Note: Descriptions are shown in the official language in which they were submitted.
05~1EI/1993 14:02 FROt1 TO 999~301#1613Z370045~ P.03
5'RA~SLATIO~
2~9~3~3
~erberts GmbH
Process, coa~cing means and apparatus for
~ - pro~uc~ion of coated gl~ss hollow bodi es
The inver~t$on relat@~ ~o the production o~ coated gla~;s
hollow ~odies, ~pQcially glass holl~w bodiec open on one s- d~,
such as glass c~r~taine~s and ~lass bo~ctles, ~y application
of a radical y a~a/or cationically polylllerizable coatiIlg means
and subseque~t ~ ening of the formed coating by ~eans of
energy-rich sad~ation.
I~ the prcsauct~o~ o~ gla~ bottles or glass co~taine~
par~ of the p~oduce~ objects occus with damages and weak placas
~shich do noe preses~t the ordinarily requir~d ~inimu~ irlterior
pressure str~n~eh of 16 - 18 b~r. In the case of stro~gly
ca~bon dioxid~-conta~.n~g bevera~es~, sue:h as, for exampl~,
cham~agne, glas$ bot~cles c;~n easily be stressed over this
mi~i~num pre~su~e l~mit, so that on ~onfulfillme~ of the
min~rrm seq~a~ert th~y car~ 'burst on ~h~ lsast strain. Since
despite spot ch8Ck c~trol it car not be entirely excludea
that s~ch o~ s leave t~e product:ion unobjec~ed-to! there
result-~ a corre~}?o~ding breakage po~ential in ~he ~illing of
be~erage$ usLde~ pre~s~re ~or exa~ple champ . g~e~ in ~he
~illing plan~s. 5'he greate ~c enda~gering p~oceed~, howev~r, from
a small perc~t;~ge of glas~ ~o~,le~ which ~arely ov~ the minimum
pressure st~erLgt~ go onto the market unobie6:~ed-~o d~spite F~e~ricus
selecting, and ~he~e throngh ext~:eme stress~ g of ~he glass
l~ottles quicicly goQs~ 1~Q10W ~he minimum pr~ssi~a.re streng~h.
MRY 10 ' 93 15: 00 P~GE . 003
~5~10/1993 14:0Z FRO~ TO 999~001~16132370045~ P.04
- 2 - 2~
As a rale, e~e~ely pressure-st~essed bottles, such as,
fo~ exa~ple, 0O75 ltr champagr~e bo~ctles, haYe as mean valu~
an intemal pl:essure strength of about 20 to 30 bar. Although
~lass is one o the ha~d~st and bri~tlest r~terials, its ~urface
is yeIIerally ~ub; ~ct to aamage . Damages occur in trade or
th the consumer, in sto~age or in the handling, in which th~o~gh
~echanical damage, for exasllple by grains of sand, the surfac~ of
glass bottl~s can be ~m~gs2d with cracks and scratches. Such damages
occurring in pr~ctice call be s~.mulated with a so-called
si~le liner t~, in which sever 1 bottl~s filled with their
o~ weigh~ rub on or~e a~oth~r in ~curning over a certain
period of time. ~ere, ~ttles coated nowadays with th~ usual
cold ~2nd impro~eme~t mea~3s, such a~, for exampl~, polyethylerle
d~spe~gion~, ten~ides, waxes etc. can ve~y ea~ily suffe~ from
~ cor~Q~pondipg sur~ce ~wag~, so that their internal pressure
s~abilitie~ ~all to ~alues below the ~ini~um requirements.
Sueh d~ma~e~ bo~tles repre~e~ ~he graates~ risk potential
for th~ c~n~um~r. In order largely to el~minate damayes o~ ~his
ty~e, on th~ pa~t of ~he glass pr~ducer~ for example champagne
bottles are ~an~f~ct~r~d for safety reasons with a corresponding
w~ll ~hicknes~, ~h~eby a highe~ weigh~ of the bottles is
accepted Ln~o the basgai~, in orde~ ~o onter into a minimu~
of d~mags ris~.
,93 l 5 01 P~GE .004
,
:
05/1~/1993 14:~3 FR~M T~ 999~001~16132370~45~ P.~5
_ 3 ~ `3
~ ncrea~ ~ gly nowadays, on ~h~ one hand by the consumer,
on the other ha~d from the marketiag side of the sellers,
decorative d~ma~ds are placed on glass bo~tles and glass
containers~ r~~any a~ filling plants of~e~ as unmist~kable
~ar~ sign a cQr~ain color tone of the glass bottles or glass
contai~ers, wi~ which they offer ~heir products to the market.
Ordinarily glass bottles are dyed with special tones in the glass
~elt i~ the area of ~h~ so-called ~eed~r. ~ere, in contrast
~0 ~he usual ~wn a~d ~reen tones, in in a restricted degree
5pecial dark-to-llght brown and green tones, in par~ also
blue tones, c~n be pr~duced. O~h~r color tones, such as,
for example, y~ to o~gge tone~, which a~e usual in
lightbul~s, cao~o~ be prod~ced in glas~ bottle , since such
colorations aS~ ~chà~ed i~ pa~ w th highly toxic s~lts, such
as cadmi~ ~al~. Also the dyeing vf gla~s wi~h other color
to~es, such a~, gor ~xampl~, deep dask bl~e or red, is likewise
to be achieved only with ~oxicologically ob~actionable heavy
me~l salts (cokaltl o~ ve~y expen~i~e addi~ives (gold).
In the literatu~e, therefore, p~otecti~e coating~ and
dQcorati~e coating~ for glass con~in~rs, such a~ glass bottles,
are described and are u~ed in pract~ce. An example for a
decorat~Ye ~pplica~ion ~ ~he ~o-called Plasti~Chield process~
~n which a foil of polyvinyl chloride or polys~yrene
is ~hrunk a~ou~d ~oetles. ~here was al50 d~3cribed the p~actice
of pro~idi~g gl2ss bot~les ~ith plas~ic co~ting~, in which there
~as also descr$bed ~he neea to apply ~uch pla~tic coating~ o~-line
~¢ed~ately after the p~o~uction of ~he gla3s bottles. In ~he
~RY 10 ' 93 15: 01 P~GE .005
.
05/10/1993 14:03 FRO~ TO 999~0~1~1613Z370~45# P.06
- 4 - 2~3~3
intern~ti~nal p~t~nt ~pplications WO ~0/05031 and Wo 90l05088 there
is describQd t~e produ~tion of transparent coa~ings on glass
cont~Lners whic~ ~re to yield a high luster and abrasion
~ .... _ , . .
resistance.~ Befo~e ~h~ applying o~ the tran3pa~2nt coati~gs,
~criptions ~d labels are appli8d to ~he glas~ containe~s which
a~e produced by t~e coati~gs. As coating means there are used
solvent-contaiD~ng lacque~s on an ac~yl basis hardenable by
ultra~iolet rad~tion. These lacquers are sprayed on, whereupon
th~ solvent i~ e~apo~ated off and the remaini~g coating is
hardened by ultr~violQt ligh~.
The know~ p~oces~es fo~ the production of a scrath- or
c~ipping protec~io~ or for the production of a decorati~
s~face ~ere p~s~ible to carry out hither~o only in th~ off-line
ope~at~o~. A~ o~ ne prod~c~ion ~as unable to pro~ide in
p~ctice. ~he on-lin~ production involves ~he production of
a large piece ~u~ber of bottl~s, fo~ example 200 to 300
bo~tles per min~te, i,e. of about 3 to 5 ~o~tles per second.
Xi~her~o no pract~cally ~æable ~ec~nology ~as available which
~a~e it possible ~t ~uch high cycle rates to p~oYide glass
~ollow bodie~ c~ a-~l glass bottles or glass con~ainers, on-line
~ith organic coat~ss, i~ orde~ ~o produce a glass~plastic
eom~osite mata~ia~.
Th~ probl~m of the inventio~, therefo~e, is t~ m~ke a~ail~ble
a protess fo~ t~ p~oduction of coatea gl~ss hollow bodies, such
as gtaS5 bottle3 ~Ad gla~s co~tainers, which can be adapted
apparatu~-wig~ aDd~p~tially to th2 current productioA processes
~Y l0 ~93 l5:02 P~GE.006
,
.,, '
.
05/10/1993 14:~34 FROM TO 999*0alttl6132370E145~ P.07
s 2~3~
fos glass ho~lo~ bodies ~nd leads ~t hish production rates to
glass hollow bodies wlth mech~nically and chemically stable
decorati~e and odor-f~ee surface.
It has proved ~hat t~is problem can be solved by a process
which rep~ese~s ~ obj~c~ o~ the invention, in which
glass ~ollo~ bodies pro~uced on-L~ne or in series succesively
~ade f~om a gla~ melt are sub~ec~ed to a cold end impro~em~nt
(~altendY~g~tu~g), ~o~ted and immedlately ~he~eupon coated with
a sol~ent-free, radically andJar cationically polymerizable
coating me~ns a~ a layer ~hickness of at lea~t g ~ , pre~erably
at le~s~ 10 ~ ~, whereupon the for~ed coatin~ is hardened by
en~rgy-rich ~adia~ion and theroupon bl~wn wi~h ai~.
T~ coat~ proc~s~ of the in~ention can be ca~ried out
ollowing upon the product~on that has occured in usual manner
o~ glass hollo~ bodi~s, such as glass bottle~ an~ glass containers.
The gla~ hollo~ bodies are produced in a manne~ familia~ to the
wo~ke~ i~ th~ ~e~d ~rom a glass melt, po~sibly provided with
a hot e~d ~mpro~emen~, coolQd and ther~upon suhjected to a
ccld ¢nd i~p~oY~e~t.
Th~ hot e~d ~p~ve~ent can be ca~ried out in usual
~a~ner a~ter ~he bo~tle production, fcr example by treatment
wi~h titaniu~ comæound~, such as tLtanium tetrachloride or
tin compounds, such a~ ~rrorqanyl compounds or tin t~trachloride.
~he hot end i~p~o~ent i5 ~ar~ied out for the elimlnation of
m~cro-cracks ~hich m~y arise in t~e area o~ the shaping.
PflGE . 007
MflY 10 '9~ 15:0Z
.
05~10/1993 14:04 FRUM TO 999~01~1613Z370045~ P.08
- 6 - 2~3~3
follow~ng ~pon the pos3ible hot end ~ro~ ment, the
gass hollow bodic~ are fed in general ~o a cooling oven, wh~reupon
a so-called c~ld impro~?eme~t is applied.
The cold islrpro~nellt se~ves in general as slippi~g protection
for thQ gla~s hollow bodies not supplied to the sorting line
~or physical qu~lity tes~ing and spot-check quality control.
slipping pro'cect:Lon ag~nts there were used, for example,
pO~ yet~lQrle aispersio~s or ten~ides, which are to avoid a
severe ~binq of the glas~ hollo~ bodies on one another
and therefore ~o a~,roid aIl ou~cer da~ge possibility.
In p~actice, followillg upon the sorting line, there occ~s
~ palleting or packing of the glas hollow bodi~s, which can
then be sent d:i~ec~ly to shipping.
Accord~ng ~o the inve~tion ther~ occurs following upon
th~ sortirlg li~e an on-lin~ coating ~i~h sub~ec~uent blowing
~itl~ air, whe~upon, if need be, a f~ther control occurs of
the appearallc~ of the coating (luster, course etc.), of the hardness,
of the laye~ ~ckne~s, of ~he Oao~ and other p~op~rties of
~e man~actured hollawglass bodies~ which can ~he~eupon be
palletea and mada ready fo~ shipment.
M~Y 10 '93 15:03 P~GE.008
05~10/1993 14: 05 FROM TO 999~001t~1613237004~;~t P. 09
- 7 ~ (; 3~
Accordin~ ~o a preferred ~o~ of execution of the i~ven~ior~
t:he cold end ~rove~ent is carried out by appryin~ of polyalkylene
glycol fatty-acid esters, in which the alkylene groups preferably
hav~ 2 to ~i:K~n a~o~. The fatty acids underlying ~he esters
are preferably hi~her fatty acids with, for ex~aple, ~ to 22
carbon a~o~, 5uch as cap~c acid, c~.prylic acid, l~uric cid
~yr~ qtinic acid, behinic acid, ~rachinic acid and, preferred
for rea~on$ o~ costs, palmitic acid ana stearic acid, suc:~ acids
being pr~sent ge~erally in the mix~ure. Such esters are
a~ailabl~ on the masket. tJsable commercial products are,
for exaalple, poly~chyl~n~ glycol fatty-acid estDrs of a mixture
o~ thQ fat~y acid~ l~st~d aboYe as examples, in which, for exa~nple,
the co~tent in palmitic acid amoun~s~ to about 40 o 55~ by wt.
and that in stea~ic ada likewi~e to about 4û ~o 559~ by wt
~ith re~pect ts~ the fatty acid constituent).
According to a pree~red form of execution the cold end
~prov@ment ~eu~s preferably used accord~ng to the in~ention
on the basis of the abo~e-desc~ibed fatty acid esters can b~ modi-
~ied by additio~ o~ sil~ne~, especially of one or more alkoxysilanes.
Such silane3 pr~se~t p~ef~ra~ly glycidy; groups; example~ are
g~mma-glycidylo~ipropyl~riwethoxy silane 2nd
gamm~-glycidylo~ipropyl-triethoxysilane. The quantita~e
ratio of ~at~y acid este~s to silane can vary from 100;10 to
1~0:1, with re~pect to th~ solid body wç~ight of the modi~ied
Gold and impso~nt m~ s.
~11qY 10 ' 93 15: 03 PFlGE . 009
05/10~1993 14:~35 FROM TO 9g9~001t~1613237~ 45~t P. 10
- 8 ~ 209~3~3
~ rhe coN end impro~emen~ means is generally sprayed in
aciueous solu~iosl, fo~ example with a solid substance con~ent
~rom 1 to 10~ b~ ~t. r pre~ably 2 ~o 5~ by wt.,
in installaticlns usual irl glass foundries, ol~tO the gla~s
hollow bodies~ obtained. These present in general ~emperatures
from llO to 139C, so that the wat~r evaporates and or~ ~he
aces o~ qlas5~ ~ollow ~odies ~her~ remains a film o~
the fatty acid esters as temporasyr.slipping protection.
S~rprisiIlgly it has proved according ~o thc inYentiOn
tha~ this fatty-aci~a es~cer 11m, whis:h possi~ly contains
silas~es, can se~ve as ad~esion impsover bet~r~Qn the glass
~ubstrate a~d t~e harde~a'ole coating later to be applied
by energy-rich raaiation, and, moreo~rer, contribu~ce to the ~npro~e-
~nt of the ~a~-~ re~i~tance (~he la~ter especially in the ca~e
of addition of "~ ~ila~e~).
~ ollowi~g u~ e c:old end i~roYement the glass hollow
bodies produced iIl the pl:Oc~x~ o~ the inver~tion can be subjected
to a u~ual-type ~ortirlg, in which the ~atty-~ci~ e~ter film
se~s a3 lubrica~t .
A~er tlle sort~ng, th~ glass hollo~ bodie~ presenti3~S~ the
cold end imp~ t can be coated with a sol~ent-free, ~adically
and/or cationically polymerizable coating agent.
~1~Y 10 '93 15:0~ P~GE.010
r ; : ;~
~5~10/1993 14:05 FRO~ TO 999*001~16132370245~ P. ll
As radically poly~erizable coating agents th~re can b~ u~ed
usual mono~ers, oligomers and/or polymers polymerizable or hard~nable
by energy-r~ Eadi~ion and, especially preferably, by W
radiation. ~uch radiation-hardenable monomers, oligomers and
~olymers ar~ ~a~iliar to the worker in the field~ ~h~y are
used alone or in mixtur~, in which connection it is to be
hee~ed that they have a viscosity ~uch tha~ an application
i5 possible in She liquid state without additon of solvents.
T~e application can occu~ in a usual ma~ner, fo~ example by
solling, dipping or f~lting. By rQa~on o~ the high speeds, howeYer,
the spray applicatio~ i preferredO Preferably the coating
agent c~np~itions are cho~en 50 ~at there is present a
~iscosity suitable for ~pray appli~ation, for example a viscosity
o~ 15 to 40, preferably 16 to 25, seco~ds at ~oom temperature,
as measured in a ~ord ~eaker, DrN 4 mm.
Examples for radically polymerizable coating age~ts,
egpecially coating agents harde~able by UV radiation, a~e
monomers, oligomers, poly~ers, copolymers or com~inations
theseof, wi~h o~e or mor~ ol~inic double ~onds, for example
ac~ylic-acid and meth~crylic-acid esters~ They can be mono-
unctional, di~Lx*ional, t~ifunctional and polyfunc~ional.
Ex~ple~ are b~yl ~m~th)ac~yla~e, dipropylen~ glycol di~m~th)asylate,
~ripropylene g~ycol di(meth)acsyla~e, ~rimethylol propane
~ri(m~th~ac~ylat~, p2ntas~ythritol-~tra(m~th)acryla~. Examples
~RY 10 '93 15:04 PRGE.011
.,
.
~5/10/1993 14:06 FRO~ TO 999*001~16132370045~ P.12
- lo 2~ 3
fo~ oligora~ærs are (meth) acryl ~uIlctional (meth) a ::ryl copolymers,
~poxiae resi~ l~etb) acrylates, such as ethyl~ne
oxide/propyle~e oxide trimethylol propane triacrylate (for
example with a molecular weight of 480); polye~ster polyols,
functionaliz~d with ~e~h)acrylic acid; mel~mines, such a~ hexameth-
oxymethyl melamir~e, parti~lly ethQ.~ized with hydroxyalkyl
(:~eth) acsylates; ~e~hanes of polyole~:, con~er~ed wi~h (e~pecially
aliph2Ltic) d~ is~ na~e-h~rdroxy (~Qe~ acryla~e adduc~s. The
expre~sion tsnee~)ac:~la~ used her~ and in the following means
at:~ylates s~ndJor me~ac~yla~es. The coating may contain
beside~ the radically h raehable monomers, oligomers and polymeLs,
al~o resins solubl~ in ~se, for exam~le ~ailicone ~Qsins,
especially t~e additon of mQ~~ silicone Lesins ~ such as,
for exaD~ple, t~e ~rade product RE~ ~0 of the raanufacture~ Wackex-
C~ernie. ~her~ s~ch resins are pre~ ed dist~ol~red in a solv~nt,
then the ~ol~ r~pl~ced by a rad1ation-ha~den2ble
~ono~ner, ~o~ ple a di tm~th) acrylat~, such as dipropylene
5~1ycol diacrylat~. For thi~ a sol~tion of the ¢ilicone re~in
i~ tre~ted ~i~h ~he ac~ te, whereapon the sol~ent is d$stilled
o~f ~ titativ~ly.
adica~ly p~lyme~f zablc coating agen~s usabl~
accosai~g ts ~ rentio~ may, according ~o ~. prsfQrrQd form o~
~eelcutio~, als~o contain adhesion facili~ator . As adhesion
facilitator~ t~er2 ~ce suit~d, for example or~a~ofunct~onal
s~lanes, esp~ci~lly ~;ilanes that co~ltain g~ycidyl g~oup~ Eszpecially
M~Y 10 '93 15:04 P~GE.01Z
05/10/1993 14:06 FROM T0 999~001~1613Z370045~ P.13
o~3~3
preferred examples ar~ 3-glycidyloxypropyltrime~hoxy silane
and 3-glycidyloxypropyltrietho~y silane, the latt~r bei~g
especially ~ red. SU~h adhesion facilitato~s may be
contained, fo~ ex~pl~, in amount from 1 to 102 by wt, with
respect to the coating agent compo~ition.
Slnce the coating age~s u~abl2 according to the inYention
are to be hard~nabl~ by rays, especially by UV radiation, they
contain p~eferably photo-initiato~s. Such pho~o~initiators
may be contai~ed, fo~ exa~ple in a~oun~s ~om 2 to 10~ by wt.
As photo-initiators usual pho~o-initiato~s are ~uited, ~uch a~
are facilia~ e field of the co~ting agent composition~
radically ha~denable by ~V radia~ion~
Example2 for pho~o-ini~iators which can be used acco~ding
~o th~ e~tion for radical polyme~ization, and which are
usual in the field of ~h~ composi~ions hard~nable by ene~gy-rich
radiations, a~ oso ~h~ch ab~orb, fo~ ex~mple, in the waYele~gth
range from 190 to 400 nm. Example~ fvr these are usual organic
pe~oxid~s ~d a~o compvunds. ~xamples for peroxides are
di-t-butyl perox~de, ~ibenzoyl peroxide, peroxocarboxylic
acids, Ruch as perv~Gacetic acid, peroxodicarbo~a~es,
such as di-sec.butyl~perpxodi~a~bonate, peroxide ethers,
~uch a~ 2^e~hy1~e~anic acid-tert.-bu~yl perester~, hydro-
pe~oxiae~, sucb ~ cumol pe~oxide a~d keton peroxide~, ~uch
as methylethyl ~etone-pero~ide. A~ ~xample ~or an azo init~ator
~Y 10 '93 15:05 P~GE.~13
05~10/1993 14:07 FROM ro 999~001~161323700~15~ P.14
- 12 -
~ Q ~
is azobisisobu~y~o nitrile~ Further examples ~or pho~o~ iators
a~e chlo~in6~-co~ai~.ng instiators, such as chlo~ contaLr.~g
aromatic c~ a~ èscribed, for e~ample, in US-A-4~089,815,
aro~a~ic ketone~, a~ describ~d in ~S-A 4,318,791 OL EP~A-
0 003 002 and EP-A-0 161 463; hydroxyal~yl phenones, as described
i~ ~S-A-4,3~7,111; phosph~x~idesl a~ described in ~P-A0 007 oa6,
0 007 508 and 0 304 783; Initiators on the basis of hydroxyalXyl
phenones, as de~cr~bod in ~S-A-4,602,097, unsaturate~ ~nitiators,
such as O~-fu~ctional aromatic compounds which were esterified,
for example, ~th acrylic acid, a~ dç~scribed in US-A-3,929,490,
~P-A-0 143 201 a~d 0 341 560; or co~bina~ions of such ~itiators,
~s descrihed or example, in ~S-A-4,017,652. ~lso favo~ably
u5ed are pho~initia.t O ~ 5 of ~he acylphosphanoxide t~ye
and o~ t~e bi~-~cylpho~phanoxide ~ypQ, such a~ are de~cribed ,
for exa~ple, in EP-~-0 413 65~. ~hey are sui~d, pos~ibily in
combin~tio~ h othe~ photo-initiator~, ~uch a~, or example,
o~ the hyd~o~yalkylphenone ~ype, e~pecially for colo~ed coatings
~hich ~e pi~Rn~ed t~a~parent to covering~ A p~eferred
e~ample for p~oto~nitia~o~s of the hydroxalkylph~none type
is l-hyd~oxy-2-~thyl~ x~l-propane-2-one.
Aceo~di~g to a p~efe~red ~or3 o execs~ion the ~n~e~tio~
relate~ to ra~ically polyme~izable co~ting agent~ which
~e u3able e~p2cially fo~ the c~ating of glaYs, fo~ exa~ple
gl~ss hollow bodie$, in t:he on-line and off-line proce~s, for
example, for the proce~ o~ the in~n~ion~ Such p~e~e~red coat~ng
~y ~ 0 ,93 ~ 5 05 P~GE .014
05/10/1993 14:07 FR0M TO 999~0al~16132370045~ P.15
- 13
2~9~3~3
~g~nt~ ~ontain
~) 1 to lO~ o~ one or more ~ilanes, i~ particular
glycidyl group-con~aining silanes as adh~sio~ facilita~ors,
for exampl~ 3-glycidy1Oxipropyltrime~hoxysilane and preferably
3-glyci~ylo~ip~opyltriethoxysila~e,
B) 1 to 10~ of one or more phosphoric acid monoes~rs of
hyd~oxyalkyl(~et~lacryl~s, i~ which the alkyl groups
preferably co~tain 1 ~o 4 carbon atoms and pref~rably
~epr~sene the ~hyl gro~p,
C) 2 to 10% ~y ~ o~ one or more p~oto-initiators, in which
tho~e of the ~ype of the hydrGxyalkyl or hydroxycycloalkyl
pheno~es a~ pre~xredt
and
D) ~s residue to 100~ by w~ di(~eth)acrylat~s, tri~me~h)
acryl~te~ a~d~or h~gher functio~al~meth)acsyla~es in the form
of monomer~, oligo~er~ and/or polymers, po~ibly together
with ~ono(~h)ac~yla~2~ ~nd/or silico~ resins,
~n ~hich th~ abo~e ~ompo~ents A) to D) add up to 100~ by wt,
a~ well a~
E) add~tionally po~sibly u~u~l lacqu~s addi~i~es, dyes a~dJor
pigmeats.
The ~ua~t~tati~e constitusn~s of lower ~nd higher-molecular
componen~ a~ ~hosen ~h~re so that the total composition
has ~pray Y~sCO~i~y-
MRY 10 '93 15:06 Pf:lGE.015
~35~10/1993 14: 013 FRO~I TO 999*0011:tl613Z3700~5tt P. 16
14 2~63~3
Accord~n~ to an especially praf~rred form of execution ofthe inYentlo~ ehe coa~ing agent contains, ~esides the abov~-
~ndicated co~ponentS A), B~ and C) in the amou~t~ given, S to
30~ by ~t of one ormoxe ~on-radiation-hardenable silicone
resin~ dissolved ln the other component~ and as residu~ to 100
by wt o~e or more di-, ~ri- tetra(~eth)acrylates and~or higher-
functional ~et~crylate~, in which tha abo~e co~ponents add
up to 1~0% by wt, a~ well as possibly in addition E)
lacquer-usual ada~ti~es, dyes and~or piqments.
Præf~rably the ~on-radia~ion-hardenable silicone re.~ins
presen~ react~ve hyd~ogen ~toms, such as, for example, hyd~oxyl
groups.
Wi~h t~e ~ilicone ~esi~ it is a matter preferably of a
Me~hylphenyl sil~co~e re~in ~hich is obtainabl~ on the market,
for example ~nder the ~rade na~e R~ 60. Such silicone resins
are pre~ent ~enerally in aissolved form, for example dissolved
in xylene andJor ~oluen~. The concentration in th~ solu~ion
lies generally o~ ~he order o~ abo~t 60~ by w~. According to
~he in~entio~ t~e ~ol~nt i~ ~aplac~d by an u~saturated, radically
polym~rizabl~ ~o~o~er dissolving the silicone resin, such as,
for example, pre~rably dip~opylene glycol diacrylate. This
can occur by a ~ixing of th~ solution wit~ dipropylen~ ~lycol
di~cryl~te a~d di~tillLng of~ o~ ~he sol~ent. Thus, ~or example,
th~re can ~e p~eparea a ~olution o~ the m~hylphenylsilicone re~in
in d~propyl2n~ glycol diacrylate in ~he weigh~ ~atio of about 60~40.
M~Y 10 '93 15:06 PRGE.016
05~10~1993 1~: 08 FROM T~ 999~01~1613Z37~045~ P.17
- 1S ~ 2~
Acco~ding to the abo~e-mention~d especially preferred
form of execution, the residue up to 100~ by wt can consist,
~or exa~plæ of a~ ethyle~eo~ide~propyleneoxide-trimethylolpropane
triacryl~te ~an oligomer with ~ mol~cular weight on the order
of 480), trlpropylQneglycoldiacrylate, dip~opyl~n~glycoldiacrylate,
trim~thylolpropan~triac~ylate, pen~aery~hritol7~etra~crylate
o~ mix~res ~hereof.
Accordi~g to ~ furthe~ e pecially preferred fo~m of execution
the coatL~g a~e~t usable accoraing to the in~ention contains, besides
t~e a~ove-;Rentioned corclpo~nts A), B) and C) in the abo~e-indi~a~ced
q~antitati~e constituent~, 5 ~o 40~ by wt of one or more di-~meth)-
acryla~e~, 5 to 40~ by ~ o~ one or ~ore t~i- an~/o~ more f~ncti~al
(~eth)acryl~ees and 0 to 20~ by wt of one o~ more ~ono(meth~-
scryla~es, as w~U as poss'~bly laqucr-usual addi~ives. Especially
p~ef~r~ed exa~ples for monofunctional acsylates usabl~ in thi~
form of ex~cution ar~ i obo~nyl-phenoxy~thyl-, tetrahydrofurane-
octyl-, di~yclopentenyl- and decylacrylate, ~hich can be
replaced e~irely or partially also by othe~ monomQrs, such as
~-vinyl~yrro~l~o~e. Po~ this for~ o~ execution especially
prefe~red e~ample~ of diacryla~es ~re hexanedioldiacrylate,
dipropyleneglyc~pled~acrylate, tripropyl~n~g~ycold~acrylate,
b~sphenol-A-diac~ylat~, a~ well also as hydroxyalkylacryl~t~s
~o~o~terified ~t~ pho~phoric aci~. For this p~e~erred for~
of execution e~pecially p~eerred examFles for tri- and more-functiona
acrylates are ~riffl~thylolpropane~riacrylate, ethyle~Qoxide/propylene
oxide-tr ~ ethylolp~opanet~iacryla~ ~oligomer with a molecul~r
weigh~ of about 480), pen~aery~hritol ~etraacrylake a~ well as
~1RY 10 '9~ 15:07 P~GE.017
.
05/10~1993 14:44 FROM TO 16132370045~ P.01
- 16 _ 2~ 3
polyfunctioDal p~osphoric acid est~rs o~ hydroxy~lkylacrylates;
poly~ste~ac~ylate~ in which it i-~ a mat~er, for exa~ple, of
~aturated polye~ers f~o~ mixtureS o~ polyvalen~ polyalcohols and
dicaboxyL~ c~d~, such as adipic acid which ara fu~ctionali2ed
wi~h ~crylic acia; ac~yl-~unctional ~elamines, such as h~xa-
methoxymethylmelaminet par~ially etheri~ied with hydroxy-
acryla~e~; r~ction ps~ducts of hydroxyac~ylate~ with dicarboxylic
acid ~rides, ~or Qxample mixtures of dica~boxylic acid
a~hydride~, ~nch a~ phthalic acid anhydride, tetrahydrophthalic
acid nnhyd~d~ andJo~ s~cinic ac~a anhydride; cycloaliphatac
and aliphatic epoxide acrylates, pos~ibly in mixture;
as well as pol~ur~thane-mcdified acrylates. In the production
of such coati~g a~e~t~ that contai~ highær-mol2cular mat~sials,
liquia monomærs ~e ~ix~d with hig~er-viscous, higher~molecula~
co~stituen~s in s~eh a~ou~ts ~ha~ spray applic~tion is achieved,
i.e., that ~he~ is achieved, ~or ~xample, a viscosity of 15-40
second~ ru~-ou~ ~i~e at ~oo~ temperature in a DIN 4 mm Ford cup~
~ o~ the proc~ss of ~he in~ention *here can be usedr besides
solvent-~see, ~adically polymerizable coating agent~, also
solve~t-~e, catio~cally polymerizable coating agents. The
coatin~ agQnts ~ay consi~ of ~ix~u~es of sol~ent-re~ radically
and catio~ically poly~erizable coating ag~nts.
As cationically polymerizable coat~ng age~ts there can be
u~d solven~-free coating agent compositions ~hat contain
compone~t~ polymeri2~b1e by e~ergy-rich radiation and
pr~ferably ~ radiatio~. A~ componQnts for 3uch coating agents
~he~e are especiall~ suited, ~or example thos~ which c~n~ain
M~Y 10 '93 15:4Z PRGE.001
05/10/1993 14:44 FRO~ TO 16132370a45~ P.02
- 17 - 2 0 9 6 3 ~ 3
a mixture o~ compon~nts co~aining epoxide gro~ps and hydroxyl
gro~ps. The epoxide group-containing compounds have at least
t~ epoxide gr~ups per molec~le, but they can also contain
three or ffi~e~ ~poxid~ -gzoups per molecule. In like man~er
the co~pon~nts usable as hydroxyl groups are at least difunctional;
there can, howe~er, also be u~ed c~mponen~s having three or more
hydroxyl g~oups per molecule.
l~ith th~ com~onents containing ~poxid~ groups and hydroxyl
groups it can be a matte~ of monomer, oligomer or polymer
compounds. T~e mo~ecular weights used there play no role, as also
~ith the raa~cally polymerizable components mentioned above:
the mixtures ~st ~erely be chosen ~n such a way ~hat per applica~ion
Visco~i~ies ~uieed i2~ par~cicular for spray application of the total
mixture are ac~ieved.
E~mple~ for usable di- and polyepoxide~ are tho~e on the
b~sis of cyclo~liphtl~ic diepoxid~, such as 3, 4-epoxycyclohexyl-
methyl-3,4-epoxycyclohexane ca~boxylate, such as the t~ade
products Cyracure ~VR 6110 o~ ~nio~ Carbide or Degacuxe ~ 126
o~ Degussa.
Fu~ther Qxumæles fo~ Qpo~ide re~ins wi~h two or more
opo~i~e g~o~p~ per xolec~le are thosa on ~he basis o~
Bisph~nol A, li~e th~ t~ade proauctS Epicote 828 o~ the Shell AG,
DER 331 of Do~ and B~ox EP 138 o~ th~ ~o~chst AG.
Mf~Y 10 ' 93 15: 43 Pf~GE . 002
' '
05/10/1993 14:~5 FROM -ru 16132370~45~ P.03
~634~
~ ere ~an ~lso b~ used lower-molecular monomers, ~or example
diglycidyl ~thers, ~uch a~ hexanedioldiglycidyl e~her
or bu~anedioldiglycidyl ether. Such diglycidyl ethers can be
u~d e~pec~ a3-re~ctive diluents for ~h~ dissolving of
higher-molecula~ products.
A~ polyol compounds thor~ can be used, for e~ample, di-
and tri~unct~o~al as well as polyfunc~io~al hlgher- and lower-mole-
cular polyols. ~here such polyols can be homo- and copolymerizates,
such a~, for e~a~ple, pol~ether polyols or adaition products of
po~yols to diepox~de~, for exampl~ ~he cycloaliphatic diepoxides
m~utioned abQ~ AS examples. Spe~ial ~xa~ple~ ~or u~able
homopolymerizates ~e polycaprolaceo~epolyols, di- a~d tr~func~ion~l,
such as the tr~a~ p~oduc~ Tone 0301 of Unio~ Car~ide~ Examples
for addition p~oducts are those o~ polyols ~uch as ~he a~o~e-
mentioned po~ycaprolactone polyol~ to diepoxide~, for example
the abo~e-me~tioned alicy~lic diepoxides, such as the ~rade
p~oducts Cy~acur~ ~VR 6379 and 6351. Through the cho~ce of
~igher or lo~ lecula~ polyols the ~lexibility of the
epoxides ~eact~ny ~ith ~ha~ in the coating can be influenced;
such polyol~, th~fore, a~e ~ ntly designated as 1exibilizers.
Into ~hQ ca~o~ically polymeri2ab1e coatinq ag~nts usable
according to ~h~ in~e~tion ~here ca~ also be worked copolymess, which
ordi~arily a~e not harde~ble by irradiation, such ag, ~or
e~ample, copolym~x~ on th~ basi~ o~ s~yrcnQ ~i~h Gl~finic monomers,
MRY 10 '93 15:43 P~GE.033
~5/10/1993 14:45 FRO~ TO 16132372045~ P.0~
- 19 ~ ~Q~
in ~hich th~ la~ter can al50 ~ontain functional ~roups, such as
hydroxyl ~roups; a preferred example for olefinically unsaturated
comonomerS iS allyl alcohol. Pr~fexably ~here can be used an
O~-functi ~ opolymer o s~yr~ne-~llyl ~lcohol with an 0~ number
of 188, such a~, for example, the trade produ~t ~ 100 of
Mon~anto Suc~ copalymoe~s are inco~porated in the hardening
of the cationically harde~able coating agent into the coaeing
~o~me~.
~ o the ca~ionically ha~denable coa~ing agents hard~nable
~y ir~adiation u~able acco~ding to ehe in~en~ion
pholo-ini~iator~ are added wh~h a~e us~ly excit~d by radia~ion and
ase famil~ar ~o the wor~er in the field. Such photo-i~itiators are
u~ed in usual a~ounts. Examples ase ~riarylsulfonium sal~s,
~ch a~ t~iarylsul~o~iumh~xafluorophosphate and
triaryl~ul~oni~hexafluoroane~mona~e; ( ~7 5-2, 4-cyclopentadien-
l-yl)~1, ~3,4,5,6~ ~ethylethyl~b~nzene~- iron(l+)-hexafluo~o-
phosph~te (1~
Tne p~oto~ ti~t~r~ can be used alone or in ~ixture.
Th~ cat~o~ically poly~eri~ble coating agents u~ableaccoraing to the ~veQtio~ ~ay contain, accordi~g to a preforred
~o~m ~f execu~ion, al~o adhesion facilit~tors. E~amples are
o~gano~uncSional ~ es, such as were de~crib~d already as
example3 for use in the radically polym~rizable coating
~e~ts~
M~Y l0 ~93 l5:43 P~GE.004
.
, ~ ' . .
05~10/1993 14:45 FROM -ro 16132370045~ P.05
~ 20 - ~ ~9~3 ~
The coating agents uged according to the invention on the
~asis of rad~cally and/or ca~ionically polymerizable binders
can be 'created ~ieh lac:quer-usual additives, such as, for exa~ple,
~lip additi~e~; tlubric~s), defoamers, flow means andfor UV-2lbsorbers.
It is a ma~t~r here of comme~cially usual products amilii~r to th~
worker in ~he field. AS 1c~w means there can be u~d, or example,
silicone oils. The coating agents used acc:ording to ~h~æ invention
s~!ay al~o cont~in p~gmen~cs and/or dy~5. It can be a matter h~re,
or example, of ~ranspar~nt pigments and~o~: covering pigmen~s
as well ag ~ra~sparent ~d/or covering dyes.
Such addiei~es, pigment~ and/or dyes are added in a~ous~ts sucb
~hat they do no~c ~d~er~ly affect the radiaeion-hard~2nability of
~he coating agen~s.
Accoraing to a pref~ær~d form of execution the cationically
polymeri~able eoat:~.D,g agents usable according to the inve~ntion
con~a:i~ 10 to 80~ by ~ o~ an epoxide resin on the basis of
c~c~o~liphatie aic~pox~de3, con~aining one or mora, at least ~wo
epoxidR group3 }?er Dso~ecule;
5 to 50~ by ~; of one Ox ~aore liquid polyol~ with at leas~ two
hydroxyl g~:oups ~ the ~tolecule, as flexibilizer,
S to 50~ by w~ o~ one or moLe liquid diglycidyl ether~; as
reactiYe thinne~s;
TOT~L P.05
~RY 10 '93 15:44 P~GE.005
~ , ,
05/10/1993 14:10 FROM TO 999~0æ1~16132370045~ P.20
- 21 - 20~ 3
5 to 30~ by w~ o one or more epoxide resin5 on the ba~is of
bisphenol ~;
o - ~0~ by wt, p~ef~rably 1 to 20% by wt, of one or several
copolymers of s~y~ene with ~ olefinically unsa~cura~ed
-- O
~onomers, ~sFec~ally allyl alcohol;
1 to 5~ by ~rt o~ one or more photo-initia~ors and
1 to 5~ by wt of OnQ or mo~e sila~es, preferably glycidyl-
~oup-cont~ini3g s~lanes,
the abo~e compone~ adding up to 100~6 by wt. ~o ~his compc~sition
there can be a~ded lacque~ usual additives, dyes and/or pigments.
In the p~oce~s acco~ding to th~ inventior~ the coating agents
poly~neri~able ~y energy-rich radia~c~on are applied prefera~ly by
spray application ~o the ~lass hollow bodiQs coat~d with th~ cold ~nd
impro~ement agen~. T~e layQr thickness is a~ least 8~m, p~efera~ly
st least 10 ~m and especially preferably at l~st 15 ,~m,
w-~h respect ~o t21Q d~y film thickne~3s achieved after the
ha~deni~g. Pr~f~ably ~he gla~;s hollow bodies to be coated
have t~mperatu~e~ of, for ~xample, 2S ~o ~0 C, especially
preferrably fro~a ~0 to 70C. If sst~ch temperat.tre~ are no longe~
preserlt af~er ~e cold e!na improvement, the glass hollow ~odies
~o be coa'ced can be ~b~ected to a pre-warm:Lng, for exa~ple
n~zzl~ ie~.
Th~ spr2ly~7 proc:ess occurs in the process of ~ch~ invention
preferably wi~ho~t u~e of a protective gas. The l2~tter, ~or
example ni~eogen, i~ ~regu~ntly necessary in known proce:sses f~
the ~chie~ement o~ n layer thick~esse~:,
MQY 10 '93 15:08 P~GE.020
E15/1~/1993 14:1EI FROM TO 999~ 16132370045~ P.21
- 22 - 2~963~3
The sp~ y~ng process takes place preferably i~ an encapgulated
spraying apparatus, ~hereby ~rotected from du~t, in which the
o~erspray obt~ned is preferably recycled. This ca~ be done, for
example by~ ecting th~ ovcrspray in a wet t~ickling w~ich
consists o~ the coating agent. The mixture o~ ov~rspray and
coa~ing agent dra~n o~f from the chamber can, i~ need b~, be
returned over a ~ilter to the wet sprinkling and/or to ~he
spraying apparatu~.
The coated glass hollow bodie~ emerging from the coa~
zone, or exa~pla the spr~ying chamber, are ~mmediately thereupon
hardened out by e~ergy-rich radiation, for example UV-radi~tion.
~his ca~ occur in a harden~ng zon~ engaged on outlet side of the
coating zonc, or example a W -drying chamber, where the
coate~ glass hollow bodies are conducted yas~ on~ or mose
ir~adiation ar~angements, such a ~V-radiators. Preferably
such radiator~ h~e power of 80 - 240 W per cm (radiator length).
In the process of th~ invention ehe coated glass hollow
bodies ~r~ su~iected, af~e~ the hardening by energy-rich radiation,
to a heat treat~en~ which leads to an aft~r-hard~ni~g, ~s well
as to extQnsi~e eliminatio~ of odorc~ ~he heat treatm~t occurs
by blowing w~h ho~ ~ir of about 100 to 400~C, preferably 200
to 300-C, ~or about S to 30 seconds, preferably 5 to 10 seconds.
For t~is ehere are ~ted, for example, a circulating air
oYe~ o~ a USUdl nozzle drier~
MRY 10 ' 93 I S: 09 P2GE .13~1
05/10/1993 14:11 FRO~ T~ 999~001#16132370045~ P.22
- 23 - 2~963~3
The~ cc~ated glass hollow bodies l~aving thQ hardening zone,
can, ater the aboqe-described heat trea~ment, be blown if need be
Wi~ cold air ~about room temperature on th~ order of 1~ to 25~C~,
U~ti~ they~re~c:hed a te~per~ture of about 40C or below.
By this blo~nç~ it becomes pos~;i})le to el~ninate any undesirad
odors, so th~ the ~:oated material c:an be s~pplied directly to
the palleting and, if need be, packing ~ith subsequent
shipping.
The proce~s of the invention is preferably carrie~ out Wit}
a~ appa~atus ~ich follo~ directly upon the usual produc~ion of
gl~ss hollow bodi4s, 3uch as bottl~ , with subsequent cold end
im~ro~e~t.
~ rhe p~ocess of the invention can be casried out on-line
follow~g upon the p~oduc~ion o glass hollow bodies and their
cold ~nd i~npro~e~ent~ Af~t~r the~ cold end improvesnent ~he bottles
are transpor~ed om~d in a usual mann~!r, for example
wi~h a con~eyor bel~, ~he bottles being ~n con~ac~t with one anothr.
Before executio~ o~ coating tho ~ottles~ are firs t singled.
This can be don~ in a tlsual mar~ne~:, for example by reception in a
wo~m which sepa~ates the glas2s hollow bodies from one ~nother ~na
subsequent sep~ration with a star wheel. The glass hollow bodies,
~or ex~pie ~he bo~tles, are the~eupon taken up pre~errably
at the upper open end by a gripping device and conducted, ha~Lging
do~;nward, to ~he ~E~rayi~g aevice.
MRY 10 ' 93 I S: 09 P~GE . 022
~5/10/1993 14:11 FROM ro 999~ 16132370045~ P.23
- 24 - ~ ~9~3~3
The g~ipping device i~ pr~ferably constructed me~al-free
in the part~ touching the glass, of a high-temperature resistant
material, for exa~ple of Te~lon poly~mide~ and/or polyphenylene
sulfide. ~ ~rably~th~ g~ipp~r is protec~ed by a t~mplat~
tm~triX) agains~ spray fogs. Th~ t~plate can be constructed
~her2 in such a ~ay that it is adjustable to prevent spray fogs from
passing into o~ onto the orifice zone of the gla~s hollow
bodies or bottles. The gripping de~ices are formed i~ such a way
tha~ the gla~ boll~w bodies can be in~roduced ~n~o the ~pr~y
zone hanging do~nward. For ~xample, the gripper devices can be
~ounted on c~ain co~veyor ar~an~m~nts.
Before the i~roduct~on of the glass hollow bodies into
the ~p~ayi~g zo~e t~ere can ~e provided a warmi~g device, for ex~mple
a no~zle drisr. This war~ing device serves to prehe~t glass hollow
bodies ~hat ~ere ~oo strongly cooled, to ~mperatures o~ 25 to
7O3C, pre~erably SO to 70~C, before the introduction into the
sprayi~g zo~e.
As spraying zo~e ~here ser~e5 p~e~erably an encapsulated
~pray cabi~ O~aQr ~0 a~sure a dust-fr~e opera~io~. ~oreo~er~
the spray cab~n is preferably ~o~med in such a way that no daylight
can be admit~d, in order to avoid prema~u~e polymerization of
th~ coating msterials hardenable by W -rays. ~his is especi~lly prefera~
when overspray ~s to be coltec~ed and ~ecycled. If ne~d ~e,
the spray cabi~ can be illuminated with W -re~ ht, for example
~ith yellow l~ght.
M~Y 10 '93 15: 10 P~GE . 023
,
05/13/1993 14:11 FROM -ro 999~001#1613237æ45~ P.24
- 25 - ~o~3~3
~ he lac~uQring or spra~ g c~bin is equipped with one or
more, pref~ra~y ~bou~ three spray guns per object to be lacquered,
sn which conte~ it is a matter of t~aveling guns. ~here can
~l~o be provided statior~ary gun5 on lift sle~s. Preferably
t~e sp~aying proces~ is carried out by compressed air or as
an airless psoce~s. ~he glass hollow bodies can be turned
by a f~iction driYe, for example at 1 to 10 revolutions per
second, in orde~ ~o e~sur~ a uniform lacqyering.
~he temperatur~ o~ lacquering by sprsying ranges, for example
between 20 and 5~ de~r~es C.
The spray ~abi~s, accordi~g to a prefarred form of eXecution
of the in~en~ion, are con~ruc~ed in such a way that a recycling
of ~he overspray of the co~ing ma~erial is possible. ~or this
the spr2y cabins a~d th~ parts touching material a~e ~referably
of high-grade 3teel, so. that no corrosion can arise ~d thQ
coating ma~e~ial ~ ~ ~ot polyr~eriz2d by met2-1 in~luences.
For the recycl~g of th~ ove~spray the spray cabin i~ equipped with
a wet trickling zo~e, ~o~ example in the ~orm of ~he back wall
of ~he ca~in. A~ ~luid for the ~prinkling of the wet trickling
~one and for ~he ~et separatio~ there is used ~he coating material
to be spr~yed. This can be retu~ned over annular and tap lines
over onQ o~ more pu~ps and possibly through filters together
~ith the o~r~pray to t~e ~et ~rickling zon~ on the one hand
and to th~ spra~ guns on ~he other hand. In ~his ~annes it is
possibl~ to avo~d ~he formRtion o~ ~astes and the solvent-f~ee
coating material ca~ be pracessed with an eficiuncy of nea~ly
~0~ .
MflY 10 '93 15: 10 PRGE .E124
, .
~5/1~/1993 14: lZ FROM TO 999~01~1613Z370045~ P.Z5
20963~3
26
~ rhe wet trickling zone can be fo~m~d in a u~ual ma~ne~.
Por example, t~e cabin can be equipped with a whirling washer or
~ith a de~ice for narrowing the air passage, whereby the air
8peed is i~s~d, as, fsr example, a ttenturi no2~1~. Ir.
aadition ~ cen~r~ ~ugal 3eparation can be provided.
Acco~d~g to a preferred fo~m of execution, behind the
whirling washe.l: or the Venturi a~vice ~here is installed an
~ddi~ ional wet s~para~ion . For ex~mple, behind the whirling
~asher or ~:he veat~lri de~ ;e there a~e present insets wit~ Raschig
rings or other cera~ic b~d.ies as W411 as po~ibly insets of
additional h~gh-gr~de steel reboT3na ~ilter ~is~;ues, in order to
ensure a com~lete separating of ~c~ae coating and o~erspray material
from ~e exh~use air.
Additionally the~e c~ thereupon be installed a wet filter
c:onsis~ing of f?lates ol: ba~s, in ord~r to ~eet the lggal oxhaust
air regui~e~en~s.
The coating agent con'caining ov~rspray, o~tained from the
~et tr~c3cling zo~ of the ~2pray cabin, can ~e r~turned through
an~ular line~ ~or the we~c ~prinkling into ~he spray ca~in a well
as ~or ~upply~ng of the ~pray guns. The annular lines are provided
~or this pu~ with pumps~ Preferably al50 filters are
~ntespo~ed 'ce~ re~D~ i~urities. ~f neea be, the coati2lg
agent obtained ~ n thQ wç~t txickli~g zone ~an be conducte~
o~er a ~supply co~aina~ ibly also to the degassing. The
d~gass~g car~ take plac~ in the suppl~r container, for example
o~rer ult~asou~d o~ by equipping a E; a subp~assus; e cham~er or by
~:un of of ~he m~,c~o~oas~ o~er a heate~ run-o:e~ plate.
~Y 10 ' 93 I S: 10 P~GE .025
,
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05/1~1993 14:12 FRO~ TO 999~001~16132370045~ P.26
- 27 ~ 63~
Prom the ~pray zo~e ~he coated glass hollow bodies are
fed to the ra~iation-hardening installation, for example a
~V-drier. In orde~ ~o achie~e a radiation shi ld ~ g, the
eonduction can occur oYe~ a usual ~type omega loop or
r~routing.
The irradiation occurs with radiator3 with power o~ the
orda~ of 80 to 240 W/G~, preferably abou~ 200 W/cm. There can
be used, for exampl~, ~ercuxy high-pressure radiators, microwave-
ignited fus.~on sy~te~ or Excimer lasers. ~he coa~ed glass hollow
bodies are conduct~d past several radiators, for example 2 to
3 radiators, in ~h~eh proeess there occu~s, fu~her, a riction-
driven ro~ation about its own axis. ~ssentially ~he production
r~te is de~enminad by ~he nu~bar o~ radiators. By the use of
se~eral ~igh-po~r r~diator~ and the rota~ion of th~ glass
hollow bod~s it is p~ssible to maintain a very compact
ma~ner of consts~ction of the d~ying installatio~.
A minimizatio~ of the dri~r l~ngth can be made by placing the
~ad~ato~s o~f~t oppositely, so ~ha~ in each case differen~ zones
o~ the glass hollow bodi~s c~n be irr~diated s~multa~eously.
The gla~s holl~ bOai~S coming from the drier are conducted
through a high-~e~mpera~r~ aft~rtrQatm~nt zone. I~ thi~ there
can take place, for ~xa~ple, a bri~ blowing w~th hot air ~a
usual nozzle drier or racirculating air oven can be used). The
air temperature is fo.r exa~pl~ from 100 to 400CC, pr~fer~bly
200 to 400C, e~cially prefer~bly 200 to 300~C a~d ~he
M~Y 10 '93 15:11 P~GE.0Z6
'' ' . ,'"' ~ ~ ;'; '
05~1~/1993 14: 13 FROM TO 999~0~1#1613237æ45~ P.27
- 28 - 2~63~3
treatment wi'ch thi~ hot air takes place, for e~camplQ, fo~ S
to 30 seconds, in whi::h process th~ glass hollow ~odies can continue
to be rota~ By such a high-temperature a~tert~eatme:Dt
t~ere OCCUr5 a~ ove*heating of ~he dried lacque~ film, ~he~eby
fragme~ts consis~in~7 of photoimeiator co~ponents and disinegratior
process as well as ~esiaual monom~rs are removed.
Thereupon ~er~ can be prescribed before and/or after ~e
~ake-off; arrang~ t divices for the blowins~ of th~ gl~ss hollow
bodies with cola a3.r ~roo~ temyera~ur~ about 15 to 2~C~. The
blowing cont~nues ~ntil there i-~ achieved a ~emperature o~ the
glass hollo~ ~odies of 4Q C or lower. By thi~ blowing ~esidua
odo~s are removed from th~ glas~ ~ollow bodies, so that these
can i~diately be co~ducted onwa~:d ~o ~he palleting, packing and
shipment.
The depos~i~ing o~ ~he glass ho~lo~ bodies from the gripping
device occ~lrs, ~or e~cample ~ a star on single-liner, for
e~cample before 'ch~ ~lowing with ccld air.
Af~er ~he coating installatio~ ~before the drying irlstallation),
im~ediat~ly a~t~ t:he d~ g in~alla~ion (before th~ hot-air
treatment 20ne, 0~ after the hot-air treatment zone) thera can
bt~ provid~d ajeC~or de-rice~ which ~ither prevent faul~ily co~.~ed
gl~ss hollDw bod~es f~oT~ e~tering the drier zone, or pr~nt
urldried or inadeguately dr~ed glass hollow ~odie~; f~om pa~ing
nto ~he t~c6~ff star ar~d leaaing there ~o foulings.
Mf~Y 10 '93 15: 1 I P~GE .027
. ' .
05/10/1993 14:13 FRO~ TO 999*0~1~161323~0045~ P.28
29 - ~0~63~3
In the att~ched figure ther~ is represented a~ example for
a pref~rred fonh of ~xecution of th~ appara~us acco~ding to the
i~ventio~ . -
_, . . .
In ~he fi5~Qre, 1 designa~s ~che inflow (input), for ex~aple ~'a conveyor belt, co~ing ~:o~ the glass hollow body production
and cold end im~?rov~ment. 2 signifies a branch-off which lead~
~o a secorld coating de~?ice of the salTle construction. ~or safe~y
xeasons it is prefe~ed according ~o t~e in~ention to carry out
~e coating and hArde~ing process i~ tande~ operation T. Over
t~e inflow 1 t:he glass hollow bodies are introd~ced into an
erlcapsulated system and, o~er a wOL~ 3 and a star 4, suspended
with the opening up~ard, introduced into the lacquering cabin
(spsay ca~in) 5. The coa~cing occu~s at the spray place 6 by
means of sp~ay g~s. The lacquering cabin is p~eerab1y equipped
wi~h a wet tri~îi~g :~o~e 7, which is rinsed with the coating
agent. This is~ rQcycled to the w~ sprinkling and to the spray
quns. l~he coa~ing e~genl; u~ed fo~: the wet sprinklingp containing
over~pray, ist collected o~ khe bottom of the cabir~ and the
Q~chaust air is i~troduce~ o~er a tusbulence zos~e or ~renturi
~02zle into ~ cabin lying behind t~e lacqueLing cabin a~d
there ara~rn off by filter insets o~ Raschig ~ings (~ot rep~esen~ed
i~ the figure) a~d pos~ib9y filter-tissue inlays of high~grade
s~eel o~er a d~off fan 8.
~ h~ coated glass ~ol~o~ bodies are ir~ 0duced, hanging, o~er
a de~lection 9, ~hic~ ~SS~ as radia~io~ protec~ion, into the
~V-drie~ 10 and there conduc~ed ~a~3t se-reral W-radiato~s '1~
~he glass h~o~ bodies eme~gin.g fro~ ~he W-dsie~ a~e contucted
trl~Y 10 '93 15: 12 PQGE .0213
~5~1~/1993 14:14 FRO~ ro 999~001~16132370~45~ P.29
- 30 - 2~3~3
hrough a high-~emperature afte~treatment installation 12,
in which case it i~ a matter o~, fo~ example, a high-temperature
an, a~d deposited over a star 13 on a single-liner 14 (tak~-off),
whe~e there caa occu~ an ~f~e~eatm~nt with cold air 15~ The
a~tertreatment wi~h col~ air can al~o occur already directly
~ollo~ina the ~igh-te~perature trea~ment, for exampl~ before
ehe star 13. 5v~r the ou~low 16 the yla~s hollow bodies are
co~duc~ed on~rd out of th~ closed system for the palleting,
p~cking and shipment. At ~he places designa~ed with A of tne
fisure the~e can be provia2d rejection devices which reject
incompletely or poorly coated glass hollow bodies or inco~pletely
dried o~ no~-dried gla~ hollow bodies. Such devices can be
con~olled by usual-type ~aul~-detec~ion systems.
3y the p~esent in~t~on there is made ~eady a proce~s
~hich m~es possible the coa~inq of glass hollow bodie~, especially
bo~tle~, in the on~ e p~ocess immediately following upon ~he
glass productio~ or gl~ss hollow body p~oducton in actual
prActic2. By ~ha p~ocess there are prepared glass/plastic
c~mposite s~b~a~ce~ tha~ yi~ld an exc211ent surface protec~iOn
o~ glass hollow ~odie~. Dangers that are yielded by sur~ace
d~mag~ of gl~ss hollow bodies, especially bottles with
rola~ively high i~ternal pressure, are therewith avoided.
I~ also beco~e* ~oss~ to produce decorative coatings,
such as ~he most di~er~e colos to~es, reproducibly. Through
the process of t~e ~nventio~ th~re is made possible a high
p~oduction ra~e which lies, for example, at ~00 to 300 bot~ïes
per minute. The p~ocess of the ~n~sntion ca~ b~ executed with
l`lflY 10 '93 15: 12 PRGE .829
"
05/10/1993 14:14 FR5M TO 999~001~16132370045~ P.30
- 31 - 2~63~3
le~rice3 of co~p~ce c~n~ruction which do not present
any l~rge ~patial demands. l~he process can be carried out
in an environmen~-fxiendly manner without solven~ emission
a~d is not~ o ~h~ readying of pro~ec~iYe gases ~ such as
nitrogen. By the use of solvent-free coating sys~ems a recycling
of the coating m~terial in the sp~ay pro~ess is possi~le~ so
that a high ef~iciency is achieved~ Odor~ess glass hollow bodies
are obtai~ed, ~he inte~io~ o which is free from contami~ations.
This i espe~ially important in the production o beve~age bottles.
The process of ~he i~vention can be applied especially fa~oræbly
for bottle~ which are to receive ~everages with high ca~bon dioxide
content, SUch as, or exa~ple, lemo~ade and champagne bo~tles.
The environ~en~al f~iendlines~ of the process o~ the inv~ntion
is also heig~e~ed ~y the mea~s that, acco~ding to a p~eferred
~or~ of exec~t~on, spccial cold end improvem~n~ means are used
which do not ha~e to be remo~ed before ~he coating.
The following exxmples s~rva ~or the explanation of coa~ing
agent comyositi~ prefe~ably u~able according to the invention.
Production of solven~-free coating agent compositions
~ith a aon~e~t o~ 3ilicone ~esins not hardenable by ray~:
The ~ilicone re~ins us~d in e~mples 1 and 2 a~e commercially
usual ~ethyl-p~e~yl-siliaone resias ~ rade product RE~60), which
~re ob~ainable a~ 6U~ solueion in ~ylene/toluene. In ord~r to
obtai~ sol~e~t-free binde~s, th~ solutions wer~ treated with
~ipropylene~lycol diacrylat~ and ~he solvent mi~ture txyle~e/~oluer.e)
~RY 10 '93 15:13 PRGE.030
05/10/1993 14: 15 FRO~1 TO 999*001~16132372~45~ P.31
- 32 _ 2 ~ 9 ~ 3 4 3
was q~alit~ ely distilled off, so ~hat there resulted a solution
of m~hyl-phenyl-silane resin of dipropylene glycol diac~ylate
of the ~he weig~t ~a~io. 60:~0.
, . ~
Example 1
The following components w~r~ mixed with one another for the
p~od~ction o~ a r~dlcally po~ 2raza~1g ~ clear coati~g age~t:
Monoe~te~ of hydroxyethylac~ylatQ wi~h phosphor-c acid 1.0% by wt
3-glycidyloxypropylt~imetho~y~ilane 3.0~ by wt
Phot~i~itiato~ hyd~oxy-cyclohexyl-phenylketone 4.0% by wt
~thyl P~R~yl-silicone r~sin 10.0% ~y wt
Dip~opyl~negly~ol ~i~cxylate 32.0% by wt
Trspropylene~ly~ol diacrylate 27.0% by wt
E~hylene oxide/p~opylen~ oxide-trime~hylol propane t~iacrylate
(Ol~go~riacrylate, mal~cula~ wei~ht 48~) 15.0~ by wt
Peneaery~hritol ~Qtraacrylate 7.0% by wt
~sual defoa~er~ 0~5~ by wt
Silicone o~l 0.5% by wt
~xampla 2
Production o~ a ~adically polymeriz~ble, white coating ag~nt
Th~ ~ollowping c~mponents Ne~e mixed with one anothe~:
Mono~st~ of hy~oxyet~ylac~ylate with phosphoric acid 2.0~ by wt
'.-glycidyloxyp~opylt~iethoxy silane 4.0~ by wt
B~nzopheno~e 0.5~ by wt
~hotoiniti~to~: 2-~ydr~y-2-~thy~ phenyl-p~op~ne~ Ae 2.5~ by wt
Pho~oi~tiator: Diphenyl-2,4,6-trimethyl-benzoyl phosphane
oxide 3.0~ ~y w~
~93 l5:13 P~GE.
,
05/10~1993 14: 15 FRO~ TO 999*001~16132370Z45~ P.32
- 324- 2~63~3
~8~hyl-phe~yl-~ilicone resin 15.0~ by wt
~ipropylen~ glycol diacrylate 30.0~ by wt
Ethylene oxide-pLopylene oxide-tr~methylol propane triacrylate
~Oligo~riacrylate~ ~olecular weight 480) 25 . 0~ by wt
~itanium dioxide 16 . 09~ by wt
Silicone oil 2. 0~ by wt
T~e following e~ s 3 to 5 describe the use of t~i- and/os
polyfunc~ional ~s~eth) acrylates:
E~ample 3
Production of a rad~ca~ly polymerizabl2, r~d coating ag~nt
The following comF~nents ~er~ mlxed ~ith one another:
3-glycidyloxypropyltr~methoxy silane 5.0~ by wt
~ono~s~e~ of hydko~ye~hylacrylate with phosphoric acid 5.0~ by wt
Photoi~itiator: l-hydroxy-cycloh~xyl-phenyl ketone2.0~ by w~
Photoinàtiator: Benzo~henone 3.0% by wt
~exanediold~Ac~ylate 20.0~ by wt
Reaetios~ prodae~ of hy~oxyAerylates with a mix~u~e of
diearboxylie acid anhydrides ~phthalie aeid anhydride,
totra~ ophth;~lic acid anhydride, suecinie aeid as~dride) 44 . O~ by ~t
Sat~ated polye~ter~ of a mix~cure of poly~ralent polyalcohols
and adipic acid, function~lizea with acrylic acid 5~096 by wt
M~Y 10 '93 15: 13 P~GE .032
,. . . .
, .
.
0S/10/1993 14: lS FRO~ TO 999*~01~16132370045~ P.33
- 33 ~ 2~ 43
~,xample 4
Production of ~ radically pol~meriz~ble, black coating ag~nt
The followi~ ponents W~se mixe~ wi~h one another:
lycidyloxypropyl-t~i~thoxysilane 3.0% by wt
~onoes~r of hydLoxyethylacr~late with phosphoric acid t.0% by wt
Photoi~iator- 2-hyd~oxy-2-methyl~-phenylpropane l-one 4.0~ by wt
Saturated polyester of a mixture of polyvalen~ polyalkcohols
and adipic acid, func~ionalized wi~h acrylic acid 22.0~ by wt
~ ca~e~chox~e~ylamil~e, par~ lly etherifie~ with
hydroxyacrylat~s 10.0% by wt
~ tane~liol ~i~c~ylat~ 14~0~6 by wt
Trimethylol propa~ t~iac~ylate 20.0~ by wt
~ixture o~ cycloalip~atic and aliphatic
epoxide acr~Lat~s, monome~:-free 15.0~ by wt
Slip medium (sil~coIle oil) 1. 0~6 by w'c
S~ot 4 . ~ ~ by
Exarnple 5
Production of a radically polymerizable, colorless coati~g agent
The follow~g. compo~ents were m~c~d with one another:
MRY 10 ~93 15:14 P~GE.033
05/10/1993 14:16 FROM TO 999~01t~16132370045~t P.34
- 34 ~ 2 ~ ~ 63 ~ 3
Reaction produc~ of hydroxyacrylates with a mixture of
diaarboxy~ic acad anhyd~ide~ (phthalic acid anhydride,
tet~ahyd~o ~ ~c acld a~hydride, succinic acid anhydride) 35.0~ by ~
3-glycidyloxyp~opy~trLme~hoxysilane 5.0% by wt
Monoester of hy~o~yethylacrylate wi~h phosphoric acid 7.0~ by ~t
Photoi~itiator: l-hydroxy-cyclohexyl-phenyl ketone5.0~ ~y ~t
~rethanized poly~c~ylate, mixture of poly~alent
polyalcohols, r~acted wi~h aliphatic diisocyanate-
hyd~oxyacrylate adducts 20~ by w~
Dipropyl~e glyeol diacrylate 8.0~ by wt
Trimethylolpropane ~iacryla~e 15.0% by w~
Silicone oil (~}ip meaium) 2.0~ by w~
Silicone-~od~fied ac~yla~ (slip medium) 3.0% by w~
Example 6
Production of a ca~ionically polymera~able, blue coa~ing agent
~e follo~ing c~pon-nts ~re mixed with on~ anothe~:
Epoxide xe~in co~taining 2 epoxide groups per ~olecul~
on the basis o~ 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-
h~xa~e carboxylat~ 50.0~ by wt
A~di~io~ product o polycaprolactone pclyol to 3,~-
epo~ycyclohexalmethyl-3,4-epoxycyclohexane carboxylate 20.0% by ~t
~xa~diOlaigly~iayl ether ~0.0% by wt
3-glycidyloxyp~opyl ~r~meehoxysilane 5.0~ by w~
MRY 10 '93 15: 14 PQGE .034
05/1~/1993 14: 16 FROM TO 999~001~1613237~045~ P.35
_ 35 _ 2~963~
Tria~ylsulfoniu~h~xafluorophosphate (photoinitia~or) 3.0~ by wt
Slip additives 1.0~ by wt
Zapon blue - 1.0~ by wt
~ .. ..
Xxample 7
P~oduction of a radie~lly polymer~zabl~, colorless coating agent
The fQllow~g componants ~ere mixed with or.e another:
Expo~ize resi~ cont~i3ing 2 epoxide groups per molecule on the basis
of 3,4-epo~ycyclohe~ylmethyl^3,4-epoxycyclohexane carboxylate 40.0~ by~
~xpoxid~ resin on the basis of bi~phenol A tEpicote 82a) ~0.0% ~Y
Butanedioldiglyc~dyl eth~r 2600~ byDt
O~-functional ~opoly~e~ on the basi~ of styrene-allyl alcohol,
0~ numbex 1~8 10.0~ by~f
3-glycidyloxypropyl~rimethyloxysil~ne 1.O~ by~r
Tr~arylsulfonium~exa~luoropho~phate (photoinitiator~ 3.0~ by~
The coating agents ~escribed. as ~xamples in examples 1 to 7
were used ~n an ~ppaEatUs such as is d~scribed in Fig 1, for the
coating o~ glass bot~les. Th~re w~ obtained odor-free fully
hardenad colo~e~ and clear bot~les.
~y ~ 0 .93 ~ 5 15 PRGE .035
',~ , '~' ': '
