CA2438755A1

CA2438755A1 - A foil or moulded body based on a transparent polymeric mixture

Info

Publication number: CA2438755A1
Application number: CA002438755A
Authority: CA
Inventors: Juergen Buehring
Original assignee: Benecke Kaliko AG
Current assignee: Benecke Kaliko AG
Priority date: 2002-09-02
Filing date: 2003-08-29
Publication date: 2004-03-02
Also published as: US20040116600A1; AR041123A1; CN1495226A; JP2004091793A; EP1394203B1; EP1394203A1; RU2003126606A; BR0303773A; DE50302221D1; PT1394203E; DE10240970A1; MXPA03007899A; US7034077B2; ATE316117T1

Abstract

The invention relates to a foil or moulded body used on a transparent and high frequency weldable polymer mixture containing a) (I) a copolymer of ethylene with about 8 to 60 % by weight of comonomers, selected from vinyl esters of saturated C2-C8 carboxylic acids saturated C1-C12 alkylacrylates and methacrylates, optionally with carbon monoxide as termonomer, and/or (II) ethylene homopolymer, ethylene copolymer, propylene homopolymer and/or propylene copolymer with about 8 to 60 % by weight of grafted units of unsaturated carboxylic acids, dicarboxylic acids, their esters and/or anhydrides or (III) a mixture of two or more of the above mentioned compounds, independently of their allocation to groups, whereby the polymers or their mixture have a melt index MFI (190°C; 2.16 kg) of about 0.2 to 15.0 g/10 min and b) a copolymer of ethylene with about 10 to 30 % by weight of C3-C12-.alpha.-olefin with a melt index MFI (190°C, 2.16kg) of about 0.2 t o 15.0 g/10min, whereby the material of the foil and of the moulded body is partially interlaced.

Description

~':7-~C'~i A foil or moulded body based on a transparent polymeric mixture FIELD OF THE INVENTION
The invention relates to a foil and a moulded body based on a transparent and high frequency weldable polymeric mixture.
BACKGROUND
Foils of the type described above are known. They are based generally on polyvinyl chloride. Polyvinyl chloride has the advantage of good HF-weldability and also of the transparency which is required in individual cases. PVC-products have been used for technical applications for many years and in the most diverse products. Owing to the trend of reducing the application of materials containing chlorine and plasticisers in all areas of life, there exists in the construction, automobile and cable sectors an urgent requirement for halogen-free alternative products.
A problem in the search for halogen-free alternative products often comprises the fact that PVC foils can very readily be welded by high frequencies as against which possible PVC replacement materials, such as for instance polyurethane foil or known thermoplastic polyolefin foils cannot be welded, or only with difficulty.
A further characteristic, which plays a role especially in the automobile sector, is sufficient cold flexibility of the material. High cold flexibility is especially important if the materials are subjected 1.o dynamic loading at low temperatures. Thus for instance polyolefin foil materials serve as decor for covered airbag systems.
In order for such a material to be suitable for such an application it must be ensured that it does not become brittle or have a high frictional index at the test temperatures (customarily -30°C), whereby the penetration of the decor by the airbag flap would be impaired. It must also be provided that the material does not splinter because of its embrittlement. These splinters could lead to injuries to the passengers.
Consequently embritt(ement of the foil material must be avoided and a desired opening of the airbag at low temperatures (free from flying particles) must be ensured.
High cold flexibility is also for instance important in storage space covers, which can be realised in the form of sheets or rollers where even in cold conditions satisfactory on and off rolling must be assured. At the same time for applications in automobile or vehicle areas stability under heat of at least 100°C must be provided.
Heat stability in this case means that the surface structure or finish must remain in the original condition following a 21-day storage at this test temperature and furthermore no additional sheen is to be seen.
The PVC-products mentioned fulfil a major part of the present requirements being discussed. They are especially also transparent, which is required in individual cases. Nevertheless they exhibit the disadvantage that they include plasticisers with their known disadvantages. Here especially the insufficient ageing stability and the emissions caused by the plasticisers should be mentioned.
Both in automobile and also in the shoe sector there are strong tendencies to replace the widespread PVC materials by halogen-free substances. However many characteristics of polyvinyl chloride can only be displayed by other material classes after very high innovative expenditure.
There are indeed certain proposed solutions, which however are not altogether fully satisfactory. Here we should mention EP 0 703 271 A1. This describes a polyolefin composition, which is thermoplastic, halogen-free and flexible at room temperature. Here ethylene vinyl acetate-copolymers as well as polyethylene with very low density are used. Although these formulations are often useful for several applications they have the disadvantage that they do not exhibit sufficient heat stability as soon as they are exposed to temperatures greater than SO°C.
The s tate of t he technology a ccording t o D E 100 18 196 A1 describes the method of production of a surface finished foil from a mass with a content of non-interlaced polyolefins and possibly other additives, whereby the foils obtained in the normal manner by obtaining a surface finish stability suitable for deep drawing are processed using electron beams, and the surface finished foil i s d eep d rawn t o a 7:j :: ;~~ .~uiJ i ~:.:~1: ~:~1 a; Oi ulL~Cl'.t lJ . ? rC _ . ~'~~CI?l' . A:3 IlOIl-lllte~'~
~~:~'C'd I:~ _~'<:e~in~ pci~~y-~~~-y~F:Y~', p~_;iy_thylel,:e, poiYp~-o~:~ylch.e ;'1.'Tll'=~1_":=; 'iY- LE-~I::T:O:y?:lE~I~.~ vv L=i ~:n ~_~, e,Ci ~,:,-iX
'::~Ee11T1S <lll:.i~~:1 ~'E".l:~l ' (.I1~~ - 0,~~~C .L~/1.12~"~ O ~' re'r~CilyTTl~r'~3 6~J:1.'-~.~1 :..., t.C"~
'; -~..:Y ,, l.f-rir_~''> ~11 ' '.1;:~Gi. 1-hf= i0_'~S OI~t.'~llifrd dyes .~,_SC1 l~y~'~~-v,'_-lc C:
s s~ii_-:, ~<:ii l y ~z' ~.I(_;:~C1 .-iLi:L~~ ~lrv;~ ~ ._T:~ ~Ii 6 f-: a~'Oi 1. l ty i3hd C'c;il ~J~' a:oL_~E~ci .~incl ~. ~,rail:ated. They a_:e however net HF 'fmlda~ L~~:.
L, Z'; ~~iEa ~7~_: r:'~i i;'!d. ;~llal:L ~ ai"~ rr COiICG-C_''1~I1S r1 ~VC-ti:vE~ cillil .y~LO'J c:l.'.oU _itl.W)c~t:'..Stwl_t_CE_'. 11y~1: L~.~~.1~W ILL.l wc~.uGUi.c y~v~-, mr::~_ .,'aLWL_L:L!. _,. Tl'c._s'.. L:1;'.l~a!lE' d C~-1_:L-'n,C~', i <;lSt"~C Xii:l ~'':J1~''_-lIl e1 aI5 U=~-LE:1: CC~:O~,ITTI~:Z"3, W ~:y ~ 1'?::' l1?T~1~1511-1~ -i '~ _'~_ l~ i;li. i. E'_ cx;., 4'7i ~.1 ':1?St=~3Y1:~'E? l~llt ;L: ilC.O':'E~1: Il'lt iir"~::lS~c.-.'_Cht., OV~JI-1~ ~;: ~y_iF, ;'e;I-f:~~y ~'Jt_i,y ,~~_,iyy;)1'~~::.1_ ',~IW-.C r:. C: C'%nt.~3.lTZS
~7C~yat',lldEr. ail <:iE~CC:rrW;11~~:~_, 'sJlttl t~_':~ ACS''-yLTt?~_i.S~:E=d Tl~. ~Ol _;3 ~~l~c a ~llc:T~l EU;UE~IICy 'wr~:IC;:eI~%.iE ~Oly?1~~~ 'Tli~C!~L;-l~Er 1S .'=~ltl'l.~laa"1'yJ
C'IE:SCI ~',~'C~,-7 ;;?11:_'~'_ C~CI-Ir. 't1 _1:~ .?c~,? ;:::. 1_ ~ ' 3 ~J ~ ~;y ~JE;:La~lt Ot ~1T1 c til~~'IE1-:E
- ~..r ,~r , C:On:CE':a. 'y ~j~Jle i C,(iIIlE;~IiO,ll~,..S ~E-:! CGe~J
i~tX~'~.'U:
:.-'W~cJl - l.~_y :J1 LIl c:~
..~iy=It ..» 1E'~_:tc~c; I:o?,l tam- gr; llr :~f vli.llyl ~vte-~ of ..iiL.L:I :t.i--~ '.~..-L., -'~~.=r.)'i':~1.1.:1~ i~lCio1 <tllGl L~1,-' _..
e_~l~ i'L~:iZ~,J~ i.i~:_t:.
:'~' 1r .?,.''c> w c;,,E~W~_~.ac~yla~e, abt-~t1': 1 try ~i~ ~ b1~' weig~lt or a : E':z.~.~~11T,T1FyI-. .,,r ;1 y ii1"':~i:l. C'V~~OI~JIll~y" ~~,r.t~-i ~
COIaLE~Il~'. O~
.~,it:el:!..f'.rYi 1,~',W ''J' ,'b:..':'- ~r 'a! .r.~1' ~fJE'1C1~:'r, ~~T'_CX
a~JOLL ~5 W~~Oc Jay ..'_j?'i;: CL <': _l::t,:'.OI7~<.:t';:_st:lC )7U1.'~ C: LF ~:1.i1 'vJlt~l d ?TiL.~t ill ~ ._;1_~_L
a~CiLll =~u"C..'. '1'.21S ~iJ~;iTTlE:i lTllXtLY~fv iS tlC~~'.~JE:VC?~
. _, t , ;; i,_,V~r~Y_CI1?~ ~,. - rs~l t 0 t~-=C 1 X51. nd?TlEJC~ r :~C?1~J01'12I1t .
1 a: LEi C:O?'LSE~C(::E'_Tli~~.'y' d:1 c~lCTl vi thfCUY"Y'C~'11t '_I-c.-PI1t10i:
i:C T;1 ~LiJ:~~~ y0 a.. ~ :~ 01:~ I',OL1ZCXE=d '7JE:~lf'S Wi 1C~7 C~C :10t ~l~ji~' R l~c~Si ,'s 1-: r'V~ ~11i:~ COI .~E'~::'L.r~-Ii".- _"I c1Z'C f L-t~F f L-OfT~13~ OC1E
T':~~i, hC)L~Jr f:-~_ C~:~I'_~ 11'LlEi t ) :::;I_:W t fl Ec~~.L'v'o1T_tal':~W '>',:.5 C~:c ?~c:Ct.E'_L : _ ~.l.u S Ct pt'.1?:
>': C ':.:~ , Ii.aLl 1,'T--.:II~'_'~~,1.''-_I-.~~;'r i~t'~ V:'C'~dct~)l~ ltl7 all:.7. :itc~~J 1t_'/
.i_ iF_v.. ~i~:;t, , . clc:-ii:l:~3~~i',' ~~'':>CU! f ~E'~,s_rJ~_itt,' W}1t'.1 C'O~d c :.C1 . . ~.!'J ~i~'~i L.I=,.iC'1: i~c.ll1'J7 ai'i~ T:L1Y'L~lE~l~IllU'-~E: X1150 E~~:C~LTGE' '1?_:

_... ~J ': _. , _ ;~ I;~,'7 . ~..~ 1' _, _. t~~t' ci LSd('~Ve-;~i_._isJE'<L:'.~ elil1SS10I'1;3 vN~llCi?
etY~E~ d~suG " i' !=Ca ..':jy }_; <T~y~i_ ~ ;c:lC:a: ';L P~~'C: tGl_~ 5.
~: j ~~~'Lp.t'j.' - ;, , ih 1C,!'%%Y~l~-~I:C;C~ trJ~~~~ tt.E' ~7rE:SF~Tlt~ 1.T.V't.'I~L1.O_1, tilE.'Li~
__ ~'.i v :1E'(=~ =1 r<:i 2 i i i.'_' ;:1 it101.11de~ bOt1?%' bciSE,-'d C7 I'1 'cl 1_ r W'l,Spr~Y E:~1:''tI:~_~
:i'-'l rE' :~~=.E=:lc~'~' ae-ld ~b_i.e~ ~. «:i.y:rie:- ,Mixture cOn;p~~iS ~
11a a~I,' a copc>lyn;er c= Ethylene with ab«u1~
tc ~~ ~ b~; weig~nt of ~'ot.lc>nomers selected from ~~~inyl tss~_e,_s f :!<'.irUratE~'d (~_:-W.~.3 :dy'17OX~1 1i: caCl.<:~S L,-L:~ cilk~Tl~=W
Y~Vlu.~ ~.. 1!1U
I.' ' t:_-: ;t='Y~~I ~L e:>, <:ipt' .OI-._~~ 1'j ~N~tr: C~lr'~~Ori C',tOT~GX1C~E.: S
~ ~.'I'.', 1' :;Ill', 111G~Gy'_ tZI~ °t~'1'.~~eTlE~
~lOITtC~~iO~ylT;e?", e;::~'lillETle . = , r(.eJl , ~:;:_ _ 11~~ ..i~ }. o it,,:;u>_1.'f'IlE''~" dlld~07=
prGpyle=le C'.OinC_i.l ;. to'~1~
r}:iout: ,. ,.:=i 6C-s toy vJeight o~ graf=ted uluit~; ':_>f i::l:i::LLIL~c~"~eC1 C:czrbJXhl-C c:CICXS, dlE:;i~__:bCiX'1TI1C clCldS, t~:Cvli' ~a L.~~rs aaTlC~~:=,Y_ :~T1~1~'dY"~.C~E.~! Jr (TTI~ c1 ITIIXtLIY'e Of t~.~'O
G~- tTlCi'E~
;?f i;.tlF' utJOVE lT;r~:I:t ~;JILE:.~ E'Olilyotl:.d8 lll;~ErJE'.TldF'I'lt~ GI
i..~le' 1' <;~I"C:~L1'~
,t=1_cacations wt ~:~~eiy !.-_h1e polymers or' their mi~_tmre have-'~y..!-~ 1Tn(ie_ Cvt'.'~ ~i..0''~:~; .~..i!!~'.~') Of a'~.~,Olir 0.<'. t;C~
i'O.0 =;'j~:10 ll;lll _i 1':!:a ") ~J,', _t :'~>~:'C;1',%tTler Of P_t~ly~.E'I'le Witl-': ctupY~OXll;lat:c~l '_ .,u; ':< 5L)~; ~:'y.' , -.1C;:lt C;~ (~.,-~',~;_.~_GiE~illi GJlt~1 ~~
1ti(='1t1.1~=a 1.I~IE::
7i'' _ ~, ~0() °~'; G . ! ~~:c~j Gt c';bCi'~t O . 2 t;( f _~ . 0 C~~1C
l:l'~.'1, W _r=:y'E.1TI
ii? 'l~:;tc:'T ? :;1 : ~: t :1~: ~;~'7 1 E.'r' OL the TT1011dPCX ~Od~J 1 S
~~~r''~,~~,' '. T.;= r' ) a .;F=r:~ .
l': I1 ilCCc:::ru~t::lE~:~ GJl th ~-~:i aSyeCt Gt tl-le lTlVeTI~ ~ OIi, c1 to-.for ;~ aawtl=!_:~e,_ x~Gdy bas ed on a tr~.zsp~trent arid hi.tJn t t 'r:.(',_l'Ilr~:' :'Jt=-'~~=:b:.E p::il!,'1?ler litlXt~,lY'~' l.~a ~ilEpctY'E~:~ <~S <~ '_ciiLCr._ ,_ I t ;~~' ~;ony> > ;~..~c>r_ f..~~ tr~c: c:~e~sired app~icatio:i, whlCh ~ma;~
t,,(~_ ,, ;:~.~~ :~i r:.~ ~rau t-e,_,~~tic pr~~t-ale. Tuns ~r': Gne~ :aspect >;i tr_e ,. '.'J~~I1r1G1i, c1 ~:c~7 ~?-: ~~1 Jl;c~~ =_S prO~Tlded ~N~llCr: i_uC;111i-_tt~~S the "1~~~~_ ~ri'C~! E.T'_:_:z' 'v;!~'id].=iC; Cdpa~~l! 1t'1l s3IlQ ~laS cili ~:laVdT?C::: C'OLQ

.-. :;i :'v 3 f- 6 '7 l 4a ~1,~.~:>;.li.ty. .1. ,~mc:tiue~,. a:i~pc:ct, an increased Leatyerat~:~f-'_ :ill . . ~ ~7 lt~s ~ :-G~..I iC~~_:C1 w1 ~.;'~Ollt I:!:JWe~'Vi:'r tI':E?
wcl CWt~~:l~ 1 t;% uI':;a ...(~! !.er_t <v_,~l l iW~x~_bility bE_~il:c, impaired. Add~tvor~ali;r, in ~.)_.t~_r ripe-~,,~, , t!,~~.mparent= product ~.~~ provi.;~F~=d..
_- ~:'~'F_:_ ~~:L, DES>C!=~~ r' i'~.C'J
'.'t:~= c..,.:Ia,r cnE-nt5 of t~:e polymer Illi:~ture prep~;L~~:~~
,.' _'E':I rl=E- ~.Ii'~.'E I1'= ,.%.'c;1-E- r-Xf) ~a ii?EGO ,._1 C~~_t. ~.L ~
~~E~.<<-u,;J:
it, ")l':'.x) :1-lE~n~. i~,1 aCC:~z'L~1I13 tC- the ~.n"lE'Cli_1C::
~_ ~~I'11:1 _: -~eS ~ C:'O-' .. ~'~:y' 1(.)llcv~ T_lW:-S1I=)-~.l It lE'S .
ACCOY~CI i Ily i ~.1..:)C.' Cctt 1~.:~It (I,1 r1 Cc~l~U: .~11',~,.. 0t- e.t~l.yiEl!.c~ 1 S
t:'c:I:;:.~;1.I1C;~ (,v~'~t: ;l i={
;':W!1'U.:l.'f'.~;:: . :S pU! aL~ C:OII1W1.Ot1'<<~:rL> 'Ilrlyl E~S':~'rp Of=
..,,,. 1__'.~_~1 '~ r.'.I2I1;::X'y'l_'.C elC1(~~, ~ -Oi_-dl.K'yJlctC2:~~J.lc'~tE''s aa'1E1 . ,._..: ~ .y."li i i f'v>, ~~~i: LC;I-loll l.'y~ ~~% 1?~~1 Cva~bOl~
'l',OIlOf:l~c~
_ __.«:'iO;TIF-i , Cell .uE~ Llsc~. F~Y'~i_eY~rE'_C~1 a:~:axTT'~pieS ar:'_ E
t~~\% ~ r'li°_ ':'1_il'vl. ~?CE'Z<'tLE' .~(~;W~l~'l;lE:r, E-C."ly.l~'11F.='-ItietMi;'laCrylc-1-f:E-CO~u)Lj%CCIc_W
~:.r_LZi'.l.c~l~r-E t t;'~ ~ut:'~_ L~;ac-~-C:'>polyeJ.'tier atlcx/O1' er_nillET( ~lt';,'~,:;1;: r~l'~~~t e-~.'O~i: ~ :'la:l~ . ~'rlE: CO:~l(JYlOI'.lC'1~
COntF°1'ir _~~ w:u; W~ L:c.':
_,1 t!:. Lai;.~(' __: S~~CIIE_'. ;3 '~O ~~~ b'v L~JelC~~-1t, 'LJ'retE:~~?bly ~.ni. =1_):J'w1i=:
a r y:- A.~, _; ;.,r ..~..a , f ~ .;,-,, -~ t . ~ ~ ~=.g. v, ~~1.~ I,vc)re preferably o_ about 1=~ too _ , i~y ':~~E~i~i:t . F~~pcc ~aliy.' ~~Y-e~:erub, a a amplees ~~re pr~ovidt..~ci by ,._'=try l c_1~E~-,~ ~.Iiy=~:.i~c:W::ate-~cpc'~ymer a~~ we~.l His ethylene_ . I_~ ~., ~ t_._ y :id C ~' z' a. ~ t v:- <:. G Ia O i ~' ,'CW t~ .

i..-..'7--,~;,,.~
Especially preferred a mixture comes into application, which falls into the group of compounds under component a) option {I) especially in the form of a mixture of various ethylene-vinylacetate-polymer types.
Apart from this terpolymers can be applied which are constructed from ethylene, one or more of the comonomers given under the option (I) and carbon monoxide. In a preferred embodiment, the individual monomer units are distributed statistically over the polymer chains. The presence of carbon monoxide can offer advantages for the capability of welding by HF. A preferred example is vinylacetate-carbon monoxide-terpolymer.
As component a) in accordance with option (II) grafted polymerizates of ethylene homopolymer, ethylene copolymer, propylene homopolymer and/or propylene copolymers can be applied whereby as the grafted monomer about 8 to 60% by weight of unsaturated carboxylic acids, dicarboxylic acids, their esters and/or anhydrides can be used. Unsaturated (di-) carboxylic acids or their derivatives are for instance acryl acids, methacryl acids, malefic acids, malefic acid anhydride and fumaric acid. Ethylene homo-or- copolymerizates grafted with malefic acid are especially preferred. Mixtures of these polymers or grafted polymers can also b a used.
As option (III) of the components a) a mixture of two or more of the compounds noted above corresponding to option (I) andlor (II) can be applied independently of their allocation to groups.
The polymer or polymer mixes of component a) have in each of the three options discussed above a melt index MFI (190°C; 2.16kg) in the range of about 0.~ to 15 g/10 min, preferably between about 0.3 to 4.0 g110 min.
The further components b) of the polymer mixture according to the invention include a copolymer of ethylene with about 10 to 30% by weight of C3-C12-a-olefin.
As a-olefin for instance ethylene, 1-butane, 1-propane, 1-pentane, 1-hexane, 1-octene and/or 4-methyl pentane-1 are used whereby especially 1-propane, 1-~..1 .. ..7~ ~ ~ -... 7 J i r ~~-It:~_:Im~, _.-hc:XC.rle a~tld 1-octet~e ai'e preferred. The cumL7>I1~>nts b.l~lve r:-i I1~E=:.~ t 1.1~.(-~<. T~i~'I ~ J~J°C; . . Z Ji'~!~) Of abCiL'.t ~1J . 0 .'j/ ~.1 Itl',.I:, p2-E-.' E L~,=t:JLi x~E;t_tN'cai~ abOu'.=
. _. ..11 _Ca _ . ~ ~'~! /'- ~ ~' ! U 1 I _ .
i- ~
I'_lE I ~~-iht_'Tl::xl_C'C' 01_ tale= ~Z~'I Val'ile~ fOZ_- <~=OillpO:lE'ilt:5 yin riltc~ b1 1:~ I~.e'_'ti C"Cl~~lCa~ , :pl~'.Ce 111 C~1E' fllc;rlLlir3C;i=Lar.it.lJ
=,.:~c: ~_> !; _e . ~f.~~I_.~.A :rwsse:~ r.m~~t hzVe sv.lffic:iel~lt stabs:_:~r~-~~
'.~ I~)t' t.~t~''t~~IiClC%1<:1. ill rtl~' Ctile2- ~lalld tl1(. pOwyTlIE~T-PllXt'~ll_;_,:, :, :a...:~r_ :!a!ve <I ~L :i.:~, ~r.': _le~T.~~ :~at>ability in the welding '~C ~rOCf~~.'~~.
~il ~.CC''W.~CciiCe= ~~ilt~-d fLIY'tE'lE_'r ellli~Gc~llilell'.= aCCOldiIlC~' t:~L~ ttl~e iTl~~E-nt::-~oli, ,'- .e ccw~r~or~ents b) can include additicnallv _t tEl.'r;?;~ntOr:?C~f' '_-? O.l'i '_rlf_ ~.~? «i.ip Or t':le rlOn-CO1?~LL~at.~'d d1E_I,_E'~.
. 1:_1-aX7lE-~ Iasr:-.~:I'.~Ll:ta'~ti~_~ --d1E_.T:eS dre 11r!eaTY ailp~latlC-d=:ellE'3, 1 W ~'' i.I?~Lati<'i- ]., i-)?~'X r~~[:;'ie, a~ky_.ldeneblCyClOaiu;E.'Tles 8',_ICil ds <~i tl'J11C:IWIiE=_2._r,C,YjOO?~I1CT1;~, ~i)''.'y'l:LCaE:nEi~JICyC:iOali;:c'lle8, :a'1C11 <.>
'~ --_u ~:.~~=nyi-2-hozbozv>ne, bicycloalkadi eves, ;~uc? as bic~uclopelvt.~<~.~i-~r,~e:; atld a l~seny:_ cyc:Laal:~enes, such as "ill'z'l;;~i'i'!i,Il~.~!ellE;~ Jr c1~~0 dl-:_'eaCt:l.Ve C!On-CO~I~Ll~ateC~
~'7.lel?e:~, ..~,.3L1,C:'I,:lS ~ .':-TiU''L'~)OT: 1'.C~1 ''TIE: Or l, G-OCtaCllene.
IJ'.~.,~~eClctilz' ~,~ eferred -~::e:~ _ --et ~lr-lide-ne-2-:~_orborllerle and/or l, ~-1-~~;;:Giena .
Tlle wei:~ht~ ~a~i.o of compoznent aj to cotnponelt bj _.~ ~J'~"Eifel,.cl~ iy 1'W'C,'vVe:_:rZ aI~OLI':; J i' : ~ anC'1 ~:c~ : f7~ , a?ld ,'110zE,-' ~:' <'i=f?"afilr' ~eL.Td-:C;'1 1~,'OLIt J~7 : ~~ i' to 60 : a() . he amount o:
;:vorr~pc~n~,rlt:s a) ~rrlc~ b) in the mater.-'_ai of the foil or of tIze -1-~ of ded br c:~,e p~-efe~wbl~, am=aunts to at least about ~~;'o by ~~.m~ic'~;_ al!:i mo~.r~ ~:rE-fwr~.b7.y av lea;~t about. 90%; by we~.~:~t-It.
T11 ao~cr:rdancE~ witrl the invention, the rrlaterial of ~~:tr:e: foil ;~,~ oitl:e rnou _ciecbody is present partly cros~:-~~ ;~r.h_eca. E;~pecia:: l~~ pr~?verrec~ the ge:i content of the ooiymer .. ..; _:i 7 w F7 ~l l '11 '~'.',.'Ll=C' -! S ~sEJ'~ tG ~~::",lli= 1 t _) '~7~r, p7~'Eii.ar~~bly bPtGJeaTl ~1~7;u1at a: ur,:d 1'~ % , ~.°=j~: <..c i :_L 1 =: r~ h~~e f eY_,-ed betw~ren bout. 10 a.ld r 0 '~ algid C. < oJ;=_Cicil ::l 1~~C~4?rdbl~' bE't~~J~WIi L~ al:d 3~) o . ~r'_'1:LS
~~i:i'. t=.~le ,~ i'.'<~tT~:~ ul'~e~ t~Ia' ;1 ilr-,,'': lIleCX r~~~'-l:C~ ?1G~! p~i0 ~ O~,;v' Of tL-lE? ~11'110Z:p~lOU:' ~~ ~.~.<WE- 1.~~ ~J' t~S~~'l;e ~J:ll: '~~lat:. thF- lnCrectSE~d ? at l0 O~
sOfL
L.ao~_~,nl.c~z- component,,, which improve the cold fle~:ibility eac.~s r c) 1_c> ii~',pairl~a~Int c>r tlm tempE-:=ra.ture stability o~~,~ing to the ~:;ro:~s-;~_ir~ltir~g. '~llc- cross-1 inki.hlg can be present alre~~dy in v~~ f~ y~~i~rm.Frr u,ixi.rlg ~:~r from or ~rfter the forc;airu:~ .r~ethod !nas 0 :..e:"a ~~E:_~z.-fozr',c ;,.
F~'t=rE-:_~zJly fC>r '=.~le OptlITll;~c~tl :'I1 Of CGl::
'_'__.~~:ibil;it,>T :-:n a.:idrdo Tlal polymer with a glass transfez y,~~ rWL:m> c~ _. ~<0~'C iJ clr.bo~died. i~e~-eby thi:w can be a ~.,_ _ .:~'Y~' _.~, ,. _l :r:F~CI t~l:'i:r'.Gpiavtl~~" E~i~3StG11E2_, pl:eft'_?~ct'i.~LV
~ t~ ' I-: tt;E- ~o~ia: <~_ l p Er_i~ll ':.y ~~ross-Bnked thermoplastic c.:lE-fin ;T!:~C~,, with a Ine.Lt i.nde:x '~1i'I (230°C: lOkg) of about _ t:~;::~ -~0 y:/lU m,_n. Tlis ~zlao reprcsent.~ for. ,~nst,a_~me ~i ~ll~ur:W_'.r-LikE:' JO~~iflle'= ;7Y~E'~ercltW~>~ a pC)ly'dlellE~ r t~,7~=1C1 C'ez'_1 i:11~~0 :.c:= _::..11't-~al l y ~~:~f~d~ 0~~2I,.atE d. Fllrt~leL" COIiIpOTIE;I'1tS
rOT.' ttlE' t.. ::i',,.S~;t_;'~T: C~'.'i:~C' C: _:: ~ E:X:i~l.~ =._t='1% cxrE: kI~O~~i T1 t0 t~IE spE=;J1c111~it "_mr ~~'>-.r t! f =;E~ ~r: ~ ~c:.~rdancE~ '.~~itl-! tine i-1ve11tion rnay I7tE: =.'r~_1T'. 1.Y1 ,.. CI:~i:!t ity Uf Lip t;~ ub0'_li= 2s.' ~ ~os,' '.vie;
~l":L ~ ~'1,_WE-'C~1 r~,, 1!~ ~= b~ v~e~ _~tlt of the ccmp~nents a? plus bj .
'rllEr ~;ol-.~mE~~- nI_~x.tl.re according tc the invenltior: care %~ m >~~-t_. j:roiil ':~m.. ~-c-''ude cusv.tomary additives, which dc~ I~ot a ~~:_~r t't_~= -ec,~ i~~~: d t~ra:TSpar~ncy of the fog ~ and Of t.~Ie :.~~.a eAo-c~ ,e ~~.-r ~m ~~~ .:~iso d:~ l:ot e~;:::entiaLly :~nf:iuel~ce ttI<e high ?_z"E.,~ltlLIlC~r G:~-~lCLUa')l~lt'y~. ~~OSS~x:7le dddlt:lVes :L11C1Llde url'~1 i_>1o:~1~~ agent:, lLlb~Yvcarlts, lic~llt prctec~ti~le agents, 'J _1':li=i :1Q''.lt~~, t~jE'.~, C?lgTilPni_S, fLalfle-YYE~tardalltS and/or a:~lt~_-r:tics . '!".le ~zdciit ive~ ar~~ c;ustornarily added .n amo~_.Iat~ <~f e.:p t~::~ 1C:=~, t'~- ~,;~~ia~at, rE~lateci to the quan; ity of polt,~::.eric uC:i.~:0l.eL_;C::. lil ' hce ~TiC.'GrpOr~atlOn Of plg,TlentS 1t 1 5 a'J_i_W-!W%' 7 d ~a~~thermore an: ad-~~antage i f the: r coucentrati cr_ l ies root ~.~~.~,-;F.re 3% by uJr igiv.t.-., prefez ably mot !,lore than 0 . ~'~ by weight .
The foil c_2r moo:~ded body according to the i Y:vwr,t.ion irc~;udi_lg the polyn-:er mixtures noted above arF:
~,az.,.L'~f~.I,:.~tured ~1 a~~c~orc~ancf~ with the normal meth<ads. Th_ru:
~~:_c=dL.<,tion of tl~e :~.ai'_ acvordir;g to the inventio!1 or of the n~,~<'_Ei:_c:l bodt~r ~sc~~~ iln ~:.he pure:~ly manual u,-ork se~oL,o.Y. Tims s:.;!'. t ::~-reiOrE' Lii::.- 1'ls~:~rlG.e Oc:~CL y b~~' e:'~t2:LlS'W :gin i:~' C:lE~ll~.~~r-Llr=
':C~ r..~_,t~~. rOrmclClVT~S ~Or L011S, wt111SL Lne rrlaIlLILaC!:urE' G1 :_:.) moulc~c-d bodiE~s c=an oe performed for inst_arlce using injection iIW~LiI dlng Oz' x; ~ os~J TT!.C>L11C~~.I1W prOCE'_SSeS . T;ieSE; prOd'~ICtS
C.'a:7 r_uen be subnli tted to the normal fur4her haandlin~, for '~115t.;~:I1C~' eve_t t~~i.T: t~'lE:' ~_iil~)Y'OVem~~:lt Of t'Ze Surface Stab111tV, .. be prop ,~a~c~ w~t-t: a ~;rotective coating. PrF-fE'~~abiy tha-. . ., ,~f~:c~_ of. t.:lEi f_~~~i 1 or o. t!~;e m.culdpd b~:~dy earl ';:~e sut;nii ~t<~d co1-ona pr~~cessi:ug, ~alasma processing or flaming to a.wpwotre it:s pril~~-ing capabiii~~y. Then optimally the pos~sibiiity ~:,xists of pr:;viding the foi..i or tlne moulded body ~:or instarlc~E~~~tll .~ sL;rface structure.
,. A fo i.i. manufactured from the polfs~mer mixture 1:~~.ar~~tit~g t. c: t=nci mve~.,;tio~~ :gall ,..~ i_~7..;,y'i for instance be manufactured as follows: Preferably the granulated raw material is mixed cold and taken to an extruder, for instance a twin screw extruder and there plastisizied. The material is then forced out through a broad slit nozzle into a stripware (foil) and taken up by the following devices. Moulded bodies are for instance obtainable by deep drawing or pressing from foil. Preferably cross-linking occurs following manufacture of the foil or of the moulded body. The foil obtained or the moulded body are advantageously halogen-free.
In accordance with an especially preferred embodiment of the invention the foil/the moulded body is formed in several layers, especially an intermediate layer in the form of a carrier layer can be present. Preferably the intermediate layer is interrupted, for instance perforated so as to improve the bonding of the overall item.
It can be advantageous if the intermediate layer is present in the form of a web, so as to facilitate stitching.
As already discussed the possibility exists of interlacing the foil or the moulded body even after its shaping. This can especially occur under the effect of electron or gamma rays. The radiation can here be performed on one side and also on both sides. The mechanical characteristics of the foil according to the invention can be controlled within determined limits by interlacing for instance by an adjusted ray dose. Advantageously here handling with electron rays is performed using a ray dose of about 10 to 500, especially about 30 to 300 kJ/m2. The gel content also, which is of major importance for the mechanical characteristics, is influenced by this.
In the context of the present invention the gel content is determined according to the extraction method, wherein following 24 hours extraction of material in boiling Xylol and 10 minutes storage in acetone at a room temperature following 24 hour drying at 60°C the quantity of the non dissolved material is determined and set in relation to the applied amount. Advantageously as already explained following the cross-linkage the overall gel content is preferably between about 1 and 60%.
Another consideration for the foil or the moulded body according to the invention is the so-called fogginct, i.e. the misting up for instance of a windscreen.
In a preferred embodiment of the invention, according to DIN 75201 B using the determination of condensation, amounts to < 1.Omg, and more preferably <
0.5mg.

.. ;.3_'~i-~;u7 The foil, especially soft foil, or the moulded body preferably finds use in the automobile sector as airbag covering, roof liner, supporting loops, rear parcel shelf, seating and back upholstery as well as the rear side covering of the front seats, sun shades, step plates, door side covering, boot covering, soft top covering, folding roof, double acting door foils or design elements in the furniture or shoe sectors.
As well as these, applications in the external covering of suitcases, book bindings etc are possible. In an advantageous embodiment as a folding roof the foil can expediently be built up from an upper and a lower foil, a carrier lying between them and possibly further foils and layers whereby the upper and lower foils include the polymer mixture of the invention.
The advantages linked to the invention are many sided. Thus in accordance with one aspect of the invention foils and moulded bodies are prepared which are not based on PVC and consequently are tree of halogens and plasticisers, but continue to show the advantageous characteristics of PVC
foils, namely transparency, capability of being welded by HF, stability under heat, flexibility when cold and in addition good UV and ageing stability. The disadvantageous emissions, which are associated with the application of PVC
foi'is containing plasticisers, can be avoided.
Thus the foils for moulded bodies according to the invention possess a surprising combination of characteristics as opposed to the state of the technology described at the beginning. The compounds have an excellent cold flexibility.
Therefore foils or moulded bodies can be made which even at low temperatures can be exposed to high dynamic loadings, without splintering. At the same time a sufficiently high temperature stability is made available. A further substantial characteristic of the polymer mixtures prepared in accordance with the invention is the capability of high frequency welding, whereby applications appear which with the systems matching the state of the technology have for a tong time not been possible.
Furthermore the foils/moulded bodies of the invention are transparent which is desirable for many applications. At the same time for applications in automobile or vehicle sectors the required stability under heat is provided, whereby further no additional surface shine appeared.

! ~ _,7 . :~ ~:
The foil or the moulded body of the invention facilitates thereby the targeted control of the characteristics profile and delivers a tailored compound for the corresponding application.
The invention is described in detail below using embodiments, which should not limit the possible applications. For the specialist, further embodiments are obvious in the context of the publication according to the invention .
Example In the examples the following application materials are used:
- EVA 1 Ethylene-Vinylacetate-Copolymer, MFI = 1g/10 min (190°C; 2.16kg) Vinylacetate content: 17% by weight - EVA2 Ethylene-Vinylacetate-Copolymer MFI =2g/10 min (190°C; 2.16kg) Vinylacetate content: 25% by weight - EVACO Ethylene-vinylacetate-carbon monoxide - terpolymer MFI =15g110 min ( 190°C; 2.16kg) Vinylacetate content: 20% by weight Carbon monoxide content: 8% by weight - PE 1 LLDPE with a density of 0.93 gll MFI =1g/10 min (190°C; 2.16kg), melting point 128°C
- PE2 VLDPE with a density of 0.87g/1 and an MFI of 0.5 g/10 min (190°C; 2.16kg), melting point 70°C

Example 1 Example 2 Example 3 (Comparison (Comparison (Invention) Example) Example) ~ -_.

~ PE2 45 35 Extrusion ratio iØ iØ iØ

Gel content [%) ~ 15 0 15 5% Module - 30C ~ 22 4 17 HF-Weldability ~~r iØ iØ iØ
~

Peeling force [N] 42 50 35 Transparent (Visual) No Yes Yes Light test stability Stage 1, loss Stages 4-5 of Stages 4-5 DIN 75202 5 cycles surface Braining Surface change following Increase in heat ageing 24 hours, None shine, None 100C flattening of Braining ~ Condensate (16h, 100C) 0,3 ~ 0,3 0,3 ~! to DIN 75201 B

i.O..................OK
Example 1 (Com~aarison example) 65% parts by weight of EVA1 and 35% part by weight of PE1 are mixed in a drum mixer and then in a twin roller extruder extruded to a 0.5 mm thick foil at 190°C.
The foils are then provided with a surface structure by pressing with a grained plate.
Pressing occurs at a pressure of 15 bar, 190°C for 5 minutes. The foil is then cross-linked.
For the HF welding test two foils are welded on a high frequency welding installation with a generator 64000 SD and press KH500, both from the Kiefel Company, at room temperature. The following welding parameters were chosen:
Welding pressure:1600N

Welding time: 4s Welding voltage:2100V

Electrodes: 150 x 5mm The physical and mechanical characteristics of the foil and the welded joints are summarised in Table 1.
It is recognised that by the addition of PE1 the E-modulus lies at -30°C at >
20MPa, and thus does not meet the requirements. Furthermore the material obtained is not sufficiently transparent. The characteristics with respect to HF
weldability, light stability and ageing stability were however fully fulfilled by the material in the heat.
Example 2 (Comparison example) The components given in the table were mixed. The manufacture of foil occurred analogue to Example 1. The cross-linking was omitted. A homogeneous foil was obtained with the characteristics given in the table.
The example shows a transparent, HF weldable foil which however because of the non-performance of cross-linking had not sufficient heat and light stability.
Example 3 Lnvention) The components given in the table were mixed together. The manufacture of foil occurred similarly to example 1. A homogeneous foil with the characteristics given in the table was obtained.

._ _ ~ ..3 ~1 - t': ~,~

Example 3 shows a foil composition as against Examples 1 and 2 which has the material characteristics of transparency, high flexibility in the cold, no heat ageing, freedom from halogens and excellent HF weldability.

Claims

1. A foil or moulded body comprising a material and a transparent and high frequency weldable polymer mixture comprising:

a) (I) a polymer that is a copolymer of ethylene and about 8 to 60% by weight of a comonomer selected from a vinyl ester of a saturated C1-C8 carboxylic acid, a C1-C12 alkylacrylate and a methacrylate, or a terpolymer of ethylene, about 8 to 60% by weight of a comonomer acid, a C1-C12 alkylacrylate and a methacrylate and carbon monoxide as termonomer, and/or (II) a polymer that is an ethylene homopolymer, an ethylene copolymer, a propylene homopolymer and/or a propylene copolymer having about 8 to 60% by weight of grafted units of unsaturated carboxylic acids, dicarboxylic acids, their esters and/or anhydrides, or (III) a mixture of two or more of the polymers of (I) and (II), independent of their group allocations, wherein the polymers or their mixtures have a melt index MFI
(190°C; 2.16kg) of about 0.2 to 15.0 g/10 min; and b) a copolymer of ethylene and about 10 to 30% by weight of C1-C12-.alpha.-olefin with a melt index MFI (190°C;

2.16kg) of about 0.2 to 15.0 g/10 min, wherein the material of the foil or of the moulded body is partially cross-linked with the polymer mixture.

2. The foil or moulded body according to claim 1, wherein the comonomer of component a) is present in an amount of about 14 to 45% by weight.

3. The foil or moulded body according to claim 1 or 2, wherein the comonomer of component (a) is present in an amount of about 14 to 28% by weight.

4. The foil or moulded body according to any one of claims 1 to 3, wherein the component a) is an ethylene-vinyl acetate-copolymer, an ethylene-methylacrylate-copolymer, an ethylene-ethylacrylate-copolymer, an ethylene butylacrylate-copolymer or a mixture thereof.

5. The foil or moulded body according to any one of claims 1 to 4, wherein the component a) is an ethylene-vinyl acetate-copolymer or a mixture of ethylene-vinyl acetate-copolymers.

6. The foil or moulded body according to any one of claims 1 to 5, wherein the terpolymer is ethylene-vinyl acetate-carbon monoxide terpolymer.

7. The foil or moulded body according to any one of claims 1 to 6, wherein the grafted units are selected from acryl acids, methacryl acids, maleic acids, maleic acid anhydride and fumaric acid.

8. The foil or moulded body according to any one of claims 1 to 7, wherein the polymer having grafted units is an ethylene homo- or copolymer grafted with maleic acid.

9. The foil or moulded body according to any one of claims 1 to 8, wherein the component a) has a melt index MFI
(190°C; 2.16kg) in the range of about 0.3 to 4.0 g/10 min.

10. The foil or moulded body according to any one of claims 1 to 9, wherein the .alpha.-olefin is ethylene, 1-butene, 1-propene, 1-pentene, 1-hexene, 1-octene or 4-methyl pentene-1.

11. The foil or moulded body according to any one of claims 1 to 10, wherein the component b) has a melt index MFI (190°C; 2.16kg) in the range of about 0.2 to 4.0 g/10 min.

12. The foil or moulded body according to any one of claims 1 to 11, wherein the component b) further comprises a cermonomer selected from the group of non-conjugated-dienes.

13. The foil or moulded body according to claim 12, wherein the non-conjugated dienes are linear aliphatic-dienes, alkylidenebicycloalkenes, bicycloalkadienes, alkenyl cycloalkenes or di-reactive non-conjugated dienes.

14. The foil or moulded body according to claim 12 or 13, wherein the non-conjugated dienes are selected from 1,4-hexadiene, 5-ehtylidene-2-norbornene, vinylcyclohexene, 3.5-norbornadiene or 1,6-octadiene.

15. The foil or moulded body according to any one of claims 12 to 14, wherein the non-conjugated dienes are 1,4-hexadiene or 5-ethylidene-2-norbornene.

16. The foil or moulded body according to any one of claims 1 to 15, wherein the partial cross-linking is expressed by a gel content of the polymer mixture of about 1 to 60%.

17. The foil or moulded body according to claim 16, wherein the gel content is between about 5 and 45%.

18. The foil or moulded body according to claim 16 or 17, wherein the gel content is between about and 40%.

19. The foil or moulded body according to any one of claims 16 to 18, wherein the gel content is between about and 30%.

20. The foil or moulded body according to any one of claims 1 to 19, wherein components a) to b) are present in a weight ratio between about 99:1 and 40:60.

21. The foil or moulded body according to claim 20, wherein the weight ratio of the components a) to b) is between about 95:5 and 60:40.

22. The foil or moulded body according to any one of claims 1 to 21, wherein the polymer mixture further comprises an additional polymer with a glass transition temperature of <= -30°C.

23. The foil or moulded body according to claim 22, wherein the additional polymer is a partially cross-linked thermoplastic elastomer.

24. The foil or moulded body according to claim 22 or 23, wherein the additional polymer is a partially cross-linked thermoplastic olefin (TPO) with a melt index MPI (230°C; 10kg) of about 5 to 30 g/10 min.

25. The foil or moulded body according to claim 22, wherein the additional polymer is a rubber-like polymer.

26. The foil or moulded body according to claim 25, wherein the rubber-like polymer is a poly(diene).

27. The foil or moulded body according to claim 26, wherein the poly(diene) is partially hydrogenated.

28. The foil or moulded body according to any one of claims 22 to 27, wherein the additional polymer is present in an amount of up to about 20% by weight based on 100% by weight of the components a) and b).

29. The foil or moulded body according to any one of claims 1 to 28, wherein components a) and b) are present in the foil or the moulded body in an amount of at least about 80% by weight.

30. The foil or moulded body according to any one of claims 1 to 29, wherein components a) and b) are present in the foil or the moulded body in an amount of at least 90% by weight.

31. The foil or moulded body according to any one of claims 1 to 30, further comprising one or more customary additives, wherein the additive does not repair the transparency of the foil or of the moulded body.

32. The foil or moulded body according to claim 31, wherein the additives are selected from the group consisting of anti block agents, lubricants, light protective agents, antioxidants, dyes, pigments, flame retardant agents and anti-statics.

33. The foil or moulded body according to claim 31 or 32, wherein the additive is a pigment in an amount of less than 3% by weight of the polymer mixture.

34. The foil or moulded body according to any one of claims 31 to 33, wherein the additive is a pigment in an amount of less than 0.5% by weight of the polymer mixture.

35. The foil or moulded body according to any one of claims 1 to 34, characterised in that it is halogen free.

36. The foil or moulded body according to any one of claims 1 to 35, wherein the material of the foil or of the moulded body is cross-linked with the polymer mixture by radiation.

37. The foil or moulded body according to claim 36, wherein the radiation is electron beam or X-rays.

38. The foil or moulded body according to claim 36 or 37, wherein the radiation is an electron beam of to 500kJ/m2.

39. The foil or moulded body according to any one of claims 36 to 38, wherein the radiation is an electron beam of 30 to 300kJ/m2.

40. The foil or moulded body according to any one of claims 1 to 39, characterised in that it is formed in several layers.

41. The foil or moulded body of claim 40, wherein the several layers comprises an intermediate layer in the form of a carrier layer.

42. The foil or moulded body according to claim 41, wherein the intermediate layer is interrupted.

43. The foil or moulded body according to claim 42, wherein the intermediate layer is perforated.

44. The foil or moulded body according to any one of claims 41 to 43, wherein the intermediate layer is in the form of a web.

45. The foil or moulded body according to any one of claims 1 to 44, having a surface, wherein the surface is subjected to corona processing, plasma processing or flaming.