CA2236147A1 - Vinylidene chloride polymer compositions and irradiated articles prepared therefrom - Google Patents
Vinylidene chloride polymer compositions and irradiated articles prepared therefrom Download PDFInfo
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- CA2236147A1 CA2236147A1 CA002236147A CA2236147A CA2236147A1 CA 2236147 A1 CA2236147 A1 CA 2236147A1 CA 002236147 A CA002236147 A CA 002236147A CA 2236147 A CA2236147 A CA 2236147A CA 2236147 A1 CA2236147 A1 CA 2236147A1
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
- B32B2307/736—Shrinkable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2327/00—Polyvinylhalogenides
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
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Abstract
A composition comprising a mixture of (1) a vinylidene chloride polymer formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one ethylenically unsaturated monomer copolymerizable therewith and (2) an amount of an aliphatic ester compound sufficient to minimize color degradation (formation of color bodies) of the vinylidene chloride polymer during and after irradiation of the composition is used to prepare a heat-shrinkable multilayer film. The composition may also contain an amount of a color stable violet or blue dye sufficient to mask color bodies formed during and after irradiation of the composition.
Description
CA 02236l47 l998-04-28 VINYLIDENE CHLORIDE POLYMER COMPOSITIONS
AND IRRADIATED ARTICLES PREPARED THEREFROM
This ~ rentiGn relates to v;.."l 1~ nEcl~l~I ide poly.-._r (PVDC) cG,.-I~osilions and filnn s 5 cGr"~,risi--y said cG..~I~os;liolls. More particularly, this i"~_utiGn relates to v;.,~rl;dene chl~ ;de cc,-~po~ s~;GnS having ;~prvv_d r Si_ ~ce to color dey~._ddtiGI~ induced by i.,a.l;dlivn.
i 1"_~ -n of PVDC films often i"",lu.~_s film prope~lie~ such as puncture ,. ~ ce,tensile al,m,yll, and tougl.ne-~s. I Ic,. _-~., under most circu."st~nces, ;-, di..liGn results in suLaldnlial d;_~lDrdtiGn, such as ye--~ y~ of the films.
Attempts have been made in the past to .~ PVDC films against color dey,--d.-tionby adding epvAi ~ d soyLean oil (ESO) or el~o~ - d linseed oil (ELO) to v;."ri I e chlc: ide copvly.--er cG..~positions. See, for e,~.--. . '~ U.S. Patent 4,714,638 and Canadian Patent 982823. 1 IG. _ver, although films conla:. ~9 ESO or ELO P!~ ~ had lower initial color (color of the film coming out of the extruder) co",i~ared to control films (no ESO or ELO
~IF ~ )~ the color of such films i.,~ ased suL.ala.J~ - 'y after i- ,c,d;~liGn, while that of the control fllms did not.
It would be desi _ ' to provide ~ s which effu~ Iy r s color dey,..d~lion of PVDC films during and after i., - n.
In a first aspect, this ;.../_.~I;GI) is a cGmposilion cGI--~Jliai"y a mixture of (1) a v;~ êchlarivepOly r (PVDC) formed from a ...onv..-êr mixture ~ I-e-~ the major co~poné~l is vi--~rl ~ene chls idë and the le., - ,dër is at least one ",onoetl"~leni--~y unsaturated ",onGr"el copoly...e.i -'e Ihe~ ;tl-, and (2) an amount of an rli, hali- ester compound sufficient to , ~ color deg~ddalion (tur",c.lion of color bodies) of the PVDC
during and after i~ d;utiGn of the co"~l~o~i'ion.
In a second aspect, this i".r- .~I;Gn iS a co",posilic~n co.,.~,. s ~9 a mixture of (1) a v;..~ .e c.hlc l ive poly---2r (PVDC) formed from a ,..onG",er mixture ~ he~ the major cor,.poner~t is v;..~li I ~e chl idë and the ~e- - .der is at least one ~.v"Getl"~le.~ --"y unsaturated I~OI-GU-_l copoly-"e. Ihe~. itl" an amount of an f ~i, ht-lic ester compound sufficient to ! ' . - color cle ~- avution (ru, ",ation of color bodies) of the PVDC, and an 30 amount of a color stable violet or blue dye sufficient to mask color bodies formed, during and ~ after i"~di~livn of the c~mpG~i';on.
In a third aspect, this i"~rel,lion is a hcat 5h~ 's m~r''' ~_r film cGr"l" ~9 a layer of a v;..~i;Jel)e cl-lG-;de pOly...el formed from a ,,,onor..- I mixture ~ he~ui.~ the major cG~pone~l is v;..~rl; I .e cl,lcl;de and the r~ ~ .der is at least one ~-~onGeth;len~ y unsaturated ..~onGmer copoly---_. ~ Ie Ihe~. ;ll-, and CG-~ an amount of an ~ h~tic ester compound sufficient to ...;. color de~-ada~ - (r~ alion of color bodies) of the PVDC, and/or an amount of a color stable violet or blue dye sufficient to mask color bodies formed, during and after i..ld ~ of the ccr.po~ilion.
The -'i, h,,lir; ester comrounds have been found to .., ~ ~ color ~ey-dd~l;on in5 PVDC films during and after i~dialiGn of the PVDC films while i...pa-li..y the dcsi.a'-le effects as a p. ~ csssiny aid durinçl film extrusion.
Vi..~ .e cl-loride poly..._r s- '-le for use in the p~Ls~ _..li.>n are well-known in the art. See, for . . Ie, U.S. Patents 3,642,743; and 3,879,359 As used herein, the term "vir.yl;~ene cl-lal;de poly..,_l enco~--passeshGmopoly~ of v;.-,ri ~ e chlG~id~:, and also 10 copoly.--_.s, te.~oly.--el~. thereof, ~ he.~:.. the major co---pG~.~nl is v;..~' 'in~e chlG~ide and the .c,, ,der is one or more elh~rh..ic -"y unsaturated ~onc~ elcopG~ le with the vlu~l; lene chl_ ide r.-onor..er.
~ cnoctl-~leni~~"y unsaturated ~OnG..._.~ e~ '-le for use in the present i..~..lion are those which can be poly...eri~d with the v;..~ e cl.lvride .nCtnG7i.e.:t, to form the 15 vi..~rlld( rOc cl~lcride poly,,,_.s. E~ s of ~-~onocU~"leni--"y unsaturated ~-~OnGn~e~s~ include alkyl a_~yl.-tes, alkyl ~,._ll.a~,.yl '~ o acrylicacid, ~..cU.ac~yl c acid, ~~n ~ acid, vinyl cl~l~r;de, ylol le and ...cU.a_. ylGnib ile The ~..GnG_lh~rlc~;c 3~y unsaturated ...~.,,ou,cr~ are desi.~ ly sel~_~ I from alkyl ac.;l ~ and alkyl .nctl.a~ fht~.s having frorn 1 to 8 carbon atoms per alkyl group. The alkyl ~ ;lat~s and alkyl r.._lha~ l - p.~f..~bly have from 1 to 4 20 carbon atoms per alkyl group. The alkyl &C.- ylut~s and alkyl ,,,cU.acl ylut~~ are most p,~f.l~bly Srl?C' i from ~ctl.~la~ lales, clh~lacl~flut~~~ and methyl ,,,ctl-a.,-yl,.lcs.
Most pr~fcncd v;."~l ~~ ~e chl~ride poly...el, include poly,.,ers formed from 91 to 96 weight percent vinylidene chlc ide and from 4 to 9 weight percent of methyl acl yl..le.
The v;nyl l .e chlaride poly---er~ are yell,e. "y formed through an err~lcion or2s suspel-siol- poly...eli~aliol. p. cess. FYe-~~r' ~ of such ploCe~5CS are des~-iL,ed in U.S.
Patents 2,558,728; 3,007,903; 3,642,743; and 3,879,359; and the ...~tl.ods d_s_-iLed by R. A.
~'es_" ~y~ in ~olw;.-~li lone Chloride, Gordon snd E~reach Sc lce P~ hels, New York, 1977, Chapter 3. Typically, the ~..G.-G...~ .Jte. - are emulsified or suspended in an ~ ,_eous phase. The acl~leous phase CG~ S a surface active agent ca~ ~ ' of emulsifying or 30 suspel ~y the ~.on~s..._.ic ~ale~ ~ in the Aqueo-ls phase. The poly.--eli~tion of the ._.iC ~at~. '- is usually carried out with heating and ~-J;1-';ol- in the pres~,nc~ of a iGI) i..iti.~t~r.
After poly...~ .tion is c~ ' !tl, the res~ ~l poly..._. ic ~.3te. idl iS vacuum :.l. i~,ped.
Thel~tlel, the slurry is cooled down, ~ C7 1~ ~ and d~ cl, and the resin is cr,ll _: I and further dried.
The ~'i, lt~4tic ester compounds s~ ~ Ie for use in the p._sel.l i-..J_nliGn for ,. ~ ~ ~g 5 color dey~d~lion in i~a-li~led PVDC films include linear and L~ ched ~ atic ester co~ro~nds, poly..._.;c ~ h ~ esters and mixtures thereof, which are esse.l ~'y free of epoxy or a~O---~l;c flJ..-,liol -' ~y and have a ~--~le ~ weight of from 300 to 8000. ~h.-~d -'i, h.Jtic ester compo~ ~nds include acetyl tributyl citrate, ac~tyl ~ ...onGylyc6~ ides~ l a of adipic, azelaic, s~l>~ic and glutaric acids; polycJt~.:. of yl~/cel~ol and pe.,laelyll,,itul and 10 poly..._.ic ~ 5, ~ ~-t ;, 6eb~ ~ s and glutarates. More ,br~h.,cd r'i~ hdtiC ester compo~mds are acetyl tributyl citrate, ac~l;lut~ d ...onoglyce. id~s, dibutyl sF bac~4t~ and poly".-:-ic ~ 'i, l ~ The most p~_h.-e d rli, h.t;c ester compounds are &cet~lat~J
".onoylyc.e-ides. These 'i, h--lic ester colnro~nds are well known in the art and are CGI~ y av - 1~
Whiletheamountofa'i~ h~licestercompoundmostadva.-~ ~eouslye, . IAy_d depends on a variety of factors, such as the specitic ...on~...el~, in general, the -1iU halic ester c~ l -ou-,d is used in an amount of from 0.2 to 15 weight percent",. .:r~, "bly from 0.5 to 10 weight percent and most pr~h.~.bly from 1 to 4 weight percent, based on the weight of the PVDC.
Violet or blue dyes su ~ I for use in the present i--~e.~ti~;n are the organic dyestutfs which are s~.rt ~ !ntly colorstableto ~ ;ll.slal1dtheacidic ~r~cess;,.g env;.~.,,...:,,lof PVDC
extrusion at about 160~C and include the 1-hydroxy 1 a. yl L.- ~Oa.~thla~lU' ~ones which are color stable. The 1 h"J~ r q L.~ ~Oa-~lh~Aq-~ ~Gnes are known and are de-~- .iLed, for ~ ' in U.S. Patent 2,419,405. The most ~ fe. ~ed violet l~ _ ~-e.~l is CG....~.e. C; ~~y known as 25 C.l. Solvent Violet 13, av ~- - -? as r~ r~' TM Violet B, a product of Bayer AG and ~ 5_u.~ zl by the formula:
Il 7 ~ CH3 O OH
The amount of violet or blue dye used must be sufficient to mask at least a portion of color bodies d ~-:loped in the vir.yl l~ne cl-lolide pGly...cr cGI;,pcS -n during i.,a.Jit.lion of the c~ po~ilion. G~ae~ 'ly, the violet or blue dye can be present in an amount of frorn 0.0005 to 0.05 weight percent, pr~f~.~bly, from 0.0007 to 0.01 weight percent and most pr~f~rably, from 0.001 to 0.005 weight percent, based on the weight of the PYDC.
The vi,-~fil(l ~e chlclide poly..._r ccm~si~ ~ n of the present i...~.ltion may also 5 contain various P ~ 3 to impart ~l e s i _ l e pl ope~ lies such as, for e~ F l e heat ~
light ~ s, proccssi,-g aids, and luL-i-,-a.-la, but s~ - 'ly ~xrlu ~g the aro...dtic or epo,~idi-~d prc,cessiD,g aids, such as dioctyl phtl ~' '~ or ~p~ d soyL,ean oil, which may not be effective to " ! F ' the color de~ ali~ n (~-,r...alion of color bodies) of the PVDC.
Each of these ad.lili~res is known and several types of each are CG~ .el ''- -~y ~.;. '- '~le 10 The v;.. ~ ene .,I.lc iJa poly.. -èr CG~ of the present i--~.. lion can be prè~,ar.d by adding the ~ ht-lic ester co~nro~ d and/or violet or blue dye to the ...onGr..el mix before or during ,~ol~,.n~ alion or to the dry v;..~ e cl.h ide poly,,,er by dry b! .~ f~ bly, the co.--~ Q s;t :n is l,repa~ ed by adding the r'i~h~lic ester comro~md ancVor violet or blue dye to the ...Gncir.._r mix to ensure a more uniform distribution of the -'i, h~-lic ester cG...pou.,d 5 and/or violet or blue dye in the resulting poly.
The violet or blue dye can also be added in the form of a COncE.nll dle by melt ~ l , .9 the conce~lt-~le with the v;..~l;dc..e cl laride c=s~ o~ lion using typical melt pr.,ccssius~
ecl~ t such as, for _A el rle two-roll comrounding mills, [I,~.bel.del mixers, Banbury mixers, single screw extruders, twin screw extruders and the like. The concel.l.ale can be 20 pl_,~ d by mixing the violet or blue dye with a carrier resin which, pr~h.~bly, is vi"~ 'enL
chlc id~ poly..,~r. '' ll,Gcls for ~.~"a. ;,.9 the co..ce.~t.dte are well-known in the art. Typically, tne carrier resin and the violet or blue dye are kl ,docl in the melt using con~_..lional melt pn~cess;"~ I_ hn ~. ~es, using typical melt plocessi,,~ ec~ al such as those ~e--lion~d previously.
If the C~ pOS:~-Gr) iS prepar~d by dry hl . ~S~. the c~."p-,~,el,ls. should be mixed to form a visually uniform a~lmiYh~e. Sl ' 'e dry tl9~ eq~, :,,e.,l includes tumble Ll~ ~de~:~7 Hobart mixers, Welex mixers, and I l~nschel high ;I n r ity mixers.
The V;"~fi I ne cl Icride poly.-,er c~ o,;lion of the present i,~e.,lion can be coextruded into a multilayer tilm with co"~ tional coextrusion ,--acl ~es. I leat 5hli~ le 30 multilayer films _. IDY~I in pach~ meats, for ~~ ~FIe, can be produced by coextruding the n~ layers into a primary tube, and then bi ~ "y slr~t~ 9 the tube by known t~chni, les, such as that desc,iL,ed in U.S. Patent 3,555,601, to form a hcat sh,i"l '-le film. ~-The h- ~ 'ly sl~etChC:J film is then i" ' I to a dosage level of up to about 5 ".a~, ~ds by passi"g it, for a m, ', through an 6ICCI~On beam i" di--lion unit or Co-60 gamma, ~c' - I
35 source. The multilayer film can have one or more layers CG~I~p~ 9 the vi,,~lidene chla idê
W O 97/17399 PCT~US96/17733 poly..._r cG.,-I~osi~;on of the present i..~re..lion and one or more layers CG---p- i ,i.-g a poly~l ' "
such as poly~ e. The vi.-ji ~ ~e chlcrid~ poly.--er layer can be s_.,d~ ;cl)ed bet~ _ ~ two or more layers of a poly~lufi... The m~ ly~r film can also have a glue layer d: 3posetl ~ah _en a vi.."l;tlene chl~ride poly...er layer and an aJiac~.-l polyel t . Iayer. The glue layer 5 l~,~ ~'ly cGmr;- i_~s ell.~rlene vinyl acetate or any pOly.~èl or cGpoly...~r having good a-Jl.esiv.
.~ pl Gpe~ t;_~.
The PVDC cv..~l-vs:livns of the present i~ tiOI) can also be ' ~ inatt ~1 into articles using cor,/~l-liv--al tati.icalion b chni~ues such as i--je: Qn ,-~ - ,9, extrusion r-~l ~- ~g, --' .de.i"~, lhe~ Ofv~ ~ ,9, and 1...- ~ ,alivn tecl,ni . ~s Articles formed ll~e~:f v-" include 10 blown and cast ~vncl yer and m~ . films, foam sheets, tubes, pipes, fibers and the like.
F 1~ 5 of such articles include flexible and rigid co~ ~ ~e~ ., used for the p,~sc. ~atiGI) of food, drink, .. - ~- - .e and other perish- '~s Eab,icJt.l articles from the p.~se.,l i~el.lion may be i-, didtëd for purposes of - ~-- -n, i",~,lv,/;..g tou~l,ness, i",provi..y solvent r~ ce and the like. I~aJ;alion with 15 about 1 to 20 Mrad is a~ . I shed, for ex_. . ~~ by passi..S~ the articles through an ele_l.on beam i" ~- i~ n unit or Co-60 i. IaJialion source. b .aJi~lion may be done during or after fab~ icalion of the article.
The tOIIG~ :..9 ~ ~,rld..~~ e,~ le s are given to illustrate the i..l/_.niOn and should not be construed to limit its scope. Unless vU~el . ;ae i- - ~ d, all parts and pe. ~;ent._gea are by 20 weight.
EXAMPLES
In the tcll_. -;.. 9 e~ s color meas~"e",~ , are taken using the f~ . i... g procedure.
Color Measu-~r._..l Color measu-~l.-e.. ls were made using a Hunter Lab Ultra Lab C~lcri.. _t.. The Gpeldti~.g CG. Qns were Illuminant D65, srec~ inel-lde~ UV off, 10~ obs_. ~rer, in a ~eSlt~.ldnce mode against â white tile. Measu,.:,,,enls were made using the CIE Lab color scale. Four measu.~.--_.-l:, were made of each sample and then ~ .aged. Of g.~at.~l interest was the change in "b" value where i,-c-- ~- "J "b" cG,,e_"vnded to a visual i"- ~~ase 30 in yall . .,ess. The "Db" values repo.led were the Jitferel~ce in y~ll_. ..ess bei _~n the i~-aJialèd sample and the ~ adiJt~v control. A positive number cGr,esponded to i". ,eased yell _ . . ,ass. It was obsel ~red that the POIY~JI vp"lene skin accounted for a "Db" of appr~ t~ Iy 4 as a result ot the i.-a~iJtiv.,. Theretv~e, the "Db" values le~.~OIled for m~ el films in Table I are all dec,èased by 4 units.
WO 97/17399 PCTnUS96/17733 r- -m~le 1 A multilayer film sample (Sample 1) c~r-.posed of outer layers of poly~ pylene and a core layer of 92.25 weight percent v;,"~l;dene chlcride/7.75 weight percent methyl acrylate, which co- - - .ed 4.0 weight percent dibutyl sehn~ale and 0.2 weight percent epoxidized h ~ ean oil, was produced by con~enlional coextrusion lcchn ~ le Prior to i- ~ - n, the film was anl - -'e ~1 at 120~F for 3 hours to ensure full c. ~1~ - of the v;."~ ,e ch~cride cGpoly.-._l. The coe~l.ud.d film was ir.adiated with 4 Mrad Co-60 gamma r J;.,tiGn at .
t~...p_. alure. Color measu- ~---t ,~ts were taken on the coextruded film prior to ;. ~ _d;~.lion (u,, ~ Jial~d) and i-n---o Iy after i.. di~tioll (i.. .~lided)accOld ~ to the color 10 measurement procedure de5_- iLed previously. The results of this test, in terms of the change in yellow color (Db), is shown in Table 1.
F- ~ 2 and 3 Two multilayer film - l~ ' e s (Sa.- . ' e!s 2 and 3) CC~ pG5~: d of outer layers of poly~,r~.~lene and a core layer of 92.25 weight percent v;.-;lid~ae cl~lalid~7.75 weight percent 15 methyi &CI jlat~, were p-ep~r~d and tested (;..~ I and color ~..eaa~ l taken) as in F- . ' 1, except that 4 percent acetyl tributyl citrate (ATBC) is added in Sample 2 and 4 percent r~ , EPZ, an ac~l;lat~ "onG~lyce.iJ2 c~,"-..~ y available frorn Cl,or i--l, was added in Sample 3, instead of the 4 ,uercenl dibutyl s- ~- ~ Color measu.t ,.._al,j of the ;-~Jiale:d films were taken as in - . Ie 1 and the results are shown in Table 1.
C~ m"al ali~e r- - l e A
A rn~ ~_. film sample (Sample A) cG,--prisi--y a 92.25 vi-,jl; 1 ~e cl.larid~J7.75 methyl ~_. ylat~ copoly.--el core layer c~ 1.2 weight percent ep~Y~ soyL ean oil was p~ ,a.~d and tested ~s in F - . I 1. The results are shown in Table 1.
CGm~ale~ re F ,;' les B and C
. film 8 1, ' ~1 (B~ 5 B and C) CGm~ a 92.25 vinylidene chlcriden.75 methyl a.,, ~ t~ copoly.,.er core layer were pr~paoed and tested as in Cc,l,,l,a,ali~e Example A
except that Sr - F I e s B and C c~. .e-cl 2.2 weight percent and 4.2 weight percent epoxi~ d soyLean oil". spe. Ii~ely. The results are shown in Table 1.
30 Co~ <~ e ExamPle D
The multilayer film of this co,..~,a. Jti~e eA. ~ ~'e was the same as that of Cor..parc.~ e F ~1 e s B snd C except that it CGi~ e ~ percent epox;~ d linseed oil and 0.2%
epo~ d so"Lea.. oil. The multilayer film is tested as in CO,-.pal~liv_ Example B. The results of the tests are shown in Table 1.
Tsble 1 - Color of PVDC Film 1~ . .. Ji~t~l vs-Samples U...... .~.c' i'~d ~b 2.7 J 2 2.7 3 3.3 A 6.1 B 6.2 C 4.5 D 5.0 Example 4 Water, suspen " .9 agent ('-: .ocelTM K4M, a product of The Dow Ci. i--' CGI..P~-..~) and buffer at a ratio of appro~ t~ Iy 1.00/.0009/0.0093 were cl;a. ged into a reactor. To the mixture in the reactor was added an organic phase con~i~li-,g of methyl z~ luh" v;..;l;~ e ne chl: idc, t-butyl per-2-LIl-~ll.exenG~It, and violet ~i~ e ~l at a ratio of 7.72/92.28/0.369/0.0005.
The ratio of water phase to organic phase was 1.25/1.00 The violet I :_ al was an a.nh.~ .Gne dyestuff, f'~ l TM Violet B (C.l. Solvent Violet 13), a product of Bayer AG and des~.iLed in U.S. Patent 2,419,405.
The ~ea~.l;Gn vessel was sealed and placed in a water bath at 25~C and mixing isbegun. The l~...pt:.~.lure was then raised to a m~Yim~rn of 84~C over the course of 630 minutestoallow poly...~ lion. The res~ poly..._~ slurrywasthen cooled, d_ ~'~ t d and dried at 80~C to remove residual water and ...ono--.e~a. The product was then flash molded at a ILn.pe.ut-lre of 165~C for 1 minute at 1000 psi fcll . _d by 2 minutes at 20,000 psi.
The yell . ..ess of the flash, ~ as d~t~. ~ed accG--' ~~ to ASTM method D 1925-70 is shown in Table ll.
CG....,c-.uthl_ ExamPle E
A poly.--el sample was p.~:pa.~d in the same manner as shown in Example 4 except the 20 '- o'~ Violet B dye is omitted. The sample was flash molded and tested in the manner shown in F - - . Ie 4. The yell . ..ess results are shown in Table ll.
C~ z.c.thre EA~ R s F and G
Roly..._~ s~.... R s were pr~pa~d in the same manner as shown in Example 4 except the '' - ~JI Violet B dye was s~hstituted with an equal amount of '-~ cl Violet 3R
25 (Cc,-..p ~ re Example F) or '' ~l~ Blue RR (CG~ JZ~ Example G) dyes. ~' r~l Violet 3R and '' ,~el~ Blue RR were - ~'es of dyes which are not sur~icie..lly color stable to ~ itl._ ~d the acidic processi,.~~ eri.~i.vl....e..t of PVDC extrusion at about 160~C. ~' -rvl VTolet 3R, a product of Bayer AG, was cG~ ,ially known as C. I. Solvent Violet 36 and ~_p~ ~sehled by the formula:
o H~N ~ CH3 H3C ~ - N~ O
H
roleY Blue RR, also a product of Bayer Ag, is cG,..r...,lcla"y known as C. I. Solvent Blue 97 and r~pr~sal.t~ d by the formula:
H3C ~ CH2-CH3 ~ , H o The s~ - Fles were flash molded and tested in the ..._n..- I shown in F -, le 4. The 10 yt!l~c~ ess results are shown in Table ll.
W O 97/17399 PCTrUS96/17733 Table ll - Color of PVDC '~ol ~q Sample In F le4 5.3 CG.. pa.athr~ Example 12.8 E
Co.. p.. dth~e F . Ie 43.9 F
C~ pa~ali~ Example 12.2 G
ExamPle 5 A m~ . film sample cGu.posed of outer layers of ~.oly~,.c.p~ .. e and a core layer of 92.25 weight pel ce..l v;- .~d I ~e c.hl ~ iden.75 weight percent rnethyl ac- yl~le, which con~ .ed 1.4% r~ EPZ p'~ ~;c~ r, an P~ ~tylat~d ...onoylyc6lidc cG------e.~ '~y av_ ' 'g form -- ~ Cl.e...' ~1, was produced by cGn~/e.-lional coextrusion lccl---i, le. Prior to i. . n, the film was ~n,~ --' I at 120~F for 3 hours to ensure full ~,.y~ ' - of the v;..;; ~le ~e 10 chlclide copoly..-ar. The coextruded film was ;--a~ d with 4 Mrad Co-60 gamma ~.lidtivn at ~ ' .l tc...~e~al.lre. The PVDC film layer was then se"z.~t~d from the poly~,rop~rlene layers. Color measu.~.--e~ were takên on the PVDC film prior to i-- d;..li~.. (u- .~di~t~d), and ;.. e~ Iy aner i.~-did ion (i~ diat~d) accGn .g to the color measurement p.~ceJu.e.
The results of this test, inclu .g the change in yellow color (Db), are shown in Table lll.
15 ExamPle 6 2000 grams of the v;..~l ~ ~e chlclide copoly.--er desc.iLed in F---m~ ' 5 was added to a Prodex high~ t~nsil~ mixer. Then 1.00 gram ''--rcl B dye was added with mixing ove app~"d.. ~ 'y 1 1/2 minutes, res~ .g in a uniform color cGrice-nt-at~. This color concê~ è
was then mixed in â tumble blender with an addilional quantity of the vir.yl;lene chlG~ ide 20 copoly..._l des_. iLed in Example 5 at a ratio of 2/98. A m~ yer film sample co...posed of outer layers of poly~,.opylcne and a core layer of the v;.-"l; ' ~e chlclide copolymer color cGnc~lt~al~ and v;..;l; I ne cl~loride copol~,...er was produced by co---l~.-lional coextrusion t~cl...i, le The resulting film was ann--'ed, i.-_ ~' d and color tested in the same manner as ~" in F~ 1 5. The results of color testing are shown in Table lll.
W O 97/17399 PCTnJS96/17733 CG.--.,a.ali~e F ~ . le H
A mul'" ~r film sample c=~..~posed of outer layers of poly"r~ pylene and a core layer of 92.25 weight ~ ,nL v;. .;li ~ ae cl Icricl~17.75 weight percent methyl a~ tc, which cor, ! .ed 1.6% ~ poxi~ d so~ Lean oil, was produced by cG~ enlional coextrusion tech. i . Ie The 5 res~ ' Iy film was a-m ~ -'~d, ;- ~adialed and color tested in the same manner as in Example 5.
The results of color testing are shown in Table lll.
Table lll Sa.. ~s U~ ~adi~t~,d ~ i Color Chanqe (~b) 2.4 6.1 3.7 6 1.7 5.9 4.2 H 2.3 7.3 5.0 ,
AND IRRADIATED ARTICLES PREPARED THEREFROM
This ~ rentiGn relates to v;.."l 1~ nEcl~l~I ide poly.-._r (PVDC) cG,.-I~osilions and filnn s 5 cGr"~,risi--y said cG..~I~os;liolls. More particularly, this i"~_utiGn relates to v;.,~rl;dene chl~ ;de cc,-~po~ s~;GnS having ;~prvv_d r Si_ ~ce to color dey~._ddtiGI~ induced by i.,a.l;dlivn.
i 1"_~ -n of PVDC films often i"",lu.~_s film prope~lie~ such as puncture ,. ~ ce,tensile al,m,yll, and tougl.ne-~s. I Ic,. _-~., under most circu."st~nces, ;-, di..liGn results in suLaldnlial d;_~lDrdtiGn, such as ye--~ y~ of the films.
Attempts have been made in the past to .~ PVDC films against color dey,--d.-tionby adding epvAi ~ d soyLean oil (ESO) or el~o~ - d linseed oil (ELO) to v;."ri I e chlc: ide copvly.--er cG..~positions. See, for e,~.--. . '~ U.S. Patent 4,714,638 and Canadian Patent 982823. 1 IG. _ver, although films conla:. ~9 ESO or ELO P!~ ~ had lower initial color (color of the film coming out of the extruder) co",i~ared to control films (no ESO or ELO
~IF ~ )~ the color of such films i.,~ ased suL.ala.J~ - 'y after i- ,c,d;~liGn, while that of the control fllms did not.
It would be desi _ ' to provide ~ s which effu~ Iy r s color dey,..d~lion of PVDC films during and after i., - n.
In a first aspect, this ;.../_.~I;GI) is a cGmposilion cGI--~Jliai"y a mixture of (1) a v;~ êchlarivepOly r (PVDC) formed from a ...onv..-êr mixture ~ I-e-~ the major co~poné~l is vi--~rl ~ene chls idë and the le., - ,dër is at least one ",onoetl"~leni--~y unsaturated ",onGr"el copoly...e.i -'e Ihe~ ;tl-, and (2) an amount of an rli, hali- ester compound sufficient to , ~ color deg~ddalion (tur",c.lion of color bodies) of the PVDC
during and after i~ d;utiGn of the co"~l~o~i'ion.
In a second aspect, this i".r- .~I;Gn iS a co",posilic~n co.,.~,. s ~9 a mixture of (1) a v;..~ .e c.hlc l ive poly---2r (PVDC) formed from a ,..onG",er mixture ~ he~ the major cor,.poner~t is v;..~li I ~e chl idë and the ~e- - .der is at least one ~.v"Getl"~le.~ --"y unsaturated I~OI-GU-_l copoly-"e. Ihe~. itl" an amount of an f ~i, ht-lic ester compound sufficient to ! ' . - color cle ~- avution (ru, ",ation of color bodies) of the PVDC, and an 30 amount of a color stable violet or blue dye sufficient to mask color bodies formed, during and ~ after i"~di~livn of the c~mpG~i';on.
In a third aspect, this i"~rel,lion is a hcat 5h~ 's m~r''' ~_r film cGr"l" ~9 a layer of a v;..~i;Jel)e cl-lG-;de pOly...el formed from a ,,,onor..- I mixture ~ he~ui.~ the major cG~pone~l is v;..~rl; I .e cl,lcl;de and the r~ ~ .der is at least one ~-~onGeth;len~ y unsaturated ..~onGmer copoly---_. ~ Ie Ihe~. ;ll-, and CG-~ an amount of an ~ h~tic ester compound sufficient to ...;. color de~-ada~ - (r~ alion of color bodies) of the PVDC, and/or an amount of a color stable violet or blue dye sufficient to mask color bodies formed, during and after i..ld ~ of the ccr.po~ilion.
The -'i, h,,lir; ester comrounds have been found to .., ~ ~ color ~ey-dd~l;on in5 PVDC films during and after i~dialiGn of the PVDC films while i...pa-li..y the dcsi.a'-le effects as a p. ~ csssiny aid durinçl film extrusion.
Vi..~ .e cl-loride poly..._r s- '-le for use in the p~Ls~ _..li.>n are well-known in the art. See, for . . Ie, U.S. Patents 3,642,743; and 3,879,359 As used herein, the term "vir.yl;~ene cl-lal;de poly..,_l enco~--passeshGmopoly~ of v;.-,ri ~ e chlG~id~:, and also 10 copoly.--_.s, te.~oly.--el~. thereof, ~ he.~:.. the major co---pG~.~nl is v;..~' 'in~e chlG~ide and the .c,, ,der is one or more elh~rh..ic -"y unsaturated ~onc~ elcopG~ le with the vlu~l; lene chl_ ide r.-onor..er.
~ cnoctl-~leni~~"y unsaturated ~OnG..._.~ e~ '-le for use in the present i..~..lion are those which can be poly...eri~d with the v;..~ e cl.lvride .nCtnG7i.e.:t, to form the 15 vi..~rlld( rOc cl~lcride poly,,,_.s. E~ s of ~-~onocU~"leni--"y unsaturated ~-~OnGn~e~s~ include alkyl a_~yl.-tes, alkyl ~,._ll.a~,.yl '~ o acrylicacid, ~..cU.ac~yl c acid, ~~n ~ acid, vinyl cl~l~r;de, ylol le and ...cU.a_. ylGnib ile The ~..GnG_lh~rlc~;c 3~y unsaturated ...~.,,ou,cr~ are desi.~ ly sel~_~ I from alkyl ac.;l ~ and alkyl .nctl.a~ fht~.s having frorn 1 to 8 carbon atoms per alkyl group. The alkyl ~ ;lat~s and alkyl r.._lha~ l - p.~f..~bly have from 1 to 4 20 carbon atoms per alkyl group. The alkyl &C.- ylut~s and alkyl ,,,cU.acl ylut~~ are most p,~f.l~bly Srl?C' i from ~ctl.~la~ lales, clh~lacl~flut~~~ and methyl ,,,ctl-a.,-yl,.lcs.
Most pr~fcncd v;."~l ~~ ~e chl~ride poly...el, include poly,.,ers formed from 91 to 96 weight percent vinylidene chlc ide and from 4 to 9 weight percent of methyl acl yl..le.
The v;nyl l .e chlaride poly---er~ are yell,e. "y formed through an err~lcion or2s suspel-siol- poly...eli~aliol. p. cess. FYe-~~r' ~ of such ploCe~5CS are des~-iL,ed in U.S.
Patents 2,558,728; 3,007,903; 3,642,743; and 3,879,359; and the ...~tl.ods d_s_-iLed by R. A.
~'es_" ~y~ in ~olw;.-~li lone Chloride, Gordon snd E~reach Sc lce P~ hels, New York, 1977, Chapter 3. Typically, the ~..G.-G...~ .Jte. - are emulsified or suspended in an ~ ,_eous phase. The acl~leous phase CG~ S a surface active agent ca~ ~ ' of emulsifying or 30 suspel ~y the ~.on~s..._.ic ~ale~ ~ in the Aqueo-ls phase. The poly.--eli~tion of the ._.iC ~at~. '- is usually carried out with heating and ~-J;1-';ol- in the pres~,nc~ of a iGI) i..iti.~t~r.
After poly...~ .tion is c~ ' !tl, the res~ ~l poly..._. ic ~.3te. idl iS vacuum :.l. i~,ped.
Thel~tlel, the slurry is cooled down, ~ C7 1~ ~ and d~ cl, and the resin is cr,ll _: I and further dried.
The ~'i, lt~4tic ester compounds s~ ~ Ie for use in the p._sel.l i-..J_nliGn for ,. ~ ~ ~g 5 color dey~d~lion in i~a-li~led PVDC films include linear and L~ ched ~ atic ester co~ro~nds, poly..._.;c ~ h ~ esters and mixtures thereof, which are esse.l ~'y free of epoxy or a~O---~l;c flJ..-,liol -' ~y and have a ~--~le ~ weight of from 300 to 8000. ~h.-~d -'i, h.Jtic ester compo~ ~nds include acetyl tributyl citrate, ac~tyl ~ ...onGylyc6~ ides~ l a of adipic, azelaic, s~l>~ic and glutaric acids; polycJt~.:. of yl~/cel~ol and pe.,laelyll,,itul and 10 poly..._.ic ~ 5, ~ ~-t ;, 6eb~ ~ s and glutarates. More ,br~h.,cd r'i~ hdtiC ester compo~mds are acetyl tributyl citrate, ac~l;lut~ d ...onoglyce. id~s, dibutyl sF bac~4t~ and poly".-:-ic ~ 'i, l ~ The most p~_h.-e d rli, h.t;c ester compounds are &cet~lat~J
".onoylyc.e-ides. These 'i, h--lic ester colnro~nds are well known in the art and are CGI~ y av - 1~
Whiletheamountofa'i~ h~licestercompoundmostadva.-~ ~eouslye, . IAy_d depends on a variety of factors, such as the specitic ...on~...el~, in general, the -1iU halic ester c~ l -ou-,d is used in an amount of from 0.2 to 15 weight percent",. .:r~, "bly from 0.5 to 10 weight percent and most pr~h.~.bly from 1 to 4 weight percent, based on the weight of the PVDC.
Violet or blue dyes su ~ I for use in the present i--~e.~ti~;n are the organic dyestutfs which are s~.rt ~ !ntly colorstableto ~ ;ll.slal1dtheacidic ~r~cess;,.g env;.~.,,...:,,lof PVDC
extrusion at about 160~C and include the 1-hydroxy 1 a. yl L.- ~Oa.~thla~lU' ~ones which are color stable. The 1 h"J~ r q L.~ ~Oa-~lh~Aq-~ ~Gnes are known and are de-~- .iLed, for ~ ' in U.S. Patent 2,419,405. The most ~ fe. ~ed violet l~ _ ~-e.~l is CG....~.e. C; ~~y known as 25 C.l. Solvent Violet 13, av ~- - -? as r~ r~' TM Violet B, a product of Bayer AG and ~ 5_u.~ zl by the formula:
Il 7 ~ CH3 O OH
The amount of violet or blue dye used must be sufficient to mask at least a portion of color bodies d ~-:loped in the vir.yl l~ne cl-lolide pGly...cr cGI;,pcS -n during i.,a.Jit.lion of the c~ po~ilion. G~ae~ 'ly, the violet or blue dye can be present in an amount of frorn 0.0005 to 0.05 weight percent, pr~f~.~bly, from 0.0007 to 0.01 weight percent and most pr~f~rably, from 0.001 to 0.005 weight percent, based on the weight of the PYDC.
The vi,-~fil(l ~e chlclide poly..._r ccm~si~ ~ n of the present i...~.ltion may also 5 contain various P ~ 3 to impart ~l e s i _ l e pl ope~ lies such as, for e~ F l e heat ~
light ~ s, proccssi,-g aids, and luL-i-,-a.-la, but s~ - 'ly ~xrlu ~g the aro...dtic or epo,~idi-~d prc,cessiD,g aids, such as dioctyl phtl ~' '~ or ~p~ d soyL,ean oil, which may not be effective to " ! F ' the color de~ ali~ n (~-,r...alion of color bodies) of the PVDC.
Each of these ad.lili~res is known and several types of each are CG~ .el ''- -~y ~.;. '- '~le 10 The v;.. ~ ene .,I.lc iJa poly.. -èr CG~ of the present i--~.. lion can be prè~,ar.d by adding the ~ ht-lic ester co~nro~ d and/or violet or blue dye to the ...onGr..el mix before or during ,~ol~,.n~ alion or to the dry v;..~ e cl.h ide poly,,,er by dry b! .~ f~ bly, the co.--~ Q s;t :n is l,repa~ ed by adding the r'i~h~lic ester comro~md ancVor violet or blue dye to the ...Gncir.._r mix to ensure a more uniform distribution of the -'i, h~-lic ester cG...pou.,d 5 and/or violet or blue dye in the resulting poly.
The violet or blue dye can also be added in the form of a COncE.nll dle by melt ~ l , .9 the conce~lt-~le with the v;..~l;dc..e cl laride c=s~ o~ lion using typical melt pr.,ccssius~
ecl~ t such as, for _A el rle two-roll comrounding mills, [I,~.bel.del mixers, Banbury mixers, single screw extruders, twin screw extruders and the like. The concel.l.ale can be 20 pl_,~ d by mixing the violet or blue dye with a carrier resin which, pr~h.~bly, is vi"~ 'enL
chlc id~ poly..,~r. '' ll,Gcls for ~.~"a. ;,.9 the co..ce.~t.dte are well-known in the art. Typically, tne carrier resin and the violet or blue dye are kl ,docl in the melt using con~_..lional melt pn~cess;"~ I_ hn ~. ~es, using typical melt plocessi,,~ ec~ al such as those ~e--lion~d previously.
If the C~ pOS:~-Gr) iS prepar~d by dry hl . ~S~. the c~."p-,~,el,ls. should be mixed to form a visually uniform a~lmiYh~e. Sl ' 'e dry tl9~ eq~, :,,e.,l includes tumble Ll~ ~de~:~7 Hobart mixers, Welex mixers, and I l~nschel high ;I n r ity mixers.
The V;"~fi I ne cl Icride poly.-,er c~ o,;lion of the present i,~e.,lion can be coextruded into a multilayer tilm with co"~ tional coextrusion ,--acl ~es. I leat 5hli~ le 30 multilayer films _. IDY~I in pach~ meats, for ~~ ~FIe, can be produced by coextruding the n~ layers into a primary tube, and then bi ~ "y slr~t~ 9 the tube by known t~chni, les, such as that desc,iL,ed in U.S. Patent 3,555,601, to form a hcat sh,i"l '-le film. ~-The h- ~ 'ly sl~etChC:J film is then i" ' I to a dosage level of up to about 5 ".a~, ~ds by passi"g it, for a m, ', through an 6ICCI~On beam i" di--lion unit or Co-60 gamma, ~c' - I
35 source. The multilayer film can have one or more layers CG~I~p~ 9 the vi,,~lidene chla idê
W O 97/17399 PCT~US96/17733 poly..._r cG.,-I~osi~;on of the present i..~re..lion and one or more layers CG---p- i ,i.-g a poly~l ' "
such as poly~ e. The vi.-ji ~ ~e chlcrid~ poly.--er layer can be s_.,d~ ;cl)ed bet~ _ ~ two or more layers of a poly~lufi... The m~ ly~r film can also have a glue layer d: 3posetl ~ah _en a vi.."l;tlene chl~ride poly...er layer and an aJiac~.-l polyel t . Iayer. The glue layer 5 l~,~ ~'ly cGmr;- i_~s ell.~rlene vinyl acetate or any pOly.~èl or cGpoly...~r having good a-Jl.esiv.
.~ pl Gpe~ t;_~.
The PVDC cv..~l-vs:livns of the present i~ tiOI) can also be ' ~ inatt ~1 into articles using cor,/~l-liv--al tati.icalion b chni~ues such as i--je: Qn ,-~ - ,9, extrusion r-~l ~- ~g, --' .de.i"~, lhe~ Ofv~ ~ ,9, and 1...- ~ ,alivn tecl,ni . ~s Articles formed ll~e~:f v-" include 10 blown and cast ~vncl yer and m~ . films, foam sheets, tubes, pipes, fibers and the like.
F 1~ 5 of such articles include flexible and rigid co~ ~ ~e~ ., used for the p,~sc. ~atiGI) of food, drink, .. - ~- - .e and other perish- '~s Eab,icJt.l articles from the p.~se.,l i~el.lion may be i-, didtëd for purposes of - ~-- -n, i",~,lv,/;..g tou~l,ness, i",provi..y solvent r~ ce and the like. I~aJ;alion with 15 about 1 to 20 Mrad is a~ . I shed, for ex_. . ~~ by passi..S~ the articles through an ele_l.on beam i" ~- i~ n unit or Co-60 i. IaJialion source. b .aJi~lion may be done during or after fab~ icalion of the article.
The tOIIG~ :..9 ~ ~,rld..~~ e,~ le s are given to illustrate the i..l/_.niOn and should not be construed to limit its scope. Unless vU~el . ;ae i- - ~ d, all parts and pe. ~;ent._gea are by 20 weight.
EXAMPLES
In the tcll_. -;.. 9 e~ s color meas~"e",~ , are taken using the f~ . i... g procedure.
Color Measu-~r._..l Color measu-~l.-e.. ls were made using a Hunter Lab Ultra Lab C~lcri.. _t.. The Gpeldti~.g CG. Qns were Illuminant D65, srec~ inel-lde~ UV off, 10~ obs_. ~rer, in a ~eSlt~.ldnce mode against â white tile. Measu,.:,,,enls were made using the CIE Lab color scale. Four measu.~.--_.-l:, were made of each sample and then ~ .aged. Of g.~at.~l interest was the change in "b" value where i,-c-- ~- "J "b" cG,,e_"vnded to a visual i"- ~~ase 30 in yall . .,ess. The "Db" values repo.led were the Jitferel~ce in y~ll_. ..ess bei _~n the i~-aJialèd sample and the ~ adiJt~v control. A positive number cGr,esponded to i". ,eased yell _ . . ,ass. It was obsel ~red that the POIY~JI vp"lene skin accounted for a "Db" of appr~ t~ Iy 4 as a result ot the i.-a~iJtiv.,. Theretv~e, the "Db" values le~.~OIled for m~ el films in Table I are all dec,èased by 4 units.
WO 97/17399 PCTnUS96/17733 r- -m~le 1 A multilayer film sample (Sample 1) c~r-.posed of outer layers of poly~ pylene and a core layer of 92.25 weight percent v;,"~l;dene chlcride/7.75 weight percent methyl acrylate, which co- - - .ed 4.0 weight percent dibutyl sehn~ale and 0.2 weight percent epoxidized h ~ ean oil, was produced by con~enlional coextrusion lcchn ~ le Prior to i- ~ - n, the film was anl - -'e ~1 at 120~F for 3 hours to ensure full c. ~1~ - of the v;."~ ,e ch~cride cGpoly.-._l. The coe~l.ud.d film was ir.adiated with 4 Mrad Co-60 gamma r J;.,tiGn at .
t~...p_. alure. Color measu- ~---t ,~ts were taken on the coextruded film prior to ;. ~ _d;~.lion (u,, ~ Jial~d) and i-n---o Iy after i.. di~tioll (i.. .~lided)accOld ~ to the color 10 measurement procedure de5_- iLed previously. The results of this test, in terms of the change in yellow color (Db), is shown in Table 1.
F- ~ 2 and 3 Two multilayer film - l~ ' e s (Sa.- . ' e!s 2 and 3) CC~ pG5~: d of outer layers of poly~,r~.~lene and a core layer of 92.25 weight percent v;.-;lid~ae cl~lalid~7.75 weight percent 15 methyi &CI jlat~, were p-ep~r~d and tested (;..~ I and color ~..eaa~ l taken) as in F- . ' 1, except that 4 percent acetyl tributyl citrate (ATBC) is added in Sample 2 and 4 percent r~ , EPZ, an ac~l;lat~ "onG~lyce.iJ2 c~,"-..~ y available frorn Cl,or i--l, was added in Sample 3, instead of the 4 ,uercenl dibutyl s- ~- ~ Color measu.t ,.._al,j of the ;-~Jiale:d films were taken as in - . Ie 1 and the results are shown in Table 1.
C~ m"al ali~e r- - l e A
A rn~ ~_. film sample (Sample A) cG,--prisi--y a 92.25 vi-,jl; 1 ~e cl.larid~J7.75 methyl ~_. ylat~ copoly.--el core layer c~ 1.2 weight percent ep~Y~ soyL ean oil was p~ ,a.~d and tested ~s in F - . I 1. The results are shown in Table 1.
CGm~ale~ re F ,;' les B and C
. film 8 1, ' ~1 (B~ 5 B and C) CGm~ a 92.25 vinylidene chlcriden.75 methyl a.,, ~ t~ copoly.,.er core layer were pr~paoed and tested as in Cc,l,,l,a,ali~e Example A
except that Sr - F I e s B and C c~. .e-cl 2.2 weight percent and 4.2 weight percent epoxi~ d soyLean oil". spe. Ii~ely. The results are shown in Table 1.
30 Co~ <~ e ExamPle D
The multilayer film of this co,..~,a. Jti~e eA. ~ ~'e was the same as that of Cor..parc.~ e F ~1 e s B snd C except that it CGi~ e ~ percent epox;~ d linseed oil and 0.2%
epo~ d so"Lea.. oil. The multilayer film is tested as in CO,-.pal~liv_ Example B. The results of the tests are shown in Table 1.
Tsble 1 - Color of PVDC Film 1~ . .. Ji~t~l vs-Samples U...... .~.c' i'~d ~b 2.7 J 2 2.7 3 3.3 A 6.1 B 6.2 C 4.5 D 5.0 Example 4 Water, suspen " .9 agent ('-: .ocelTM K4M, a product of The Dow Ci. i--' CGI..P~-..~) and buffer at a ratio of appro~ t~ Iy 1.00/.0009/0.0093 were cl;a. ged into a reactor. To the mixture in the reactor was added an organic phase con~i~li-,g of methyl z~ luh" v;..;l;~ e ne chl: idc, t-butyl per-2-LIl-~ll.exenG~It, and violet ~i~ e ~l at a ratio of 7.72/92.28/0.369/0.0005.
The ratio of water phase to organic phase was 1.25/1.00 The violet I :_ al was an a.nh.~ .Gne dyestuff, f'~ l TM Violet B (C.l. Solvent Violet 13), a product of Bayer AG and des~.iLed in U.S. Patent 2,419,405.
The ~ea~.l;Gn vessel was sealed and placed in a water bath at 25~C and mixing isbegun. The l~...pt:.~.lure was then raised to a m~Yim~rn of 84~C over the course of 630 minutestoallow poly...~ lion. The res~ poly..._~ slurrywasthen cooled, d_ ~'~ t d and dried at 80~C to remove residual water and ...ono--.e~a. The product was then flash molded at a ILn.pe.ut-lre of 165~C for 1 minute at 1000 psi fcll . _d by 2 minutes at 20,000 psi.
The yell . ..ess of the flash, ~ as d~t~. ~ed accG--' ~~ to ASTM method D 1925-70 is shown in Table ll.
CG....,c-.uthl_ ExamPle E
A poly.--el sample was p.~:pa.~d in the same manner as shown in Example 4 except the 20 '- o'~ Violet B dye is omitted. The sample was flash molded and tested in the manner shown in F - - . Ie 4. The yell . ..ess results are shown in Table ll.
C~ z.c.thre EA~ R s F and G
Roly..._~ s~.... R s were pr~pa~d in the same manner as shown in Example 4 except the '' - ~JI Violet B dye was s~hstituted with an equal amount of '-~ cl Violet 3R
25 (Cc,-..p ~ re Example F) or '' ~l~ Blue RR (CG~ JZ~ Example G) dyes. ~' r~l Violet 3R and '' ,~el~ Blue RR were - ~'es of dyes which are not sur~icie..lly color stable to ~ itl._ ~d the acidic processi,.~~ eri.~i.vl....e..t of PVDC extrusion at about 160~C. ~' -rvl VTolet 3R, a product of Bayer AG, was cG~ ,ially known as C. I. Solvent Violet 36 and ~_p~ ~sehled by the formula:
o H~N ~ CH3 H3C ~ - N~ O
H
roleY Blue RR, also a product of Bayer Ag, is cG,..r...,lcla"y known as C. I. Solvent Blue 97 and r~pr~sal.t~ d by the formula:
H3C ~ CH2-CH3 ~ , H o The s~ - Fles were flash molded and tested in the ..._n..- I shown in F -, le 4. The 10 yt!l~c~ ess results are shown in Table ll.
W O 97/17399 PCTrUS96/17733 Table ll - Color of PVDC '~ol ~q Sample In F le4 5.3 CG.. pa.athr~ Example 12.8 E
Co.. p.. dth~e F . Ie 43.9 F
C~ pa~ali~ Example 12.2 G
ExamPle 5 A m~ . film sample cGu.posed of outer layers of ~.oly~,.c.p~ .. e and a core layer of 92.25 weight pel ce..l v;- .~d I ~e c.hl ~ iden.75 weight percent rnethyl ac- yl~le, which con~ .ed 1.4% r~ EPZ p'~ ~;c~ r, an P~ ~tylat~d ...onoylyc6lidc cG------e.~ '~y av_ ' 'g form -- ~ Cl.e...' ~1, was produced by cGn~/e.-lional coextrusion lccl---i, le. Prior to i. . n, the film was ~n,~ --' I at 120~F for 3 hours to ensure full ~,.y~ ' - of the v;..;; ~le ~e 10 chlclide copoly..-ar. The coextruded film was ;--a~ d with 4 Mrad Co-60 gamma ~.lidtivn at ~ ' .l tc...~e~al.lre. The PVDC film layer was then se"z.~t~d from the poly~,rop~rlene layers. Color measu.~.--e~ were takên on the PVDC film prior to i-- d;..li~.. (u- .~di~t~d), and ;.. e~ Iy aner i.~-did ion (i~ diat~d) accGn .g to the color measurement p.~ceJu.e.
The results of this test, inclu .g the change in yellow color (Db), are shown in Table lll.
15 ExamPle 6 2000 grams of the v;..~l ~ ~e chlclide copoly.--er desc.iLed in F---m~ ' 5 was added to a Prodex high~ t~nsil~ mixer. Then 1.00 gram ''--rcl B dye was added with mixing ove app~"d.. ~ 'y 1 1/2 minutes, res~ .g in a uniform color cGrice-nt-at~. This color concê~ è
was then mixed in â tumble blender with an addilional quantity of the vir.yl;lene chlG~ ide 20 copoly..._l des_. iLed in Example 5 at a ratio of 2/98. A m~ yer film sample co...posed of outer layers of poly~,.opylcne and a core layer of the v;.-"l; ' ~e chlclide copolymer color cGnc~lt~al~ and v;..;l; I ne cl~loride copol~,...er was produced by co---l~.-lional coextrusion t~cl...i, le The resulting film was ann--'ed, i.-_ ~' d and color tested in the same manner as ~" in F~ 1 5. The results of color testing are shown in Table lll.
W O 97/17399 PCTnJS96/17733 CG.--.,a.ali~e F ~ . le H
A mul'" ~r film sample c=~..~posed of outer layers of poly"r~ pylene and a core layer of 92.25 weight ~ ,nL v;. .;li ~ ae cl Icricl~17.75 weight percent methyl a~ tc, which cor, ! .ed 1.6% ~ poxi~ d so~ Lean oil, was produced by cG~ enlional coextrusion tech. i . Ie The 5 res~ ' Iy film was a-m ~ -'~d, ;- ~adialed and color tested in the same manner as in Example 5.
The results of color testing are shown in Table lll.
Table lll Sa.. ~s U~ ~adi~t~,d ~ i Color Chanqe (~b) 2.4 6.1 3.7 6 1.7 5.9 4.2 H 2.3 7.3 5.0 ,
Claims (35)
1. A composition comprising a mixture of (1) a vinylidene chloride polymer (PVDC) formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one monoethylenically unsaturated monomer copolymerizable therewith, and (2) an amount of an aliphatic ester compound sufficient to minimize color degradation (formation of color bodies) of the PVDC during and after irradiation of the composition to a dosage level of from 1 to 20 megarads, the composition being free of acrylate/styrene copolymers, aromatic or epoxidized processing aids, and monomer alkyl acrylate or methacrylate having 10-18 carbon atoms in the alkyl moiety.
2. The composition of Claim 1, wherein the monoethylenically unsaturated monomer is not vinyl chloride.
3. The composition of Claim 1, wherein the monoethylenically unsaturated monomer is an alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, vinyl chloride, acrylonitrile, or methacrylonitrile.
4. The composition of Claim 1, wherein the aliphatic ester compound is a linear or branched aliphatic ester compound, polymeric aliphatic ester or mixtures thereof, and essentially free of epoxy or aromatic functionality and has a molecular weight of from 300 to 8000.
5. The composition of Claim 4, wherein the monoethylenically unsaturated monomer is methylacrylate, ethylacrylate or methyl methacrylate and the aliphatic ester compound is acetyl tributyl citrate, an acetylated monoglyceride, a diester of adipic, azelaic, sebacic or glutaric acid; a polyester of glycerol or pentaerythritol, or a polymeric adipate, azelate sebacate or glutarate.
6. The composition of Claim 5, wherein the monoethylenically unsaturated monomer is methylacrylate and the aliphatic ester compound is acetylated monoglyceride.
7. The composition of Claim 1, wherein the aliphatic ester compound is present in an amount of from 0.2 to 15 weight percent, based on the weight of the PVDC.
8. The composition of Claim 1, wherein the aliphatic ester compound is present in an amount of from 0.5 to 10 weight percent, based on the weight of the PVDC.
9. The composition of Claim 1, wherein the aliphatic ester compound is present in an amount of from 1 to 4 weight percent, based on the weight of the PVDC.
10. A composition comprising a mixture of (1) a vinylidene chloride polymer (PVDC) formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one monoethylenically unsaturated monomer copolymerizable therewith, and (2) a violet or blue dye comprising an anthraquinone, in an amount sufficient to mask color bodies formed during and after irradiation of the composition.
11. The composition of Claim 10, wherein the monoethylenically unsaturated monomer is an alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, vinyl chloride, acrylonitrile, or metacrylonitrile.
12. The composition of Claim 11, wherein the monoethylenically unsaturated monomer is methylacrylate, ethylacrylate or methyl methacrylate.
13. The composition of Claim 12, wherein the monoethylenically unsaturated monomer is methylacrylate
14. The composition of Claim 10 wherein the violet dye is a compound represented by the formula:
15. The composition of Claim 10, wherein the violet or blue dye is present in an amount of from 0.0005 to 0.05 weight percent, based on the weight of the PVDC.
16. The composition of Claim 15, wherein the violet or blue dye is present in an amount of from 0.0007 to 0.01 weight percent, based on the weight of the PVDC.
17. The composition of Claim 16, wherein the violet or blue dye is present in an amount of from 0.001 to 0.005 weight percent, based on the weight of the PVDC.
18. A composition comprising a mixture of (1) a vinylidene chloride polymer (PVDC) formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one monoethylenically unsaturated monomer copolymerizable therewith, (2) an amount of an aliphatic ester compound sufficient to minimize color degradation (formation of color bodies) of the PVDC during and after irradiation of the composition and (3) a violet or blue dye comprising an anthraquinone, in an amount sufficient to mask the formed color bodies.
19. The composition of Claim 18, wherein the aliphatic ester compound is present in an amount of from 0.2 to 15 weight percent, and the violet or blue dye is present in an amount of from 0.0005 to 0.05 weight percent, both weight percentages based on the weight of the PVDC.
20. A multilayer film comprising at least one layer of a vinylidene chloride polymer (PVDC) formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one monoethylenically unsaturated monomercopolymerizable therewith and sandwiched between two or more layers of a polyolefin, wherein the PVDC layer contains an amount of an aliphatic ester compound sufficient to minimize color degradation (formation of color bodies) of the PVDC layer during and after irradiation of the multilayer film to a dosage level of from 1 to 20 megarads, the composition being free of acrylate/styrene copolymers, aromatic or epoxidized processing aids, and monomer alkyl acrylate or methacrylate having 10-18 carbon atoms in the alkyl moiety.
21. The multilayer film of Claim 20, wherein the monoethylenically unsaturated monomer is not vinyl chloride.
22. The multilayer film of Claim 20, wherein the monoethylenically unsaturated monomer is an alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, vinyl chloride, acrylonitrile, or methacrylonitrile.
23. The multilayer film of Claim 20, wherein the aliphatic ester compound is a linear or branched aliphatic ester compound, polymeric aliphatic ester or mixtures thereof, and essentially free of epoxy or aromatic functionality and has a molecular weight of from 300 to 8000.
24. The multilayer film of Claim 23, wherein the monoethylenically unsaturated monomer is methylacrylate, ethylacrylate or methyl methacrylate and the aliphatic ester compound is acetyl tributyl citrate, an acetylated monoglyceride, a diester of adipic, azelaic, sebacic or glutaric acid; a polyester of glycerol or pentaerythritol, or a polymeric adipate, azelate sebacate or glutarate.
25. The multilayer film of Claim 24, wherein the monoethylenically unsaturated monomer is methylacrylate and the aliphatic ester compound is acetylated monoglyceride.
26. The multilayer film of Claim 20, wherein the aliphatic ester compound is present in an amount of from 0.2 to 15 weight percent based on the weight of the PVDC.
27. A multilayer film comprising at least one layer of a vinylidene chloride polymer (PVDC) formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one monoethylenically unsaturated monomercopolymerizable therewith, and sandwiched between two or more layers of a polyolefin, wherein the PVDC layer contains a violet or blue dye comprising an anthraquinone, in an amount sufficient to mask color bodies formed during and after irradiation of the multilayer film.
28. The multilayer film of Claim 27, wherein the monoethylenically unsaturated monomer is not vinyl chloride.
29. The multilayer film of Claim 27, wherein the monoethylenically unsaturated monomer is methyl acrylate.
30. The composition of Claim 27, wherein the violet dye is a compound represented by the formula:
31. The multilayer film of Claim 27 wherein the violet or blue dye is present inan amount of from 0.0005 to 0.05 weight percent based on the weight of the PVDC.
32. The multilayer film of Claim 27 wherein the PVDC layer further comprises an amount of an aliphatic ester compound sufficient to minimize color degradation (formation of color bodies) of the PVDC layer during and after irradiation of the multilayer film.
33. An irradiated multilayer film having at least one layer comprising the composition of Claim 1.
34. An irradiated multilayer film having at least one layer comprising the composition of Claim 10.
35. An irradiated multilayer film having at least one layer comprising the composition of Claim 18.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55543995A | 1995-11-09 | 1995-11-09 | |
| US08/555,439 | 1995-11-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2236147A1 true CA2236147A1 (en) | 1997-05-15 |
Family
ID=24217262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002236147A Abandoned CA2236147A1 (en) | 1995-11-09 | 1996-11-05 | Vinylidene chloride polymer compositions and irradiated articles prepared therefrom |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0859811A1 (en) |
| JP (1) | JP2000500511A (en) |
| KR (1) | KR19990067401A (en) |
| CN (1) | CN1202189A (en) |
| AU (1) | AU1116697A (en) |
| CA (1) | CA2236147A1 (en) |
| WO (1) | WO1997017399A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7371804B2 (en) | 2004-09-07 | 2008-05-13 | Ophthonix, Inc. | Monomers and polymers for optical elements |
| US8000013B2 (en) * | 2004-09-07 | 2011-08-16 | Ophthonix, Inc. | Tinted lenses that correct for high order aberrations |
| US7701641B2 (en) * | 2006-03-20 | 2010-04-20 | Ophthonix, Inc. | Materials and methods for producing lenses |
| EP3068828B1 (en) | 2013-11-11 | 2018-09-05 | Dow Global Technologies LLC | A process to produce a vinylidene chloride-based heteropolymer |
| WO2017094075A1 (en) * | 2015-11-30 | 2017-06-08 | 日立化成株式会社 | Food packaging film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2429165A (en) * | 1945-05-04 | 1947-10-14 | Dow Chemical Co | Vinylidene chloride polymer compositions stable to light |
| JPS4987765A (en) * | 1972-12-26 | 1974-08-22 | ||
| JPS5333250A (en) * | 1976-09-08 | 1978-03-29 | Kureha Chem Ind Co Ltd | Vinylidene chloride resin film |
| US6291565B1 (en) * | 1994-05-19 | 2001-09-18 | The Dow Chemical Company | Food packaging film |
| JP3523340B2 (en) * | 1994-08-30 | 2004-04-26 | 呉羽化学工業株式会社 | Vinylidene chloride polymer moldings |
| US5538770A (en) * | 1994-11-18 | 1996-07-23 | W. R. Grace & Co. -Conn. | Vinylidene chloride film with controlled gas permeability |
-
1996
- 1996-11-05 WO PCT/US1996/017733 patent/WO1997017399A1/en not_active Application Discontinuation
- 1996-11-05 JP JP9518278A patent/JP2000500511A/en active Pending
- 1996-11-05 CA CA002236147A patent/CA2236147A1/en not_active Abandoned
- 1996-11-05 EP EP96941964A patent/EP0859811A1/en not_active Withdrawn
- 1996-11-05 AU AU11166/97A patent/AU1116697A/en not_active Abandoned
- 1996-11-05 KR KR1019980703411A patent/KR19990067401A/en not_active Application Discontinuation
- 1996-11-05 CN CN96198196A patent/CN1202189A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997017399A1 (en) | 1997-05-15 |
| KR19990067401A (en) | 1999-08-16 |
| EP0859811A1 (en) | 1998-08-26 |
| CN1202189A (en) | 1998-12-16 |
| AU1116697A (en) | 1997-05-29 |
| JP2000500511A (en) | 2000-01-18 |
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