CA2238035A1 - Multilayer interference pigments - Google Patents
Multilayer interference pigments Download PDFInfo
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- CA2238035A1 CA2238035A1 CA002238035A CA2238035A CA2238035A1 CA 2238035 A1 CA2238035 A1 CA 2238035A1 CA 002238035 A CA002238035 A CA 002238035A CA 2238035 A CA2238035 A CA 2238035A CA 2238035 A1 CA2238035 A1 CA 2238035A1
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- layers
- metal oxide
- refractive index
- pigments
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/14—Colouring matters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/302—Thickness of a layer with high refractive material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/303—Thickness of a layer with low refractive material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2220/00—Methods of preparing the interference pigments
- C09C2220/10—Wet methods, e.g. co-precipitation
- C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment
Abstract
Multilayered interference pigments are composed of a transparent substrate material coated with alternating layers of metal oxides with low and high refraction indexes. The layers of metal oxide with a low refraction index are optically inactive. The thickness of the layers of metal oxide with a high refraction index is an integral multiple of the optical thickness required to obtain the desired interference colour. The thickness of the layers of metal oxide with a low refraction index is comprised between 1 and 20 nm.
Description
19 r1P~I '98 11:50 1'1ERCK PI~ITENT Gl''l~H 49 6151 727191 5.3~13 FILE, ~tN TH~ r ~
~EXT-TRANSLA~i~N
-- 1 .
~ltiluy~r ~te~~~ronc~ ~ ~n ~ e inven~ion r~latR~ to multilayer inter~erence pigments consis~ing of a tran~parent c~r~ier material coat~d with ale~nsti~g l~e~ of me~al ~x~des o~ low a~d hi~h re~ractive index.
Multilayer inter~ren~e ~ig~ent~ with al~ernating layer~ o~ materi~l~ o~ high and low refractive i~dex are ~o~. They dif_er in re~pect ~ the carrier material and o~ ~he material for the individual la~ers, and in the prepara~icn ~rocess. ~he layers are pre~ed either by precipitation in a wet pro~e~s or by vapour de~ositicn or sput~ring under vacuum. The layers a~pli~d ko the ~arrier or to a rel~a~e ~yer are all opticall~ active ~ nd ~ontribute to the development o~ the inte~erence c~lour~. The carrier m~ri~l~ are o~ica~ly ac~ive only in excep~ion~ case~.
US 4,43~,010 de~cri~es a mu~tilayer inrer~erence pigment conAi~ting of a c~ntr~l layer o~ a re lective material ta~inium) and alternaeing l~ye~s o~ two transparent, diel~c~ri~c mat~rials o~ high and low refr~c~
ti~e index, ~or exampIe tit~nium dioxide and silicon dioxide, on bo~h ~ides o~ ~he cen~ral alumini~m layer ~his pigment i~ used ~or ~he printing o~ securiti~.
JP H7-759 (Ko~oku) de~cribe~ a multilayer inter-~S feren~e pig~ent with a metalllc lu~tre. It con~ist~ ofa ~ubstrate coated with alt~rnating la~er-~ o~ ti~ni~m dioxide and ~ilic~n dioxide. ~he ~u~trate i~ formed ~rom alwmin~u~, ~old or ~lver ~lake~ or ~akes of mi~a an~
~la~s coated with metals.
H7-246 366 describe~ a multilaye~ inter~erence pigment with alternating layer~ of a material o~ high refractive index and a mate~i~l o~ low ~e~rac~ive i~de~.
The sub~trate used is glas-~ and, ~or the coating, 6ilicon dioxlde and ~i~anium dioxid~. The indi~idual laye~s 35 po~es~ a~ opti~ kne~ w~i¢~ i~ ~n integ~al m~l-tiple o~ a quarter o~ the wavelen~th at which inter-~erence i-~ expected. This res~lts, ~or the titani~m dioxide layers, in a layer ~hi~kness o~ 44.~ nm at a CA 02238035 l998-05-l9 19 1'1~I '98 11:50 r1ERCK PRTENT Gl'1BH 49 6151 7Z7191 5.4~13 - a -re~ractive ;~R~ o~ 2.7 and, for the ilico~ dioxld~.
layer~, in a lay~r thickness o~ 80 nm at a re~racti~e i~d~x of ~.5.
In the pigments described a~ove, the ~ilicon dioxide lay~ a~t a~ optically a~ti~e ~yerx ~hi~
optically activR e~ct ~egins with ~ layer thickness o~
~bout 20 nm. Si}icon dioxide layers, however, are al~o employed as dif~usion h~rrier~ in condu~tive pi~mants.
For instance, EP 0 373 575 de~cribes conductive platelet-~orm pigment~ co~si~~ing of ~ pla~elet-~or~ me~al o~ide ar ~ a ~la~el~t ~or~ ma~rial coated with m~tal oxide, and a conductive layer, the metal axide layer and c~n-ducti~e la~er bein~ ~a~ted by ~ silicon dioxide layer which prev~nts ions ~rom the sub~trate or ~rom the metal oxide layer di~using in~o the conduc~ive l~yer in ~he cour~e of calcinin~; otherwi~e, the conductivity o~ the a~timony-~oped ~n oxide layer i~ reduced. T~e t~ickne~s o~ the silicon d;oxide interlayer i~ between 8 and 30 nm a~ conccntra~io~ o~ ~rom 5 to.~0% ~y weight o~ sio~
based on the s~bs~ra~e.
It h~s ~urpri ingly been ~ound that the quality o~ cu~tom~y commerci~l inter~eren~e pigments in re~pect o~ their mechanical properties can be markedly improved i~, in the ~tal oxide l~yer~ o~ high re~rac~ive index, 2S at lea~t one in~erlayer o~ another metal oxide i~
.,_, arranged which posses~e~ no optical activity.
~ ~eatu~e o~ ap~ropriate metal oxide~ is that de3pite their low thickneY~ the~ are obtained a~ ~ la~er even a~ter the calc~ning o~ the pi~ment, since they do not readily ~orm mixed phase~ with the su~ro~ metal oxide~ of high re~active index Moreover, they ha~e a markedly lower re~ractive i~ex ~han the metal oxide~
which ~orm thc optical layer The invention t~ere~ore provides multilayer 35 interference pi~men~cs consist;Lng o$ a carrier material eoaced w~th alte~natin~ layer~ o~ metal oxide3 o~ high and low re~ractive inde~, the l~yer(~ o~ the m~t~1 oxide o~ low re~ractivc index bein~ optically inacti~e The in~ention additionally provides a proce3s ~or CA 02238035 l998-05-l9 19 1'1RI '98 11-50 ~IERCK PRTE~IT Gl'1BH ~9 6151 7Z7191 5.5~13 preparing the noYel pi~ent~, ~n whi~ the tran~parent carrier ma~erial i~ ~u~pended in water and coa~-ed in alternation with a metal oxide.~ydrate of hi~h re_ractive i~dex ~nd ~ metal oxi~e hydrate of low refractive indcx ~y addition and hydrolysis of ~h~ coxre~ond~ng ~ater-col~le metal compounds, the p~ necessary for the ~recip-itation o~ the respec~ive metal oxide hydrate bein~
e~tablished and kept constant by simultaneou~ addition o~
acid or ~a~e, and then the coated carri~r mAterial i~
separat~l of~ from the aqueous ~iu~pen~ion, dried, an~ i~
deQired, calcined.
The invention p~ovides, furthe~more, ~or the use - o~ the no~el ~igmen~ ~o~ pigmenti~g pain~, p~inting inks, pla~tics, ~laz~s ~or ceramics and gla~ , as well a~
cosm~tiC~.
~or this purpo~e they can be employed as mixture~
with cuctomar~ co~mercial pigments, for exam~le i~organic or or~anic ab~orb.~ion pigment.q, metal-ef~ect pigm~nts and LCP. pi~m~n ~0 Th~ carrier ma~erial i~ mi~a, anot~r phyllo~
i~te, gl~s~ flakes, or platelet-~orm ~ilicon dioxide, which i~ prepare~ by the techni~ue described in WO
9~/~8237 on a continuou.~ belt by ~olidifi~ion and hydroly~s o~ a waterglass solution.
Z5 The metal oxide o~ ~i~h refra~tive ~ndex ~an ~e an oxide or mixtures of oxides with or witho~ ~rbing ~roper~ie~. su~h a~ Tio2, ZrO~, Fe~O3, Fe3O~, Cr2O3 or ZnO, or a compound o~ hi~h re~ractive index ~uch as, ~or example, iron ti~anate~, iron oxide hydrat~s an~ tit~nium suboxide~, ~ mixture5 ~ndtor mixed phase~ of these compound~ with one ano~her or with other metal o~ide~
~ he ~1 oxid~ ~ lo~ re~ra~ti~e index is sioi, Al~03, AlOO~, ~03 or ~ mixture ther~o~ and ~an likewi~
h~ve absoxbing or non--ab~orbing properties. I~ desixed;
the oxide layer of low -re~r~c~ive index may include alkali metal oxides and alkaline ear~h metal oxides as c~n~ t i tuent s .
T~e metal oxide layers are pr~rably applied by a wet-ch~mical method, i~ whi~h oontext it i~ p~sible t~
~9 1'1RI '98 11:51 ~1ERCK PRTENT G~1DH 49 G151 7Z7191 5.6~13 e~ploy.~he wet-chemical coating techni~ues de~elo~ed ~or the pr~paration o~ pearl lustre pi~ments; techni~ue~ o~
~hi~ kind are descri~ed, ~or example, in DE 14 67 468, ~E 19 5~ q8~, DE 20 ~9 56~, DE 2~ 14 ~45, DE 2~ 15 191, DE ~2 44 2g8, DE 23 13 331, ~E 25 2Z 572, ~E ~1 37 808, D~ 31 37 80~, ~E 31 5~ ~43, ~E 31 51 ~54, DE ~1 51 ~55, DE 32 11 602, DE 32 35 017, or el~ in ~urther patent documents and ot~er publications.
For ~oa~ing, ~he ~b~tra~e particle~ are ~U3-~n~ed in water, and one or more hyd~olysa~le metal ~alt6 are A~e~ at a p~ which i~ appropriate ~or hydrolysis and i~ chosen such that the metal ~Yi ~oe an~Jox me~l o~ide hydrates ar~ precipitated directly onto the particle~
without any in~tance~ o~ cecondary precipitatio~. The p~
15 i8 kep~ con~a~t us~lly by simul~aneou~ meter~d addition of a ~a~e or alknli. The pigments are su~se~uent~
~eparated of ~, wa~hed and dried ~nd, if deaired, eal-' cined, the c~lcination temperature posaibly beinyoptimized in re~pect o~ the particular coating. I~
~e~ired, ~ollowi~g the application o~ individ~al cQating~
the ~igment~ ean.~e separated o__, dried and, i~ desired, calci~ed ~e~o~e being ~e~uspended ~or the applic~tion oi ~urther lay~rs by precipitati~.
Pre~erably, u-~e is made o~ titanium dioxide as 2~ the metal oxide o~ high re~rac~ve index and o~ silicon dioxide a~ the metal oxide o~ low re~ra~tiv~ index ~o~ th~ application o~ the titaniu~ dioxide layers, pre~erence is given ~o the ~echnique descrihed i~
US ~,~53,001 An ayueous tit~ni~m ~ olution i~ slowly to a ~uspension, heated to a~out 50 100~C, in pa~tic-ular 70 - ~0~, o~ the mate~ial to be coated, and a s~bst,3ntially ~onstant p~ o~ about 0.5 ~ 5; in ~articu~ar a~out 1 5 - ~.5, ls maintained ~y ~im~ltan~ou~ metered addition of a base, for example ~queo~ ,~m~onia soluti~n o~ aque~us alkali m~tal hydroxide ~olution. As ~oo~ a~
the d~ired ~ayer thi~knes~ of the TiO~ precipitation ha~
en ~eac~d, the addition o~ ~he titanium .~alt ~olution ~nd of the ~a9e i~ 3topped CA 02238035 l998-05-l9 19 M~I '98 11:51 MERCK PRTENT Gl'113H 49 6151 7Z7191 5.7~13 .
~ his p~oce~s, also termed the ti~ratio~ ~o~e~, iB notable for the ~a~t that it avoi~ an excess o~
titanium ~alt. This i8 achieved ~y supplying ~o t~e hy~rolysis only that qU~ntity per unit time which is necessary for uni~orm coatin~ with the hydrat~d TiO~ a~d which can bo re~eived per unit time by the available ~urface area o~ the particle~ to b~ coated. ~her~ iY
there~or~ no ~roduc~on of hydrated tit~nium ~ioxide ~ar~-icles no~ precipi~ated on ~he sur~ace ~o be coated.
10For the applica~ion o~ the Qilicon dioxide layers, ~he ~o~lowing ~roce~ o ~e e~ployed; a.sod~'u~
silicate ~olution is metered into a suspension, ~eated to ~~ about ~0 - 1004C, in particu~ar 7Q - 80aC, o~ the material to be ~oated. The pH is held con~tant at 1.5 to 10, pre~erabl~ at ~ ~ to 8 ~, ~y ~imultaneou~ addition o~
10% hydrochloric acid. Stirring i~ ca~ri~d out for ~urther 3~ ~in~te~ ~ollowin~ addition o~ the silicate ~olution.
~t i~ al80 pos~ible to alter the powder colour o~
the pi~ment by applying ~urther layer~, ~or example eolo~red metal oxide~ or PrusYian Blue, tr~nsition ~l com~ound~, ~uch a~ compounds o~ Fe, Cu, Ni, Co or Cr, ~or examp~e, or organic oompo~nd~ ~u~h as d~e~ or colour lakes.
25It i~ ~dditionally possible to subiect the ~i~ished ~igme~ ~o an a~tercoating or aftertreatment process which further incr~a~ea ~he 3~abil~ty to ~ig~t, weathe~ ~nd ~he~i~ , or whi~h facilitate~ the handling of the pi~ment, especially i~6 incoxporatio~ in~o di~~er-30 ~nt media . 9u~ table a~tercoatin~ and a~tertr~e~
proce~e~ are tho-~e de~cri~ed, ~ e~m~le, in D~-C
22 1~ 191, ~-~ 31 ~1 354, ~3~A 32 35 017 or DE-A 33 34 5~8 ~he substance~ additionally ~lie~ ~ake up only 35about O 1 to 5~ by wei~ht, pre~erably abo~t 0.5 to 3~ by wei~ht, of ~he ove~all pig~ent Pre~erence is al~o ~ive~.~o an additional co~ing with complex salt pigment~, e~ecially ~yanofe~rate complexc~, for ex~mple Pru~sian ~lue and Turnbull.~s Blue, CA 02238035 l998-05-l9 19 r1RI '98 ll:5Z ~1ERCK PRTENT G11BH 49 6151 727191 5.8~13 a~ i~ descri~ed i~ E~ ~ ~412 173 ~sic] and DE 23 13 332.
The ~ovel pi~ment can ~180 be ~oated w~h organac dyes ~nd, in particular, wit~ phthalocyanine or metal phthalo~yanine ~nd~or i.~danthr~ne dye~ in accordance with DE 4009 567 ~hi~ is done by preparin~ a su-~pen~ion o~
t~e pigm~nt in a ~olution of the d~e and then h~ingin~
thi~ ~u~pensi~n together wieh a solvent in which the ~y~
~s o~ low or zero ~olubility.
The thicXness of the interlaye~ o~ metal- oxides l~ o~ lo~ xefra~iv~ i~dex wi~hin ~ ~et~l oxide layer ~
hi~h refractive index is from l to 20 nm, pre~erably ~rom to lO nm. Within this ran~e, a me~al oxide laye~ of low re~ractive index, fcr example 3i~icon dioxide, i~
optically inactive, which is an essential ~eat~re o~ the .15 present invention.
The thi~kn~s o~ the layers o~ me~l oxide~ of high refra~tive index i~ b~tween 20 and 350 nm, pre~er-a~ly ~etween 40 and 260 nm. since the interlayer~ o~ low-refractive-i~dex metal oxide~ gre~ly i~e~e ~
mechanical 3ta~ility of th~ layer~ of high-re~ractive-.
index ~tal o~ides, it is al~o possible to prepare thic~er laye~s o~ adeguate stability. In p~actice~ .
however, layer thicknes~es o~ only up to 260 nm ~re:
e~ployed, w~i~ in ~he c~se o~ a titaniuffl diox~de-mic~
pi~ment correspond~ to IIIrd-order ~reen.
_~ .
The n~mber and position o~ the interlayers i~
depende~ on ~he ~ot~1 l~yer thi~kne~ of the met21 oxide layer o~ high re~ractive index The interlayer is pre~r-~bly arranged ~ch ~hat ~he laye~ thickne~s of the m~tal oxide layer~ o~ hi~h re~ractive index ~orresponds ~o the o~tic~1 thic~ess, ~r ~o ~n integral mul~i~le ~ this optical thickne~s, which is necessary ~or the respective inte~e~e~ce c~lour. ~or ~xample, ~or a IIIrd-order gr~en the interlayers would ~e axra~g~d ~uch ~t one laye~ i~
located at Ist-order gre~n and a ~econd layer at IIn~-order green Thi~ i~ ~lid ~or pure interference colours In ~ di~erent c~3e, the ~killed worker can de~ermine the op~imum posiL~ on o~ th~ interlayers without any in~entive exertion. For exam~le, a more yellow III~d-~r~er g~een i~
. .
CA 02238035 l998-05-l9 19 MP~I ~98 11:52 IrlERCK PRTENT G1~1~3H 49 6151 7Z~191 5.9~13 o~ained i~ the interlayer is placed toward~ I~nd-order ~old, compared wi~h ~ pure III~d-order ~reen in which the interlayer is arranged o~ ~ IInd-order ~reen.
~x~le 100 g of ~ot~ium mica (10-60 ~1 are ~u~pended in 2 1 of deioni~ed water. The ~uspen~ion i~ heated ta 75~C, a~ju~t~d t~ a p~ o~ 1.8 with dilute hydrochlo~ic acid, ~ir~t o~ all coat~d with SnO, by.~i~g 3.3 ml~min of SnCl4 ~olu~ion (~om ~.~ g o~ SnCl4 and 0.75 g o~ con~
1~ hydrochloric acid in 100 ml of deionized wate~). The p~
s held constant using 32 ~ ~odium hydroxide solution Stirring i~ contin~ed for 15 ~inute-~ ~nd.~hen coating with ~iO2 is carried out under the same pH~temperat~e ~on~ition~ ~y adding 1.5 ml~min o~ Tl~lc ~olu~i~n ~400 g of TiCl4~1) and holding the pH c~nstant with 32 ~ sodium hyaroxide solution. Coating i~ inte-rr~pted a~ter the IInd-order green end point ic re~he~
stirring i~ ~ontinued ~or 15 mln~es, the ~H i~ ~j~ted to ~.O with dilute ~o~i~m hydroxide solution (ov~r ~e.
course o~ about 15 minute~), and then stirring is con-tinued ~or 10 ~i~utes ~ore Coatin~ with Sioa is the~ carri~d ouS by ~ddi~g 3 ml/~in o~ ~odiu~ ~ilicate sol~tion (~rom 7.3 ~ o~
~odium ~ilicate wi~h 27 ~ SiO~ ~nd ~0 ml o~ deionized water~ without pH compensation. Afte~ward-~, ~tirrihg ~
~ontinued' ~or 1~ minute~, the pH is read~usted to 1.8 with di~ute hydroch~oric acid ~ver the cour~e of ahout 10 minutes), an~ a ~econd Tio2 l~yer is applied a~
described above by ~dding TiClC solutlon. Coating is interrupted af ter the IIIrd-order green com~ari~on en~
point has ~een reached, s~irring i~ ~ontinued ~or 1~ min~te~, ~nd then ~e pigment i~ ~iltexe~ o~ wi~h suctio~, washed, dried and calcined at 850~C ~ox 30 minute~.
The pigment obtained has an intense green i~ter~
ference calour The division o~ the Tio~ layers is ~ollow~:
CA 02238035 l998-05-l9 19 r1RI '98 11: 53 ~1ERCK PRTENT G~113H 49 6151 7Z7191 5.10il3 , 18t laysr; ~bou~ 17 0 n~
Znd laye~ a~out 85 nm ~otal layer: abo~ 260 n~
~ he thickn~s o~ the SiOa i~terlayer i~ a~ou~
5 nm.
Com~ari 8 on Example 100 g o~ p~ta~$um miCa ~10-~0 ~m) ~xe ~u~pended in ~ 1 of ~eionized water. The suspension i~ heated to 75~~, ~dju~ted to a ~.H a~ 1.8 with dilu~e.hydroc~loric acid, ~irst of all coated with SnO~ by ~; n~ 3 . 3 ml~in o~ SnCl~ solution (from 2.2 g o~ SnCl4 and O . 75 g of conc.
hydx~ochlo~iç a~id i~ 100 ~nl of d~i~nized w~e~) . ~.
is held c~n$tant using 32 % 80dium hydroxide 801ution.
Stirrin~ i~ con~inued ~or lS ~i~utes and then 1~ coatin~ .with TiQ i~ carried out under the 3ame p~temperature condi~i~n~ by ~dding 1. 5 ml~min ~ Ti~1~
~olu~i~ t400 g o~ TiCl~l) and holdin~ thR pH c~n~t~nt with 32 ~ sodium hydroxide solution. ~oating i~ inter-rupted a~ter the II~r~-order ~reen en~ point ha~ been rea~hed, ~irrin~ is continued ~or 15 minute~, and the~
the p~gmen~ ~s ~iltered o~ with ~uction, wa~hed, dried and calcined a~ 850UC ~or 30 mi~ute~. Thè thicknes~ of the Tio~ layer i~ a~out 2~5 nm. The pigme~t obtained~i~
~uch ~ak~r i~ the st~ength o~ the inter~eren;ce c~lour than the pi~m~nt prep~red in a~corda~ce wi~h the i~ven-tion. The platelets ~how severe cracks and i~tance~ of ~lakin~ in the Tio~ layer.
.
~olour ~haracteris~ics o~ the re~ul~ing p~gment~ ~Hunter - L, a, ~) on the ~asis o~ nitro.~el}ulose coat~ng card~
NC coating c~d~ a~e p~pared by care~ully di~e~ing O.9 g o~ pigment in 5~.5 g ~ N~ ~arnish, devolatilizing the ~ix~re. and then applying ït with th.e aid o~ a doctor ~lade t~ a card having a h~l~bl~k and hal~-white sub~trate. The wet ~ hickne~s i~ 500 ~m A~ter drying, the colour data are mea~ured u~der ~he 19 1'1RI '98 11: 53 ~lEl~!CK PRTENT G~1BH 49 6151 7Z7191 5.11~13 g ~tated geometries.
~omor,ry 450~ 2.5~22.5~ 45~~0 Bl~bcJc ~zd ~ c~ c~L ~l~r!~ e!~¢l L 3 b L ~ 3 r- ~ b Exan~le 2a.6 -li 4 -4.0 63 5 -28.3 +5.7 el3.0 +11.5. --0 8 CO~p~r~GOn ~;xa~lc~ '3e.. 4. -5.3 -3.7 5~.9 -:~1.3 +5.g a5.4 ~7.9 ~:0.8 The ~d~nt~ge~ ~ the pigmen~ o~ing ~ the invention relative to the compari~on example are very e~idenO:
Colour stren~th, repre ented by t~e ne~ative a value glos~
~22.5~J22.5~):
28.3 a~ again~t ~1 3 Ll~;n~nce, repre~ente~ by the C val~e glcss (22 5O~22.5O~;
63.5 as against 5~.
Glo~s, repre~e~ted ~y the ~gloss ~u~b~r~' L~-~, 5D~Z, 5 _~45 ~O
55.Q as against ~.2 CA 02238035 1998-0~-l9
~EXT-TRANSLA~i~N
-- 1 .
~ltiluy~r ~te~~~ronc~ ~ ~n ~ e inven~ion r~latR~ to multilayer inter~erence pigments consis~ing of a tran~parent c~r~ier material coat~d with ale~nsti~g l~e~ of me~al ~x~des o~ low a~d hi~h re~ractive index.
Multilayer inter~ren~e ~ig~ent~ with al~ernating layer~ o~ materi~l~ o~ high and low refractive i~dex are ~o~. They dif_er in re~pect ~ the carrier material and o~ ~he material for the individual la~ers, and in the prepara~icn ~rocess. ~he layers are pre~ed either by precipitation in a wet pro~e~s or by vapour de~ositicn or sput~ring under vacuum. The layers a~pli~d ko the ~arrier or to a rel~a~e ~yer are all opticall~ active ~ nd ~ontribute to the development o~ the inte~erence c~lour~. The carrier m~ri~l~ are o~ica~ly ac~ive only in excep~ion~ case~.
US 4,43~,010 de~cri~es a mu~tilayer inrer~erence pigment conAi~ting of a c~ntr~l layer o~ a re lective material ta~inium) and alternaeing l~ye~s o~ two transparent, diel~c~ri~c mat~rials o~ high and low refr~c~
ti~e index, ~or exampIe tit~nium dioxide and silicon dioxide, on bo~h ~ides o~ ~he cen~ral alumini~m layer ~his pigment i~ used ~or ~he printing o~ securiti~.
JP H7-759 (Ko~oku) de~cribe~ a multilayer inter-~S feren~e pig~ent with a metalllc lu~tre. It con~ist~ ofa ~ubstrate coated with alt~rnating la~er-~ o~ ti~ni~m dioxide and ~ilic~n dioxide. ~he ~u~trate i~ formed ~rom alwmin~u~, ~old or ~lver ~lake~ or ~akes of mi~a an~
~la~s coated with metals.
H7-246 366 describe~ a multilaye~ inter~erence pigment with alternating layer~ of a material o~ high refractive index and a mate~i~l o~ low ~e~rac~ive i~de~.
The sub~trate used is glas-~ and, ~or the coating, 6ilicon dioxlde and ~i~anium dioxid~. The indi~idual laye~s 35 po~es~ a~ opti~ kne~ w~i¢~ i~ ~n integ~al m~l-tiple o~ a quarter o~ the wavelen~th at which inter-~erence i-~ expected. This res~lts, ~or the titani~m dioxide layers, in a layer ~hi~kness o~ 44.~ nm at a CA 02238035 l998-05-l9 19 1'1~I '98 11:50 r1ERCK PRTENT Gl'1BH 49 6151 7Z7191 5.4~13 - a -re~ractive ;~R~ o~ 2.7 and, for the ilico~ dioxld~.
layer~, in a lay~r thickness o~ 80 nm at a re~racti~e i~d~x of ~.5.
In the pigments described a~ove, the ~ilicon dioxide lay~ a~t a~ optically a~ti~e ~yerx ~hi~
optically activR e~ct ~egins with ~ layer thickness o~
~bout 20 nm. Si}icon dioxide layers, however, are al~o employed as dif~usion h~rrier~ in condu~tive pi~mants.
For instance, EP 0 373 575 de~cribes conductive platelet-~orm pigment~ co~si~~ing of ~ pla~elet-~or~ me~al o~ide ar ~ a ~la~el~t ~or~ ma~rial coated with m~tal oxide, and a conductive layer, the metal axide layer and c~n-ducti~e la~er bein~ ~a~ted by ~ silicon dioxide layer which prev~nts ions ~rom the sub~trate or ~rom the metal oxide layer di~using in~o the conduc~ive l~yer in ~he cour~e of calcinin~; otherwi~e, the conductivity o~ the a~timony-~oped ~n oxide layer i~ reduced. T~e t~ickne~s o~ the silicon d;oxide interlayer i~ between 8 and 30 nm a~ conccntra~io~ o~ ~rom 5 to.~0% ~y weight o~ sio~
based on the s~bs~ra~e.
It h~s ~urpri ingly been ~ound that the quality o~ cu~tom~y commerci~l inter~eren~e pigments in re~pect o~ their mechanical properties can be markedly improved i~, in the ~tal oxide l~yer~ o~ high re~rac~ive index, 2S at lea~t one in~erlayer o~ another metal oxide i~
.,_, arranged which posses~e~ no optical activity.
~ ~eatu~e o~ ap~ropriate metal oxide~ is that de3pite their low thickneY~ the~ are obtained a~ ~ la~er even a~ter the calc~ning o~ the pi~ment, since they do not readily ~orm mixed phase~ with the su~ro~ metal oxide~ of high re~active index Moreover, they ha~e a markedly lower re~ractive i~ex ~han the metal oxide~
which ~orm thc optical layer The invention t~ere~ore provides multilayer 35 interference pi~men~cs consist;Lng o$ a carrier material eoaced w~th alte~natin~ layer~ o~ metal oxide3 o~ high and low re~ractive inde~, the l~yer(~ o~ the m~t~1 oxide o~ low re~ractivc index bein~ optically inacti~e The in~ention additionally provides a proce3s ~or CA 02238035 l998-05-l9 19 1'1RI '98 11-50 ~IERCK PRTE~IT Gl'1BH ~9 6151 7Z7191 5.5~13 preparing the noYel pi~ent~, ~n whi~ the tran~parent carrier ma~erial i~ ~u~pended in water and coa~-ed in alternation with a metal oxide.~ydrate of hi~h re_ractive i~dex ~nd ~ metal oxi~e hydrate of low refractive indcx ~y addition and hydrolysis of ~h~ coxre~ond~ng ~ater-col~le metal compounds, the p~ necessary for the ~recip-itation o~ the respec~ive metal oxide hydrate bein~
e~tablished and kept constant by simultaneou~ addition o~
acid or ~a~e, and then the coated carri~r mAterial i~
separat~l of~ from the aqueous ~iu~pen~ion, dried, an~ i~
deQired, calcined.
The invention p~ovides, furthe~more, ~or the use - o~ the no~el ~igmen~ ~o~ pigmenti~g pain~, p~inting inks, pla~tics, ~laz~s ~or ceramics and gla~ , as well a~
cosm~tiC~.
~or this purpo~e they can be employed as mixture~
with cuctomar~ co~mercial pigments, for exam~le i~organic or or~anic ab~orb.~ion pigment.q, metal-ef~ect pigm~nts and LCP. pi~m~n ~0 Th~ carrier ma~erial i~ mi~a, anot~r phyllo~
i~te, gl~s~ flakes, or platelet-~orm ~ilicon dioxide, which i~ prepare~ by the techni~ue described in WO
9~/~8237 on a continuou.~ belt by ~olidifi~ion and hydroly~s o~ a waterglass solution.
Z5 The metal oxide o~ ~i~h refra~tive ~ndex ~an ~e an oxide or mixtures of oxides with or witho~ ~rbing ~roper~ie~. su~h a~ Tio2, ZrO~, Fe~O3, Fe3O~, Cr2O3 or ZnO, or a compound o~ hi~h re~ractive index ~uch as, ~or example, iron ti~anate~, iron oxide hydrat~s an~ tit~nium suboxide~, ~ mixture5 ~ndtor mixed phase~ of these compound~ with one ano~her or with other metal o~ide~
~ he ~1 oxid~ ~ lo~ re~ra~ti~e index is sioi, Al~03, AlOO~, ~03 or ~ mixture ther~o~ and ~an likewi~
h~ve absoxbing or non--ab~orbing properties. I~ desixed;
the oxide layer of low -re~r~c~ive index may include alkali metal oxides and alkaline ear~h metal oxides as c~n~ t i tuent s .
T~e metal oxide layers are pr~rably applied by a wet-ch~mical method, i~ whi~h oontext it i~ p~sible t~
~9 1'1RI '98 11:51 ~1ERCK PRTENT G~1DH 49 G151 7Z7191 5.6~13 e~ploy.~he wet-chemical coating techni~ues de~elo~ed ~or the pr~paration o~ pearl lustre pi~ments; techni~ue~ o~
~hi~ kind are descri~ed, ~or example, in DE 14 67 468, ~E 19 5~ q8~, DE 20 ~9 56~, DE 2~ 14 ~45, DE 2~ 15 191, DE ~2 44 2g8, DE 23 13 331, ~E 25 2Z 572, ~E ~1 37 808, D~ 31 37 80~, ~E 31 5~ ~43, ~E 31 51 ~54, DE ~1 51 ~55, DE 32 11 602, DE 32 35 017, or el~ in ~urther patent documents and ot~er publications.
For ~oa~ing, ~he ~b~tra~e particle~ are ~U3-~n~ed in water, and one or more hyd~olysa~le metal ~alt6 are A~e~ at a p~ which i~ appropriate ~or hydrolysis and i~ chosen such that the metal ~Yi ~oe an~Jox me~l o~ide hydrates ar~ precipitated directly onto the particle~
without any in~tance~ o~ cecondary precipitatio~. The p~
15 i8 kep~ con~a~t us~lly by simul~aneou~ meter~d addition of a ~a~e or alknli. The pigments are su~se~uent~
~eparated of ~, wa~hed and dried ~nd, if deaired, eal-' cined, the c~lcination temperature posaibly beinyoptimized in re~pect o~ the particular coating. I~
~e~ired, ~ollowi~g the application o~ individ~al cQating~
the ~igment~ ean.~e separated o__, dried and, i~ desired, calci~ed ~e~o~e being ~e~uspended ~or the applic~tion oi ~urther lay~rs by precipitati~.
Pre~erably, u-~e is made o~ titanium dioxide as 2~ the metal oxide o~ high re~rac~ve index and o~ silicon dioxide a~ the metal oxide o~ low re~ra~tiv~ index ~o~ th~ application o~ the titaniu~ dioxide layers, pre~erence is given ~o the ~echnique descrihed i~
US ~,~53,001 An ayueous tit~ni~m ~ olution i~ slowly to a ~uspension, heated to a~out 50 100~C, in pa~tic-ular 70 - ~0~, o~ the mate~ial to be coated, and a s~bst,3ntially ~onstant p~ o~ about 0.5 ~ 5; in ~articu~ar a~out 1 5 - ~.5, ls maintained ~y ~im~ltan~ou~ metered addition of a base, for example ~queo~ ,~m~onia soluti~n o~ aque~us alkali m~tal hydroxide ~olution. As ~oo~ a~
the d~ired ~ayer thi~knes~ of the TiO~ precipitation ha~
en ~eac~d, the addition o~ ~he titanium .~alt ~olution ~nd of the ~a9e i~ 3topped CA 02238035 l998-05-l9 19 M~I '98 11:51 MERCK PRTENT Gl'113H 49 6151 7Z7191 5.7~13 .
~ his p~oce~s, also termed the ti~ratio~ ~o~e~, iB notable for the ~a~t that it avoi~ an excess o~
titanium ~alt. This i8 achieved ~y supplying ~o t~e hy~rolysis only that qU~ntity per unit time which is necessary for uni~orm coatin~ with the hydrat~d TiO~ a~d which can bo re~eived per unit time by the available ~urface area o~ the particle~ to b~ coated. ~her~ iY
there~or~ no ~roduc~on of hydrated tit~nium ~ioxide ~ar~-icles no~ precipi~ated on ~he sur~ace ~o be coated.
10For the applica~ion o~ the Qilicon dioxide layers, ~he ~o~lowing ~roce~ o ~e e~ployed; a.sod~'u~
silicate ~olution is metered into a suspension, ~eated to ~~ about ~0 - 1004C, in particu~ar 7Q - 80aC, o~ the material to be ~oated. The pH is held con~tant at 1.5 to 10, pre~erabl~ at ~ ~ to 8 ~, ~y ~imultaneou~ addition o~
10% hydrochloric acid. Stirring i~ ca~ri~d out for ~urther 3~ ~in~te~ ~ollowin~ addition o~ the silicate ~olution.
~t i~ al80 pos~ible to alter the powder colour o~
the pi~ment by applying ~urther layer~, ~or example eolo~red metal oxide~ or PrusYian Blue, tr~nsition ~l com~ound~, ~uch a~ compounds o~ Fe, Cu, Ni, Co or Cr, ~or examp~e, or organic oompo~nd~ ~u~h as d~e~ or colour lakes.
25It i~ ~dditionally possible to subiect the ~i~ished ~igme~ ~o an a~tercoating or aftertreatment process which further incr~a~ea ~he 3~abil~ty to ~ig~t, weathe~ ~nd ~he~i~ , or whi~h facilitate~ the handling of the pi~ment, especially i~6 incoxporatio~ in~o di~~er-30 ~nt media . 9u~ table a~tercoatin~ and a~tertr~e~
proce~e~ are tho-~e de~cri~ed, ~ e~m~le, in D~-C
22 1~ 191, ~-~ 31 ~1 354, ~3~A 32 35 017 or DE-A 33 34 5~8 ~he substance~ additionally ~lie~ ~ake up only 35about O 1 to 5~ by wei~ht, pre~erably abo~t 0.5 to 3~ by wei~ht, of ~he ove~all pig~ent Pre~erence is al~o ~ive~.~o an additional co~ing with complex salt pigment~, e~ecially ~yanofe~rate complexc~, for ex~mple Pru~sian ~lue and Turnbull.~s Blue, CA 02238035 l998-05-l9 19 r1RI '98 ll:5Z ~1ERCK PRTENT G11BH 49 6151 727191 5.8~13 a~ i~ descri~ed i~ E~ ~ ~412 173 ~sic] and DE 23 13 332.
The ~ovel pi~ment can ~180 be ~oated w~h organac dyes ~nd, in particular, wit~ phthalocyanine or metal phthalo~yanine ~nd~or i.~danthr~ne dye~ in accordance with DE 4009 567 ~hi~ is done by preparin~ a su-~pen~ion o~
t~e pigm~nt in a ~olution of the d~e and then h~ingin~
thi~ ~u~pensi~n together wieh a solvent in which the ~y~
~s o~ low or zero ~olubility.
The thicXness of the interlaye~ o~ metal- oxides l~ o~ lo~ xefra~iv~ i~dex wi~hin ~ ~et~l oxide layer ~
hi~h refractive index is from l to 20 nm, pre~erably ~rom to lO nm. Within this ran~e, a me~al oxide laye~ of low re~ractive index, fcr example 3i~icon dioxide, i~
optically inactive, which is an essential ~eat~re o~ the .15 present invention.
The thi~kn~s o~ the layers o~ me~l oxide~ of high refra~tive index i~ b~tween 20 and 350 nm, pre~er-a~ly ~etween 40 and 260 nm. since the interlayer~ o~ low-refractive-i~dex metal oxide~ gre~ly i~e~e ~
mechanical 3ta~ility of th~ layer~ of high-re~ractive-.
index ~tal o~ides, it is al~o possible to prepare thic~er laye~s o~ adeguate stability. In p~actice~ .
however, layer thicknes~es o~ only up to 260 nm ~re:
e~ployed, w~i~ in ~he c~se o~ a titaniuffl diox~de-mic~
pi~ment correspond~ to IIIrd-order ~reen.
_~ .
The n~mber and position o~ the interlayers i~
depende~ on ~he ~ot~1 l~yer thi~kne~ of the met21 oxide layer o~ high re~ractive index The interlayer is pre~r-~bly arranged ~ch ~hat ~he laye~ thickne~s of the m~tal oxide layer~ o~ hi~h re~ractive index ~orresponds ~o the o~tic~1 thic~ess, ~r ~o ~n integral mul~i~le ~ this optical thickne~s, which is necessary ~or the respective inte~e~e~ce c~lour. ~or ~xample, ~or a IIIrd-order gr~en the interlayers would ~e axra~g~d ~uch ~t one laye~ i~
located at Ist-order gre~n and a ~econd layer at IIn~-order green Thi~ i~ ~lid ~or pure interference colours In ~ di~erent c~3e, the ~killed worker can de~ermine the op~imum posiL~ on o~ th~ interlayers without any in~entive exertion. For exam~le, a more yellow III~d-~r~er g~een i~
. .
CA 02238035 l998-05-l9 19 MP~I ~98 11:52 IrlERCK PRTENT G1~1~3H 49 6151 7Z~191 5.9~13 o~ained i~ the interlayer is placed toward~ I~nd-order ~old, compared wi~h ~ pure III~d-order ~reen in which the interlayer is arranged o~ ~ IInd-order ~reen.
~x~le 100 g of ~ot~ium mica (10-60 ~1 are ~u~pended in 2 1 of deioni~ed water. The ~uspen~ion i~ heated ta 75~C, a~ju~t~d t~ a p~ o~ 1.8 with dilute hydrochlo~ic acid, ~ir~t o~ all coat~d with SnO, by.~i~g 3.3 ml~min of SnCl4 ~olu~ion (~om ~.~ g o~ SnCl4 and 0.75 g o~ con~
1~ hydrochloric acid in 100 ml of deionized wate~). The p~
s held constant using 32 ~ ~odium hydroxide solution Stirring i~ contin~ed for 15 ~inute-~ ~nd.~hen coating with ~iO2 is carried out under the same pH~temperat~e ~on~ition~ ~y adding 1.5 ml~min o~ Tl~lc ~olu~i~n ~400 g of TiCl4~1) and holding the pH c~nstant with 32 ~ sodium hyaroxide solution. Coating i~ inte-rr~pted a~ter the IInd-order green end point ic re~he~
stirring i~ ~ontinued ~or 15 mln~es, the ~H i~ ~j~ted to ~.O with dilute ~o~i~m hydroxide solution (ov~r ~e.
course o~ about 15 minute~), and then stirring is con-tinued ~or 10 ~i~utes ~ore Coatin~ with Sioa is the~ carri~d ouS by ~ddi~g 3 ml/~in o~ ~odiu~ ~ilicate sol~tion (~rom 7.3 ~ o~
~odium ~ilicate wi~h 27 ~ SiO~ ~nd ~0 ml o~ deionized water~ without pH compensation. Afte~ward-~, ~tirrihg ~
~ontinued' ~or 1~ minute~, the pH is read~usted to 1.8 with di~ute hydroch~oric acid ~ver the cour~e of ahout 10 minutes), an~ a ~econd Tio2 l~yer is applied a~
described above by ~dding TiClC solutlon. Coating is interrupted af ter the IIIrd-order green com~ari~on en~
point has ~een reached, s~irring i~ ~ontinued ~or 1~ min~te~, ~nd then ~e pigment i~ ~iltexe~ o~ wi~h suctio~, washed, dried and calcined at 850~C ~ox 30 minute~.
The pigment obtained has an intense green i~ter~
ference calour The division o~ the Tio~ layers is ~ollow~:
CA 02238035 l998-05-l9 19 r1RI '98 11: 53 ~1ERCK PRTENT G~113H 49 6151 7Z7191 5.10il3 , 18t laysr; ~bou~ 17 0 n~
Znd laye~ a~out 85 nm ~otal layer: abo~ 260 n~
~ he thickn~s o~ the SiOa i~terlayer i~ a~ou~
5 nm.
Com~ari 8 on Example 100 g o~ p~ta~$um miCa ~10-~0 ~m) ~xe ~u~pended in ~ 1 of ~eionized water. The suspension i~ heated to 75~~, ~dju~ted to a ~.H a~ 1.8 with dilu~e.hydroc~loric acid, ~irst of all coated with SnO~ by ~; n~ 3 . 3 ml~in o~ SnCl~ solution (from 2.2 g o~ SnCl4 and O . 75 g of conc.
hydx~ochlo~iç a~id i~ 100 ~nl of d~i~nized w~e~) . ~.
is held c~n$tant using 32 % 80dium hydroxide 801ution.
Stirrin~ i~ con~inued ~or lS ~i~utes and then 1~ coatin~ .with TiQ i~ carried out under the 3ame p~temperature condi~i~n~ by ~dding 1. 5 ml~min ~ Ti~1~
~olu~i~ t400 g o~ TiCl~l) and holdin~ thR pH c~n~t~nt with 32 ~ sodium hydroxide solution. ~oating i~ inter-rupted a~ter the II~r~-order ~reen en~ point ha~ been rea~hed, ~irrin~ is continued ~or 15 minute~, and the~
the p~gmen~ ~s ~iltered o~ with ~uction, wa~hed, dried and calcined a~ 850UC ~or 30 mi~ute~. Thè thicknes~ of the Tio~ layer i~ a~out 2~5 nm. The pigme~t obtained~i~
~uch ~ak~r i~ the st~ength o~ the inter~eren;ce c~lour than the pi~m~nt prep~red in a~corda~ce wi~h the i~ven-tion. The platelets ~how severe cracks and i~tance~ of ~lakin~ in the Tio~ layer.
.
~olour ~haracteris~ics o~ the re~ul~ing p~gment~ ~Hunter - L, a, ~) on the ~asis o~ nitro.~el}ulose coat~ng card~
NC coating c~d~ a~e p~pared by care~ully di~e~ing O.9 g o~ pigment in 5~.5 g ~ N~ ~arnish, devolatilizing the ~ix~re. and then applying ït with th.e aid o~ a doctor ~lade t~ a card having a h~l~bl~k and hal~-white sub~trate. The wet ~ hickne~s i~ 500 ~m A~ter drying, the colour data are mea~ured u~der ~he 19 1'1RI '98 11: 53 ~lEl~!CK PRTENT G~1BH 49 6151 7Z7191 5.11~13 g ~tated geometries.
~omor,ry 450~ 2.5~22.5~ 45~~0 Bl~bcJc ~zd ~ c~ c~L ~l~r!~ e!~¢l L 3 b L ~ 3 r- ~ b Exan~le 2a.6 -li 4 -4.0 63 5 -28.3 +5.7 el3.0 +11.5. --0 8 CO~p~r~GOn ~;xa~lc~ '3e.. 4. -5.3 -3.7 5~.9 -:~1.3 +5.g a5.4 ~7.9 ~:0.8 The ~d~nt~ge~ ~ the pigmen~ o~ing ~ the invention relative to the compari~on example are very e~idenO:
Colour stren~th, repre ented by t~e ne~ative a value glos~
~22.5~J22.5~):
28.3 a~ again~t ~1 3 Ll~;n~nce, repre~ente~ by the C val~e glcss (22 5O~22.5O~;
63.5 as against 5~.
Glo~s, repre~e~ted ~y the ~gloss ~u~b~r~' L~-~, 5D~Z, 5 _~45 ~O
55.Q as against ~.2 CA 02238035 1998-0~-l9
Claims (7)
1. Multilayer interference pigments consisting of a transparent carrier material coated with alternating layers of metal oxides of low and high refractive index, the layers of the metal oxides of low refractive index being optically inactive.
2. Interference pigments according to Claim 1, characterized in that the layer thickness of the metal oxide layers of high refractive index is an integral multiple of the optical thickness which is necessary for the desired interference colour.
3. Interference pigments according to Claim 1 and 2, characterized in that the layer thickness of the metal oxide layers of low refractive index is from 1 to 20 nm.
4. Interference pigments according to claims 1 to 3, characterized in that the overall thickness of the metal oxide layers of high refractive index is divided optically by the interlayers of low refractive index into individual layers of the same Ist- or Ist- and IInd-order interference colour.
5. Use of the pigments according to Claims 1 to 4 for pigmenting paints, printing inks, plastics, cosmetics and glazes for ceramics and glass.
6. Use according to Claim 5, characterized in that the pigments are employed as mixtures with customary commercial pigments.
7. Paints, printing inks, plastics, cosmetics and glazes for ceramics and glass which are pigmented with a pigment according to Claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19638708A DE19638708A1 (en) | 1996-09-21 | 1996-09-21 | Multilayer interference pigments |
| DE19638708.6 | 1996-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2238035A1 true CA2238035A1 (en) | 1998-03-26 |
Family
ID=7806427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002238035A Abandoned CA2238035A1 (en) | 1996-09-21 | 1997-09-06 | Multilayer interference pigments |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0882099B2 (en) |
| JP (1) | JP4689771B2 (en) |
| CN (1) | CN1081660C (en) |
| AU (1) | AU4621197A (en) |
| BR (1) | BR9706789A (en) |
| CA (1) | CA2238035A1 (en) |
| CZ (1) | CZ155598A3 (en) |
| DE (2) | DE19638708A1 (en) |
| MX (1) | MX204339B (en) |
| TW (1) | TW455621B (en) |
| WO (1) | WO1998012266A1 (en) |
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| US8088214B2 (en) | 2005-02-12 | 2012-01-03 | Basf Corporation | Transparent goniochromatic multilayer effect pigment |
| US8268069B2 (en) | 2004-08-13 | 2012-09-18 | Merck Patent Gmbh | Pearlescent pigments |
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| KR101443753B1 (en) * | 2010-02-24 | 2014-09-23 | 샨토우 롱후아 펄 러스터 피그먼츠 씨오., 엘티디. | Angle-dependent interference pigments |
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| JP2016519172A (en) * | 2013-03-15 | 2016-06-30 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Ultraviolet reflective pigment and method for producing and using the same |
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| JP2021519846A (en) | 2018-04-04 | 2021-08-12 | アルタナ アーゲー | Effect pigments based on colored hectorite and coated colored hectorite and their manufacture |
| US11364708B2 (en) | 2019-07-08 | 2022-06-21 | Vdi Llc | Dielectric thin film coatings for unidirectional and bidirectional wavelength selective reflective color generation |
| CN113861668B (en) * | 2021-11-17 | 2023-02-28 | 尼伦化学(上海)有限公司 | High-refractive-index and high-wear-resistance TPU (thermoplastic polyurethane) particle and preparation method thereof |
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|---|---|---|---|---|
| DE2244298C3 (en) † | 1972-09-09 | 1975-06-19 | Merck Patent Gmbh, 6100 Darmstadt | Pearlescent pigments and processes for their manufacture |
| GB1556272A (en) † | 1976-05-26 | 1979-11-21 | Mearl Corp | Iron oxide coated mica nacreous pigments |
| US4879140A (en) * | 1988-11-21 | 1989-11-07 | Deposition Sciences, Inc. | Method for making pigment flakes |
| DE3842330A1 (en) * | 1988-12-16 | 1990-06-21 | Merck Patent Gmbh | CONDUCTIVE LABEL-SHAPED PIGMENTS |
| JP3073836B2 (en) † | 1992-07-02 | 2000-08-07 | メルク・ジヤパン株式会社 | Pearlescent pigment having discoloration resistance and method for producing the same |
| JP3389360B2 (en) * | 1994-01-18 | 2003-03-24 | マツダ株式会社 | Light interference material and paint containing the same |
| DE4437753A1 (en) * | 1994-10-21 | 1996-04-25 | Basf Ag | Multi-coated metallic gloss pigments |
| DE19525503A1 (en) † | 1995-07-13 | 1997-01-16 | Basf Ag | Goniochromatic gloss pigments based on transparent, non-metallic, platelet-shaped substrates |
| DE19618569A1 (en) † | 1996-05-09 | 1997-11-13 | Merck Patent Gmbh | Highly transparent multilayer interference pigments for lacquers, inks, cosmetics, laser-markable plastics etc. |
-
1996
- 1996-09-21 DE DE19638708A patent/DE19638708A1/en not_active Withdrawn
-
1997
- 1997-09-06 CZ CZ981555A patent/CZ155598A3/en unknown
- 1997-09-06 CA CA002238035A patent/CA2238035A1/en not_active Abandoned
- 1997-09-06 EP EP97944842A patent/EP0882099B2/en not_active Expired - Lifetime
- 1997-09-06 WO PCT/EP1997/004850 patent/WO1998012266A1/en active IP Right Grant
- 1997-09-06 CN CN97191302A patent/CN1081660C/en not_active Expired - Lifetime
- 1997-09-06 AU AU46211/97A patent/AU4621197A/en not_active Abandoned
- 1997-09-06 MX MX9803990A patent/MX204339B/en active IP Right Grant
- 1997-09-06 BR BR9706789A patent/BR9706789A/en not_active IP Right Cessation
- 1997-09-06 JP JP51423598A patent/JP4689771B2/en not_active Expired - Lifetime
- 1997-09-06 DE DE59711278T patent/DE59711278D1/en not_active Expired - Lifetime
- 1997-09-18 TW TW086113517A patent/TW455621B/en active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6875264B2 (en) | 2003-01-17 | 2005-04-05 | Engelhard Corporation | Multi-layer effect pigment |
| US8268069B2 (en) | 2004-08-13 | 2012-09-18 | Merck Patent Gmbh | Pearlescent pigments |
| US8088214B2 (en) | 2005-02-12 | 2012-01-03 | Basf Corporation | Transparent goniochromatic multilayer effect pigment |
| US8282729B2 (en) | 2005-02-12 | 2012-10-09 | Basf Corporation | Transparent goniochromatic multilayer effect pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4689771B2 (en) | 2011-05-25 |
| AU4621197A (en) | 1998-04-14 |
| MX204339B (en) | 2001-09-21 |
| EP0882099A1 (en) | 1998-12-09 |
| CN1081660C (en) | 2002-03-27 |
| WO1998012266A1 (en) | 1998-03-26 |
| MX9803990A (en) | 1999-07-31 |
| TW455621B (en) | 2001-09-21 |
| CZ155598A3 (en) | 1998-09-16 |
| BR9706789A (en) | 1999-04-13 |
| CN1205022A (en) | 1999-01-13 |
| EP0882099B1 (en) | 2004-02-04 |
| DE59711278D1 (en) | 2004-03-11 |
| EP0882099B2 (en) | 2009-04-08 |
| JP2000501774A (en) | 2000-02-15 |
| DE19638708A1 (en) | 1998-04-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |