As this bonding result, finished the second optical data recording medium 10B.
As mentioned above, in preparation method, on the basis of the output (laser power in this example) of the laser beam 38 that is used to write down visual information according to embodiment of the present invention, in the dyestuff that in regulating colored substrate 22a, contains and/or the addition of pigment, make colored substrate 22a.Then, on colored substrate 22a, form visual information recording layer 24.Therefore, even when therein can be on label surface using colored substrate 22a among the second optical data recording medium 10B of drawing image, also the output control of laser beam 38 can be suppressed to minimum.In addition, can use shades of colour.Therefore, can also respond the needs of wherein wishing the change color of increase fully.
Figure 11 shows the various integrated modes for the color of colored substrate 22a and visual information recording layer 24.The example combinations 1 to 5 that shows among Fig. 7 only is for example.Can certainly expect and adopt other combination.
[being used to write down the method for visual information]
The method that is used to write down visual information according to embodiment of the present invention comprises: write down visual information on above-mentioned first optical data recording medium 10A and second optical data recording medium 10B visual information recording layer 24 separately, it is characterized in that, will be used for being used on visual information recording layer 24, writing down visual image in the identical laser beam 38 (referring to Fig. 5 and 6) of the laser beam 38 of data record layer 18 identifying recording layers.
Carry out the method that is used to write down visual information by the service recorder unit, make and on the first optical data recording medium 10A and second optical data recording medium 10B visual information recording layer 24 separately, to write down visual information according to embodiment of the present invention.
Now, will provide in further detail the explanation of formation according to two kinds of recording methods (first recording method and second recording method) of the visible information recording of the present embodiment.
At first, first recording method is configured for the recording method of record visual information on according to the visual information recording layer 24 of the optical data recording medium 10 of the present embodiment, wherein uses the laser beam 38 identical with the laser beam 38 that is used for recorded information on visual information recording layer 24 to write down visual informations.
In second recording method, use in optical data recording medium 10 footpaths the upwards laser beam 38 of swing, on visual information recording layer 24, write down visual information, in addition, wherein along substantially the same track, repeatedly with optical data recording medium 10 irradiation.In first recording method, be similar to first recording method equally, preferably: use and be used in the identical laser beam 38 of the laser beam 38 of data record layer 18 identifying recording layers the record visual information.
According to first recording method, owing to can use and be used for writing down visual informations in the identical laser beam 38 of the laser beam 38 of data record layer 18 identifying recording layers, so can in a recording unit, share the use of laser 38, the hardware resource of recording unit can be suppressed to minimum necessity, and the general user uses this equipment can easily write down visual information.And, in optical data recording medium 10,, be also advantageous in that: can form high-contrast and excellent visual visual information (image etc.) because visual information recording layer 24 comprises paintedly.Although most preferably carry out on the visual information recording layer 24 of optical data recording medium 10 forming the record of the visual information of image etc. by first recording method and second recording method, the present invention is not limited only to these methods.
In first recording method and second recording method, can use the single CD drive (pen recorder) that all has registering capacity for two-layer, carry out the record of the visual information of the image etc. on visual information recording layer 24, and the record of the data on data record layer 18.Under the situation of using so single CD drive, behind visual information recording layer 24 and data record layer 18 any enterprising line item, with the medium counter-rotating, and can be at the enterprising line item of another layer.CD drive as having the ability of record visual information on visual information recording layer 24 can adopt by Japanese publication and announce 2003-203348, and Japanese publication is announced disclosed CD drive such as 2003-242750.
In addition, when on visual information recording layer 24, writing down visual information, recording unit makes optical data recording medium 10 and laser adapter move relative to each other along the surface of optical data recording medium 10, simultaneously corresponding to the literal that in forming image, uses, the view data of picture etc. is regulated and so synchronous laser beam 38 that relatively moves, make to visual information recording layer 24 irradiation laser bundles 38, and can write down visual information.Such structure is disclosed in for example Japanese publication and announces among the 2002-203321.
Usually by once carrying out the record of standard digital data along oval-shaped track illuminating laser beam 38 basically.Usually, when in coloured recording layer, forming pit, because emphasize the formation of pit, to obtain enough reflectivity and depth of modulation, thereby can be discerned by CD drive, so as the pigment that is used for painted recording layer, select once irradiating, can obtain the enough reflectivity and the pigment of depth of modulation by above-mentioned laser beam.
For this, recently,, proposed to announce disclosed system among the 2002-203321 in above-mentioned Japanese publication as the image forming method of new design.Adopt this system, by along the irradiation of substantially the same track repeatedly, comprise the visual information of document image in pigment or the painted visual information recording layer 24 etc. therein laser beam 38.In addition, in normal optical disk, because it is default diametrically to be used to form the position of pit, so laser beam 38 can not be in the upwards swing of the footpath of optical data recording medium 10.On the other hand, in said system,, by along substantially the same track irradiation repeatedly, form visual information in addition with laser beam 38 by making laser beam 38 in the upwards swing of the footpath of optical data recording medium 10.The pigment that uses in the present embodiment is suitable for any in the said system, and by above-mentioned recording method, can form the high and strong visual information of contrast, and in addition, its photostability excellence.
With reference now to Figure 12 and 13,, the details of above-mentioned visible information recording will be explained.
Figure 12 shows the track of the laser beam 38 that is used to form the image irradiation.
At first, as shown in Figure 12, lasing light emitter is arranged on interior all sides of optical data recording medium 10 and exists first image to form radial position place of position.Then, detect position θ in a circumferential direction, and each image in a circumferential direction forms the position, laser power is switched to predetermined height output (promptly, value when the visible light characteristic of visual information recording layer 24 changes, for example 1mW or on), described image forms the position by the view data indication relevant with radial position.As a result, each position in the high-level laser beam of exporting 38 of irradiation has changed the visible light characteristic (that is, change color etc.) of visual information recording layer 24, and carries out image formation.Based on the corresponding laser power control information of the colouring information of colored substrate 22a, control laser beam 38 laser power.By detecting in the pre-pit 32 that in the pre-pit district 30 of optical data recording medium 10, forms or the information that in BCA, writes down, obtain laser power control information.
Then, with optical data recording medium 10 rotation once and when turning back in a circumferential direction normal place, by feed motor etc. lasing light emitter is carried predetermined spacing Δ r on peripheral direction, and each image in a circumferential direction forms the position, laser power is switched to predetermined height output, and described image forms the position by the view data indication relevant with radial position.Repeatedly carry out these operations then, thus, under each situation of taking turns,, and carry out image formation lasing light emitter mobile in succession predetermined spacing Δ r on peripheral direction.
Figure 12 shows according to such image formation operation, the track of laser beam 38 on the surface of optical data recording medium 10 (be the surface of visual information recording layer 24 sides, below be also referred to as " label surface ").At part 46 places of drawing thick line, laser power is switched paramount output level, and carry out image formation.Show the enlarged drawing of laser beam 38 among Figure 13 at the track at part 46 places of drawing thick line.As shown in Figure 13, laser beam 38 is upwards swung in the footpath of optical data recording medium 10, and by along substantially the same track irradiation repeatedly, forms image.For each recording unit, the swing width of laser beam 38 and the number of times that laser beam 38 is shone along substantially the same track are set herein.
Adopt above-mentioned image forming method,, do not scan, and lasing light emitter is once moved to the radial position that has next image formation position, carry out image then and form with respect to not existing image to form the radial position of position.If separation delta r is big,, also may form wherein gapped image even will form diametrically the image that links up the time.If make separation delta r littler, can make such gap unshowy, still, forming the needed period of image on whole label surface increases, and forms the time that image need be longer.
Use is announced disclosed equipment among the 2002-203321 in Japanese publication, drive the tracking actuator by vibration signal (sine wave, triangular wave etc.), described vibration signal produces circuit by vibration signal and produces when carrying out image formation, object lens are upwards vibrated in the footpath of dish.Therefore, laser beam 38 is vibrated diametrically, made, can carry out image and form for not existing gap (or its intermediate gap is few) still under the situation of big relatively separation delta r.For example, can be with the frequency configuration of vibration signal at several approximately kHZ.In addition, for example, separation delta r can be arranged on about 50 to 100 μ m.
About the further detailed content of above-mentioned image forming method, can announce 2002-203321 with reference to Japanese publication.
Be used for comprising at least: the laser adapter and the rotating mechanism that is used for rotary CD information recording carrier 10 that are used for illuminating laser beam 38 at the pen recorder of data record layer 18 record data.Under the state of rotation, by with laser 38 from data record layer 18 irradiation of laser adapter to optical data recording medium 10, can carry out the record on data record layer 18 and duplicate.The structure of such pen recorder itself is known.
Then, will the record of the data on data record layer 18 (pit information) be made an explanation.At data record layer 18 is under the situation of coloured type, at first, with the not recording optical information recording medium 10 as above discussed in the rotation of predetermined recording linear velocity, from laser adapter illuminating laser beam 38.According to the laser beam of irradiation, the painted absorption laser of data record layer 18 makes and the rising of temperature part wherein to produce the space (pit) of wishing, and as the result of its changes in optical properties, recorded information.
The wave recording of laser beam 38 when forming single pit can be train of impulses or individual pulse.Ratio with respect to the actual length that will write down (pit length) is important.
For the pulse width of laser beam 38, preferably with respect to 20% to 95% scope of the actual length that will write down, more preferably 30% to 90% scope, and more preferably 35% to 85% scope again.When wave recording is train of impulses, expression as the train of impulses sum in above-mentioned scope.
For the power of laser beam 38, although this function according to line speed record and difference is under the situation of 3.5m/sec at line speed record, preferred 1 to 100mW scope, more preferably 3 to 50mW scope, and more preferably 5 to 20mW scope again.In addition, under the situation that line speed record is doubled, the preferable range of laser beam 38 power correspondingly becomes 2 of such scope 1/2Doubly.In addition, in order to improve recording density, the NA of the object lens that use in adapter (numerical aperture) is preferably more than 0.55, and more preferably more than 0.60.
In the present embodiment,, can use the semiconductor laser of oscillation wavelength in 350 to 850nm scopes as laser beam 38.
Then, will be that the situation of inversion of phases is given an explaination to data recording layer 18.Under the situation of inversion of phases,, wherein can repeatedly carry out phase transformation between crystalline phase and amorphous phase by the irradiation of laser 38 by above-mentioned material composition data recording layer 18.Will recorded information the time, with the laser beam 38 pulse short irradiations of boundling, the phase change recording layers partial melting that becomes thus.Then, the part of fusing is cooling and curing fast by thermal diffusion, forms the amorphous state record mark thus.In addition, when wiping, laser beam 38 is shone on the record mark part, and still be equal to or higher than Tc by being heated to the melting point that is lower than data record layer 18, then cooling gradually makes the crystallization of amorphous state record mark, and its original not record situation is recovered.
Then, explain the present invention in further detail below with reference to embodiment.But, should be appreciated that to the invention is not restricted to embodiment described below.
(embodiment 1)
The optical data recording medium of embodiment 1 is a DVD-R type optical data recording medium, obtains by two dishes are bonded together.To the method for the optical data recording medium that is used to make embodiment 1 be made an explanation below.
Use polycarbonate resin, forming thickness by injection moulding is that 0.6mm and diameter are first substrate 16 of 120mm, wherein is mounted with screw type (spiral fashion) groove (degree of depth: 130nm, width: 300nm, track pitch: 0.74 μ m).
Then, 1.5g is dissolved in 2,2,3,3 of 100ml by the oxonol dye of following general formula (ch-63) expression and 1.5g by the oxonol dye of following general formula (ch-64) expression, in-tetrafluoro-1-propyl alcohol, with the preparation coating fluid.By spin-coating method coating fluid is coated on the surface that is formed with prefabricated groove 40 of first substrate 16, forms data record layer 18 thus.
Figure A20068004494800671
Figure A20068004494800672
Subsequently, silver being sputtered on the data record layer 18, is first reflection horizon 20 of 120nm to form film thickness.Then, by spin coating method, coating ultra-violet curing resin (SD 318 of Dainippon Ink andChemicals company limited preparation) then, by using ultraviolet light irradiation, makes resin solidification, is first protective seam of 10 μ m with cambium layer thickness.According to above-mentioned steps, produce data carrier part 12.
Subsequently, in order to form visual information recording layer 24, with the phthalocyanine dye of 1.50g altogether by following general formula (ch-65) expression, with by the cyclonite cyanine dye of following general formula (ch-66) expression with metallic atom, as shown in Figure 14, be dissolved in 2 of 100ml, 2,3, in 3-tetrafluoro-1-propyl alcohol, with preparation visual information recording layer coating fluid.The visual information recording layer is formed on second substrate 22 by spin coating with coating fluid, with thickness with 0.6mm and the diameter of 120mm.
Subsequently, on silver-colored sputter visual information recording layer 24, forming film thickness thus is second reflection horizon 26 of 120nm.Then, by spin coating method, coating ultra-violet curing resin (SD 318 of Dainippon Inkand Chemicals company limited preparation) then, by using ultraviolet light irradiation, makes resin solidification, is second protective seam of 10 μ m with cambium layer thickness.According to above-mentioned steps, produce visual information recording medium segment 14.
Subsequently, carry out the following step, so that data carrier part 12 and visual information recording medium segment 14 is bonded to each other, to finish the first optical data recording medium 10A.At first, will act on first protective seam that cationic polymerization type bonding agent (by Sony Chemical preparation, SDK 7000) is printed on data carrier part 12 respectively slowly by serigraphy and on second protective seam of visual information recording medium segment 14.In this program, the sizing grid that is used to carry out the galley of serigraphy is 300 orders.Subsequently, with data carrier part 12 and visual information recording medium segment 14 from corresponding protection layer side bonded to each other after, use metal halide lamp irradiation ultraviolet light immediately.Afterwards, two surfaces are suppressed and placed 5 minutes, to make optical data recording medium according to embodiment 1.
(embodiment 2 to 4)
In optical data recording medium according to embodiment 2 to 4, with with embodiment 1 in substantially the same mode prepare the first optical data recording medium 10A, difference is: as shown in Figure 14, change the content of the metallic atom that contains in the coating fluid that adopt, that be used to form the visual information recording layer when the visual information recording layer 24 of the visual information recording medium segment 14 that forms embodiment 1.
(contrast evaluation)
On the optical data recording medium of making according to first to fourth embodiment, the record that carries out as described below.
Use is announced disclosed recording unit among the 2002-203321 in Japanese publication, promptly have the laser adapter of emission of lasering beam 38 and be used for the recording unit (is that the semiconductor laser of 660nm is as laser beam sources with wavelength) of the rotating mechanism of rotary optical information recording carrier, draw condition based on the driving shown in Figure 15 A, carry out the drafting of the evaluation map picture on visual information recording layer 24.In the case, with optical data recording medium and laser adapter when the surface of optical data recording medium relatively moves, under the condition of the linear velocity of 3.5m/sec and 8mW recording power, relatively move synchronously corresponding to the view data modulating lasering beam 38 of hope with this, apply state irradiation visual information recording layer 24 with focus thus, and the record visual information.At this moment, make the upwards swing of the footpath of laser beam 38 on optical data recording medium, laser beam 38 is become irradiation repeatedly along substantially the same rail, with the record visual information.In addition, therein under the state by rotating mechanism rotary optical information recording carrier, be used for the laser beam 38 radiation data recording layers 18 of self-excitation optical pickup unit, can carry out the record of pit information.
Adopt the spectrophotometer measurement condition shown in Figure 15 B, on the embodiment 1 to 4 of record visual information as implied above thereon, the laser radiation part of measurement optical information recording layer 24 and laser is the absolute reflectance of illuminated portion not, and determine value Sv, will be worth Sv thus and get and make the contrast evaluation number by the following formula surface.CIE standard spectrum luminescence efficiency is shown among Figure 16.
Sv = ∫ 410 720 | D ( λ ) - U ( λ ) | V ( λ ) dλ ∫ 410 720 D ( λ ) V ( λ ) dλ
D (λ): the spectral reflectivity of the part of laser radiation (%)
U (λ): the spectral reflectivity of the non-irradiated part of laser (%)
V (λ): CIE standard spectrum luminescence efficiency
And, by the Sv value that following formula is determined, provide 5-the step evaluation criterion.Evaluation criterion as shown in Figure 17.According to the evaluation criterion of Figure 17, estimate contrast.Evaluation result is presented among Figure 14.
The light permanance and the heat durability excellence of the image that all obtains by embodiment 1 to 4.In addition, as what understood by the contrast evaluation result of Figure 14, embodiment 1 to 4 all in, contrast is gratifying, and obtains lively document image.
Certainly, according to optical data recording medium of the present invention, be used to prepare the method for this optical data recording medium, be used to write down the method for visual information, and the method for potpourri and this potpourri of use is not limited to above-mentioned embodiment, but under the situation that does not depart from main idea of the present invention or fundamental characteristics, can implement such structure and feature with other various forms.

Claims (15)

1. optical data recording medium, it can be by irradiation laser bundle (38) recorded information, and described optical data recording medium comprises:
Visual information recording layer (24) will write down visual information on visual information recording layer (24),
Wherein said visual information recording layer (24) contains dyestuff and at least a metallic atom, and described metallic atom is selected from: Na, Mg, K and Ca.
2. optical data recording medium according to claim 1, wherein said dyestuff are to be selected from least a in the following dyestuff: oxonol dye, cyanine dye, azo dyes, phthalocyanine dye and pyrroles's methylene dye.
3. optical data recording medium according to claim 1 and 2, wherein with respect to the described dyestuff of 1kg, the ratio with 0.1 to 100g contains described metallic atom.
4. according to any one described optical data recording medium in the claim 1 to 3, wherein said dyestuff also contains the cyclonite cyanine dye and has the phthalocyanine dye of central metal copper.
5. optical data recording medium according to claim 4, wherein with respect to the content of 50g as the Cu of described central metal, the ratio with 0.1 to 10g contains described metallic atom.
6. according to any one described optical data recording medium in the claim 1 to 5, it comprises:
First substrate (16);
Be formed on the data record layer (18) on described first substrate (16);
Be formed on first reflection horizon (20) on the described data record layer (18);
Be formed on the adhesive phase (28) on described first reflection horizon (20);
Be formed on second reflection horizon (26) on the described adhesive phase (28);
Be formed on the described visual information recording layer (24) on described second reflection horizon (28); With
Be formed on second substrate (22) on the described visual information recording layer (24).
7. optical data recording medium, it comprises:
Colored substrate (22a); With
Visual information recording layer (24), described visual information recording layer (24) is formed on the described colored substrate (22a), and on described visual information recording layer (24), by laser beam (38) record visual information,
Wherein form so described colored substrate (22a): on the output basis of described laser beam (38), be adjusted in the dyestuff that contains in the described colored substrate (22a) and/or the addition of pigment.
8. optical data recording medium, it comprises:
Coloured first substrate (22a);
Visual information recording layer (24), described visual information recording layer (24) is formed on described first substrate (16), and on described visual information recording layer (24), by first laser beam (38) record visual information;
Second transparency carrier (22); With
Data record layer (18), described data record layer (18) is formed on described second substrate (22), and on described data record layer (18), by second laser beam (38) digital-information recording,
Wherein form so described first substrate (16): on the output basis of described first laser beam (38), be adjusted in the dyestuff that contains in described first substrate (16) and/or the addition of pigment.
9. optical data recording medium, it comprises:
Coloured first substrate (22a);
Visual information recording layer (24), described visual information recording layer (24) is formed on described first substrate (22a), and on described visual information recording layer (24), by first laser beam (38) record visual information;
Second transparency carrier (16);
Data record layer (18), described data record layer (18) is formed on described second substrate (16), and on described data record layer (18), by second laser beam (38) record data,
The laser beam control area that wherein will be used to control described first laser beam (38) is placed in described first substrate (22a) side, and described laser beam control area has the laser power control information that is used to control laser power corresponding to the colouring information of described coloured first substrate (22a).
10. optical data recording medium according to claim 9 will comprise that wherein in pre-pit (32), prefabricated groove and the coding pattern of described laser power control information at least one is formed in the described laser beam control area.
11. method that is used to prepare optical data recording medium (10B), described optical data recording medium (10B) comprises: colored substrate (22a) and be formed on visual information recording layer (24) on the described substrate (22a), and wherein can write down visual information at described visual information recording layer (24) by the laser beam (38) from described substrate (22a) side irradiation, described method may further comprise the steps:
The dyestuff that contains in described substrate (22a) by the basic adjusted in described laser beam (38) output and/or the addition of pigment form described colored substrate (22a); With
Go up formation described visual information recording layer (24) at described substrate (22a).
12. method that is used to prepare optical data recording medium (10B), described optical data recording medium (10B) comprises: coloured first substrate (22a), be formed on the visual information recording layer (24) on described first substrate (22a), second transparency carrier (16), with the data record layer (18) that is formed on described second substrate (16), wherein can write down visual information at described visual information recording layer (24) by laser beam (38) from described first substrate (22a) side irradiation, and can go up digital-information recording at described data record layer (18) by the laser beam (38) from described second substrate (16) side irradiation, described method comprises:
Substrate forms step: the dyestuff that contains in described first substrate (22a) by the basic adjusted in described laser beam (38) output and/or the addition of pigment form described first substrate (22a);
First recording layer forms step: go up at described first substrate (22a) and form described visual information recording layer (24); With
Second recording layer forms step: go up at described second substrate (16) and form described data record layer (18).
13. one kind be used for as claim 1 to 10 any one defined as described in optical data recording medium as described in the method for record visual information on the visual information recording layer, described method comprises:
To be used for writing down the described laser beam (38) that visual information is used as going up at described visual information recording layer (24) in the same laser beam (38) of described data record layer (18) identifying recording layer.
14. method that potpourri is used to form optical data recording medium with visual information recording layer (24), on described optical data recording medium, can be by irradiation laser bundle (38) recorded information, and wherein can go up the record visual information at described visual information recording layer (24), described method comprises:
Described potpourri is used for the described visual information recording layer (24) of described optical data recording medium,
Wherein said potpourri is made up of dyestuff and at least a metallic atom, and described metallic atom is selected from: Na, Mg, K and Ca.
15. potpourri, it is used to form the visual information recording layer (24) of optical data recording medium, on described optical data recording medium, can be by irradiation laser bundle (38) recorded information, and wherein can go up the record visual information at described visual information recording layer (24), wherein said potpourri is made up of dyestuff and at least a metallic atom, and described metallic atom is selected from: Na, Mg, K and Ca.
CNA2006800449480A 2005-11-30 2006-11-29 Optical information recording medium, method for visible information recording, method for use of mixture and mixture Pending CN101322189A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109937144A (en) * 2016-11-17 2019-06-25 索尼公司 Invertibity recording medium, coating and external component for invertibity recording medium
CN112433285A (en) * 2020-12-04 2021-03-02 长春理工大学 Absorption type narrow-band filter

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109937144A (en) * 2016-11-17 2019-06-25 索尼公司 Invertibity recording medium, coating and external component for invertibity recording medium
CN112433285A (en) * 2020-12-04 2021-03-02 长春理工大学 Absorption type narrow-band filter

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