U.S. patent application number 11/214386 was filed with the patent office on 2006-03-16 for crosslinkage pressure-sensitive adhesive substances by means of electron beams.
This patent application is currently assigned to tesa Aktiengesellschaft. Invention is credited to Bernd Dietz, Marc Husemann, Werner Karmann, Maren Klose, Hermann Neuhaus-Steinmetz.
Application Number | 20060054264 11/214386 |
Document ID | / |
Family ID | 7636137 |
Filed Date | 2006-03-16 |
United States Patent
Application |
20060054264 |
Kind Code |
A1 |
Husemann; Marc ; et
al. |
March 16, 2006 |
Crosslinkage pressure-sensitive adhesive substances by means of
electron beams
Abstract
A process for crosslinking a coating of pressures sensitive
adhesive systems on a backing material, characterized in that the
pressure-sensitive adhesive system present on the backing material
is irradiated with accelerated electrons by means of an irradiation
means, the backing material coated with the pressuresensitive
adhesive system to be irradiated runs via a roller, there is a
contact medium between the roller and the backing material during
irradiation.
Inventors: |
Husemann; Marc; (Hamburg,
DE) ; Dietz; Bernd; (Ammersbek, DE) ; Karmann;
Werner; (Hamburg, DE) ; Klose; Maren;
(Seevetal, DE) ; Neuhaus-Steinmetz; Hermann;
(Ahrensburg, DE) |
Correspondence
Address: |
Kurt G. Briscoe;Norris, McLaughlin & Marcus P.A.
18th Floor
875 Third Avenue
New York
NY
10022
US
|
Assignee: |
tesa Aktiengesellschaft
Hamburg
DE
|
Family ID: |
7636137 |
Appl. No.: |
11/214386 |
Filed: |
August 29, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10220582 |
Sep 3, 2002 |
6939588 |
|
|
PCT/EP01/02792 |
Mar 13, 2001 |
|
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11214386 |
Aug 29, 2005 |
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Current U.S.
Class: |
156/60 ;
156/272.2; 427/487 |
Current CPC
Class: |
Y10T 156/10 20150115;
C09J 7/20 20180101 |
Class at
Publication: |
156/060 ;
156/272.2; 427/487 |
International
Class: |
B32B 37/00 20060101
B32B037/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 23, 2000 |
DE |
100 14 563.9 |
Claims
1.
2. The process of claim 15, wherein the roller is thermally
conditioned.
3. The process of wherein the contact medium does not remain
permanently on the roller but instead is applied to the roller
before the irradiating and removed from the roller again after the
irradiating.
4. The process of claim 15, wherein the contact medium is
introduced into the process with the backing.
5. The process of claim 15, the contact medium is a liquid.
6. The process of claim 15, wherein the contact medium comprises
one or more additives selected from the group consisting of alkyl
alcohols, glycols, ketones, amines, carboxylates, water-soluble
cellulose derivatives, sulfonates and/or surfactants.
7. The process of claim 15, wherein the backing coated with the
pressure-sensitive adhesive system runs over the roller under
applied pressure.
8. The process of claim 15, wherein a surface of the roller is
electrically conductive or semiconducting.
9. The process of claim 15, wherein the contact medium and/or the
roller and/or a surface of the roller are grounded.
10. The process claim 15, wherein the roller possesses a surface
texture, in particular a roughening of the surface.
11. The process claim 15, wherein the roller is a steel roller,
especially one which carries the coating for improving the
corrosion resistance and/or wettability, the coating being composed
in particular of suitable metals, metal oxides or ceramic.
12. The process claim 15, wherein the contact medium is applied to
the roller by means of a fluid applicator.
13. The process claim 12, wherein the fluid applicator is thermally
conditionable.
14.
15. A process for crosslinking a coating of a pressure-sensitive
adhesive on a backing, said process comprising the following steps:
a) providing a combination comprising said pressure-sensitive
adhesive coated on a first face of said backing; and b) irradiating
the combination with accelerated electrons to crosslink the
pressure-sensitive adhesive; wherein a second face of the backing
is between the first face and the roller, and a contact medium is
between the roller and the second face.
16. The process of claim 2, wherein the roller is thermally
contained in a range of from -10.degree. C. to 200.degree. C.
17. The process of claim 16, wherein the roller is thermally
contained in a range of from 5.degree. C. to 150.degree. C.
18. The process of claim 5, wherein the contact medium comprises
water.
19. The process of claim 18, wherein the contact medium is water
admixed with one or more soluble or partly soluble additives.
20. The process of claim 10, wherein the roller possesses a
roughening of the surface.
21. The process of claim 11, wherein the roller carries a coating
for improving corrosion resistance and/or wettability.
22. The process of claim 21, wherein the coating is composed of
metals, metal oxides or ceramics.
23. The process of claim 15, wherein the combination comprises a
release layer on said second face of said backing.
24. A method of adhering an adhesive tape to a substrate, said
method comprising the following steps: a) producing an adhesive
tape by a process comprising the process of claim 15; and b)
adhering the adhesive tape to a substrate.
Description
[0001] This application is a division of U.S. application Ser. No.
10/220,582, filed Sep. 3, 2002, now allowed, which is a 371 of
PCT/EP01/02792, filed Mar. 13, 2001, which claims foreign priority
benefit under 35 U.S.C. .sctn. 119 of the German Patent Application
No. 100 14 563.9 filed Mar. 23, 2000.
[0002] The invention relates to a process for the electron beam
crosslinking of pressure-sensitive adhesive tapes while avoiding
damage to the release layer on the reverse.
[0003] The service properties of adhesive tapes are determined
quite essentially by the properties of the pressure sensitive
adhesive (PSA). Its adhesive is composed of at least one high
molecular mass elastomer plus where appropriate one or more
tack-defining resins and also further additions for modifying the
properties, improving the stability, etc. For further information
on the composition, preparation, and properties of adhesive tapes,
refer to the article "Tapes, Adhesive" in Ullmann's Encyclopedia of
Industrial Chemistry, Sixth Edition, 2000 Electronic Release,
Wiley-VCH, Weinheim 2000.
[0004] To produce the adhesive tapes, the adhesives are applied in
one or more thin films to suitable backing or carrier materials
such as films, papers, nonwovens, wovens, etc. For this purpose
they must be converted into a fluid state of appropriate viscosity,
which can be done by dissolving them in solvents, dispersing them
in liquids or, in the case of those known as hotmelts, by melting
them at elevated temperatures. These coatings are subsequently
solidified by evaporating the solvent or dispersion medium or by
cooling the hotmelts to give the pressure-sensitive adhesive. The
hotmelts in particular, but also the other pressure-sensitive
adhesives, lose their strength again by heating, thereby limiting
the scope of use. This can be prevented by crosslinking, thereby
expanding the scope for use of the adhesive tapes thus produced.
Crosslinking comprehends all reactions which lead to a chemical
bond between the polymer chains of the elastomer. This can be
achieved by means of chemically initiated or radiation-chemically
initiated reactions. The latter may in turn be initiated by UV
radiation or by high-energy radiation such as accelerated electrons
(EBC). Preference is given to employing radiation crosslinking (UV
and EBC technology), since these reactions take place very quickly
and do not require thermally labile groups. A further process for
preparing pressure-sensitive adhesives starts from reactive liquid
monomers and oligomers, which are cured by a radiation to form a
cohesive pressure-sensitive adhesive. An overview has been given by
Karmann and Zollner in "Radiation Curing of PSA--An Overview",
RadTech Europe, Maastricht 1995. Since there are no fundamental
differences between the above-described crosslinking and curing,
both are referred to below as "crosslinking".
[0005] The UV technology is relatively inexpensive in terms of
apparatus. Owing to the photoinitiators required and the absorption
of light by the adhesives, however, crosslinking cannot be carried
out unrestrictedly. For example, transparent acrylic PSA tapes can
be crosslinked efficiently up to a maximum of about 100 g/m.sub.2.
In the case of adhesives comprising resins or fillers, the limits
are much lower. For natural-rubber adhesives, UV crosslinking is
even less favorable. The EBC technology is significantly better
suited to 35 this purpose. Fortunately, a majority of the polymers
used for PSAs such as the polyacrylates, natural rubber and other
polydiene rubbers, ethylene-vinyl acetate, polydimethylsiloxanes,
are polymers which crosslink predominantly under the influence of
electron beams (see, for example, J. E. Wilson, "Radiation
Chemistry of Monomers, Polymers, and Plastics" Marcel Dekker, Inc.,
New York, 1974). Given a sufficiently high electron accelerating
voltage, even PSAs with film thicknesses more than several 100
g/m.sup.2 are penetrated almost completely, and crosslinked,
irrespective of their composition. Further advantages here are the
rapidity of these processes, the minimal requirements imposed on
the structure and composition of the components to be crosslinked
(UV-active groups need not be present), and the ability to regulate
the operation precisely. Nevertheless, this technology too has
disadvantages. In order to achieve uniform crosslinking of the
adhesive, the adhesive tape must be transirradiated with sufficient
uniformity, so that even the backing films are subjected to more or
less high radiation doses. In this process, some polymers become
degraded, and so become brittle and lose mechanical load-bearing
properties. Other polymers undergo discoloration during and after
irradiation. Particularly serious damage occurs to release layers,
which are frequently present on the reverse of the backing films in
order to obtain a desired adjustment of the unwind force after the
tape has been wound up: following exposure to radiation, they lose
activity, as a result of which the unwind forces of the adhesive
tapes rise unacceptably. This applies in particular to silicone
layers following storage at elevated temperatures.
[0006] This damage can be reduced if the adhesive tape runs 30 with
its reverse over a thermal conditioning plate under the electron
accelerator or is on a metallic thermal conditioning roller, both
of which act as radiation traps. Nevertheless, the effect is
inadequate at radiation doses above about 10 kGy.
[0007] Patent application DE 198 46 902 A1 describes how, by
choosing the accelerating voltage, it is possible to keep the
radiation dose absorbed by the release layer on the reverse of a
release liner low and to crosslink the adhesive film with a
substantially higher radiation dose. In the case of unfavorable
thickness ratios between the adhesive film and the backing,
however, the possibilities are limited.
[0008] It is an object of the invention, therefore, to provide a
process for electron beam crosslinking of pressuresensitive
adhesives which makes it possible to prevent or at least very
substantially reduce the damage for the reverse of the release
layers without having to restrict the radiation dose needed for the
crosslinking of the adhesive film, and to do so even when the
thickness proportions between adhesive layer and backing are
unfavorable.
[0009] Surprisingly, and unforeseeable for the skilled worker, it
has been found that an advantageous procedure of this kind is
possible by introducing a suitable contact medium between the
reverse of the adhesive tape and the roller, especially a thermal
conditioning roller, during the irradiation process.
[0010] The invention accordingly provides a process for electron
beam crosslinking of a coating of pressuresensitive adhesives on a
backing material, characterized in that [0011] the
pressure-sensitive adhesive film located on the backing material is
crosslinked by electron beams by means of an irradiation means,
[0012] the backing material coated with the pressure-sensitive
adhesive system to be crosslinked runs over a roller during
irradiation, [0013] there is a contact medium between the roller
and the backing during irradiation.
BRIEF DESCRIPTION OF THE DRAWING
[0014] The invention will now be described in greater detail with
referene to the drawing, wherein:
[0015] FIG. 1 is a depiction of a setup for carrying out a process
embodiment according to the present invention.
[0016] The contact medium is preferably removed in whole or in part
from the backing material following irradiation.
[0017] Contact between the backing material and the roller must be
ensured over the entire irradiation area of the backing material
provided with the pressure-sensitive adhesive system.
[0018] Preferably in accordance with the invention, this 5 process
is carried out in a unit composed of an electron accelerator, a
roller, preferably a thermal conditioning roller, a fluid
applicator, and, if desired, a drying unit.
[0019] In a very advantageous procedure, the roller is thermally
conditioned. In the text below, in all cases where reference is
made only to the roller, the thermal conditioning roller is
expressly included as one of the preferred embodiments. The thermal
conditioning of the roller is situated preferably within a range
from -10.degree. C. to 200.degree. C., with very particular
preference from 5.degree. C. to 150.degree. C.
[0020] The roller used is commonly an earthed metal roller which
absorbs the incident electrons and the x-rays which form in this
case. It is preferably equipped with an effective thermal
conditioning system in order to ensure dissipation of energy,
particularly in the form of heat energy. In order to prevent
corrosion it is normally covered with a protective coat. This coat
is preferably selected so as to be wetted effectively by the
contact medium. In general, the surface is conductive. It may also
be more favorable, however, to coat it with one or more coats of
insulating or semiconducting material.
[0021] Rollers which can be used advantageously for the inventive
process are steel rollers, especially those which carry a coating
for improving the corrosion resistance and/or wetability, these
coatings preferably being of appropriate metals (chromium, for
example), metal oxides or ceramic.
[0022] In the inventive process the contact medium is applied
advantageously either to the reverse of the backing or to the
described roller; it is also possible, however, for it to be
applied contactlessly, by spray application, for example. During
electron beam irradiation, the contact medium is located between
the roller and the backing material.
[0023] The contact medium of the invention that is used is a
material which is capable of producing a contact between the
backing material and the roller's surface, particularly a material
which fills the cavities between backing material and roller
surface (for example, unevennesses in the roller's surface,
bubbles).
[0024] Appropriate for this purpose are fluid materials which may
be present within a wide viscosity range. Accordingly, the contact
medium may be composed, for example, of a pressure-sensitive
adhesive or of another material which flows onto the backing
material and so displaces the air between backing and roller.
Moreover, soft, "conforming" materials may be used as the contact
medium. On the one hand, it is possible preferentially to use
pliable materials such as, for example, soft rubber, plasticized
PVC, other plasticized polymers, and similar materials. If they are
are firmly connected to the roller, they must exhibit sufficient
radiation resistance and also, preferably, sufficient thermal and
electrical conductivity.
[0025] It is particularly advantageous in accordance with the
invention, especially when using contact media lacking sufficient
radiation resistance, not to leave the contactmedium permanently on
the roller but instead to apply it to the roller before the
irradiation operation and to remove it from the roller again after
the irradiation operation. The latter principle may be realized,
for example, in an excellent way in accordance with the invention
by introducing it into the process with the backing material: for
example, in the form of a film which runs onto the roller with the
backing material. In a further advantageous embodiment, the contact
medium is in the form of a replaceable covering on the roller. The
contact medium may be replaced during the irradiation operation
(continuous replacement) or between the individual irradiation
operations (discontinuous replacement). The continual replacements
prevent it being so severely impaired by the ongoing irradiation
that it loses its function.
[0026] In particular in the case of sufficient radiation 10
resistance or sufficiently low radiation load, however, it may
likewise be advantageous, for corresponding variants of the
inventive process, for the contact medium to remain permanently on
the roller.
[0027] It has been found very advantageous in accordance with the
invention to use as the contact medium a liquid which where
appropriate comprises additives for additional functions. These
include the increasing of wetting and of electrical conductivity
and the scavenging of free radicals and other reactive species
generated by the absorbed radiation.
[0028] As a contact liquid it is possible with advantage to use
water, which satisfies the required objectives of the
invention.
[0029] In a further variant, which is outstandingly suitable in the
sense of the invention, the contact medium is admixed with
substances which are at least partly soluble therein. For water as
a contact medium, examples of additions include alkyl alcohols such
as ethanol, propanol, butanol, hexanol, without wishing to be
restricted in the selection of alcohols by these examples. Also
very advantageous are, in particular, relatively long-chain
alcohols, glycols, polyglycols, ketones, amines, carboxylates,
sulfonates, watersoluble cellulose derivatives, and the like.
[0030] A lowering of the surface tension may also be brought about
by the addition of small amounts of nonionic and/or anionic and/or
cationic surfactants to the contact medium. In the simplest case,
commercial washing compositions or soap solutions can be used for
this purpose, preferably in a concentration of several g/l in water
as the contact medium. Particularly suitable are specific
surfactants which can be used even at a relatively low
concentration. Examples are sulfonium surfactants (e.g.,
(.beta.-di(hydroxyalkyl)sulfonium salt), furthermore ethyoxylated
nonylphenylsulfonic acid ammonium salts. Here, reference may be
made in particular to the state of the art under "surfactants" in
Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000
Electronic Release, Wiley-VCH, Weinheim 2000.
[0031] As contact media, the abovementioned liquids may also be
used without the addition of water, in each case individually or in
combination with one another. In order to enhance the properties of
the contact media (for example, to increase the shear resistance,
reduce the transfer of surfactants or the like to the liner
surface, and thus improved cleaning possibilities of the end
product) it is further possible with an advantage to add salts,
gels, and similar viscosity-raising additives to the contact medium
and/or to the adjuvants employed.
[0032] In the case of a liquid contact medium, one possible
outstanding procedure is to run a second roller (application
roller), advantageously having a wettable or absorbent surface,
through a bath containing the contact medium, wetting or
impregnating it with the contact medium in the process, and, by
contact with the first roller, applying or spreading on a film of
this contact medium. Other embodiments of the applicator may also
be realized.
[0033] The term "rollers" is used below for the first roller
(roller in accordance with the entry in the main claim, including
the thermally conditionable embodiment) and the second roller as
application roller. A third roller (contact roller) which is also
to be introduced is referred to consequently as the contact
roller.
[0034] Typical irradiation means which are employed in the
inventive embodiment of the process are linear cathode systems,
scanner systems, and segmented cathode systems, where electron beam
accelerators are concerned. A detailed description of the state of
the art and of the most important process parameters can be found
in Skelhome "Electron Beam Processing" in Vol. 1 "Chemistry &
Technology of UV & EB Formulations for Coatings, Inks &
Paints", publ. by Sita Technology, London, 1991.
[0035] The accelerating voltages are situated in the range between
40 kV and 500 kV, preferably from 80 kV to kV. The radiation doses
employed range between 5 to 150 kGy, in particular from 20 to 100
kGy.
[0036] The guided supply of the backings to be irradiated, i.e. the
release-coated materials such as papers, films, nonwovens and the
like, see later on below, is advantageously performed under a
certain contact pressure. This ensures that, on the one hand, no
air bubbles are included between the reverse of the backing and the
(first) roller and that, secondly, the amount of contact liquid is
limited to the necessary measure. The contact pressure can be
achieved by setting an appropriate web tension or by applying
pressure using a contact roller. In this case, the surface of the
contact roller must have a sufficient release effect so that the
pressure-sensitive adhesive film on the surface of the backing does
not stick to it. Further possibilities include pressure applied by
air jet or air cushion or by electrostatic forces.
[0037] Contact rollers can be, for example, steel rollers as well,
and ceramic rollers are also suitable. Preference for use as
contact rollers is given to those which are manufactured from
elastic material, especially rubber rollers or silicon rubber
rollers, or those which possess an elastic or rubberized surface.
The rubber hardness of the contact roller material or of the 5
contact roller surface is preferably from 30 to 100 shore (A), in
particular 40-80 shore (A). In accordance with the state of the
art, the covering of the contact roller may be composed of EPDM,
Viton or Silicon rubber or other elastic materials.
[0038] In one advantageous variant of the process, the contact
medium is electrically conductive or becomes electrically
conductive during and/or after irradiation.
[0039] A further development of the process of the invention is
distinguished by the fact that the roller and/or the surface of.
the roller are electrically conductive or semiconducting. This
makes it possible to improve additionally the prevention of damage
to the backing material.
[0040] Where the coating roller is not composed of material which
is conductive per se, such as is the case with steel or another
metal, for example, an additive which ensures sufficient
conductivity may be added to the roller material. This can be
achieved by adding carbon black or metal dusts or metal particles
or by doping, the conductivity preferably being ensured at least
during electron beam irradiation.
[0041] Moreover, it is very advantageous for the process of the
invention if the contact medium and/or the roller and/or the
surface of the roller are grounded.
[0042] Moreover, the roller may be microscopically smooth or have a
slightly textured surface. It has been found appropriate for it to
possess a surface texture, especially a roughening of the surface.
This makes it possible to improve wetting by the contact
medium.
[0043] In an advantageous further development of the inventive
process, the contact medium is applied to the roller by means of a
fluid applicator. It has also been found very positive for the
progression of the process of the invention if the fluid
application as well is thermally conditionable.
[0044] As being crosslinkable in a particularly advantageous way
with this process it is possible to use, as the pressure-sensitive
adhesive system, acrylic, naturalrubber, synthetic-rubber, silicon
or EVA adhesives; from this group, particular advantage is
possessed by the acrylic pressure-sensitive adhesives. Naturally,
the process can also be used, however, to process all other
radiation-crosslinkable pressure-sensitive adhesives known to the
skilled worker, as set out, for example, in the "Handbook of
Pressure Sensitive Adhesive Technology" by Donatas Satas (van
Nostrand, New York, 1989).
[0045] One inventive use of the crosslinked pressure-sensitive
adhesive system produced in accordance with one of the preceding
claims is, with particular advantage, its use for an adhesive tape,
it being possible for the adhesive tape to be provided on one or
both sides with a self-adhesive layer.
[0046] An adhesive tape of this kind does not lose its advantageous
service properties by crosslinking, especially its
unwindability.
[0047] As acrylic pressure-sensitive adhesives it is possible in
particular to use elastomer (Co)polymers having the following
composition, without wishing to be unnecessarily restricted by this
information: [0048] (A) acrylic and methacrylic acid derivatives of
the general formula CH.sub.2.dbd.CH(R.sub.1) (COOR.sub.2) with a
fraction of 65-100 percent by weight, where R.sub.1.dbd.H or
CH.sub.3 and R.sub.2=an alkyl chain having 2-20 carbon atoms,
[0049] (B) vinyl compounds containing functional groups (by way of
example, maleic, fumaric and/oritaconic acid, maleic anhydride,
styrene, styrene compounds, vinyl esters, especially vinyl acetate,
vinyl alcohols, vinyl ethers, acrylamides, etc.), with a fraction
of 0-35 percent by weight.
[0050] For natural-rubber adhesives, the natural rubber is ground
to a molecular weight (weight average) of not below 100 000
daltons, preferably not below 500 000 daltons, and is additived.
The electron-beamcrosslinkable synthetic-rubber adhesives can also
be employed.
[0051] For producing pressure-sensitive adhesive tapes, these
elastomers are optionally blended with crosslinkers: suitable
crosslinker substances in this context are, in particular,
bifunctional or polyfunctional acrylates.
[0052] Moreover, for preparing pressure-sensitive adhesives these
elastomers are optionally blended with at least one resin.
[0053] Tacifying resin for addition which can be used include
without exception all known tacifier resins and those described in
the literature, provided they exhibit at least partial
compatibility with the elastomer. Representatives that may be
mentioned include the pinene, indene, and colophony resins, their
disproportionate, hydrogenated, polymerized, esterified derivatives
and salts, the aliphatic and aromatic hydrocarbon resins, terpene
resins and terpene-phenolic resins, and also C5, C9, and other
hydrocarbon resins. Any desired combinations of these and further,
resins may be used in order to set the properties of the resulting
adhesive in accordance with what is desired. Express reference may
be made to the depiction of the state of the art in the "Handbook
of Pressure Sensitive Adhesive Technology" by Donatas Satas (van
Nostrand, 1989)
[0054] The acrylic PSAs may further be blended with one or more
additives such as aging inhibitors, light stabilizers, ozone
protectants, fatty acids, resins, plasticizers, blowing agents,
nucleators, and accelerators.
[0055] They may further have. been filled with one or more fillers
such as fibers, carbon black, zinc oxide, titanium dioxide, solid
microbeads, silica, silicates, and chalk, the addition of
blocking-free isocyanates also being possible.
[0056] In the case of rubber/synthetic rubber as starting material
for the adhesive, further variation possibilities exist, whether
the said material is from the group of the natural rubbers or of
the synthetic rubbers or whether it comprises any desired blend of
natural rubbers and/or synthetic rubbers, it being possible to
select the natural rubber or the natural rubbers, in. principle,
from all available grades, such as, for example, crepe, RSS, ADS,
TSR or CV grades, depending on the required purity and
viscositylevel, and it being possible to select the synthetic
rubber or synthetic rubbers from the group consisting of randomly
copolymerized styrene-butadiene rubbers (SBR), butadiene rubbers
(BR), synthetic polyisoprene (IR), butyl rubbers (IIR), halogenated
butyl rubbers (XIIR), acrylate rubbers (ACM), ethylene-vinyl
acetate (EVA) copolymers, and polyurethanes and/or blends thereof.
Also, preferably, it is possible to add thermoplastic elastomers
with a weight fraction of from 10 to 50% by weight to rubbers in
order to improve their processing properties, this fraction being
based on the overall elastomer fraction. As representatives,
mention may be made at this point in particular of the particularly
compatible styrene-isoprene-styrene (SIS) and styrene
butadiene-styrene (SBS) types.
[0057] As plasticizers which are likewise to be added, it is
possible to use all the plasticizing substances which are known
from adhesive tape technology. These include, among others,
paraffinic and naphthenic oils, (functionalized) oligomers such as
oligobutadienes, oligoisoprenes, liquid nitrile rubbers, liquid
terpene resins, vegetable and animal oils and fats, phthalates,
functionalized acrylates.
[0058] The pressure-sensitive adhesives blended in. this way are
applied directly from solution or as hotmelts to a backing (PP,
BOPP, PET, nonwoven, PVC, polyester, polyamide, foam, etc.) or
release paper (glassine, HDPE, LDPE, etc.) or are laminated by
transfer (backings and release papers are backing materials in the
sense of the claims).
[0059] For crosslinking, the pressure-sensitive adhesive tape is
guided over a roller which is provided with the contact medium. It
is preferred to use water, whose effectiveness can be enhanced by
adding the additives described above. The film of contact liquid on
the roller compensates unevennesses in the roller's surface and
carrier and so prevents cavities between the roller and the backing
material.
[0060] The pressure-sensitive adhesive tape is irradiated with
electron beams directly on this roller. The accelerating voltage is
chosen so that the electrons pass almost completely through the
pressure-sensitive adhesive tape.
[0061] Where the liquid film which fills the cavities is present,
and where the inventive procedure described is being used, damage
to the reverse of the backing material is totally avoided or at
least greatly reduced. As a result of the elimination or reduction
of damage to the reverse, the unwind properties of the PSA tape are
retained or undergo only slight deterioration.
[0062] The experimental arrangement for the electron beam curing of
the pressure-sensitive adhesive tapes described, i.e., their
crosslinking by irradiation with electrons, is depicted in FIG. 1.
In the setup chosen in this example and shown in FIG. 1, one of
many possible embodiments of the crosslinking unit is shown by way
of example, without thereby wishing to undertake any unnecessary
restriction.
[0063] The thermal conditioning roller 1 is likewise wetted with a
film 311 of the contact medium by contact with a second roller 2,
which is partly located in a tank 3 containing the contact medium
31. As contact medium 31 it is preferred to use water, to which
optionally the abovementioned additives are added. In order to form
a stable water film 311, the thermal conditioning roller 1 may
possess a textured surface. This surface may be obtained by
roughening, similar to the conditions relating to an engraved
roller, but even in the case of macroscopically smooth surfaces the
microscopic surface roughness brings about sufficient wetting with
the contact medium 311.
[0064] Position 41, from which the PSA tape (the backing material
52 coated with the PSA 51) is introduced, is variable; in this
depiction, the PSA tape is laid onto the roller in the 12 o'clock
position (41) and additionally is pressed with a contact roller 9.
The irradiation unit 6 is located in the 3 o'clock position (42).
The position 42 of the electron-beam source 6 can be varied in
accordance with the guiding of the PSA tape, but at least in the
irradiation window (42) the PSA tape 5 ought to possess complete
contact with the liquid film 311 on the thermal conditioning roller
1. The PSA tape 5 leaves the thermal conditioning roller 1 in the 5
o'clock position (43); this position as well can be located
differently in the various embodiments of the unit.
[0065] For the purpose of additional conduction of the charge away
from it, the thermal conditioning roller 1 may be grounded (7). In
addition, the liquid-feeding roller 2 may also be grounded, in
order to prevent unnecessary electrical voltages and hence a
current flow or creeping currents in the unit.
[0066] After it has been irradiated and has left the thermal
conditioning roller 1, the adhesive tape 5 passes through a drying
unit 8 in order to remove some or all of the contact medium 311
from the backing material 52. Drying here may take place thermally,
by exposure to IR radiation and/or radiation of another wavelength
range, or mechanically (by stripping off, wiping off, etc.). Also
possible is drying in a stream of air, and any other drying
method.
[0067] In order to document the invention, the series of
experiments described below were conducted, without wishing to be
unnecessarily restricted through the choice of examples.
Description of the Experiments Carried Out
Preparation of the Acrylic PSA
[0068] A 200 L reactor conventional for free-radical
polymerizations was charged with 2400 g of acrylic acid, 3200 g of
N-tert.butylacrylamide, 4000 g of methylacrylate, 30.4 g of
2-ethylhexyl acrylate, and 30 kg of acetone/isopropanol (97:3).
After nitrogen gas had been passed through the reactor for 45
minutes with stirring, the reactor was heated to 58.degree. C. and
20 g of 2,2'-azo-isobutronitrile (AIBN) were added. The external
heating bath was then heated to 75.degree. C. and the reaction was
carried out constantly at this external temperature. After a
reaction time of 1 h, a further 20 g of AIBN were added. The
reaction was terminated after a time of 48 h, and the product was
cooled to room temperature.
Production of the Test Tape
[0069] The adhesive was then applied on a standard unit to 23 .mu.m
PET film (Mylar.RTM. from Du Pont) and dried (the units employed
are described in the section on "Production Methods" in "Tapes,
Adhesive" in Ullmann's Encyclopedia of Industrial Chemistry, Sixth
Edition, 2000 Electronic Release, Wiley-VCH, Weinheim 2000). The
application rate was approximately 50 g/m2. Before being wound up,
the adhesive was lined with siliconized release paper from
Lauffenberg. This composite was then cut into strips 1.9 cm wide on
a slitting unit and wound into rolls.
Electron Beam Irradiation
[0070] Electron beam irradiation was carried out using an
instrument from Electron Crossl.inking AB, Halmstad, Sweden. The
release paper to be irradiated (glassine paper with 1.2 g/m2
poly(dimethyl)siloxane from Laufenberg) was guided through
underneath the Lenard window of the accelerator on a thermal
conditioning roller which is present as standard. In the
irradiation zone, the atmospheric oxygen was displaced by flushing
with pure nitrogen. The web speed was in each case 10 m/min. For
the inventively irradiated material, the thermal conditioning
roller was replaced by a special roller with a wettable surface
coating and an applicator unit for the contact liquid in accordance
with FIG. 1. The release paper was pressed on with a rubberized
contact roller (60 shore A), so that air inclusions were prevented.
The thickness of the film of liquid was from approximately 0.01 to
0.1 mm. The other process parameters are indicated in the table
below.
Measurement of the Release Force
[0071] About 1 h after irradiation, strips of the test tape with
the adhesive were placed without bubbles onto the side of the
irradiated release paper facing the thermal conditioning roller and
were pressed on with a 2 kg steel roller. This composite was
subsequently stored, either for 1 day at room temperature (about
20.degree. C.) (designation: 1 d RT) or for 7 days at 70.degree. C.
(designation: 7 d 70.degree. C.).
[0072] To measure the peel force (release force) the side of the
test tape was fastened to a steel rail and the release paper bonded
to it was peeled off at an angle of 180.degree. and a speed of 300
mm/min. The tensile force required to achieve this (in cN/cm) was
measured on a tensile testing machine under standardized conditions
(23.degree. C., 50% atmospheric humidity).
Results:
[0073] The conditions and the results of the experiments are
compiled in the table below. TABLE-US-00001 Release force Ex-
Radiation Accelerator after am- Contact dose voltage 1 d RT .sup.#
7 d 70.degree. C. ple liquid (kGy) (kV) (cN/cm) (cN/cm) 1 0 0 2 8
2a None 10 200 12 30 2b 50 200 * ** 3a Aqua dist. 10 200 8 20 3b 50
200 21 ** 4a 5% n-butanol 10 200 3 9 4b 50 200 5 10 5a 5% tert- 10
200 4 9 5b butanol 50 200 4 12 6a 6% Alcostop 10 200 7 16 6b 200 22
23 .sup.# Room temperature (about 23.degree. C.) * partial
splitting of the release paper ** release paper splits (1) Alcostop
.COPYRGT. (YARN Products Company GmbH, Willich): aqueous solution
of cellulose gum, anionic surfactants, polypropylene glycol,
defoamers, and buffer substances
[0074] In the case of the unirradiated control sample (Example 1)
the release force was very low and even on storage for 7 days for
70.degree. C. did not: rise above 8 cN/cm. In the case of the
electron-beam-irradiated samples (example 2a, 2b) on the other
hand, a sharp rise in the release force was found. Even with a
radiation dose of only 10 kGy (example 2a) it was 12 cN/cm. This
effect intensified through storage at 70.degree. C., and after 7
days rose to 30 cN/cm.
[0075] Crosslinking with a radiation dose of 10 kGy is in practice,
however, too low for many high-performance adhesive tapes;
consequently, an experiment with a radiation dose of 50 kGy was
conducted in addition (example 2b). Here, the observed effect
occurred even more sharply. On unwinding, the release material
showed markedly perceptible defects as a result of picking. After
storage at 70.degree. C., the release paper split completely, such
an adhesive tape would no longer be unwindable.
[0076] After the damage to the backing had been demonstrated with
the reference samples 2a and 2b, a corresponding series of
experiments was conducted with the inventive roller arrangement,
using pure water as contact medium. This is done employing the same
test tape as in examples 2a and 2b. Within the bounds of
measurement accuracy, the radiation doses were situated in the same
range, so that the values are directly comparable with one
another.
[0077] The results can be seen in the table under examples 3a and
3b. At a radiation dose of 10 kGy there was a reduction in the
damage to the release paper; however, increasing the radiation dose
to 50 kGy led to a marked increase in the release force. After
storage at 70.degree. C. for 7 days, there was again splitting of
the release paper, which would make such an adhesive tape unusable.
A comprehensive improvement was achieved when a small amount of
alkyl alcohol such as n-butanol or tertbutanol was added to the
water (in each case in a form of 5% addition). The initial values
after one day corresponded virtually to the unirradiated release
paper, and even after storage at 70.degree. C. only a slight
increase in the release forces was found. This behavior was not
substantially impaired even by high radiation doses of 50 kGy. The
values obtained were within a readily acceptable range for the
pressure-sensitive adhesive tapes.
[0078] Example 6a, 6b shows that it is also possible to employ
commercially customary fountain solutions, such as are customary in
the printing industry. Alcostop.RTM. from VARN is an aqueous
solution comprising cellulose gum, anionic surfactants,
polypropylene glycol, defoamers, and buffer substances.
[0079] It is possible to find that the inventive process is
outstanding suitable for preventing, or at least maintaining within
an acceptable range, the reverseside damage of backing materials
during irradiation with electron beams. The pressure-sensitive
adhesive tapes produced and crosslinked in this way are very
suitable for industrial use and no longer exhibit the disadvantages
of the prior art.
* * * * *