Note: Descriptions are shown in the official language in which they were submitted.
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The present invention provides. a writo-once optiaat data carrier using Cu
phthalvcya~tine sulfonamides as dyes, in particular for l,.D-Rs, and also
application
of the dyes mentioned ab4ve to a polymcc substzate (in particular
polyearbonate) by
spin~~oatiag.
Write-once compact disks (CD-Rs) have recently experienced enormous rrolaime
growth accompanied by a simultaneous drop in price. The msi.a component in the
manufacturing cost is the information-Burying dya. The prior art comprises the
use
of expensive cyanine, phthatocyaniae aid axe dye systems which ate synthesised
specifically for the spactral requirements and the solubility required.
in the patent literature, the necessity for usia,g such expe:>sive modified
phthalocyaniae dyes is based e.g. on the following arguments:
~ Specific substituents prevent the formation of dye associates is thin
ftlrns.
Associates adversely altar the absorption spectrum for applicatiot~ as optical
24 data stores (LJS 5124067).
Speci$c substitaents prnwant ctystatiisatiou of ttlc dyes in thin i!tlms.
Crystallites
adve~ely alter the layer homogeneity for application, as optical data stores
(BP-
A2-519419).
~ Only specific substitueats enable Solubility of the ,generally sparingly
soluble
phthalocyaaines iu those solvents which do not interfere with the groove
sh~ucture of the ir~jeGtion mouldad plastic substrate whey spin-coating on a
plastics substrate (mainly polyca~onate) (US S 124067).
~ ~aaora! ads~l~ with r l~,a a~tuia radltu (pd, Pt, Rts, Ru, ti, VO) 'have to
be used
in order to achieve the highest possible ro&active index at the write and read
wavelengths (780 - 820 nrn), which guaraatc;es a high signal modulation for
application as CD Rs (LAP-A1-0SI3390).
CA 02375669 2001-11-29
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~ Specilrc substituents and central atoms enable a high molar absorption
0200400). This high molar absorption is ne~quirud for sutl~ciently high
modulation of the read signal for thm CD-R speeifir~'ton {US 512407).
Patent EP-Al-519395 (Eastm~sn Kodak Co,) describes metal phthaiocyaaine
dyes with certain sulfonamide groups (SOZNRtR~) fox write-once optical data
stores.
Patent fP-A-0517794b (Taiyo Yuden) deacribea csulfonautide derivatives
of a zixrc phthalocyaniru; dye as the information layer for optical data
stores. 't'he
dye is intended to be sviuble in alcohol and Ccllosolve.
Those typos of highly specialised dye systems are expansive and therefore
prevent
the cost-effective production of e.g. write-once compact discs (CD-Rs).
Accordingly, the object of the inveatiou is the provision of a simple to
synthesise
phthaloeyanine dye which complies with the higls requirements (such as light
stability, favourable sigttsl-to-noise ratio, application to a substrate
material witlwut
causing damage, ete.) for use as the infozznation layer in a write-once
optical data
carrier (primari'f~y a CD-R). This ~wrould mean that this dye could ba
prepared much
mart cheaply and would therefore enable more cost-e~'e~ctive production.
Therrefore the invaation provides a write-once optical data carrier containing
a
transparent plastics substrate to the surfaoa of which is applied a wcitabl~
inforz»ation layer and optionally a reflection layer, cbaracierisod in that at
least one
phihalocyanine dye of the general fornnula I is present in the veritable
iiafonnation
7.5 layer.
The invention also provides a proceas for producing a moulded part consisting
of a
tranapatont rubttrato to the eurf~o of which ix~ appliad a veritable
intbrniation layer
containing a dye, wherein the dye contains a phthalocyanine dye of the general
34 formula I and is worked up using a solvent mixture.
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The invention also provides use of the phthalxyaaine dyne of the formula ~, in
particular sulfonuuide group-containing copper phxhalocyarritle dyes of the
formula
I, in optical data carriers.
The phthalocyanine dye according to the invention caa be represented by the
formula
(I) given below;
(SO,-ICI-A NR'R~1.
CuPc
formula I
~' tSQ3~r
in Which
CuPc represents a copper phthalocyaninc group,
A represents an optionally substituted straight chain or braached Cz-Cs
a~~ylene
such as e.8_ ethyleac, prop;Acene, butylene, pentylerte, hexylene,
R~ sad R=, independently, reprc9cnt hydrogen or each optionally represent a
substituted straight chain yr breached Ci-C6 alkylene such as e.g. methylene,
ethylene, propylene, butyioae, pentyleney hexylene, in particular a sub~cuted
C~-Cs hydcoxyalkyi gnou~P as well as sa unsubsdtuted Cues alltyl group,
or R' and Rs, tvgcther with the uitr~ogea atam to which they are bonded, form
a het~erocyclit S- or d-metahered ring Which optionally contains another
heteroatom, e.g. S, N or O,
x is 2.0 to 4.0,
y is 0 to I .S and
the sum of x aad y is 2.0 to .4.0, preferably 2,5 to 4Ø
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Mixtures of the dyes m~tionsad above raay aLRO be used.
Production of the write.once optical data carrier according to the inventive
us
achieved by spin-coating the dye itself or the dye in combination with other
dyes or
with suitable solvents onto a transpsreztt substrate. For coating purposes,
the dye,
with or wiWout additives, is dissolved in a suitable solvent or solvent
mixture in
such a way that the dye constitutes 100 or fewer parts by weight to 100 parts
by
weight of solvent. Then this primary dye solution can be diluted with a
further
suitable solvent in such a way that the dye constitutes 20 or fewer parts by
weight to
100 parts by weight of solvent. The veritable infortnatioa layer is tlbea
metallised
under roduced pressure, by aputterirtg or vapour deposition, acrd then
provid~.d with a
protective lacquer.
The substrates rnay b~ produced firm optically transparent plastics which, if
required, have been suhjooted to surface treatment. Preferred plastics are
polycarbonates and po~,yacrylates, as well as polycycloolefins.
Solvents and solvent mixtures for use when applying a coating of the dye are
chosen,
on the one hand, for their ability to dissolve the dye and, on the other hand,
for
having a minimal effect on the substrate. Solved which era good at dissolving
dyes
according to tho invention are e.g. bcnZyl alcohol, water acidified with
acetic acid, or
fluorinated alcohols. Suitable solves which have a sazall effcxt on the
substrate are
alcohots, ethera, l~ydr~ocarbons, hatogetiated hydrocarbons, Cellosolvr~,
ketunes.
Exarnpies of such solvents are a~ethanoL, ethanol, propaaol, 2,~,3,~-
tetrsftuoroprvpanol, diacetonc 'alcohol, teaachloroethaaa, dichloromethane,
diethyl
ether, dipropyl ether, dibutyl ether, methylcellosolve, ethylcellosolve, 1-
methyl-2-
prt~panal, rno~ylat'hjri kotone, 4-hydrwcy-~-methyl-2-pcnts~none, t~~cane,
cycloheacane, ethylcyclohexaac, octxae, benzene, toluene, xyleuo. Pz'eferred
solvents
~o are hydrocarbons and aloohols because they exert the snnallest effect ca.
the substrate.
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Particularly suitable solvent mixtures for dyes according to the invention are
those
consisting of bctuy[ alcohol, water acidified with acetic acid or fluorinated
alcahots
tziixed with the solvents mentioned above. The initial preparation of a
solutaon in
benxyl a1oohol, water acidified with acetic acid or fluorinated alcohols
followed by
dilution with one ofthe solvents rrtentioned above is particularly preferred,
Suitable additives for tho wri,table information layer are stabilisers,
wetting agents,
hinders, dilueQts and sensitisers,
14 The reflection layer nay be prepared from any metal or metal alloy which is
conventionally used for veritable optical data carriers. Suitable metals or
metal alloys
may be vapaw deposited and sputtered and contain e.g. gold, silver, copper and
their
alloys with each other or with other metals.
The protective lacquer on top ~.~' the re~le~etion layer may consist of
LTVwuring
acrylates.
An intermediate layer which grotects the reflection layer from oxidation may
also be
present.
Writabte optical data carriers accords to the i»v~tion may contain pre-written
Read Only Memory (ROlvf j areas, as described in 'tJS 494t16I 8 ~('Taiyo
Yuden). The
surface of the substrate rioay coutayn a separate thermally deforraable layer,
ass
described in US 4990388 ('Taiyo Yudea).
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Exa es
The following prep~tive tx8mples illustriiee the preparation of dyes according
to
the invention.
a !e 1
138 g copper phthalocyanin~ are introduced into '700 g chloroaulforsic acid
with
stirring. 'I3e mixture is heated m 136°C - 138°C over 1 hour
arui held at 136°C -
138°C for 6 hours. The mixture is cooled to 8S°C, I30 g of
thionyl chloride are
allowed to run its at 85°C - 90°C aver the course of 2 hours and
stirring is then
continued for 4 hours at 90°C. After cooling to 20°C -
30°C, the reaction raixturc is
discharged onto a mixture of 1 1 water and 1 kg ice. Furthermore, the
temperature is
~tainad at 4°C by adding ice. The precipitated sulfvchloride is
filtered off under
suction, washed with about 1 1 of ioe water and dried under suction. The moist
~lisr
cake (abaut 600 g) is introduced into a mixture of Z50 xnl water and 250 g ice
and
the pH is adjusted to 7 at 0°C using i0 % atrsngth caustic soda
solution. Then 100 g
1-amino-3-dimethylamiavproparuo arse allowed to rurr in, wherein the pH rises
to
about 10.5. ?he mixtures is allowed to warm up to ZO°C with stirring,
the termparature
is a~airEtained at 20°C for 1 hour, heated t~o 44°C and than
stirring is continued for 1
hour at 40°C. The pH is maintained at about 10 for the entire bone
using 1U%
strength caustic soda solution. The mixture is allovwed to cool to room
temperature,
tho pH is adjusted to $.5 using dilute sulfuric acid, washed with 1 1 water in
portions
and dried under vacuum at 60°C - 80°C.
269 g of dye which corresponds to the approximate formula Id when in ~.e form
of
the gee acid are obtxinod.
~GNa
flOaNt~L~Cht=-CH:~~GHi-N.~a formula If
CuPc
''w'(30sH?os
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138 g copper phthalaayauiue ate iutraduced iato 560 g chlorosulfonic acid with
stirring, The asixture is heated tw 114°G - 112°C aver 1 hover
end held at 110°C~ -
112°C for 5 hvur.~. The mixture is cooled to 85°C, 85 g of
thionyl chlot'ide are
allowed to ~ is at 85°C - 90°C over the course of 2 hours sad
atirr:ag is them
continued for 3 hours at 90°C. After cooling m 24°C -
30°C, the reaction mixture is
discharged onto a mixture of 1 1 water sad 1 kg ice. Furthermore, the
temperature is
raaiataiaed at 0°C by adding ico. Tb~c precipitated sulfochloridc is
futered off wader
suction, washed with about 1 I of ice water and dried under suction. 'the
moist filter
cake (about 740 g) is introduced into a previously made up mixture of 840 zril
ice
water and 160 g of l.amino-3-dimethyi-a=ninopropaue over the coeu~~ of 1 hour
and
with cooling. The temperature should then increase and at the end of the
introduction
procedure is zaised first to 40°C sad they to 70°C. The
iemperahue is held at 70°C
I S fvr I hour, the product is f~ltemd Wider suction, washed rwith 1 I warm
water in
portions and dried uadGr vacuuru at 60°C - 80°C.
252 g of dye which eorrespoads to the approxiu~ate formula lIi when in the
forest of
the free acid are obtaiua~d.
~CHa
CuPc SOxNH-CHx-~CHarCHi N-...CH formula 3I'I
3
s,a
Examale 3
I3$ g copper pl~alocyanlae are ~iatroftlcad into 500 g chlorvsulfonic acid for
one
hour with st~n~t~g. Tha ~tur~e is hesubod to I00°C - I G2°C ovar
I hour sad held at
100°C - 102°C for 6 hoiu~s. T'$e raixture is cooled to
80°C, 1S0 g of thioayl chloride
are allowod to runt in at 80°C over the course of 2 hours and stirring
is then
coatiasr~ed fvr'4 hours at 80°C. A.#ler cooling to 20°C -
30°C, the rcactioa mixture is
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discharged eeuo a mix~cure of 1 1 wat~ar and 1 kg ice. Furthermo~, the
tcrx~p~shue is
main~ait~ed at 0°C by adding ice. 'fhv precipitated sulfoc~hloride is
filtered off wader
suction, washed with about 1 1 of ice water attd dried wader suction. 1"he
moist filter
cake (about 600 g' is introduced late a previously made ~tp ~ni~t~ut~e of 700
gal ice
S water and 150 ,g N-methyl N-t3-aminopxopyl~.etbanoiamiae over the course of
1
hour with cooling. The temperature should then increase atLd at the end of the
introduction procedure is raised ~~st to d0°C sad the» to 70°C.
?he te~mperaxure is
held at 70°C for 1 hocu; the product is faltered wader suction, washed
with I 1 warm
water is portions and dried wader vacuum at 60°C - 80°C.
t0
256 g of dyrc which cotrc;sponds to the appreucimate forrnuIa IV when in the
form of
the free acid are obtained.
CH
15 CuPc SOzNN~!GH2-CHz-CHz N.~,.C~~~~-OH f°rmula N
2,s
'The substituents gcar~tee a solubility of more than 50% is banzyl alcohol,
and high
20 solubility in water scidifial with acetic acid.
'The following examplGS explain the mve~tion is mon detail.
Ele 4
A 37.5°i6 solution Of the dye in benzyt alcohol was prepared at room.
tempaaturc.
'this stock soIutian was diluted with diacetone alcohol to give a 7.S% dye
solution.
17~i: wlution was applied to a pngrooved potyGarboaate subs~te by mrans of
spiu-
coating. 'fkta progroovod paly~c~ was produced as a disk by mearu of
i:;jection
moulding. The dimensions of the disk and flaw groove struchwe oeri~esponded to
tlbose which a~ uarmally used for CD-RS, L00 am of gold was vapour deposited
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oatv the disk with the dyne 1$ytr as an infvrtnation carrier. Then a W-cur~g
acxylic
lacquer was applied by ~eaas of spin~coating and etu~ed with a UV lamp. Using
a
co~ao~ercial test writer for Cb~Rs {Pulstec G1M'T 2000 x 4), e.g. at 12 mW
writing
power and s 1x writs spe~ad (1.4 m!s), a modulation height of 47% (30
°i6 to 70°~/o is
the CD-It specification) was obtained for the 3T signal sad 69°i6 (~60%
is the CD-R
specification) vas obtsinad for the l 1T signal when reading the information.
TI-.e
ncflectivity in the ~rvvves end on the flat sdetions was 72°~6 and 75%
respectively
before wtitiag. The specificatiaa for CD-Rs requires >65%. The molt absorption
of
the dyer measurod is beazyl alcohol, was about 100 000 1!(mol cm) with a ~ at
690 nm and is thus much lower than the molar absorption of > 200 000 l/(mol
em)
cited in US 51240b7, which should be desirable for a dyo for optical data
gtarage.
Example S
A 3'7.5% solution of the dye in lxazyl alcohol was prepared at room
temperature.
'Ibis stock solution was diluted with diacetona al.~cohol to giYC a 7.5% dye
solution.
This solution was applied to a pregroovad polycarbonato substrstG by u~esrrs
of spin-
roaring. "fba pmgroovcd polyrcacbanate was produced as a disk by means of
injection
moulding. The dimensions ef the disk and fhc groove structure corr~poaded to
those which are nor~oally used for CI3-Ra. 100 nm of silver was ,vapour
deposited
onto the disk with the dye layer as an infbrmation carrier. Then a UV-curing
acryfic
lacquer was applied by mesas of -ooathag and anred with a UV lamp. Ubiag a
comnnerciai test writer for CD-Fts ('Pulstec OMT 2000 x 4), e.g. at 15 mW
writing
power and Zx write speed (2.8 mls), a~ modulotioa height of ~419~0 {30
°i6 to 70% is the
CD-R specificati~oa) was obtained far the 3T signal and 71% (>6t?% is the GD-R
specification) was obtained far the lIT signal when reading the informatiorL
The
refleclivify lo the grooves and on the flat sections was 72°~ and
75°r6 respectively
b~to wcf~. The ~a &~ Gla~Rt tsqnir~ ~65'y6. Tho molar abavrpticm of
the dye, measured in bcaayi alcebwl, was about 100 000 il(mol cm) with a h",~
at
690 am. end, is thus much lower thaw the tnoiar absorption of > 200 000
1/(msrl cm)
ritod ip us 5124067 which should be desirable 5or a dye fior optical data
storage
