CN100366615C - Reactive materials for limited play optical devices and methods of making same - Google Patents
Reactive materials for limited play optical devices and methods of making same Download PDFInfo
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- CN100366615C CN100366615C CNB2003801041598A CN200380104159A CN100366615C CN 100366615 C CN100366615 C CN 100366615C CN B2003801041598 A CNB2003801041598 A CN B2003801041598A CN 200380104159 A CN200380104159 A CN 200380104159A CN 100366615 C CN100366615 C CN 100366615C
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Abstract
Methods and apparatus are provided for making an optically readable storage media in which the reading beam passes through a bonding layer configured with a reactive material that transforms from an optically transparent state to an optically opaque state after exposure to a predefined stimulus, thereby inhibiting axes to the data encoded on the optically readable storage media. The method includes steps of synthesizing a blocked dye combining the blocked dye with a carrier material curing the resultant combination deblocking the dye to produce a reduced day in the resultant bonding layer exposing the optically readable storage media with the reactive material in its bonding layer to a predetermined stimulus. In a further aspect of the present invention methods and apparatus are provided for making an optically readable storage media wherein the reading light passes through the bonding layer and the data encoded information is encoded on the L1 substrate. In yet another aspect of the present invention methods and apparatus are provided for making an optically readable storage media with at least two mechanisms for limiting access to the encoded data of the optically readable storage media.
Description
Required the pendent US temporary patent application No.60/415 of application on October 2nd, 2002 here according to 35 U.S.C. § 119 (e), 480; With the pendent non-temporary patent application No.10/163 that has required application on June 5th, 2002 according to 35 U.S.C. § 120,10/163,855 of application on June 5th, 473,2002,10/163 of application on June 5th, 2002,10/163,474 of application on June 5th, 472,2002, with 10/163 of application on June 5th, 2002,821 right of priority, and they have all required the US temporary patent application No.60/295 of application on June 5 calendar year 2001,903 right of priority.It is for reference that the disclosure of all above-mentioned patent applications all is introduced into this paper.
Invention field
The present invention relates to optical readable data storage medium and, more particularly, relate to the method for manufacturing of the data storage medium of optical readable, composition and goods, wherein data were obtained in the limited time.
Background of the present invention
CD such as CD and DVD can sell and rent to the human consumer.The content of CD can have music, film, video clips file, software or data.The purchase price of CD and DVD is high; This has reflected the value of information encoded on dish, as film or software, rather than the manufacturing cost of these CDs.Usually, content provider as film studio or software company, does not wish to sell with low price their duplicate that long-life information is arranged on market.And the user usually wishes only to obtain content information in a short time and with low price.The leasing of CD and DVD makes human consumer's lower expense when having to buy medium such as the fruit human consumer obtain content information, be trouble but need to return physical medium.Therefore wish to have limited broadcast/expiration optical medium, the user can buy with low price, solved content provider relevant they the life-span of content in market problem and do not have today videotape film and lease existing shortcoming of need returning.Also wish with low-cost and make this type of optical medium with minimum change to the existing manufacture method of CD.At last, content provider is glad to provide their content by limited broadcast/expiration optical medium in order to make, and the mechanism of the broadcast of restriction medium should not abolished easily, makes that exceeding the predetermined usage period can obtain content.
Before this, above-described low cost, the limited content life-span, lease avoiding of return, the prevention that attempt is abolished is also fully satisfied many requirements of the minimum change of existing manufacture method.What still need is the solution that has satisfied all these requirements simultaneously.One embodiment of the invention relate to and satisfy these requirements.
SOME METHODS has been proposed limited broadcast (expiration) CD of making based on layer, this layer do not interfere from a kind of that state (for example to the interference of reading (" opaque ") of this layer interference data on CD in the non-interference of reliably reading (" the transparent ") change of state of information on the CD, referring to US patent No.5,815,484 (" people such as Smith "), introduce for reference here with whole disclosures, with US patent No.6,011,772 people such as (" ") Rollhaus, introduce for reference here) with whole disclosures.This interference becomes dark colour owing to this layer, reflection, and high birefringence, rust staining bubbles, and bob is split, corrosion, bending changes the comprehensive of refraction performance or these, also has other possibility.
CD with this type of layer can be used in manufacturing in a predefined manner (as be exposed to ambient oxygen sometime in) the limited broadcast CD (as DVD) that cancels, this layer response in being exposed to atmosphere oxygen or the stimulation of reading the light of laser change to opaque state from vitreous state.This type of CD can find various industrial application, watches video image as the moment of selecting the human consumer by the human consumer but need not to send back to the CD of expiration.
Can be applied on the surface of CD with various technology by the interfering layer that stops reading of data that CD is become to read.Yet these methods have many shortcomings.For example, it can allow this layer be converted to the process counter-rotating of opaque state by finding a kind of method, as CD being exposed to reductibility chemical substance (it makes the oxidizing reaction counter-rotating), or, abolish by fully removing this layer by chemical process (as solvent) or mechanical means (as polishing or polishing).Therefore simultaneously, increase an extra play manufacturing of CD is complicated, for example need additional fund equipment and the additional step in manufacture method and improved cost and/or reduced the output that CD is made.
Can stop the protective layer of all attempts of abolishing this CD can be applied on the surface of interfering layer through engineering design, a kind of approach that uses by at least some people among the inventor.Yet, during will being introduced in the manufacturing processed, this introduces another step, and further increase cost and may further reduce manufacturing output.
In addition, because protective layer still is on the surface of CD, it is still removed by chemical process (as solvent) or mechanical means (as polishing or polishing), or is abolished by the chemical substance that can spread pierce through the protection layer and the reactive layer of arrival.
As explained above, when making the expiration CD, hope is used to be had cost-efficient manufacture method and makes (defeatable) CD that is difficult for abolishment.In addition, but wish that also CD can be converted to expiration status from broadcast state fast.In the middle of numerous benefits, this can reduce the variation of the reproduction time among optical media player and driving mechanism, although the following fact is arranged: but player in the market and driving mechanism have sizable mutability on the ability of playing CD under the situation that given deterioration is arranged on their the physics play property (as to reading the reflection of light rate of laser).
The present invention's general introduction
, the limited play optical devices with the reactive layer of intermediary is provided and makes its method aspect first of the present invention.
Second aspect of the present invention, provide a kind of method to allow master (master) produce the substrate of the storage media that many substrates type, optical readable get, the topological framework that wherein has many pits and wrinkle ridge is used to produce the counter-rotating pattern of topological framework, and the counter-rotating pattern of topological framework is as the topological framework of master.
A third aspect of the present invention, the method of the storage media that forms many substrates, optical readable is provided, the light that its medium has the information that is determined to be in on-chip many pits and wrinkle ridge and this informational needs passes subtegulum by transmission reads, and wherein binder layer will be gone up substrate and subtegulum bonds together.
The 4th aspect of the present invention, data storage device is provided, it has first substrate of many pits that the material of having determined in the above to be reflected covers and wrinkle ridge and has second substrate, and the tack coat that wherein contains reactive agent (the predetermined stimulation of its response and suppress optical transmission) is between first substrate and second substrate.
The 5th aspect of the present invention provides the tackiness agent of be used to bond first substrate and second substrate, wherein the tackiness agent reactive materials that comprises solid support material and make the substrate of data coding become and not can read.
A sixth aspect of the present invention provides a kind of mechanism, it cause the data of on the data storage medium of optical readable, storing at first become not can read with next destroyed.
A seventh aspect of the present invention, the data storage medium of the optical readable with first substrate and second substrate is provided, wherein first substrate and second substrate at least a has information coding characteristic structure, and the tack coat between first substrate and second substrate, wherein tack coat comprises solid support material and reactive materials, and reactive materials changes to the optics opaque state owing to the result of predetermined stimulation from vitreous state.
A eighth aspect of the present invention, the method for making tackiness agent be provided to bond first substrate and second substrate, the wherein dyestuff of close and protect and solid support material blending, and the dyestuff of close and protect deblocking and formed the not sealing dyestuff of the form of reducing subsequently.
According to another plyability embodiment of the present invention, the compound that a class is shown below has been described: (I)
Wherein
Y is O, S, Se, CR
17R
18, NR
13, and R
13, R
17, R
18Be selected from hydrogen independently of one another, C
1-C
3The aryl of alkyl and replacement and unsubstituted aryl;
R
2, R
5, R
6And R
9Respectively be independently selected from hydrogen, halogen, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, aryl, nitro, azo and fused-aryl;
R
3, R
4, R
7And R
8Be selected from NR independently of one another
10R
11, OR
12, hydrogen, alkyl, aryl, azo, and fused-aryl; With
R
10, R
11, R
12, R
14, R
15And R
16Be selected from hydrogen independently of one another, unsubstituted C
1-C
6Alkyl, the C of replacement
1-C
6Alkyl, unsubstituted C
1-C
6Alkoxyl group and the C that replaces
1-C
6Alkoxyl group, benzyl or aryl.
The summary of accompanying drawing
Fig. 1 is the schematic cross-section view of choice phase of process that is used for duplicating the physics pressing mold of DVD-5 substrate in manufacturing.
Fig. 2 is the schematic cross-section view of individual layer DVD-5 disc.
Fig. 3 is the schematic cross-section view that illustrates the manufacturing of standard DVD-5 and read.
Fig. 4 describes single-surface single-layer, single-surface double-layer, the diagram of the DVD structure of dual-layer, single-sided and double-layer and double-side type.
Fig. 5 is a graphic representation of describing the relation of the refractive index of individual layer and DVD-dual layer and substrate thickness.
Fig. 6 is the synoptic diagram of reading possibility that illustrates individual layer and DVD-dual layer.
Fig. 7 illustrates the schematic cross-section view that the improvement of tack coat DVD-5 structure is arranged in reading the light path of laser.
Fig. 8 illustrates manufacturing that the modified form of tack coat DVD-5 structure is arranged and the schematic cross-section view that reads in reading the light path of laser, wherein female pressing mold is used for molding and processes this L1 substrate.
Fig. 9 is the schematic cross-section view that illustrates the pressing mold reference plane of standard DVD-5 structure, and wherein pit and wrinkle ridge are molded in the L0 substrate.
Figure 10 is the schematic cross-section view that illustrates the pressing mold reference plane of modified version DVD-5 structure, and wherein pit and wrinkle ridge are molded in the L1 substrate.
Figure 11 is the figure that describes the atomic force microscope images of DVD-5 father's pressing mold.
Figure 12 is the figure that describes the atomic force microscope images of the female pressing mold of DVD-5.
Figure 13 is the figure that describes from the atomic force microscope images of the L1 layer of the modified version DVD-5 of female pressing mold molding.
Figure 14 is the schematic cross-section view that illustrates the manufacturing of modified version DVD-5 and read, and wherein the L1 layer is that uncle's pressing mold molding forms, and the direction of volution recording channel reverses in the master forming process.
Figure 15 is the schematic cross-section view that illustrates the pressing mold reference plane of modified version DVD-5 structure, wherein pit be on the surface of wrinkle ridge and wrinkle ridge be on the reference plane of L1 substrate.
Figure 16 is the schematic cross-section view that illustrates the pressing mold reference plane of modified version DVD-5 structure, wherein pit be on the reference plane of L1 substrate and wrinkle ridge be on the reference plane of L1 substrate.
Figure 17 illustrates the potential route of synthesis of synthetic of triisopropyl silyl oxygen base carbonyl leucomethylene blue.
Figure 18 explanation is 1, and there be the cyan reflection density and the time relation of the storage media of the optical readable that scribbles triisopropyl silyl oxygen base carbonyl leucomethylene blue down in 4-diazabicyclo [2,2,2] octane.
Figure 19 is the figure that describes the spectral absorption of methylenum coeruleum.
Figure 20 is the schematic cross-section view that illustrates modified version DVD-9 structure, wherein L0 layer segment ground metal lining.
Figure 21 A and 21B are the figure that describes the Koch test-results of modified version DVD-5 structure, and wherein pit is to be molded as depression by use father pressing mold in the L1 substrate, and wherein the direction of volution recording channel reverses in the master forming process.
Describe in detail
Some CD such as DVD are comprised of two plastics half sheets (" substrate "), they be metal lining and be bonded together with middle tack coat. Hope is interfered with the intermediate layer between two substrates and is read laser, in order to stop reading of this disc. This will more be difficult to abolish the disc of (defeat), because two and half sheets of CD protection interfere with layer. The intermediate layer has still been guided the method for disc expiration as interfere with layer. For example, typically allow the oxygen diffusion for the manufacture of the Merlon of DVD substrate and arrive in the middle of reactive layer and caused the reaction of the expiration that causes disc.
In addition, wish tack coat itself is used as interfering layer, for example change the chemical composition of tack coat by the introducing of reactive materials. This can simplify the manufacturing of limited broadcast CD, because do not need extra play, and the trial of abolishing limited broadcast mechanism by removing this one deck will destroy CD itself, because tack coat is crucial for the integrality of CD. Yet in the CD such as DVD-5 of some type, tack coat is not in light path. Fig. 2 has illustrated the cross sectional view of the layer that has for DVD-5 structure typical case. Therefore although tack coat plays effect (reflective metallic that for example contacts with tack coat by corrosion) in the expiration termination procedure that does not rely on the DVD-5 that utilizes the direct interference of reading laser, can not prevent from reading state that laser reads in the data on the CD and make the termination that expires of the disc of this type by tack coat is transformed into. Because usually wish by disc being become to read with reading method that laser implement to interfere, wish to have with intermediate adhesive layer and be in the similar disc of DVD-5 in the light path.
The restriction that depends on the interference of reading laser in the expiration termination procedure is used in the CD, data encoding structure (such as the pit of the metal lining on polycarbonate substrate) typically is retained in the expiration disc, although read the information that laser has been prevented from reading this coding. As long as these data structures exist, always might read the laser obtaining information disc is abolished by allowing. Therefore hope has the additional mechanism of the recovery of the data of preventing, as for good and all wiping these data by infringement integrality of data structure on CD.
When considering when combining with following narration and accompanying drawing, these and other target of the present invention and embodiment are when understanding better and understand.Yet it should be understood that following narration, although the preferred embodiments of the invention and their many specific detail have been described, only is that unrestricted meaning provides for illustration purpose.Can make many changes and improvements within the scope of the present invention under the premise of without departing from the spirit of the present invention, therefore the present invention includes all these improvement.
Following this specification sheets and constituting the illustrative of accompanying drawing illustrated of a part of this specification sheets but non-limiting embodiments by reading, constitute advantages and features of the invention and will become more obvious for the notion of knowing of the component of model system provided by the present invention and operation.Should be pointed out that illustrational in the accompanying drawings feature not necessarily describes in proportion.
We describe different aspect of the present invention and several corresponding embodiment and embodiment now.
DVD is the prevailing CD that is used for the distribution of film.DVD is made up of two agglutinating plastic substrates, typically is called L0 and is called L1 for top-side substrate for bottom substrate, and wherein " top " and " bottom " refers to the DVD play position when read the bottom, and this is general agreement.These substrates are from such as polycarbonate, and the material of acrylate or polyolefine and so on is made, and this material is injected in the mould with the fusing form and pushes down on pressing mold.The process that manufacturing is used to duplicate the physics pressing mold of DVD-5 substrate is called master and forms (Mastering).Use follow procedure, it is in Fig. 1 illustrated:
1. the polished and coating primer 10 of float glass blank 5 is to strengthen the binding property with photo-resist layer 15.
2. apply photo-resist coating 15, the baking and be exposed to laser to carry out record.The formatted data signal is used to regulate the cutting laser of laser beam record (LBR) machine, and it produces pit 20 in the glass disc.
3. Bao Guang glass develops then and stay pit 20 and wrinkle ridge 25 on whole surface.
4. this " glass master " then has thin (110nm) metal level of sputtering method plating so that the surface becomes the satisfied needs of electroplating of electroconductibility.
5. then glass master is put in the electroplate liquid, nickel is formed into required thickness (typically 0.300mm) therein.
6. this " metal father mould " (or " father's pressing mold 30 ") separates with glass master 35 then and cleans.In this step, metal father mould 30 can be used in the moulding technology, if but this part in duplicating, destroy or damage, then whole process must repeat.
7. therefore, most manufacturing firm will grow by " metal mother " by (or " female pressing mold 40 "), and it is the negative-appearing image of father's mould 30.Typically, four female pressing molds 40 can be from 30 growths of father's mould but are not had the decline of quality, and from each master mold 40 nearly 8 pressing molds (" sub-pressing mold 45 ") of can growing.
Pressing mold be sent in the copying equipment and master mold 40 in order to rearrange or replacement part and storing.
For DVD-5, it is the individual layer disc in Fig. 2 illustrated, and L0 substrate 100 has covered the thin reflecting layer 105 of aluminium by sputtering method.This has produced the metallic coating (L0 layer) between 60 and 100 dust thickness.On 100 of L0 substrates bonding, 110 to the blank L1 substrates 110, as illustrated in fig. 3.For DVD-9, it is a dual layer disc, and the L0 layer is as the metal level of extremely thin, half reflection and form, and typically is made up of gold.Go up formation total reflection aluminium lamination at L1 substrate (L1 layer).Two substrates are used suitable jointing material (it forms transparent bonding layer) bonding subsequently and are formed the DVD-9 disc.
Find out in the DVD family illustration that in Fig. 4 the DVD disc can contain one or two information layer for each substrate, obtain dissimilar disc capacity, as DVD-5200 (single face, individual layer, the 4.7Gbyte capacity), DVD-9205 (single face, bilayer, the 8.5Gbyte capacity), DVD-10210 is (two-sided, individual layer, the 9.4Gbyte capacity), DVD-14 is (two-sided, single-surface single-layer, single-surface double-layer, 13.2Gbyte capacity), with DVD-18 215 (two-sided, bilayer, 17Gbyte capacity).
Set up the standard entity, their suggestions, the technical specification of recommending and/or arranging various disk formats and/or disc data capacity are to guarantee the various media player play that different disc formats and/or disc data capacity can be sold by media player manufacturing firm and/or to read.The example of standard entity includes but not limited to that DVD Forum (www.dvdforum.org) and European Computer Manufacturers Ass. (" ECMA ") are (www.ecma-international.org).
For example, dual layer disc such as DVD-9 205 must meet " DVD Specifications forRead-Only Disc, Part 1 Physical Specifications Version 1.0 ", and it requires following parameters:
1. total disc thickness comprises tack coat 110, and wall and label should be 1.20mm+0.30mm/-0.06mm
2. the refractive index of transparent substrate (RI) should be that the refractive index of 1.55+/-0.10 wall should be (RI+ of substrate/-0.10)
3. the thickness of transparent substrate regulation is relevant with its refractive index.Typically for the polycarbonate of RI=1.56, the one-tenth-value thickness 1/10 of disc substrate is 0.57mm～0.63mm (referring to Fig. 5 A and 5B)
The standard entity does not provide technical specification for wall (tack coat 110) thickness of DVD-5 200 and DVD-10 210 forms, meets as above RI correlation technique specification as long as total disc thickness meets DVD technical parameter and half disc (substrate of molding).
Information in DVD is to form in the pit 20 of corresponding data layer and the wrinkle ridge 25 (not being the data area of pit) and encode being molded onto neutralize metal lining subsequently of substrate.Pit and wrinkle ridge are worked out in the volution recording channel, and for DVD-5 200, it is to begin and read to the outside propulsive clockwise direction of disc according to the inside from disc.The reference area of the disc that is occupied by data is not used for this tracking that reads laser (tracking).Read laser, it has the wavelength of 630-650 nanometer in a vacuum, focus on by penetrating and half-reflecting L0 layer 100 on the L0 layer 100 of DVD-5 200 or DVD-9 205, or on the L1 of DVD-9 layer 115 and it reflect back into photoelectric detector.From the process that is converted to wrinkle ridge 25 from pit 20 or vice versa, form interference figure, it can be detected and be caused the change of its electrical output signal by photoelectric detector.These changes in the electrical output signal of photoelectric detector can make player read in the information that writes down on the DVD.
Dual layer disc, as DVD-9 series 205, typically utilize a kind of in two kinds of methods of reading of disc information:
Double-deck parallel record path (PTP) disc 299 will have introducing 300 and draw 305 zones in two-layer, as shown in FIG. 6.For each layer, introduce the inside radius that 300 zones are positioned at disc and draw the outside radius that 305 zones are positioned at disc.The layout of this layout structure and individual layer 320 discs is similar.Reading for two-layer of data carried out, as at DVD-5, in 200 from the inside radius of disc to outside radius.For having on disc after the proper authorization, the PTP method can allow the quick access from the layer to the layer, for example for background information and note being provided in a recording channel and providing film simultaneously in another recording channel.
Double-deck relative record path (OTP) 325 discs as shown in FIG. 6, provide from the seamless successive possibility of the playback of 100 to L1 115 layers of L0.First information layer (L0) 100 is from the zone beginning of the introducing on the inside radius of disc and terminate in so-called region intermediate 330 on the outside radius.Second information layer is from the region intermediate on the outside radius 330 beginning with terminate in 300 zones of drawing on the inside radius of disc.The reading of data 335 that is stored on the disc will be till beginning on the inside radius of first information layer and advancing to the region intermediate 330 of this one deck.Be transformed into then in the region intermediate in second information layer, so that continue to implement from outside radius to the data read 305 zones of drawing on the inside radius of the second layer (L1) 115.
Single-layer optical disc
An example of the present invention is the CD that is similar to DVD-5, and wherein, DVD-5 is different with standard, and typically the middle layer 400 as tack coat 401 is in (for example, referring to Fig. 7) in the light path that reads laser.(following label is " special DVD-5 design # 1 ") in one embodiment of the invention, this disc is by reading information manufacturing with reflecting layer 410 counter-rotatings of standard DVD-5 with via substrate 415 that does not contain information and tack coat 401.In another embodiment of the invention (below label be " special DVD-5 design # 2 "), the direction of volution recording channel counter-rotating in the master forming process, the substrate upset " putting upside down " and the information that contain information read via substrate 415 that does not contain information and tack coat 401.In the CD of this type, tack coat 401 is an integral parts that read the light path 405 of laser.Even the structure of " special DVD-5 " disc described here is different from standard DVD-5, but player is still play this disc, is standard DVD-5 as it.
This embodiment of the present invention is for allowing the manufacturing of low-cost " limited broadcast " CD (it has resistant function to the attempt of abolishing it) have important advantage.Especially, do not need to introduce any extra play because compare it with standard DVD-5, it can create on the equipment that is designed to make the DVD-5 disc but equipment is had minimum change.In addition,, improve this one deck and will obtain the disc that is very difficult to abolish, because interfering layer 400 is being protected respectively by two substrates 415 of CD and 420 to interfere the data read that pre-determined stimulus is responded because tack coat 401 is in the light path 405.For example, it is unpractical polishing off interfering layer 400 from disc, because this destroys disc probably.Similarly, attempt damages the structural integrity that bonding/interfering layer destroys CD probably in other respects.
We describe the manufacturing of three embodiments of the present invention now in detail, and we are " special DVD-5 " design 1,2 and 3 with their labels.
Special DVD-5 design # 1
In one embodiment of the invention, above method is duplicated L1 disc substrate 420 and modification by using female pressing mold.Fig. 3 has shown how pressing mold or father's mould are used for the normal individual layer DVD-5 of molding substrate.Fig. 8 has illustrated by tack coat 401 these discs of formation that use female pressing mold 40 and be used in the light path 405 and has made this example of the present invention.
Information is coded on 100 of the L0 in the standard DVD-5 of common molding, wherein " pit " 20 and " wrinkle ridge " 25 be molded on the L0 substrate 100 and plating reflective metal coating 105, as at Fig. 2, shown in Fig. 3 and Fig. 9.In one embodiment of the invention, female pressing mold 40 is used for molding L1 face 420, as shown in Figure 8.This one side subsequently metal lining and with blank L0 substrate 415 bonding, allow tack coat 401 be in the light path 405, as shown in Figure 10.By using the specified layer thickness of 0.055mm+/-0.015, the thickness of L0 substrate 100 in moulding process as goal-setting in 0.55mm～0.57, obtain the focal length of the disc thickness (comprise tack coat) consistent, allow player be in and read in the normal focusing range of L0 layer 100 with standard DVD technical specification.Therefore player is understood this disc as standard individual layer DVD-5.Test in place shows that space layer can as one man maintain 0.045～0.065mm aborning.This variation and reduction thickness of the disc of molding processing of having controlled has aborning been kept focus and optical parametric still within the technical specification of being set by DVD license issuing organization and hardware manufacturing producer (that is DVD Forum).
For copying equipment, keep no change in most actual compacting that is applied in production and the adhesive segment.The main region that changes is among the LBR (laser beam record) and developing regional in master forms.Typically, master is to cut with bigger pit volume, to compensate plastic shrinkage and to duplicate poor efficiency.The ratio of pit and land area is to measure by the term that is called asymmetry on disc.Because asymmetry is the ratio of pit and land area, with because for typically by I3 to each definite pit zone of I14 pit, equate or relative land area I3 to I14 wrinkle ridge so have, typically make manufacturing firm more easily targeted set positive asymmetry (higher pit zone), calculate the loss in copying to plastic substrate.For example, this master can cut with positive 10～12% asymmetry that are, and the net result that forms from molding can be 5～7%.The technical specification of disc substrate is :-0.05≤asymmetry≤+ 0.15.For the DVD disc, positive asymmetry has been represented the bigger pit volume of comparing with land area.
For this embodiment of the present invention, the hope change, improves in the asymmetry that is used on female pressing mold of molding so that obtain higher asymmetry value on father's pressing mold subsequently in the asymmetry set(ting)value on the LBR.Asymmetry can be by changing the power of exposure, focus strength and compensation level, development time/end point determination, or baseline (how laser diode blocks the control of laser explosure light beam apace between double exposure) and change on master.Many other possible methods control asymmetry are arranged, but primary process (basic process) or set(ting)value control are the easiest realizations.Also making from this method of female pressing mold molding does not need to grow additional pressing mold and having eliminated because the caused production loss of this family's method.
In this embodiment of the present invention, pit 20 is molded in the L1 layer 420 by using female pressing mold 40, the result, and the surface of pit 20 raises with respect to the reference plane 450 of L1 layer 420, as shown in Figure 10.This reference plane 450 typically is used for the tracking (tracking zone) of disk player.On the contrary, pit 20 is as the cavity molding in L0 substrate 100, as shown in FIG. 9 in normal DVD-5.Resemble the common agreement that it is in the play position when read the bottom by use describing disc, with the following agreement that we provide, unless otherwise mentioned, pit 20 is lower than reference plane 450 in normal DVD-5, and wrinkle ridge 25 is in (referring to Fig. 9) on the reference plane 450.In aforesaid embodiment of the present invention, blank L0 substrate 415 and tack coat 401 in the light path 405 that reads laser, be lower than L1 substrate 420 and in L1 substrate 420 surface of pit 20 be lower than reference plane 450 and wrinkle ridge 25 is in (referring to Figure 10) on the reference plane 450.Be noted that this structural requirement pit 25 with unconventional mode molding (they stretch out from the reference plane 450 of disc), this can be by realizing from female pressing mold 40 moldings processing L1 substrate 420.Figure 11 has shown atomic force microscope (AFM) image of father's pressing mold 30 of DVD-5, and Figure 12 has shown that the afm image of corresponding female pressing mold 40 and Figure 13 show the afm image that designs the L1 layer of #1 from the special DVD-5 of female pressing mold 40 moldings.
The needed molding of this embodiment of the present invention can bring some challenge.In typical Shooting Technique, polymer materials flows along the pit on pressing mold 20, and these pits raise from reference plane 450.This is than from the easier enforcement of the molding of master mold, and wherein polymer materials must flow in the cavity, and the latter constitutes pit 20 on independent part.When this raw material flowed on the surface of female pressing mold 40, molecular chain cooled off by contacting with the colder reference surface of pressing mold.After mould fully filled up, must exert pressure then forced colder polymer materials to enter into pit 20 cavitys.Produce disc though this method can be regenerated in the technical specification of standard DVD-5 configuration, this moulding technology is more difficult.Yet technician in the art is by regulating the operational characteristic of mould machine, for example by improving mold surface temperature and tackling this type of challenge cycle time.The suitable material that has higher melt flow speed in addition can both use, as PMMA or high melt flow rate (MFR) polycarbonate.For example, the SPOQ research grade polycarbonate of General Electric has the twice of the melt flow rate (MFR) of standard level polycarbonate.
As long as the refractive index (RI) of used binding agent is substantially equal to the RI of L0 substrate 415, the thickness of tack coat 401 is uniform, overregulated with compensation tack coat 401 existing in the light path 405 of reading layer with the thickness of L0 substrate 415, player can not be with special DVD-5 design # 1 and standard DVD-5 differentiation.Experience shows, the disc that can play can create under the situation of these adjustings, because most player is followed DVD technical parameter (for example, DVD Forum and/or ECMA) by halves, as long as not many with departing from of technical parameter.
Embodiment 1: special DVD-5 design # 1
Father's pressing mold 30 is handled (mastered) with the symmetry that improves a little (positive asymmetry=compare with wrinkle ridge 25 big pit 20).Asymmetry can increase and decrease in many ways.The simplest method and a kind of method that is used for this design are the development times (end point determination set(ting)value) that improves this pit 20 of overdevelopment.By prolonging developing process, can improve volume around the pit volume of exposed portion, cause to be converted to positive asymmetry.
Female pressing mold 40 is 30 growths of uncle's pressing mold, and is the same with the normal family method.The dish substrate is to form from female pressing mold 40 moldings, has utilized by the caused bigger depression of positive asymmetry.From help to compensate the after contraction of pit 20 with the formed big pit 20 of female pressing mold 40 moldings, it is extremely crucial for the main body of substrate now, rather than the cavity in the standard moulding technology.Typically, the pit 20 that molten plastic is centered around normally in (father 30 or son 45) pressing mold flows, and flows around hill as the river.Along with the rising of liquid level, hill or pit 20 will be submerged.When molten plastic flows through colder stamper surface, form the top layer from the teeth outwards, the latter plays a part heat insulator.This can allow plastics keep in order there not to be under too much stress or the refrigerative situation to form needed its flow velocity of pit volume.For special DVD-5 design #1, plastics have to flow in the depression of female pressing mold 40, rather than center on the protuberance of father/sub-pressing mold 30 and 45 respectively.This is difficult, because when stream of plastic was crossed female pressing mold 40 surperficial, it formed the top layer once more from the teeth outwards.Along with the injection that continuation is arranged and this mould volume of filling/retention time can increase, the plastics of fusing must be forced to and enter in the depression then.Because typically solidify below the second-order transition temperature of plastics on this top layer, this material does not flow freely in the depression.Because forming, the pit in the L1 substrate 420 of special DVD-5 design #1 is not in the light path that reads laser with plastics, this material can be filled with bigger power but be need not to consider degree of birefringence and unrelieved stress, though because restricted to pressure by the caused warpage of excessive stuffing pressure (inclination) on plastics.In this embodiment, being combined with of the bigger depression in female pressing mold 40 and the die temperature of raising helps duplicate required pit 20.Typically, be used for the direct water spray system of mold heated and refrigerative, the safety interlocking of 120 ℃ of top temperatures has limited the temperature of water.By making 50/50 solution of spent glycol and water, this temperature can keep under 130 ℃ top temperature effectively.The temperature of this increase helps the top layer is remained on melted state, near its second-order transition temperature, has promoted the duplicating of L1 substrate 420 of special DVD-5 design #1.Equally, female pressing mold 40 must be filled with molten plastic apace, to prevent skinning from the teeth outwards.
The L1 substrate 420 of molding is bonded to blank L0 substrate 415 by using the curable DVD tackiness agent of optical grade UV (with being used for the same of DVD-9 production), makes the design # 1 of special DVD-5.L0 substrate 415 be with 0.55～0.57mm thickness (that is, and than standard DVD half sheet thin the 30-50 micron) molding is with the tack coat of compensation in light path, therefore kept and the depth of focus the same in standard DVD-5 for the layer that contains information.
Special DVD-5 design # 2
The electronics of optical media drives comprises DVD player, typically is designed to read in contained information in the layer on the disc, and this finishes to the caused interference figure of the transformation of " pit " 20 from " wrinkle ridge " 25 by being identified in this layer.This pit 20 usually comes molding to approximate greatly and typically how much to be lower than 1/4th the height that reads Wavelength of Laser.For example, the typical wavelengths that reads laser in DVD is 635-650 nanometer (in a vacuum), or the material of RI=1.55 (being that the material typical case who is used for making the DVD substrate has) be 410-420nm and therefore in standard DVD-5 the height of pit 20 should be about 100-105 nanometer.Therefore, 20 the transformation or vice versa corresponding to the path that reads laser of only about half of wavelength from wrinkle ridge 25 to pit, or the phase transformations of about 180 degree.Two identical ripples of phase differential with 180 degree will interfere with each other and offset and the electronics of CD-ROM driver is designed to detect interference figure.By using the standard agreement of the disc of reading from below, the surface of pit 20 is under the surface of wrinkle ridge 25 in standard DVD-5, with 20 transformation is that " downwards " changes from wrinkle ridge 25 to pit, and 25 transformation is " make progress " transformation from pit 20 to wrinkle ridge.If the height of pit 20 is to read 1/4th of Wavelength of Laser, then 20 transformation is that " downwards " corresponding to the phase transformations of+180 degree changes and 25 transformation is " making progress " transformation corresponding to the phase transformations of-180 degree from pit 20 to wrinkle ridge from wrinkle ridge 25 to pit in standard DVD-5.If " make progress " and " downwards " change and to have differed 360 degree, as in above-described situation, then their effect is identical.This one of them connotation is, the pit 20 of DVD-5 is molding in the opposite direction, promptly, about quarter wave that pit surface ratio wrinkle ridge 25 surfaces are high, no matter unlikely be subjected to the influence that detected transformation is in " making progress " or " downwards " direction with the electronics of Disc player, no matter promptly pit 20 zones are higher or lower than wrinkle ridge 25 zones.
In standard DVD-5, laser pickup will be by focusing on the pit of arranging in the volution recording channel 20 and L0 substrate 100 is read.The rotation of disc is to be in clockwise direction in counter-clockwise direction (from reading a side of laser) and this volution recording channel.Suppose under the situation that does not change the electrical signal that detects by player and pit 20 directions can be reversed, pit 20 is by using usually (father/son) DVD-5 pressing mold 30/45 as caving in molding 500 in L1 substrate 420, as shown in Figure 14 in another embodiment of the invention.The direction of volution recording channel is to reverse in master forms (mastering) process, because disc will read from a side of tack coat 401, rather than according in standard DVD-5, passing this substrate like that.
Formed disc has the same information encoded with DVD-5, though pit 20 forms in L1 layer 420: the surface of pit 20 be on the surface of wrinkle ridge 25 and wrinkle ridge 25 be on the reference plane of L1 layer 420, as shown in Figure 15.These pit 20 width, length, highly and shape provided in order to encode the data in DVD and gone up needed corresponding HF signal.Signal adopts eight to 14 modulation (EFM) signals to encode.Pit 20 edges and sidewall slope are used to distinguish 0 and 1 logic transition.This causes as 3 unit lengths to measured pit 20 unit of length of 14 unit lengths, and this has set the frequency limitation of the EFM signal of reading from disc.This measurement is commonly called the 3T-14T signal, and wherein T refers to for some time.As long as pit 20 is to duplicate with standard manner, then player still can be distinguished pit 20 zero positions and final position, reads from the negative simultaneously, correctly discerns its data attribute.This is the preferred embodiments of the invention in many cases, because do not need from female pressing mold 40 moldings, for normally this situation of above special DVD-5 design # 1.
How many actual heights of pit 20 typically is lower than the quarter wave that reads laser in standard DVD-5.This wishes to be avoided in the wrinkle ridge transition process at pit the elimination fully of reflector laser, and this has promoted the function of player electronics.For example, 0.88
*The value of (optical maser wavelength)/4 is recommended sometimes, i.e. about 90 nanometers for the material of RI=1.55.Therefore hope molding pit 20 surfaces in this embodiment of the present invention make it how much to be higher than and read 1/4th of Wavelength of Laser, and the variation that designs on the light path that is reading laser among the #2 from wrinkle ridge 25 to pit 20 the transition process at special DVD-5 will accurately be to have grown a wavelength than the respective change in standard DVD-5 like this.For example, if read optical maser wavelength and be 650 nanometers (promptly, 420nm in the polycarbonate substrate of RI=1.55), with the pit in standard DVD-5 be 90 nanometers, pit 20 in the present embodiment (special DVD-5 design #2) can be with 120 nanometers one half-wavelength (210nm) of the position on design # 1 middle distance pit 20 surfaces (that is) molding.
Embodiment 2: special DVD-5 design # 2
Being used for molding processes the special pressing mold of the L1 substrate 420 of special DVD-5 design # 2 and forms technology (mastering process) by improved master and produce, wherein the sense of rotation of laser beam recorder turntable is inverted in working angles, cause being formed on normal DVD-5 in the volution recording channel gone up in the opposite direction of respective party.This pressing mold is by forcing turntable to be produced rotating on the opposite direction during normal DVD-5 with cutting, and content information is imported in the laser beam recorder as the DVD-5 image.Be generally the predefined sweep velocity of DVD form and set manually to the speed that forms typical 3.49m/s in (mastering) at the DVD-5 master.L1 substrate 420 carries out molding then on the master die molding machine of being installed for the DVD-5 manufacturing.
In the L1 substrate 420 of molding some are by using the curable DVD adhesives of optical grade UV to blank L0 substrate 415, to make the design # 2 of special DVD-5.With the same in embodiment 1, L0 substrate 415 is with the thickness of 0.55～0.57mm (promptly, thinner 30～50 microns than standard DVD half sheet) molding with the tack coat 401 of compensation in light path, therefore for the layer that contains information keep with standard DVD-5 in the identical depth of focus.For the disc that bonds, the half reflection metal deposition device that machine is arranged on the DVD-9 mode of production and L0 layer is off-line then.Regulate then set time with compensation because the needed minimizing on curing exposure of the semi-reflective layer that lacks is solidified for the DVD-5 disc sets substantially and disc overturns by the L0 layer and solidifies.This function typically is DVD-9 production and keeps.
Disc is tested with Koch DVD pilot system then and is play in four different DVD player.They and common DVD-5 disc indistinguishably carry out, as shown in Figure 21 and 22.Equally, these discs do not have error ground to play at two DVD-ROM driving mechanisms of additional three DVD player neutralization.
In the substrate of molding some are used to make the disc (referring to embodiment 9) with reactive tack coat.
Special DVD-5 design # 3
The electronics of optical media drives, comprise DVD player, can be through can being that the basis is identified in pit 20 in the layer on the disc and wrinkle ridge 25 and reads in the information that is comprised in the layer on the disc after the design by absolute and/or relative altitude with these pits 20 and wrinkle ridge 25, therefore in information coding layer, between " make progress " and " downwards " transformation, distinguish, but be not subjected to the influence of pit 20 and the rising of wrinkle ridge 25 for the reference plane 450 of this layer.Therefore in another embodiment of the invention, in the master forming process direction of volution recording channel be counter-rotating and pit 20 and wrinkle ridge 25 reverse, the wrinkle ridge 25 and the wrinkle ridge 25 that become on formed pressing mold 30 of pit 20 becomes pit 555 as a result.L1 substrate 420 is then by using 550 normal (father) pressing molds 30 to come molding and being bonded to blank L0 substrate 415.Formed disc has the same information encoded with DVD-5, the relative altitude of pit and wrinkle ridge and in information coding layer " make progress " and " downwards " transformation be equal to DVD-5.Specifically, the surface of pit is lower than the surface of wrinkle ridge.Yet, although the surface of wrinkle ridge is on the reference plane of L0 layer in standard DVD-5, the surface of wrinkle ridge 560 in this embodiment (corresponding at the pit on the standard DVD-5) is on the reference plane of L1 layer, and pit 565 (corresponding to the wrinkle ridge on common DVD-5) is higher than this reference plane, as shown in Figure 16.
Reactive tack coat
Another embodiment of the invention is to introduce reactive materials in the middle layer.In one embodiment, the middle layer is the tack coat of disc.
In one embodiment of the invention, the stimulation of triggering reaction is the exposure to atmosphericoxygen.After being exposed to oxygen, the opaque and translucent layer of the oxidized formation of leucomethylene blue (for example, dark blue dyestuff, methylene blue) that reactive materials is for example colourless basically.Data storage medium with opaque/semitransparent layer no longer can be play in the medium player.Become the opaque time that spends by adjusting it, this method is used to provide the restriction broadcast type data storage medium that the required life-span is arranged for certain application.
Reactive layer, it not only comprises carrier but also comprise reactive materials, enough transmissivities should be had at first so that data are retrieved by data storage medium equipment, formed one deck subsequently, the latter stops the data retrieval (for example, the light of its absorption resistance q.s is incident light and/or reflected light) of being undertaken by this equipment under Wavelength of Laser in giving locking equipment.Typically, allow to have an appointment 50% or the layer of bigger initial percentage reflectivity from the reflecting layer can both use, wherein about 65% or bigger initial percentage reflectivity be preferred and about 75% or bigger initial percentage reflectivity be preferred.In case medium has been exposed to oxygen, for example, air, (for example reach the desirable time, the desirable proper reproduction time of medium), this layer preferably includes about 45% or percentage reflectivity still less, is preferred below wherein about 30% or 30%, be preferred and about 15% or 15% to be especially preferred below about 20% or 20%.
Possible reactive materials include, but not limited to oxysensible colourless or the reduction form thiodiphenylamine, fen piperazine, and azophenlyene, their member comprises: methylene blue, brilliant cresyl blue, Basic Blue 3, methylene green, Taylor's indigo plant, Meldola indigo plant, new methylene blue, thionine, Nile blue, lapis lazuli, with Tolylamine 0, and comprise at least a reaction product and binding substances in the following formula material; Their structure provides below:
Methylene blue 657,618nm
The process that the synthetic method of leucomethylene blue and oxygen dependence reoxidize the blue dyestuff of subunit that forms coloured form under provide:
Except above reactive materials, other a lot of dyestuffs and light sealing material can be used for making data storage medium to become limited broadcast type after synthetic.For example, other possible reactive materials can be at US patent No.4, finds in 404,257, and it is hereby incorporated by reference and US patent No.5, and 815,484, it is hereby incorporated by reference.Additional example comprises,
(a) colourless azines, as at US patent No.4, those disclosed in 710,570 is introduced for reference here with full content
Wherein:
X is O, S, NR
2
Z constitutes fused aromatic or heterocyclic system
N is 0 or 1 and allow a R
1The substitution in ring base
Q represents CR
4R
5, R wherein
4And R
5In at least one be electronegativity group or R
4And R
5Can form ring, or
When X was S, Q can represent NR
3, R wherein
3Be aromatics or heterocyclic group.
(b) quinone imides comprises phenylene blue, indophenols, and indoaniline, and as at US patent No.5, those disclosed in 424,475 is introduced for referencely and for example here with full content, comprise following:
X wherein, Y and Z can be but be not limited to: hydrogen, alkyl, alkoxyl group, aryl, the alkyl of replacement, alkoxyl group, and aryl, OH, CN, halogen, NR
6R
7, SR
8, SO
2R
9, R wherein
2-R
9Can be hydrogen, alkyl, aryl, the alkyl or aryl of replacement, or the expression formation can contain heteroatoms and substituent aromatics or the needed atom of aliphatics member ring systems.
(c) anthraquinone; With comprise, for example,
R wherein
1And R
2Can be but be not limited to: hydrogen, alkyl, alkoxyl group, aryl, the alkyl of replacement, alkoxyl group, and aryl, OH, CN, halogen, NR
5R
6, SR
7, SO
2R
8, R wherein
5-R
8Can be hydrogen, alkyl, aryl, the alkyl or aryl of replacement maybe can be represented to constitute and can contain heteroatoms and substituent aromatics or the needed atom of aliphatics member ring systems.
(d) acridine; With comprise, for example,
Acridine
R wherein
1-R
4Can be but be not limited to: hydrogen, alkyl, aryl, the alkyl or aryl of replacement, or expression constitutes and can contain heteroatoms and substituent aromatics or the needed atom of aliphatics member ring systems, and R
5Can be but be not limited to: hydrogen, alkyl, aryl, the alkyl of replacement and aryl.
(e) and two-and and triarylmethane dye, as at US patent No.5, those disclosed in 330,864, this patent is introduced for reference here with its full content and is for example comprised,
R in the triarylmethane formula
1=aryl
Wherein X and Y can be but be not limited to: hydrogen, alkyl, alkoxyl group, aryl, the alkyl of replacement, alkoxyl group, and aryl, OH, CN, halogen, NR
6R
7, SR
8, SO
2R
9, R wherein
2-R
7Can be hydrogen, alkyl, aryl, the alkyl or aryl of replacement, or the expression formation can contain heteroatoms and substituent aromatics or the needed atom of aliphatics member ring systems.Be appreciated that R1 can be the aryl that replaces.
Additional reactive materials includes, but not limited to the pH indicator substances, carries out photopolymerisable material, produces the chemical substance of sedimentary material and photoactivation.
Reactive materials can further comprise at least a mixture that comprises any above-mentioned reactive materials.
In one embodiment of the invention, this reactive materials mixes with carrier so that be deposited on and/or be impregnated at least a portion on surface of substrate.Possible carrier comprises thermoplastic acrylic polymer, vibrin, Resins, epoxy, polythiol (polythiolenes), the ultraviolet curing organic resin, urethane, thermosetting acrylate polymkeric substance, Synolac, Vinylite etc. and comprise the binding substances of at least a above-mentioned carrier; Polyester comprises, the reaction product of aliphatic dicarboxylic acid (for example comprising fumaric acid or toxilic acid) and glycol (as ethylene glycol, propylene glycol, dimethyltrimethylene glycol etc.) for example, and the reaction product and the mixture that comprise at least a above-mentioned reaction product.
Some Resins, epoxy, it can be used as organic resin, comprises the monomer that contains one or more epoxy-functionals, and dimerization is oligomeric, or the aggretion type epoxy material.For example, dihydroxyphenyl propane and Epicholorohydrin, or the reaction product of Epicholorohydrin and phenol formaldehyde resin, or the like.
Other organic resin can be the form of mixtures of polyolefins and polythiol, as people such as Kehr, and US patent 3,697,395 and 3,697, described in 402, they are introduced into for reference.
The reactive layer of non-binding type
Randomly, this reactivity layer can be by using various paint-on techniques, and as the japanning method, pickling process sprays, spin coating, and silk screen printings etc. are applied on the substrate.For example, reactive layer can with the relative volatility solvent, preferred organic solvent mixes, this solvent is an inert basically to polycarbonate, that is, do not damage and the negative impact polycarbonate, but it can dissolve carrier.The example of some suitable organic solvents comprises oxalic acid ethylene glycol, butyl cellosolve, low-level chain triacontanol etc.
For top coat, reactive layer also can be chosen wantonly and contain various additives, as matting agent, and tensio-active agent, thixotropic agent etc. and comprise the reaction product and the binding substances of at least a above-mentioned additive.The thickness of reactive layer is to depend on employed concrete reactive materials, its concentration and required absorption characteristic initial and reactive layer after for some time of expection in reactive layer.
The development of the reactive compounds of sealing
One embodiment of the invention are reactive compounds uses in reactive layer of closing form.These compounds will be in the scheduled time after disc manufacturing or the packing deblocking and typically at disc by before the human consumer use.The stimulation (for example atmosphericoxygen) that triggers reaction (this reaction cause disc becomes can't play) in the manufacturing processed at disc can trigger this reaction, with therefore need take some measures so that when reactive compounds is not activated in the disc manufacturing processed, this is desirable.For example, for the reaction that oxygen triggers,, need in oxygen-free environment such as nitrogen atmosphere, carry out otherwise make unless use the closing form of reactive compounds.
One embodiment of the invention comprise the purposes that the reactive materials of chemical sealing and/or modification and/or protection is used to produce CD, and this CD triggers sexual stimulus and/or external trigger (for example oxygen, pH changes) and becomes afterwards and can not play being exposed to.The dyestuff and the method for preparing dyestuff former of the sealing of specific illustrative are disclosed.Also disclose colourless dyestuff former, it allows this colourless dyestuff former with acceptable speed deblocking and oxidation, and dyestuff and dyestuff former are applied over method on the CD, on the surface of CD and as the tack coat of CD.Also disclosed is the purposes that alkali is used for improving the speed that methylene blue produces in the layer of the leuco dye that contains close and protect on CD or CD, and sillylation reagent such as hexamethyldisilazane are used for being stabilized in the purposes of leuco dye of the close and protect of coating fluid.
In one embodiment of the invention, from packing, take out the CD (limited broadcast CD) that becomes and to play afterwards in order to be manufactured on, this CD is introduced the composition that contains leuco dye in reactive layer, this dyestuff can be oxidized to coloured dyestuff, the latter is absorbed in the light under the Wavelength of Laser of reading of Disc player, stops enough to read that laser becomes CD from the CD emission can't to play.The oxidation of leuco dye can be exposed to atmosphericoxygen and cause by the coating that contains dyestuff, the atmosphericoxygen diffusion runs through coating and comes oxidation leuco dye molecule.The problem that this coating is set on the surface of disc is that coating is removed by the user and disc becomes the possibility that forever can play.Another problem that this coating is set on the surface of CD is, needs additional step in the CD manufacturing processed, and higher cost must be arranged, the special machine processing of production unit and the low productive rate of making inevitably.At last, the oxysensible fluid that is used to form this coating is difficult to dispose, because its oxygen susceptibility.
Be coated in the lip-deep certain methods of CD at the fluid that will contain leuco dye, wherein some as mentioned above, coating is that solvent type and solvent must evaporate to obtain containing leuco dye and the hard coat of any other component of required in polymeric matrix (typically being combined in the polymeric matrix).For solvent based coating several shortcomings are arranged.At first, most solvent fluid is dished out and is difficult to maybe can not reclaim owing to solvent evaporation makes from disc in the spin coating manufacturing processed, and it is contaminated-fluid (improving the cost of this technology) and but also stain coating equipment not only.Secondly, the evaporite ratio of solvent is more time-consuming, and this has reduced the speed of making cated disc and the cost that has therefore improved this method.Once more, in coating and drying process, must in producing apparatus, discharge, increase the cost of institute's installed device and adopt the disc duplicator of this manufacture method to be provided with technology and environment obstacle for considering by the solvent vapour that CD gave out that applies.
If that leuco dye is coated in is solvent-free, in (following generally be called " UV solidified ") layer of light or radiation curing, if identical with the CD tack coat of two substrates (both form the CD such as the DVD of some type for they) that are used to bond with this one deck, then all problems of discussing in two paragraphs in front can both be avoided.The major obstacle that produces a kind of like this system is, many leuco dyes, especially leucomethylene blue (below be called " LMB ", it is used for making DVD to become in the system of solvent-borne type, surface-coated by the inventor and can't plays), can suppress to be used for the curable type monomer of UV curing as usually as the free radical and the cationic polymerization of those types of the acrylate monomer of the tackiness agent of bonding DVD substrate.The dyestuff of oxidation (comprising methylene blue) also is the inhibitor of this type of polymerization.Like this, in the UV curable compositions, add leuco dye (it contains some oxidations, colored dyestuff inevitably) and will stop the UV solidified to take place, or the UV that slows down solidifies, and make this method become more uneconomical by reducing the speed of making disc.In addition, if any oxygen or other oxygenant be present in want in the solidified layer then UV solidified process can cause some leuco dyes oxidized, make product contain oxidation dye prematurely, the latter can interfere the readable of disc or change the speed that disc becomes and can't read after being exposed to oxygen.
Chemical mode sealing (being called " protection " and/or " modification " sometimes) leuco dye (being also referred to as " colourless dyestuff former ") is known and has been used for application such as " carbonless copy paper " recent decades.Especially, the leucomethylene blue of closing form is known and has been used for this type of application and at least a this compounds that benzoyl-leucomethylene blue (BLMB) can have been bought from the market.Yet, we find BLMB can be not enough easily deblocking obtain acceptable restriction DVD playing back product.Other sealing leucomethylene blue compound also has this problem, and perhaps deblocking is too easy, makes to produce oxidable leucomethylene blue before the desirable time in coating fluid.
We have found that, triisopropyl silyl oxygen base carbonyl leucomethylene blue (below be called " TIPSOCLMB "), the explanation and being described among the embodiment 4 in Figure 17 of the synthetic method of its structure and illustrative has following performance of making us desireing and can be used to produce limited DVD playing back:
1. it is easily synthetic from the starting raw material that is purchased in two steps.By the BOC-LMB that separates and purify and produce in first step as shown in Figure 17, TIPSOCLMB prepares from pure compound rather than from the very impure methylene blue of typical case.
2. it can be introduced in the acrylate formulation of describing in embodiment 5, it can stablize (for the methylene blue that changes into oxidation) several at least weeks being lower than under 0 ℃ the temperature therein, make and in an equipment, to prepare the coating preparation, be used for another equipment that DVD makes with being transported to, if necessary.
It can be in a week or shorter time deblocking, presumably utilize the hydrolysis reaction involve water or other nucleophilic reagent to realize, described water or other nucleophilic reagent can be provided in the acrylate formulation or absorb from the atmosphere of making DVD or be provided in the DVD wrapping material.Show that the nucleophilic reagent can be used for deblocking is fluorion and carboxylic acid ion, both can be at deblocking under the condition of neutral pH basically.
4. the LMB of deblocking is stable (for being oxidized to methylene blue) at oxygen in the presence of not.The speed of LMB oxidation in the presence of oxygen of deblocking can be controlled by the effective pH that regulates the coating preparation.Well known in the prior art is that along with the pH raising of environment, the rate of oxidation of LMB can improve.Therefore, the interpolation by alkaline matter improves rate of oxidation, this alkaline matter dissolve in contain in base material deblocking or sealed L MB or not with used base material or substrate reaction.A kind of this type of basic cpd is DABCO (1,4-diazabicyclo [2.2.2] octane), a kind of amine.Other amine can add or alternative the use.In addition, the interpolation of strong protonic acid such as camphorsulfonic acid can be reduced in the speed of LMB oxidation in the polymeric film.
5. under water or the non-existent situation of other nucleophilic reagent, it is stable solid, can store some months at least after synthetic, even in the presence of oxygen.The acrylate type coating fluid that contains TIPSOCLMB can be disposed in the presence of oxygen, until till the deblocking reaction generation, this reaction is enough slowly, makes that the disposal of coating fluid can be carried out in normal (undried) air and not be difficult in the DVD manufacturing processed.
Embodiment 3:BocLMB preparation
T-BOC-LMB: in the deionized water of the 3.6L in 22 liters of flasks, add the methylene blue trihydrate of 600 grams, dissolve by stirring.With V-Brite B (V-Brite B), 600 grams add in the stirred solution of covering with nitrogen.Through adding 10% sodium hydroxide solution of 2.4L in 10 minutes, add the methylene dichloride of 9.6L subsequently.The tip speed of agitating vane should be a 130-150 feet per minute clock; Stir the too fast undue broken layer/emulsion that obtains.Solution stirring 30 minutes.After stirring 30 minutes, allow two separate.Leucomethylene blue/dichloromethane layer N
2Pressurization is transferred in the 4L separating funnel, and it also is equipped with N
2Bubbler.Transfer is that branch two portions are finished, and allows certain hour by two separate.This dichloromethane solution is transferred in 12 liters of flasks that fill nitrogen that overhead stirrer is housed, shown in following figure.
When this dichloromethane solution has fully been transferred in the flask, 30 4-dimethylaminopyridines that restrain are joined in the solution.Separating funnel with the feed hopper displacement of the di-t-butyl two-fold carbonic ether that contains 770g, is added drop-wise in the LMB dichloromethane solution then then, and solution stirs a whole night at ambient temperature.In each step of this technology, must cover leucomethylene blue solution with nitrogen carefully.Remove the methylene dichloride of about 95+% by distillation, added about 9 liters of heptane at this moment.Distillation is proceeded, and reaches till 52 ℃ up to the overhead product temperature.Formed pewter solid filters and uses the heptane of 3L, uses the methanol wash of 3L then, obtains the t-BOC-LMB of 360g (58% productive rate).
Methylenum coeruleum (Tipsoc-LMB)
The Tipsoc-LMB that may comprise by product is synthetic
CH
2Cl
1(methylene dichloride [75-09-2]) is as reaction solvent.
Hexane [110-54-3] or hexane class [3513-42-5] are used for aftertreatment.
Tipsoc-LMB: in 12 liter of three neck round-bottomed flask of overhead stirrer, feed hopper, condenser and nitrogen bubble device is housed, 360g t-BOC-LMB is dissolved in the 2.5L methylene dichloride, obtains blue solution.Add 2 of 240g in this solution, the 6-lutidine is subsequently through dripping the trifluoromethanesulfonic acid triisopropyl silyl ester (TipsOTf) of 430g in 1 hour.The turquoise reaction mixture stirred 6 hours under refluxing then and stirs at ambient temperature a night.
Solution is concentrating under vacuum on the rotatory evaporator then, removes the methylene dichloride of the overwhelming majority, obtains dark green blue mixture.With this mixture separated into two parts with each several part is added in the hot heptane of 3L.Need in this step and whole subsequent step, not allow heptane touch moisture.Stir separately, till the mazarine residue separates from the hot n-heptane solution that contains Tipsoc-LMB.Hot n-heptane solution decantation from residue comes out, at N
2Cooling is 48 hours in the airbag, filters then.Product is at N
2Filter in the atmosphere, wish at utmost to reduce the moisture contact, and in the nitrogen bag the dry firstling that obtains the Tipsoc-LMB of 268g.
By making the Tipsoc-LMB recrystallization 2.5 liters of boiling heptane that 268 Tipsoc-LMB that restrain are dissolved in the decolorizing charcoals (Pac 200, obtain from Norit Americas Inc) that contain 14 grams.In small-scale recrystallization, Calgon AQ-30 dustless carbon black also is effective.The n-heptane solution of heat, it should be colourless basically, filters through the packing layer of super-dry Celite, cooling then obtains 99.75% pure Tipsoc-LMB of 200 grams, m.p.118-119.
Embodiment 5: contain the preparation of the coating fluid of TIPSOCLMB
80mg TIPSOCLMB
80mg Irgacure 819 (Ciba Geigy; Sensitizing agent)
4.0ml CD-501 acrylate (Sartomer; Propoxylation [6] Viscoat 295)
18.5mg 1,4-diazabicyclo [2.2.2] octane (" Dabco "; Aldrich; Alkali)
155 μ l 1,1,1,3,3,3-hexamethyldisilazane (" HMDZ "; Aldrich; Stablizer)
Weighing TIPSOCLMB, Irgacure 819 and Dabco join in the Brown Glass Brown glass bottles and jars only, add stirring rod, and CD-501 is poured over the weight that wherein reaches suitable, add HMDZ by syringe then.In the time of several minutes dried nitrogen is blown in the bottle, then with the bottle capping, lid covers with Parafilm (parafilm).Content at room temperature stirs at least two hours with dissolved solids.If do not use all materials, then in bottle, blow with nitrogen, capping and cover with Parafilm, and in refrigerator, store; Before opening, bottle is heated up, prevent that water condensation is in bottle.
Embodiment 6: the surface scribbles the preparation of the disc of TIPSOCLMB/ acrylate formulation
Transparent half disc of DVD (not the 0.6mm thickness of metal lining and 120mm diameter polycarbonate disk) or full DVD (with the back-to-back bilayer that bonds together of tackiness agent) are placed in the middle on the laboratory spin coating turntable with roughly 60rpm speed rotation.The solution from embodiment #5 of 4ml utilizes syringe then, applies equably in an annulus with about 34-40mm diameter at distance disc center.Speed of rotation is increased to about 200rpm then apace and kept about 15 seconds, has caused forming the acrylate/TIPSOCLMB fluidic coating of about five micron thickness.Speed of rotation slows down then; Unnecessary fluid is wiped from the disc edge with flimsy material and alkali solvent (if available words), then disc is transferred on the laboratory stand.At this moment, disc is accepted about five flashes of light of Norlite 400 xenon flash lamps under the highest set(ting)value.Time between twice flash of light is by the charging of photoflash lamp decision, but should be enough, thereby is unlikely the stress (typically about 5 seconds) that induces increase curing from the heat that produces.This process will obtain transparent, uncoloured, full solidified acrylate films.Other disc does not prepare with not containing Dabco or containing the similar acrylate formulation that is equivalent at 10 times Dabco of the Dabco described in the embodiment 5 amount yet.
Embodiment 7: interlayer scribbles the preparation of the disc of TIPSOCLMB/ acrylate formulation
DVD half disc upwards is placed on the aforesaid turntable between two parties with data surface.It is static that turntable keeps, and fluid is assigned on the data surface with the mode of syringe with the drop that produces about 3-5mm circle simultaneously.These on the diameter of 30-40mm with about 3mm spacing spacing equably.Need the agglutinating disc to allow data side place then towards solution, and by the edge arch upward a little leave the bottom disc.This disc descends at a certain angle, until till forming first point of contact between drop and the last disc.We do not wish will go up immediately disc and are placed on the disc of bottom, owing to air of carrying secretly and follow-up foaming.Therefore, in order to realize more uniform capillary flow, we rotate disc in rotating in the clockwise direction, allow disc keep bending a little simultaneously under light pressure, till each drop begins to form the kapillary bridged ring.In case this capillary loop is completed into, last disc can loosen with capillary action to be proceeded.We can wait for this capillary flow covering surfaces, or we can rotate disc with 100rpm, till material arrives largest outer diameter at least.At this moment, turntable can start and rotate 5 seconds under about 500rpm.This will make wall (binder layer) levelling and remove unnecessary material from OD (maximum outside diameter).Disc edge wiping and disc then then carries out UV and solidifies.Importantly before solidifying, two disc two halves align as close as possible and arrange to avoid the centre hole misalignment, a follow-up playback problem.At this moment, disc is accepted about 20-30 the flash of light of Norlite 400 xenon flash lamps under the highest set(ting)value.Time between twice flash of light is by the charging of photoflash lamp decision, but should be enough, thereby is unlikely the stress (typically about 5 seconds) that induces increase curing from the heat that produces.This process will obtain transparent, uncoloured, full solidified acrylate films.Other disc does not prepare with not containing Dabco or containing the similar acrylate formulation that is equivalent at 10 times Dabco of the Dabco described in the embodiment 5 amount yet.
Embodiment 8: deblocking and the oxidation of TIPSOCLMB and be included in the effect of the alkali in the coating preparation in the disc of surface and interlayer coating
The disc of preparation is cut into six " fragments " and this fragment separately at dried nitrogen described in embodiment 6 and 7, store in dry air or the room air (average RH about 30%), then periodically with their cyan reflection density of X-Rite 504 densometers records (sample of storing in nitrogen is only tested in the beginning of experiment with when finishing, because their are observed no change and wish at utmost to reduce their exposures to oxygen).In all cases, the sample of storing in nitrogen shows does not have methylene blue (MB) to produce, positive according to expectation.With with respect to 1.0 equivalents of TIPSOCLMB with 1,4-diazabicyclo [2.2.2] octane (Dabco) is incorporated into and will makes deblocking/oxidation rate that the acceleration of highly significant is arranged in the acrylate formulation, compare with contrast (Figure 18), and this compound of higher concentration is in fact not too effective.In general, open wide sample (have the TIPSOCLMB layer to be coated on DVD half disc but without any those samples that cover) and only produce MB a little quickly, show that the deblocking of LMB and oxidation are not subjected to water or oxygen significantly via the not restriction of the transfer of the 0.6mm layer of polycarbonate of metal lining than sandwich structure.On the contrary, the deblocking of TIPSOCLMB is the rate limiting type probably in these systems.Be presented at MB faster in the room air than in dry air without any the control sample of the alkali that is added and produce, point out aerial moisture to quicken deblocking in this sample.
Embodiment 9 illustrates reactive tack coat and how to be incorporated among the special DVD-5 design # 2, and therefore having produced can normal play and the disc that becomes subsequently and can't play as DVD-5.
Embodiment 9:TIPSOCLMB is incorporated in the special DVD-5 design # 2 tack coat
Carrying out one group tests to test and contains TIPSOCLMB, Irgacure-819, Dabco, 1,1,1,3,3, whether the formulation of 3-hexamethyldisilazane (as the fluid stable agent) and Sartomer CD-501 acrylate monomer can produce the DVD that can play as the DVD tackiness agent.By using the formulation of in embodiment 5, describing, filter through 1.0 μ m glass syringe strainers, fluid designs on #2 half disc with the special DVD-5 of injector to inject to the transparent or metal lining of making as in Example 2.DVD half disc upwards is placed on the aforesaid turntable between two parties with data surface.It is static that turntable keeps, and fluid is assigned on the data surface with the mode of syringe with the drop that produces about 3-5mm circle simultaneously.These along the diameter of about 30-40mm with circle equably at interval.Need the agglutinating disc to allow data side place then towards solution, and by the edge arch upward a little leave the bottom disc.This disc descends at a certain angle, until till forming first point of contact between fluid and the last disc.We do not wish will go up immediately disc and are placed on the disc of bottom, owing to air of carrying secretly and follow-up foaming.Therefore, in order to realize more uniform capillary flow, we rotate disc in rotating in the clockwise direction, allow disc keep bending a little simultaneously under light pressure, till each drop begins to form the kapillary bridged ring.In case this capillary loop is completed into, last disc can loosen with capillary action to be proceeded.We can wait for this capillary flow covering surfaces, or we can rotate disc with 100rpm, till material arrives largest outer diameter at least.At this moment, turntable can start and rotate 5 seconds so that tackiness agent becomes thinner with about 500rpm, has obtained 50 μ m binder films (being measured by profilometry).This will make wall (binder layer) levelling and remove unnecessary material from OD (maximum outside diameter).Disc edge wiping and disc then then carries out UV and solidifies.Importantly before solidifying, two disc two halves align as close as possible and arrange to avoid the centre hole misalignment, a follow-up playback problem.At this moment, disc is accepted about 20-30 the flash of light of Norlite 400 xenon flash lamps under the highest set(ting)value.Time between twice flash of light is by the charging of photoflash lamp decision, but should be enough, thereby is unlikely the stress (typically about 5 seconds) that induces increase curing from the heat that produces.This method will obtain and can test transparent, uncoloured, the full solidified acrylate films of playing on the player at DVD.
Disc is made under the home condition; in the nitrogen box, placed 3-4 days subsequently; remove dissolved oxygen in substrate (in this embodiment, estimating cost 12-20 hour), allow the TIPSOCLMB deblocking become LMB (cost is 2-3 days in this embodiment) then.
Special DVD-5 design # 2 disc takes out from the nitrogen box subsequently, and measures the reflectivity under the 650nm wavelength, as the function of time.Disc is transparent and can play 12-16 hour, became mazarine after the period and become to be lower than 2% reflectivity under 650nm in 24 hours and can't play at this section.
Multiplayer optical disk
DVD family illustration in Fig. 4 is found out, is being designed from simultaneously reading the multiwalled double-layer CD, and (bonding) layer is in the light path at interval.For DVD-dual layer, the given technical specification of this space layer be 0.055+/-0.015mm.For the thickness of the substrate that light path agglutinating DVD-dual layer is arranged 0.55mm～0.64mm typically.
In the tack coat 800 of the dual layer disc of arbitrary type, introduce the reactive compounds that suppresses to read laser and will only suppress player and read L1 layer 805, because tack coat 800 is not in the light path that reads L0 layer 810.In addition, the metal 815 in L0 layer 810 can be used as barrier layer, prevents that with controllable manner pre-determined stimulus thing such as moisture or oxygen from penetrating in the reactive compounds in tack coat 800.
A kind of method around these potential problems is as follows.Typically, when player or driving mechanism began to read disc, it sought catalogue or block of information (referring to Fig. 6) in the introducing zone of L0 layer 810.When authorizing this disc, might allow L0 introduce 820 zones and contain the order of directly reading L1 layer 805.In order to read L0 layer 810 play sequence is guided to L1 layer 805, we are to L0 layer 810 metal lining.This may interfere reactive bonding material 800, cause unsettled or uncontrolled reaction kinetics, and this depends on the perviousness of metal level.Around a solution of this problem is to change metal plating layer for the sheltering of L0 semi-reflective layer 800, and the latter typically extends to the 58mm-59mm radius on disc, relatively near introducing zone or information data zone on L0.
In order to promote the activation of reactive materials 800, for example, when the activation stimulator is oxygen or moisture (they are prevented from arriving reactive tack coat 800 because of L0 metal level 820), the part of L0 layer 810 can be masked in the metal lining process, the part of reactive like this layer than be easier to be exposed to stimulator and so the corresponding part of L0 layer with loss of function.These discs have the partly L0 layer 810 of metal lining, as shown in Figure 20.For example, if the only introducing zone of L0 layer 810 or program begin part by metal lining, then player can read and introduce district's data, and can obtain the information that is stored on the L1 layer 805.Because the only zonule on L0 layer 810 is by metal lining, sizable part of reactive tack coat will directly contact with L0 substrate 810, and it typically can be by stimulator such as oxygen or moisture penetration.When reactive tack coat responded suitable stimulation and begins to be read laser interference, player no longer can read the corresponding part of L1 layer 805.
Another embodiment of the invention is to adopt authorization technique, as serializing and the branch's order of being carried out by optical media player, makes certain part of disc become to read with assurance and will interfere other parts or the whole disc that reads disc.That part that the becoming for this purpose of disc can't be read can be in the individual layer of individual layer disc, or in any layer of multilayer disc.For example, one embodiment of the invention are by forming through the DVD-9 that authorizes, certain part of L1 layer is become can't read will the interference disc other parts, or disc is whole.For example, read the L0 layer and introduce the zone and will guide player to read the part of L1 layer, the latter begins to become when laser (cause disc can not operate) is read in interference at reactive layer and not can read.The DVD-9 disc can be authorized to, so that all or part of of L1 layer is absolutely necessary for any information of playing on L0 and/or L1.For example the chapter of each on disc can be authorized, so that it needed to read in some information on the L1 before operation.
In another embodiment of the invention, the activation of reactive materials promotes by the deposition of control L0 layer.For example, gold or silver or silicon L0 layer can form the granulous branching structure by the fast deposition of sputtering method is known, and be easier of oxygen and moisture penetration.Simultaneously, can deposit thin L0 layer, it is easier to by oxygen and moisture penetration.Although depositing granular or thin L0 layer is unacceptable for disc permanent, archival quality, usually be enough for disc limited use, expiration.
Embodiment 10: have TIPSOCLMB to be incorporated into DVD-9 disc in the reactive tack coat
There is the DVD-9 of parallel record road coding can have two visibly different layers that supply playback usefulness.Write in the master process (data mastering process) at coding or data, the introducing zone of usually finding on the L0 disc can have information to tell to read arbitrary layer or two-layer read of player from disc.Therefore, for this embodiment that uses reactive matrix material, reactive layer can stop from the playback of L1 layer does not influence L0 simultaneously.For this embodiment that makes corresponding L0 and L1 master (masters), L0 and L1 substrate are normally by molding and metal lining.
Equally among two DVD half discs and the above embodiment 9 contain TIPSOCLMB by use, Irgacure-819, Dabco, 1,1,1,3,3,3-hexamethyldisilazane (as the fluid stable agent) and bond in the adhesive formulation of the Sartomer CD-501 acrylate monomer described in the embodiment 5.Solution filters via 1.0 microns glass syringe strainers.DVD half disc upwards is placed on the aforesaid turntable between two parties with data surface.It is static that turntable keeps, and fluid is assigned on the data surface with the mode of syringe with the drop that produces about 3～5mm circle simultaneously.These along the diameter of about 30～40mm with circle equably at interval.Need the agglutinating disc to allow data side place then towards solution, and by the edge arch upward a little leave the bottom disc.This disc descends at a certain angle, until till forming first point of contact between fluid and the last disc.We do not wish will go up immediately disc and are placed on the disc of bottom, owing to air of carrying secretly and follow-up foaming.Therefore, in order to realize more uniform capillary flow, we rotate disc in rotating in the clockwise direction, allow disc keep bending a little simultaneously under light pressure, till each drop begins to form the kapillary bridged ring.In case this capillary loop is completed into, last disc can loosen with capillary action to be proceeded.We can wait for this capillary flow covering surfaces, or we can rotate disc with 100rpm, till material arrives largest outer diameter at least.At this moment, turntable can start and rotate 5 seconds so that tackiness agent becomes thinner with about 500rpm, has obtained 50 μ m binder films (being measured by profilometry).This will make wall (binder layer) levelling and remove unnecessary material from OD (maximum outside diameter).Disc edge wiping and disc then then carries out UV and solidifies.Importantly before solidifying, two disc two halves align as close as possible and arrange to avoid the centre hole misalignment, a follow-up playback problem.At this moment, disc is accepted about 20～30 flashes of light of Norlite 400 xenon flash lamps under the highest set(ting)value.Time between twice flash of light is by the charging of photoflash lamp decision, but should be enough, thereby is unlikely the stress (typically about 5 seconds) that induces increase curing from the heat that produces.This method will obtain and can test transparent, uncoloured, the full solidified acrylate films of playing on the player at DVD.
Disc is made under the home condition, places 7 days in the nitrogen box subsequently, removes dissolved oxygen in substrate (estimating cost 12-20 hour), allows the TIPSOCLMB deblocking become LMB (estimating cost 5-6 days) then.This disc takes out from the nitrogen box subsequently, but then on the Pioneer player on L0 and L1 layer normal play 2-3 days.After being exposed to ambient oxygen and reaching 7 days, disc becomes on the L1 layer and can't play, and they can normally be play on the L0 layer subsequently.
Embodiment 11: the partly DVD-9 disc of the L0 layer of metal lining is arranged
With the same among the above embodiment 10, form the DVD-9 master tape, wherein the data area be on layer L1, determine with the L0 layer only be used to provide introduce the zone and with disk types and information-related follow-up catalogue.In playback procedure, L0 introduces the district and will instruct disc to read from the L1 data surface.In this case, we do not need all to be metallized in the whole surface of L0 layer, because there is not information to read from introducing outside the zone.Therefore, make the DVD-9 master tape, wherein introduce and command information on the L0 with the data area on L1.Typically, the metal lining masking layer is planted the zone that has covered the 25mm-118mm diameter on two-layer.Covered 25.2mm and begun being not less than 48mm diameter place because introduce area data, only covered this introducing district so metal lining is sheltered to reduce to the diameter of maximum 48mm and follow-up block of information.This will allow reflected signal read in the introducing district on the L0 floor and be transformed into the L1 floor then realizes data playback, need not to read by additional half reflection metal.
In this embodiment, we produce annular masking blade, and it enters into metal lining OD and shelters assembly.From sheltering that OD is counted, we can reduce to the diameter of metal lining and allow to introduce the zone of resetting by record.We are just introducing the blasnket area expansion outside the 48mm diameter, so that compensation is for the eccentricity tolerance of sheltering the position.In addition, transfer to the disc zone of metal lining in order to prevent reflection peak when reading the L1 layer from the transparent plate panel region, the edge of sheltering raises a little and is higher than disc so that cause shade or the layer homogeneity of gradual change.This will cause gradually focus-compensating rather than big " road surface deceleration projection (speed bump) " the radially noise that causes it and focusing error so that deflect away from technical specification and perhaps skip recording channel.
The same bonding among formed DVD-9 two halves sheet and the embodiment 10.The DVD-9s that is constructed tests playability in the Pioneer DVD player and in the DVD-ROM driving mechanism, placed 7 days in the nitrogen box subsequently, and the TIPSOCLMB deblocking becomes LMB as a result.This disc takes out from the nitrogen box subsequently and is transparent and can plays 12-16 hour, becomes mazarine after this, becomes and can't play.This disc is prevented from effectively from L0 or L1 read out information.
The timing of control reaction
Preferably, the quality of data of disc should keep high and fail apace then and cause descending fast from the ability of CD read-outing data in predetermined duration of service.A benefit of this embodiment of the present invention is, for the stimulation of vast type, as requires material to diffuse through those of barrier layer, can cause remarkable advantage for the timing characteristic of reaction introducing reactive materials in the middle layer.
A kind of method that realizes above-mentioned desirable timing characteristic is to use reactive interstitial matter between disc two substrates, as the front already as described in, it reacts with the material that need diffuse through the substrate of disc.For example, if reactive materials to the oxygen sensitivity, then needs the time of prolongation, in this time, when diffusing through the disc substrate, oxygen do not react generation.In case oxygen arrives reactive layer, corresponding reaction is fast, causes the quick expiration of disc.
When oxygen is used as this diffusate, in the different steps of disc manufacturing, need to remove the oxygen that has been dissolved in the disc.This can pass through, and for example, disc is stored the suitable time in a vacuum or in the environment of anaerobic realize.Determine in theory and experimentally that 24 hours is to extract the suitable time that is dissolved in dissolved oxygen in the 0.6mm thickness polycarbonate disk substrate out.Additionally, if use the reactive materials of sealing as previously described like that, then oxygen scavenging material such as iron or organometallic compound can be used for extracting oxygen out from CD before the reactive materials deblocking of sealing.This method has several manufacturing advantages; For example, it can avoid oxygen extraction in disc is made by comprise oxygen scavenging material in the packing of disc, requires to allow the extraction of oxygen be taken place after disc manufacturing and packing.
Periodic another method of the expiration of control disc comprises the appropriate protection material of the content of limited, control at reactive layer or near reactive layer, as being antioxidant for reactive layer with the situation that oxygen reacts.The protection material causes that with prevention the reaction of disc expiration takes place, and till the time that for example antioxidant consumes, disc is degenerated apace and become and can't play in this time.For example, can pack with disc, so that the protection disc is avoided oxidation in packing with the organometallic compound of oxygen reaction.Additionally, organometallic compound can be incorporated in the substrate, and therefore this metal level is protected in for some time relaying continuation of insurance after packing has been opened.
The consumption of protection material combines with the diffusion of trigger material via the disc substrate, and causing had longer delay before the disc expiration, or makes that the characteristic of expiration process such as the steepness of reflectivity decline are had more refined control.
The embodiment of antioxidant in reactive layer
Additionally, this protection material can be a reductive agent, and it can be incorporated in the reactive tack coat itself.The concentration of TLMB also changes and shows in the experiment with effect therein, and reproduction time is proved to be the influence of the amount that is subjected to changing ethyl stannous caproate reductive agent (referring to Table I) biglyyer.
| Concentration | Reproduction time (hrs) | |||
| Preparaton # | TLMB | Thylhexoic acid Sn (II) | | Long |
| A | ||||
| 1％ | 2％ | 14 | 22 | |
| |
1％ | 4％ | 38 | 55 |
| C | 0.5％ | 2％ | 18 | 26 |
| D | 0.5％ | 4％ | 46 | 58 |
Table I
The DVD-5 disc contains by use that the binder formulation of TIPSOCLMB makes, and in the atmosphere of anaerobic in 60 ℃ of deblocking 48 hours.At this moment, disc is exposed to the environment room air, and the speed of methylene blue coupling development is to come quantitative with the X-Rite reflection densitometer.Short reproduction time is selected to be that cyan density increases by that time of 0.35, and it corresponding to the playability parameter cutoff under 45% reflectivity, is representative with the inferior quality DVD player roughly.Long reproduction time is selected to be that cyan density increases by that time of 0.85, and it corresponding to the playability parameter cutoff under 10% reflectivity, is representative with the high quality DVD player roughly.
The most probable mechanism that this prolongation is play is that colorless form is got back in the initial methylene blue dye reduction that forms, till most reductive agent consumes.Another kind of mechanism as main oxygen scavenqer oxygen consumed before leuco dye is influenced, also is possible as stannous compound.
Estimate that in the intramatrical transport property of solidified rate of reduction is had remarkably influenced; In fact, the monomeric calculating second-order transition temperature (Tg) that is used for this embodiment is-34 ℃.In this type of soft matrix, suitable molecular mobility should exist, and contacts with the molecule of realizing reductive agent and dye molecule.
Candidate's reductive agent can comprise other Sn (II) compound that dissolves in the UV curing formulation, as methyl ethyl diketone acid group inner complex, and fatty a-amino acid inner complex and salt; Soluble iron (II) compound is as fat carboxylate and inner complex such as acetyl pyruvate; Xitix and its derivative are as anti-bad blood acyl group palmitate; Quinhydrones is as 2,5 di tert amlyl hydroquinone; The alkyl azanol; Hydrazine; The dithionate that the solubilising counter ion are arranged; Reductibility carbohydrate such as glucose; Alpha-alcohol ketone is as hydroxyacetone; Suitable boron and the silicon hydrate that replaces.Though many these materials are insoluble in the reactive adhesive formulation of the present invention, the more suitable selection of monomer and oligopolymer can allow a kind of use in these candidate's reductive agents, and good tackiness agent and dyestuff stabilization performance still is provided simultaneously.
The photobleaching that stops the expiration disc
(PHS-XE-01 for example can be from ChemFirst ElectronicMaterials L.P, 14785 Preston Road for polycarboxylated styrene, Suite 480, Dallas, Texas75254-912 obtains), have been found that it is effective photostabilizer of azines in the UV cure adhesive.The enhancing of azines is Photostabilised to be occurred in the formulation that selected monomer mixture has more hydrophobic propertys.Hydrophobic property can characterize by alcohol groups content in this system; The alcohol radical of low amount causes more hydrophobic base, compares with the alcohol of higher amount.In an experiment, monomeric ratio (Sartomer SR395, isodecyl acrylate; Sartomer SR495; The caprolactone acrylate; With Sartomer SR349, ethoxylated bisphenol a diacrylate) change, make that the wt% of SR495 (monomer of hydroxyl) is at 39%-62%.In the formulation of low pure content, found the improvement light stability of methylene blue (deblocking on the spot and oxidation via TIPSOC-LMB produce) in cured binders separately.
Embodiment A
By preparing a series of part A mixture in the liquid mixture that under 60 ℃, polycarboxylated styrene (PHS) is dissolved in the two kinds of Sartomer monomers (SR495 and SR349) that change ratio.Order is added alkaline deblocking catalyzer Tinuvin 292 and light trigger after whole PHS dissolvings.Formed mixture is stirred to and obtains till the transparent mixture.By the TIPSOC-LMB powder dissolution being prepared part B solution in Sartomer SR395 with a little intensification.
| Part A stock solution (gram) | |||
| Component | I | II | III |
| SR495 | 30.0 | 40.0 | 50.0 |
| SR349 | 30.0 | 20.0 | 10.0 |
| PHS | 9.78 | 9.78 | 9.78 |
| T292 | 0.232 | 0.232 | 0.232 |
| IC819 | 1.60 | 1.60 | 1.60 |
| Part B stock solution (gram) | |
| Component | |
| SR395 | 12.0 |
| TIPSOC-LMB | 0.960 |
Prepare complete active bond agent composition by in the middle of three kinds of aforesaid part A formulations that under violent jolting, the part B of 0.27 gram added to 3.58 grams each.The component ratio of three kinds of formulations is shown in the following table.
| ％(wt/wt) | |||
| Component | I | II | III |
| SR495 | 39.00 | 51.94 | 64.93 |
| SR349 | 39.00 | 25.97 | 12.98 |
| PHS | 12.70 | 12.7 | 12.7 |
| T292 | 0.30 | 0.3 | 0.3 |
| IC819 | 2.08 | 2.08 | 2.08 |
| SR395 | 6.49 | 6.49 | 6.49 |
| TIPSOC-LMB | 0.52 | 0.52 | 0.52 |
Solidify these tackiness agents by the 0.6 complete tackiness agent that restrains is deployed between two transparent LO polycarbonate half discs and with exposures in 2 seconds of Xenon Corporation DVD xenon flash lamp, assemble disc.Colourless disc in 60 ℃ of baking ovens through 24 hours deblocking be oxidized to methylene blue.The relative rate of deblocking is from coming quantitative cyan optics density estimation with the X-Rite reflection densitometer at white background; The higher density of methylene blue shows higher deblocking transformation efficiency.After time, a coloured disc and a row's 40W cold light type fluorescent lamp bulb writes down the cyan optical density (OD) at a distance of 2 inches placements 9 days at this section after the period at deblocking; Higher density shows the reservation methylene blue dye and the therefore better light stability of higher amount after the time shutter.Following table shows that deblocking speed improves along with the monomer SR495 that containing alcohol of higher amount and for the low SR495 that measures best light stability (fast light according to fadedness) arranged.
| Cyan density (X-Rite) | |||
| Formulation | ％SR495 | 24hrs 60℃ | Illumination in 9 days |
| I | 39 | 2.02 | 2.43 |
| II | 52 | 2.35 | 1.36 |
| III | 65 | 2.78 | 1.05 |
Binding agent with the preparation of alkoxylate monomer has shown similar effects: the amount that improves Sartomer monomer SR502 (ethoxylation-9 tri methylol triacrylate) and CD501 (propoxylation-6 tri methylol triacrylate) can cause the worse light stability of TIPSOC-LMB deutero-methylene blue, even in the presence of polycarboxylated styrene.
The additional benefits of uv stabilization of polymer agent is that the photostabilizer of higher concentration can be incorporated in the binder blend, and wherein to be found only be because full-bodied result to the upper limit.The concentration of PHS is prepared up to the spendable tackiness agent of 25wt%; Common haplotype phenol organic compound tends to form crystal, and this has been found that and limits their solubleness in the reactive adhesive formulation and therefore their application therein.
Can be purchased from ChemFirst Electronic Materials L.P, also being found in by the prepared polymeric phenol of the acid catalysis addition of hydroxyphenyl methyl alcohol of being known as PHS-B be effective as photostabilizer very much this system.The 4-hydroxy styrenes for example also demonstrates Photostabilised effect with the multipolymer of vinylbenzene and butyl acrylate in binding resin; It here is effective that many multipolymers are estimated.
The light stability of the azines except methylene blue is also improved because of the interpolation of polycarboxylated styrene polymkeric substance.
Embodiment B
This embodiment is by means of the photobleaching that is used for preventing the oxidation disc that makes of photostabilizer (polycarboxylated styrene).The disc that the chromophoric undue photobleaching of methylene blue will cause the failure of limited broadcast mechanism and obtain playing after being exposed to intense light source.
This embodiment also comprises the use of reductive agent, and it causes the prolongation of reproduction time.The ethyl stannous caproate of 4% level in this formulation provides reproduction time about 24 hours disc, and uses this formulation but the disc that do not add the reductive agent manufacturing provides about 8 hours reproduction time.
| Part A: | ||
| Component: | Wt.grams | Final Wt% |
| Sartomer SR440 | 32.50 | 10.08％ |
| Sartomer SR238 | 65.00 | 20.16％ |
| Sartomer SR495 | 97.50 | 30.24％ |
| PHS8E01 | 39.00 | 12.09％ |
| Tinuvin 292 | 0.75 | 0.23％ |
| Irgacure 819 | 5.20 | 1.61％ |
| Part B: | ||
| Component: | Wt.grams | Final Wt% |
| Sartomer SR339 | 65.00 | 20.16％ |
| TIPSOC-LMB | 4.50 | 1.40％ |
| Stannous 2-ethylhexoate | 13.00 | 4.03％ |
By at first blending Sartomer monomer SR440, SR495 and SR231 (Exton, PA 19341 for SartomerCompany, 502 Thomas Jones Way), under agitation and a little rise to 60 ℃ of dissolving polycarboxylated styrene (PHS-8E01 then; Triquest, LP, 14785Preston Road, Dallas, Texas 75254-9123), prepare part A.Continuing under the stirring, add Tinuvin 292 (Ciba Specialty Chemcals, 540 WhitePlains Road, Tarrytown, NY 10591-9005), add Irgacure 819 (CibaSpecialty Chemcals, 540 White Plains Road subsequently, Tarrytown, NY10591-9005).Mixture stirs in the dark, till evenly.Part A is very stable and can approximately storing the several months under the room temperature in the dark before using.
TIPSOC-LMB is dissolved in prepares part B among the SartomerSR339 by in nitrogen atmosphere, being warming up to 50 ℃ a little.After cooling, add ethyl stannous caproate (Sigma-Aldrich), solution stirs tout court, till evenly.The limited stability of part B and should in 8 hours, using.
By part B is added in the part A, at room temperature acutely mixing in the dark, prepare complete reactive adhesive subsequently then.This tackiness agent used within mixed four hours.
In addition, improve light stability by adding resorcinol derivatives such as 4-Sucrets or 4-chloro resorcinol.Further improve light stability by the TIPSOC concentration that raising puts in the disc.
Monomer is selected
Monomer is in the above-described embodiments selected for the contribution of following performance at them:
Dissolving power
Monomer of the present invention has and keeps whole components at dissolved state with in storage process and do not contain the good capacity of particulate matter in the mixing process of part A and B.
Viscosity
Because the polymkeric substance attribute of preferred photostabilizer (PHS) tends to cause uncured resin that high mixture viscosity is arranged, most monomer is selected for their the low viscosity attribute in each functional group.The low viscosity of uncured resin help in assembling process between two and half substrates of DVD, to launch and the process of spin coating binding agent in good flow characteristics is provided.
Surface tension
Uncured adhesive obtains promoting in manufacturing processed in the expansion between the disc two halves also has the binding agent of low surface tension.
Deblocking speed
The TIPSOC group uses the material of using always for hydrolysis reaction to come deblocking; That is to say that water and alcohols are by means of the catalysis of alkali and acid.The target of deblocking speed is at room temperature to form enough LMB in the disc of solidified packing in a week.
Owing to add the reproduction time that reductive agent prolonged
The cured binders that relies on the useful reproduction time of stannous 2-ethylhexoate prolongation has found to show long reproduction time, when using the hydrophilic monomer of higher amount.In some disc systems, this will be never in the curing disc of SR495 changed in the disc of 40%SR495 is arranged in 10 hours 24 hours.
Cohesive strength
Polyfunctional acrylate is used to provide certain cross-linking density, and this helps the firm and intensity of settable cementitious resin.This is with bonding alignment and the physical size that helps to keep the DVD disc.
Light stability
When high polar ion azines is reducing along with the amount that increases PHS when forming in the polar medium, the Photostabilised of azines partly taken place.
Monomer from above embodiment comprises:
SR495：
The polarity of grams of monomer blend help to utilize the gained azines that PHS realized was Photostabilised.In the above-described embodiments, the SR495 of low amount contains pure caprolactone acrylate, and the disc that can cause expiring has better light stability, and still the hydroxyl of low amount has disadvantageous effect for the deblocking speed of TIPSOC-LMB in the disc of initial formation.So, the optimum quantity of structure division that contains alcohol is by these two kinds of effects, and light stability and deblocking speed are determined, and is about 30% caprolactone acrylate for above embodiment.
The high polar monomer of candidate that improves deblocking speed has similar disadvantageous effect for light stability; Other monomer that these comprise oxyethane and propylene oxide derivative and contain the polyether structure part.Also observe similar effects for the N-vinyl pyrrolidone.These and other hydrophilic acrylate has advantage in containing other azines of binding agent, suppose to have the proper equilibrium of every performance.
The monomer of candidate's hydroxyl also includes, but are not limited to hydroxyethyl acrylate, the vinylformic acid hydroxypropyl ester, and hydroxybutyl acrylate, diethylene glycol monoacrylate and methacrylic ester, according to availability, they are suitable for toxicity and disposal.
SR238, hexanediyl ester
This polyfunctional acrylate helps cross-linking density, and this can promote the intensity of cure adhesive.SR238 also causes the low viscosity of uncured mixture and the hydrophobic characteristics of cured resin consumingly.Also estimate to provide other polyfunctional acrylic ester of good result, suppose the reequilibrate of aforesaid performance, comprise Viscoat 295 (SR351), with 1,3-and 1,4 butanediol diacrylate (SR212 and SR213), pentaerythritol triacrylate (SR444), tetramethylol methane tetraacrylate (SR295), Dipentaerythritol tetraacrylate (SR355) and Dipentaerythritol five acrylate (SR399).The alkoxylate polyfunctional monomer also can use under every performance has the situation of appropriate balance.Oligomeric monomer such as epoxy and urethane acrylate, they can have advantage typically be higher than the material of describing on the viscosity in this publication in some systems.
SR440, the isooctyl acrylate ester
The introducing of isooctyl acrylate ester (SR440) and isodecyl acrylate (SR395), they are low surface tension material (difference 28 and 28.6 dyne/cm), observed the amount that can reduce the bubble of introducing in manufacturing processed and therefore higher disc productive rate is provided.Find that SR440 is more preferred than SR395, because its wider dissolving power that combines with other monomer for PHS.These monomers also cause low viscosity easily, low Tg and low polarity.
Many other alkyl acrylates estimate to have similar effect.
SR339, vinylformic acid phenoxy group ethyl ester
This aromatic monomer is as integral part B monomer, because it provides the excellent dissolution ability for the methylene blue of TIPSOC-LMB and formation unintentionally.Have been found that a spot of TIPSOC-LMB deblocking does not influence the function of formed disc.Low polar monomer force methylene blue as the crystal score from, this need filter and prevent the disc defective.Another benefit of SR339 is that it provides polarity for solution, easily mixes mutually with the part A that contains PHS but do not cause to precipitate or other disadvantageous mixing phenomena.The reduction that disadvantageous effect is a light stability of SR339, but this system can measure reequilibrate with higher PHS amount or low SR495.
Additional deblocking mechanism
Carbamate can be as the protecting group of amine.Carbamate can be removed (deblocking) by the whole bag of tricks.These methods comprise, for example, the bronsted lowry acids and bases bronsted lowry hydrolysis, hydrogenolysis is with β-cancellation, chemical reduction, electrolysis, pyrolysis and the photolysis of alkali.(referring to T.W.Greene and P.G.M.Wuts, Protective Groups in Organic Synthesis 3rd Edition, John Wiley ﹠amp; Sons, pp 503-550,1999 and the reference wherein quoted.)
In addition, deblocking mechanism also can discharge all ingredients, and the latter is used for or assists the generation of leuco dye or heat-tinting dyestuff.For example, patent #JP 2000343837A (here introducing with full content) uses the heat of acid to discharge the deblocking of catalysis t-BOC-LMB.Photic acid producing agent also can use in a similar manner.The photic release of group can be used in oxidation leuco dye (referring to for example US patent 3,445,234, introducing for reference with full content here).Simultaneously, discharge via the heat of the amine of the hydrolytic action of amino formate and also be known and comprise that for example, US patent 6,015,771 is introduced for reference here with full content.
A. pyrolysis
US patent 4,602,263 and US4,826,976, both are hereby incorporated by reference with full content, have instructed the purposes of heat-labile carbamate structure division protection dyestuff.
B. photolysis
The unsettled protecting group of photochemistry is known.Referring to, for example, V.N.R.Pillai, Synthesis, 1 (1980); Leuco methylene blue color formers with UVlight including t-BOC (J Photopolymer Science and Technology, 14,245-250 (2001); With Japanese Patent No.JP06032940, to introduce for referencely here, its uses leucomethylene blue amino formate to measure UV radiating amount.
Additional photolabile protecting group comprises, for example, and those that describe in reference below and the reference of wherein quoting.Tetrahedron Letters, No.12, pp1029-1030,1979; Proc.Natl.Acad.Sci.USA, Vol 96, pp 1193-1200, February 1999; Tetrahedron Letters, 40, pp 1441-1444,1999; And Synthesis, pp 1-26, January 1980.Following amino formate can divide by photolysis: between carboxylamine-and the nitrophenyl ester, carboxylamine 3,5-dimethoxy-benzyl ester, carboxylamine o-nitrophenyl ester, carboxylamine 2-(2-nitrophenyl) ethyl ester, carboxylamine 4-methoxyl group phenacyl ester and carboxylamine 3,4-dimethoxy-6-nitrobenzyl ester.
C. electrolysis
Example be included in following reference and the reference wherein quoted in those materials of describing:
1.L.Van Hijfte and R.D.Little，J.Org.Chem.，50，3940(1985)
2.M.F.
and G.E.Heinsohn，J.Am.Chem.Soc.，94，5139(1972)
3.V.G.Mairanovsky，Angew.Chem.Int.Ed.Engl.，15，281(1976)
D. β-cancellation/auxiliary β-cancellation
One aspect of the present invention provides the compound of structural formula (I):
(I)
Q is any group that can experience acid or basic hydrolysis.Q can be removed under suitable recommended, causes the decarboxylation of free amine group manthanoate group then.Q also can be a kind of group, and this group is the closed ring that forms on carbonyl, removes the close and protect group, obtains leuco dye.The painted form that oxidation forms this dyestuff if form, takes place in leuco dye so deblocking in the presence of oxygen.The representative group of Q can be, but be not limited to C
1-C
6Alkyl, C
1-C
6Alkoxyl group ,-CH
2CH
2X, aryl, the aryl of replacement, benzyl, the benzyl of replacement, and SiR
14R
15R
16, wherein X is the structure division that the leavings group of E1 or E2 elimination reaction (β-cancellation) can take place or can be used as nucleophilic reagent that can closed loop; R
14, R
15And R
16Be selected from hydrogen independently of one another, unsubstituted C
1-C
6Alkyl, the C of replacement
1-C
6Alkyl, unsubstituted C
1-C
6Alkoxyl group, the C of replacement
1-C
6Alkoxyl group, benzyl and aryl.Referring to for example, T.W.Greene and P.G.M.Wuts, Protective Groupsin Organic Synthesis, 3rd Edition, John Wiley ﹠amp; Sons, pp 540-2,1999 and the reference wherein quoted.
Therefore, a second aspect of the present invention provides the compound of structural formula (II):
Z is any group that β-elimination reaction can take place.Open, in general, be connected in the nitrogen of being protected by the formamyl structure division on the corresponding formamyl oxygen, a kind of group of β-elimination reaction can take place, will be under the alkaline condition of gentleness deblocking.This structure can be represented by structural formula (III):
Structural formula (III)
Wherein Z is the substituting group (carbanion-stabilization group) that can activate the adjacent structure part, and LZ itself can represent shielded group, and the latter must at first activate so that assist β-cancellation.Referring to, for example, T.W.Greene and P.G.M.Wuts, Protective Groups inOrganic Synthesis, 3
RdEdition, John Wiley ﹠amp; Sons, pp 540-545,1999 and the reference wherein quoted, β-elimination reaction can take place in it.Wherein " dyestuff " is the colourless precursor (" dyestuff-precursor ") of dyestuff when occurring with the formamyl structure division, and Z-L-is substituted in and makes this precursor keep its colorless form on the dyestuff former, at least till β-elimination reaction causes.
That β-elimination reaction is well known in the prior art and represent alkali promoted 1, the 2-elimination reaction.When carboanion-when stabilization group Z is positioned at the β position of leavings group, the release of leavings group in this reaction (in above structural formula (III)-formamyl-dyestuff) can quicken widely.The selection of stabilization group Z has determined the d/d speed of leavings group (formamyl-dyestuff).Any structure part that β-elimination reaction takes place can be as the Z-L in above structural formula (XI), if the cancellation speed of this structure division can provide dyestuff with useful speed in given color generation structure.At the sulfone of beta substitution, the rate constant of various leavings groups is by people such as Charles J.M.Stirling, J.Chem.Soc. (B), 672-684 (1970) in the elimination reaction of the phenyl ketone of beta substitution and the ester of beta substitution; People such as Charles J.M.Stirling, J.Chem.Soc.Chem.Commun., 941 (1975); And CharlesJ.M.Stirling, Acc.Chem.Res.12,198-203 (1979) reports.Example from some leavings groups of carbon system comprises-SMe;--SPh;--SePh;--OPh;--OMe;--P (O) is (OEt)
2--NHTs;--C (Me)
2NO
2--N (Me) Ts;--N (Me) Ac;--N (Ph) Ac;--N (Ph) Ts;--N (Ph) CO
2CH
2Ph and--N (Me) CO
2Ph, Me wherein, Et, Ph, Ac and Ts represent methyl respectively, ethyl, phenyl, ethanoyl and tosyl group.Especially, the formamyl leavings group that combines with sulfone is by Kader, A.T.andStirling, C.J.M., J.Chem.Soc.Chem.Commun., 363, (1962) report.
Various acid amides are used to protect amine functional group (Greene pp.550-564) in the prior art.Simple acid amides is very stable to acid or basic hydrolysis generally.Yet the halogen acetyl derivative makes for the unstable of weak acid hydrolysis that this structure division is actual and can be used in the application of the present invention.Especially; trifluoroacetyl group can be special ideal (R.S.Goody and R.T.Walker; Tetrahedron Lett.; 289 (1967) and the substituting group (E.R.Kroft that contains the adjacent hydroxyl that can participate in the intramolecularly hydrolysis; P.Dorff and R.Kullinig; J.Org.Chem., 54,2936 (1989)).Another useful method is used in activation (by reduction, photolysis, hydrolysis, silyl-group division) back by intramolecular cyelization splitted acid amides.Auxiliary splitted notion summarize below (referring to, for example, people such as T.W.Greene p.561).As an example, it can have the alcohol radical of being protected with the form of ester, this ester after hydrolysis, induce by intramolecularly add on the amidocarbonylation going the protection.
In this reaction mechanism, R
2NH represents can be used for the leuco dye that dyestuff forms.
II. Xin Yidai dyestuff
Do not need directly to form by suppressing interfere with layer of the present invention that reading of data become disc can't to play from sealing precursor such as above those disclosed of oxysensible leuco dye.
1. embodiment can be used the intermediate of sealing/protection, will cause when activation (by in the aforesaid method any) leuco dye to form in step by step mode " on the spot ".Colourless leuco dye is oxidized to highly colored dyestuff then in the presence of oxygen.Forming the indigo-blue following reaction mechanism of blue dyes is the example of this embodiment.
One or more one-level intermediates each other or and one or more secondary intermediates between oxidative coupling can form highly colored compound.These coloring systems are similar to those in photograph/imaging industry.It is known that color developer forms with being coupled in the dyestuff chemistry of coupling agent structure division with the dyestuff that replaces on the coupling carbon that pyrolysis, photodissociation or the removable leavings group of hydrolysis method are arranged.These intermediates can use method well known in the prior art to be protected or seal and the deblocking by any activation the in the method discussed above.The intermediate of deblocking forms in the reaction in color then and freely interacts.
E. the combination of deblocking method
The combination of deblocking can be applied to single leuco dye (referring to auxiliary β-cancellation); be applied to the mixture (each adopts different deblocking methods) of multiple leuco dye; or be applied to various deblocking radical protections single plant leuco dye mixture (referring to; for example; Krieg-Kowald; the published utility patent application No.2002/0102499A1 of US patent application publication US, on August 1st, 2002, and introduce for reference here with its full content).
Should be appreciated that the bound energy of any disclosed deblocking mechanism is enough in has better control to deblocking kinetics, improve interfering layer stability or other relevant stability requirement of dyestuff (or leuco dye) satisfied and sealing for bleaching.For example, the attempt of photobleaching takes place in the enough oxidation dyes (methylene blue) of further guarding against those interest concessions to be produced with the auxiliary deblocking reaction of alkali of the bound energy of the deblocking of basic hydrolysis and photolysis.
The broadcast of disc in following generation player prevents to expire.
The CD in following each generation and player typically are developed the user for this technology to provide higher performance with other user.For example, DVD provides more large storage capacity and follow-on " blue laser " DVD of comparing with CD that improved capacity will be provided, and compares with the DVD of today.The optical storage media in follow-up each generation as " DVR " form of present exploitation, will have even bigger capacity and characteristic.
Optical media player typically can be play the disc in each generation in the past through the engineering design.For example, although CD Player uses the laser with 780 nano wave lengths to read CD, DVD player typically uses their laser that reads with 650 nano wave lengths to read the CD disc.DVD of future generation (" blue laser DVD ") is designed the laser with the 450-460 nano wave length to read; Should will use in 405nm left and right sides emitted laser by " DVR " form.Following generation player probably can be enough their 450-460 nanometer or 405 nanometer lasers read present DVD.
Be used for being suppressed at the dyestuff that reads laser of present Disc player typically through interfering by the employed laser that reads of these players after the design; Yet this type of dyestuff does not interfere this to read the following player of laser, and it has more short wavelength probably.This has hinted the expiration disc, though they can't play in the monobasic player at present, but but they become and can play in the following generation player time spent.The dyestuff that reads laser that is used for being suppressed at present DVD player typically is designed to interfere 650 nanometers to read laser; Yet this type of dyestuff can not interfered the laser that reads in the 450-460 nanometer range.For example, methylene blue, it is to suppress a kind of in the dyestuff reading of people such as Smith suggestion, although be strong absorption in 650 nano wave lengths, it is substantial transparent (referring to Figure 19) in the 450-460 nanometer range.Hinted that expiration DVD can play in blue laser DVD player.
Another embodiment of the invention is a kind of CD, and it can't be play in following generation player, the disc that therefore prevents to expire at following generation player (for example, blue laser DVD player) but the time spent become and can play.This can be by in the light path of disc, introduce interfering following generation player the alternative interference layer that reads laser and suppress therefore that disc reading in this type of player realize.Layer like this can be by introducing the laser that reads do not interfere in certain type player, but interfere the dyestuff or the pigment that read laser (or change the response pre-determined stimulus into interfere) in the player of other type to design.For example, trypaflavine [135-49-9], under the 635-650 nano wave length be substantial transparent but under 450-460 and 405 nano wave lengths strong absorption (in ethanol, under 462nm, maximum absorption is arranged, molar absorptivity=37,000M
-1Cm
-1).Additionally 9, two (phenylacetylene base) anthracenes [10075-85-1] of 10-do not absorb in the 635-650 nanometer range yet, but in 450-460 and 405 nanometer range be strong absorption (in hexanaphthene, under 455nm, maximum absorption is arranged, molar absorptivity=33,000M
-1Cm
-1).The dyestuff and the pigment that can be used in other type of the blue laser of sealing (at 450-460 or 405nm) comprise aromatic hydrocarbons, azoic dyestuff, cyanine, polymethine, carotenoid, half cyanines, styryl, quinaldine red, tonka bean camphor, two-and triaryl methyne class, anthraquinone, nitro and nitroso-group.As mentioned above, methylene blue is a substantial transparent under the 450-460 nano wave length, but absorbs consumingly in the 635-650 nanometer range.
In one embodiment of the invention, the alternative interference layer is the special layer in reading the light path of laser.In another embodiment, it is likely preferred embodiment, because it does not introduce additional design element for CD, another element of this selectivity interfere with layer and disc such as substrate or reactive layer combine.For example, this can pass through suitable dyestuff or pigment, as trypaflavine [135-49-9] or 9, two (phenylacetylene base) anthracenes [10075-85-1] of 10-, polycarbonate or other mixed with polymers with the substrate that is used for the molding disc, or in the expiration disc responding property layer, as the tack coat in the special DVD-5 design of describing in front, realize.
Randomly, reactive materials belongs to the dye type that is known as the Fluoran dyestuff.The Fluoran dyestuff can be sealing and/or protection and/or partially modified with chemical structure.In case this Fluoran dyestuff of deblocking is in response to triggering sexual stimulus and/or stimulus, with the colourless black that is transformed into.Such system does not need additional dyestuff or pigment to guarantee, in case expiration, disc can't be play in the media player of different wave length.
Prevent the use of the additional mechanism that data are recovered
Another embodiment of the invention is to combine by the additional mechanism that suppresses to read the recovery of information encoded in laser mechanism that reads that prevents CD and the data structure that prevents on disc.These additional mechanism can be after design regularly have low accuracy control for their activatory, and compare by suppressing to read the mechanism that laser plays a role.Therefore wish that will read laser by interference controls the mechanism of the expiration of CD and combine with the additional mechanism of the recovery that for good and all prevents data on CD.For example, disc can be by in the time of control, and for example in afterwards about 24 hours of predetermined stimulation (as take out disc from its packing), layer that will be in light path becomes opaque and becomes and can't play from transparent transition.In addition, secondary mechanism can be corroded the metal level on disc, and such mechanism worked in week in longer time such as 1-2, and triggers by stimulation identical or that A is different.Additional mechanism providing additional operation also can use, as the additive of the polycarbonate material of the formation disc of degrading, this process can be by identical stimulation (as being exposed to ambient air), or different stimulation (as the centrifugal force that is produced when disc is play in CD or DVD player) triggers.Other of these standby mechanism triggers sexual stimulus can comprise air, light, physical motion and from making or the various factors of time that encapsulation begins to calculate and so on.Many other mechanism are possible.
A kind of method that realizes this purpose is the layer of metal refining silver, and the latter by the material that adopted for this purpose or two substrates by current material such as tack coat or CD separates with the aluminium lamination that contains information.This silver layer can above or below the aluminium lamination and if below therefore (with reading in the light path of laser) it need be enough transparent at first, so can read in the information on the aluminium lamination.
In one embodiment of the invention, the DVD-9 disc is to utilize the reactive tack coat of being made up of the material with suitable dielectric properties and utilize the suitable selection of the metal for L0 and L1 to make.For example, L0 can be formed with L1 and can be made up of aluminium by silver.
When silver layer and aluminium lamination are separated by suitable dielectric materials, then after being exposed to oxygen silver as negative electrode (O
2Be reduced in the above) and aluminium as anode.As long as produce short circuit between silver layer and aluminium lamination, corrosion is fast.The generation of short circuit is caused by the growth that the silver tree dendritic crystal passes barrier material.In order to pass barrier material growth dendrite, wish to use material with some ionic conductivities.Several suitable barrier materials are formed or are contained polyacrylic ester by polyacrylic ester.If polyacrylic ester is hydrolysis slightly, or if like this, for example, vinylformic acid 2-hydroxyethyl ester copolymer will have some ionic conductivities.Preferably poly-(vinyl cyanide), or poly-(4-vinylpridine), or the multipolymer of poly-(1-vinyl imidazole).All these should conductive silver, copper or thallium ion (Ag
+, Cu
+Or Tl
+).Because its toxicity, thallium is not too preferred.
Chemical equation is as follows:
The silver oxidation by air:
4Ag+O
2→ Ag
2O (with the lacquer complexing)
Ag
2O+H
2O+ coordination agent → 2Ag
+(complexing)+2OH
-
Ag
+By aluminium reducing, its oxidized (if Ag
+Be easy active in lacquer, it is designed to conduct Ag
+)
Ag
++Al→Al
3++3Ag
0
Al
3++3OH
-→Al(OH)
3→Al(O)OH+H
2O
The silver tree dendritic crystal begins to produce silver from aluminium.When two-layer short circuit, (Al) anode of battery and (Ag) " conversion " between the negative electrode close.Corrosion is fast with catastrophic.Technician in the art will appreciate that other similar metal can replace Al and Ag in the present embodiment.
Additionally, one embodiment of the invention have been utilized the technology of using in photographic industry.This technology is used for removing silver after the development of colour phhotograpy at dye image and resembles.This realizes that by the technology that is called " bleaching " wherein silver resembles and is oxidized to silver ions, removes (photographic fixing) with silver-colored solvent then.Enumerating of possible oxygenant is a large amount of and comprise, for example, and the mechanism of describing below:
Oxygen
Fe
+2→Fe
+3
Fe
+3+Ag→Fe
+2+Ag
+
The ferrous ion atmospheric oxygen changes into iron ion, and it can silver suboxide and forms ferrous ion, it so that finish this circulation once more.This silver ions can move, and has therefore damaged information integrity.The redox reaction thermodynamics that becomes is more favourable, this depend on the sequestrant (counter ion) that is used for dissolved iron (EDTA, oxine, phenanthroline, the methyl ethyl diketone acid group, ferrocene, or the like).
In addition, have known all cpds in photographic art now, they are as the promotor of bleaching action.These comprise, for example, but meaning without limits: the polyethylene oxide polymer that contains the side chain of being with sulfide group, mercapto-triazole, dimercaptothiodiazole, mercaptoimidazole, mercapto-tetrazole, imidazoles, single thioglycerin, Gelucystine, halfcystine, cystamine, thiourea derivative, thioamide compound, the amino alkylidenyl thio-alcohol, or the like.Be known as and prevent that also showing of be shaded or hidden for foliage agent can be used as bleach boosters.
According to another overlapping embodiment of the present invention, Fe
+ 2With the dissolving of low potential sequestrant, the latter replaces with the noble potential sequestrant according to deblocking mechanism after packing.
Randomly, quinhydrones-quinone redox chemistry method can be used for realizing the effect identical with ferrous salt.The quinhydrones of sealing in wrapping material deblocking and being exposed to atmospheric oxygen changes into quinone after the air, and then can silver suboxide.This process also can be utilized bleach boosters.
Additionally, via reactive layer for good and all other method of corrosion data layer can both use.For example, certain embodiments of the present invention can have tack coat, and it promotes the corrosion of reflective metallic or involves the diffusion of some materials from the tack coat to the reflecting layer.For example, the existence of halide-ions has been observed and can have been corroded thin silver layer and stop reading of DVD.Mechanism can be imagined can discharge or activate halide-ions, therefore stops reading of data.In other embodiments, the additional mechanism part that is not adhesives.For example, the precursor of corrosives can deposit with metal level contiguously.When oxygen or some other suitable substances diffuse through substrate and arrive corrosive precursor, can initiation reaction, cause producing corrosives, the latter for good and all destroys data structure on disc through certain hour.Additionally, material in the substrate of disc such as polycarbonate can carry out engineering design, so that it is degraded through certain hour, therefore make disc become unavailable.These materials and reaction are known to the skilled in the art.
The another kind of composition of performance similar functions is a kind of composition that As time goes on modification takes place substrate itself.The modification of substrate can cause that it changes its optical quality, has therefore damaged the signal that arrives reader.These optical qualities can comprise its refractive index or its transparency.
In addition, the modification of substrate can cause that bottom metal layer changes its optical property, as mentioned above.In this way, the substrate of time-sensitive and/or lacquer can combine with the reflecting layer, become non-reflectivity.
The transparency of polymeric film can be by any change the in the following method: the reaction of film and water; The reaction of film and oxygen; Or the crystallization of polymkeric substance, mean the more aligned arrangement of polymer molecule in film.
For example, can select substrate, it can be by airborne component such as oxygen or water change.For example, oxygen can this substrate of oxidation, causes that its transparency or its refractive index change.Additionally, substrate can be absorbed in airborne water through design, causes its swelling and its optical property of change.Another example is that this substrate can be passed in time and changes its perviousness to oxygen, therefore allows the oxidation of metal level.At latter event, the overall time sensitivity of optical medium can be the function of the performance in substrate and/or lacquer and reflecting layer.
This substrate or metal level also can be to specific optical wavelength sensitivities after preparation.Be exposed to the variation that these wavelength will cause the optical quality of this layer, therefore damaged the signal that arrives reader.Example comprises the photopolymerization of substrate; The light of acid or alkali produces; The light of singlet oxygen produces; Fractionation (for example, the division of crosslinked hydrogen bond) with polymkeric substance.The introducing of the catalyzer of photoactivation in substrate or metal level can help this process.
Following paragraph should be deleted.You misread the use of my indigoide colors.I have two kinds of indigoide colors may use.1) they are possible examples that produce on the spot of leuco dye; in fact the dyestuff that means colorless form synthesizes (by deblocking mechanism) with unprotected form in disc; when being highly insoluble because of them when forming 2), they can also be as an example that stops the sedimentary generation of reading laser.
Therefore, the present invention has described illustrative embodiment of the present invention on specifics to a certain degree.Should be realized that, define by claims, under the situation that does not break away from wherein contained notion of the present invention, can improve or change illustrative embodiment of the present invention though the present invention explains according to prior art.
Equivalent
It is evident that for the those skilled in the art under the present invention the present invention can implement according to the form different with above concrete those disclosed under the prerequisite that does not break away from spirit of the present invention or essential characteristic.Therefore aforesaid specific embodiments of the present invention is considered to indicative, without limits effect.Scope of the present invention is illustrated in claims, but is not limited to the embodiment that comprises in front the narration.
Claims (29)
1. compound in structural formula I: (I)
Wherein
Y is O, S, Se, CR
17R
18, NR
13, R wherein
13, R
17, R
18Be selected from hydrogen or C independently of one another
1-C
6Alkyl;
R
2, R
5, R
6, R
9, R
3And R
8Be selected from hydrogen or C independently of one another
1-C
6Alkyl;
R
4And R
7Be selected from NR independently of one another
10R
11, and R
10, R
11, R
14, R
15And R
16Be selected from hydrogen and C independently of one another
1-C
6Alkyl.
2. the compound of claim 1, wherein Y is S.
3. the compound of claim 1, wherein R
4Be NR
10R
11
4. the compound of claim 1, wherein R
7Be NR
10R
11
5. the compound of claim 1, wherein Y is S; R
4And R
7Be NR
10R
11And R
2, R
3, R
5, R
6, R
8And R
9Be selected from hydrogen or C independently of one another
1-C
6Alkyl.
6. the compound of claim 5, wherein R
14, R
15And R
16Be selected from hydrogen or C independently of one another
1-C
6Alkyl.
7. the compound of claim 6, wherein R
14, R
15And R
16Be selected from methyl independently of one another, ethyl, n-propyl or sec.-propyl.
8. the compound of claim 7, wherein R
14, R
15And R
16It is sec.-propyl.
9. the compound of claim 8, wherein R
2, R
3, R
5, R
6, R
8, and R
9Respectively be hydrogen; R
10And R
11It respectively is methyl.
10. the compound of claim 1, wherein Y is 0.
11. the compound of claim 10, wherein R
4Be NR
10R
11
12. the compound of claim 10, wherein R
7Be NR
10R
11
13. the compound of claim 10, wherein Y is O; R
4And R
7Be NR
10R
11And R
2, R
3, R
5, R
6, R
8And R
9Be selected from hydrogen or C independently of one another
1-C
6Alkyl.
14. the compound of claim 13, wherein R
14, R
15And R
16Be selected from hydrogen or C independently of one another
1-C
6Alkyl.
15. the compound of claim 14, wherein R
14, R
15And R
16Be selected from methyl independently of one another, ethyl, n-propyl or sec.-propyl.
16. the compound of claim 15, wherein R
14, R
15And R
16It is sec.-propyl.
17. the compound of claim 16, wherein R
2, R
3, R
5, R
6, R
8, and R
9Respectively be hydrogen; R
10And R
11It respectively is methyl.
18. the compound of claim 1, wherein Y is N.
19. the compound of claim 18, wherein R
4Be NR
10R
11
20. the compound of claim 18, wherein R
7Be NR
10R
11
21. the compound of claim 18, wherein Y is N; R
4And R
7Be NR
10R
11And R
2, R
3, R
5, R
6, R
8And R
9Be selected from hydrogen or C independently of one another
1-C
6Alkyl.
22. the compound of claim 21, wherein R
14, R
15And R
16Be selected from hydrogen or C independently of one another
1-C
6Alkyl.
23. the compound of claim 22, wherein R
14, R
15And R
16Be selected from methyl independently of one another, ethyl, n-propyl or sec.-propyl.
24. the compound of claim 23, wherein R
14, R
15And R
16It is sec.-propyl.
25. the compound of claim 24, wherein R
2, R
3, R
5, R
6, R
8, and R
9Respectively be hydrogen; R
10And R
11It respectively is methyl.
26. the compound of structural formula II:
27. the compound of structural formula II I:
28. the compound of structural formula IV:
29. optical medium comprises:
First substrate and second substrate, wherein at least one in first substrate and second substrate has the information coding characteristic;
Tack coat between first and second substrates;
Wherein this tack coat is transformed into opaque state and comprises from vitreous state:
Solid support material, wherein this solid support material comprises thermoplastic acrylic polymer, vibrin, Resins, epoxy, polythiol, ultraviolet curing organic resin, urethane, thermoset acrylics base polymer, Synolac, at least a in Vinylite and their binding substances;
Reactive materials, wherein reactive materials comprises and is selected from azine, piperazine, thiazine, colourless azine, quinonimine, phenylene blue, indophenols, indoaniline, anthraquinone, acridine, diarylmethanes, the reduction form of at least one dyestuff in triarylmethane and their binding substances; With
Photostabilised material, wherein Photostabilised material comprises at least a polymeric phenol material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41548002P | 2002-10-02 | 2002-10-02 | |
| US60/415,480 | 2002-10-02 | ||
| US10/651,627 | 2003-08-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1717395A CN1717395A (en) | 2006-01-04 |
| CN100366615C true CN100366615C (en) | 2008-02-06 |
Family
ID=35822516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801041598A Expired - Fee Related CN100366615C (en) | 2002-10-02 | 2003-10-02 | Reactive materials for limited play optical devices and methods of making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100366615C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100157760A1 (en) * | 2006-08-04 | 2010-06-24 | Koninklijke Philips Electronics N.V. | Optical storage medium with limited access |
-
2003
- 2003-10-02 CN CNB2003801041598A patent/CN100366615C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1717395A (en) | 2006-01-04 |
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