CA2238617A1 - Pressure-sensitive adhesive article based on partially oriented and partially crystallized elastomer - Google Patents

Abstract

A pressure-sensitive adhesive article comprises a substrate having a layer of a pressure-sensitive adhesive thereon. The pressure-sensitive adhesive comprises an elastomer having a partially oriented and partially crystallized elastomer component. Also disclosed are methods of preparing the adhesive article.

Description

-CA 02238617 1998-OF,-2', PRE~SSUR~5-SENSITIVE AD~ESIVE ARTICLE BASED ON
PARTLALLY ORIENTED AND PARTIALLY
CRYSTAl,~,~7.~,n E~LASTOMER

BACKGROIJND OF THE INVENTION

~ield of the Invention This invention relates to pressure-sensitive adhesive articles co~ lg substrates or backings coated with such adhesives, a hot-melt process for ~ g such adhesive-coated b~cl~inSgc, and the use of such articles. More specifically, this invention relates to articles that incorporate a pressure-sensitive adhesive having a partially oriented and partially cryst~lli7.qd elastomer component which, in a particularly plt:rell~d embodiment, imparts a~ ,oLlopic peel behavior to the adhesive.

Description ofthe Related Art Pressure-sensitive adhesives ("PSAs") are typically provided in the form of a tacky adhesive coating that is disposed on a backing (e.g., a tape or a sheet made of polymeric film, metal foil, paper, cloth, release liner, etc.). Such adhesives are useful for adhesively bonding two surfaces together with light finger-pressure, so as to form a relatively weak bond that usually can be easily broken by peeling the adhesive-coated tape or sheet to remove it from the surface to which it is ~t~checl Preferably the adhes*e-coated tape or sheet can be removed without ~m~ing the surface and without leaving adhesive residue behind. A PSA article commonly usedtoday is Scotch~M brand m~cking tape made by the 3M Company, which began using rubber-based PSAs for such articles in the late 1920s.
A solvent-free, hot-melt process for preparing a PSA from a tackified non-- therrnoplastic elastomer, such as natural rubber, polyisobutylene, and other hydrocarbon elastomers, is described in the PCT international patent application (of the ~ccign~e hereof) published May 26, 1994 as WO 94/11175. The process uses a CA 02238617 1998-0~-2~
wo 97/22675 PCT/US96/18090 continuous compounding device that has a sequence of alternating conveying zonesand processing zones which masticate the elastomer and mix the elastomer, tackifier, and adjuvants to form the adhesive. Molten adhesive may be pumped through a coating die in the form of a thin film and directly onto a support which preferably comprises a moving web that passes around a heated coating roll Japanese kokai patent application no. HEI 7~1995]-18227, published January ~0, 1995, describes anisotropic adhesive material having an adhesive layer on at least one side of a base having anisotropic flexibility and corrugated or cord-like structure.
U.S. Pat. No. 5,156,911 (Stewart), issued October 20, 1992, discloses skin-activated, temperature-sensitive adhesive assemblies. In one embodiment there isan adhesive that is substantially non-tacky at or below room temperature, becomes aggressively tacky at skin temperature, but reverts to its substantially non-tacky condition upon cooling (e.g., by applying ice or a cold pack~. Regardless of theembodiment, the adhesive includes a cryst~lli7~hle polymer that may be crosclinke-l Similar materials are described by R. Clarke et al. in "Temperature Switchable Pressure Sensitive Adhesives," Adhesives A~e, September, 1993, pp. 39-41.
There is a desire for adhesives that have anisotropic peel behavior (i.e., di~el~,lL adhesion when peeled in di~lc:llL directions). Such adhesives would beuseful in many applications (e.g., graphic application tapes and other uses described more fully below). If an adhesive article having such properties could be provided independent of a backing, substantial flexibility in backing selection would be possible. It would also be desirable if a known adhesive composition could be m~nllf~ctnred in a manner to provide such properties. There is also a desire foradhesives having heat activatable tack as these would be useful in situations where low initial tack is advantageous, especially if known adhesive cornpositions can be m~mlf~ctured in a manner to provide such properties.

SU~ARY OF THE INVENTION
In one aspect, the present invention provides a pressure-sensitive adhesive article comprising a substrate and a pressure sensitive adhesive layer thereon. The -CA 02238617 1998-0~-2~
wo 97/22675 PCT/US96/18090 pressure sensitive adhesive comprises partially oriented and partially cryst~lli7ed elastomer. Preferably, the molecular repeat units of the elastomer are partiallydirectionally oriented and exhibit partial crystallinity. By "partially oriented" it is meant that the elastomer is sufficiently oriented that the orientation can be revealed by optical birefringence, infrared dichroism, or x-ray diffraction. By "partially crystalline" it is meant that the elastomer has sufficient crystallinity to be detected by di~l~nLial sc~nning calorimetry or X-ray diffraction.
Va~ying the degrees or extents of orientation and crystallinity in the elastomer can advantageously infl~l~nce the properties of the PSA. For example, in l O one embodiment of this invention, the orientation and crystallinity of the elastomer are sufficient to impart anisotropic peel forces to a PSA article (e.g., a substrate or backing on which the PSA is coated). The anisotropic peel force is an unusual property because the force nec~s~ry to peel the PSA article from a surface to which it is adhered varies when measured along ~irrel elll axes. That is, the PSA
article displays different adhesion when peeled from the surface in different directions. The degrees of orientation and crystallinity of the elastomer can besufficient to cause (1) the peel force measured in the direction parallel to thepreferred orientation to be substantially less than that observed for a PSA of the same forrnulation but whose elastomer is not oriented, and to cause (2) the peelforce measured in the direction perp~ lic~ r to the l~r~Ç~ d oriçnt~tion to be substantially greater than that measured in the parallel direction. Generally, the peel force in the parallel direction will be less than 90%, preferably less than 50%, and most preferably less than 10%, of the higher peel force (i.e., the peel force in the perpent1ic~ r direction).
When the PSA article is made by extruding the adhesive, the pl~re~lt;d orientation of the elastomer will generally be the "machine direction" (or "MD"), that is, parallel to the extrusion coating line. The direction perpendicular to the extrusion coating line is generally referred to as the "cross direction" (or "CD").
For example, in the case of PSA-coated tape made by extruding a hot melt of tackified-natural rubber PSA onto a continuously moving web backing, the peel force of the tape is substantially di~relelll depending on whether the tape is peeled CA 022386l7 l998-0~-2~
WO 97/22675 ~ PCT/US96/18090 from an adhered surface in the direction parallel to the extrusion coating line (the m~.hine~ direction) or the cross direction (i.e., the direction perpPnriic -l~r or transverse to the extrusion coating line).
Generally, the ratio of the peel force in the m~(~hine direction to the peel force in the cross direction is less than 1, more preferably about 0.9 to 0.002.However, heating the anisotropic PSA to a temperature above the melting point oforiented, crystalline regions of the elastomer irreversibly converts the PSA to an çss~nti~lly or substantially isotropic state, the ratio of the MD peel force to the CD
peel force being e~sçnti~lly 1.
The unique anisotropic peel force property enables PSA articles ofthe invention (e.g., PSA-coated tapes or sheets~ to be advantageously used in graphic arts applications, (e.g., a premask tape, a prespace tape, a graphic art film, die-cut products, or dry transfer lettering, such as the graphic arts products described by Satas, supra, Chap. 32). The anisotropic PSA articles of this invention can also be used as a diaper f~tenin~ tape, a wall decoration film, or other constructions wherein dirrelellLial peel is desirable.
As the degrees of orientation and cryst~lli7~tion in the elastomer increase, they become sufficient to impart to the PSA tack and peel r~si~t~nce which are relatively low in both the machine and cross directions (and much lower than that of a PSA having the same formulation but in which the elastomer is non-oriented andnon-crystalline). However, when such a low-tack embodiment of the PSA is heated above the melting point of the oriented, crystalline elastomer the elastomer crystals melt, the orientation relaxes, and the adhesive properties (tack and peel re~i~t~nce~
irreversibly convert to the higher tac}~ and peel r~ict~nce typical of conventional PSAs of the same forrnulation. Where the degrees of orientation and crystallinity are sufficient to produce relatively low tack and low peel force in both the m~chine and cross directions, these two adhesive properties will increase upon heating and become ~sst~nti~lly or substantially the same in both the m~chine and cross direction.
That is, the PSA layer will become isotropic.

CA 02238617 1998-0~-2~

In another embodiment7 a PSA article of this invention with an initially low-tack adhesive layer is selectively heated to provide a pattern of spatially-varying regions of high and low tack to control the adhesive force of the article.
The invention also relates to various processes, such as a process of bonding one or more substrates or objects together by applying the PSA article to the bonding surfaces. Another aspect of the invention provides a process of L,~n~7re,ling one or more objects from one location to another location, by applying to the surfaces of such objects the PSA7 and transferring the resulting bonded product to the other location.
In another aspect of this invention, a PSA article is made by a solvent-free, hot-melt process which can use7 for example7 the compounding devices7 pumps7 dies, and coating rolls which are described in published PCT application WO
94/111757 which description is incorporated herein by reference.
The process of making a PSA of this invention7 in one aspect7 comprises (a) masticating or milling a normally solid7 undeformed7 uncured elastomer capable of orientation and strain-in~ ced cryst~lli7~tion7 such as uncured natural rubber or polyisobutylene; (b) optionally7 blending such elastomer with tack-in~ cing additives; (c) heating the masticated elastomer or elastomer/tackifier blend above room temperature (>23~~) to form a hot7 tacky substance; (d) shaping by shearing7 elong~tinp;, stretching or e~çnclin~ the hot substance to induce stress and strain therein7 thereby partially molecularly orienting the elastomer; and (e) cooling or q~-enching the resulting hot7 oriented composition to a temperature below the melt temperature of the oriented elastomer and at a cooling rate fast enough to induce partial cryst~lli7~tion in the elastomer in its oriented state.
The hot~ tacky substance can be stretched or extended by extruding it7 for example through the slot of an extrusion die. The film-extrudate can be coated or deposited on a backing7 such as a biaxially-oriented polyester film or a releasesurface7 and then cooled7 thereby providing a PSA article of this invention7 such as a PSA tape or sheet. The cooling can be carried out, for example, by depositing the PSA extrudate on a web (backing~ conveyed by a coating roll having chilled watercirc~ tin~ through its interior. Alternatively, the hot, tacky elastomer-co~ ing CA 02238617 1998-0~-2~
WO 97/22675 PCT/US96/18090.

substance and a thermoplastic precursor of the backing can be coextruded as a l~min~te. The PSA extrudate coated on the backing or the coextruded l~min~t~
may be stretched and cooled to induce the partial orientation and cryst~lli7~tion.
The m~nllf~cturing process can affect the extents of orientation and, as a result, the properties of the PSA. For example, if the cooling rate is relatively slow, then the cooled PSA may have high tack and isotropic peel force. As the cooling rate is accelerated, the PSA will have less tack and the peel force will be moreanisotropic. At relatively fast cooling rates, the cooled PSA may have quite lowpressure-sensitive tack and low or imperceptible peel force. The desired rate ofcooling (to produce the desired orientation, cryst~lli7~tion and, thus, the desired degrees of anisotropy, tack, and peel force~ will vary and depends on factors such as the particular adhesive components used and the amounts thereof, the temperature of the shaped adhesive, the thickness of the PSA coating, the particular equipment and operating conditions used to make the PSA article (e.g., line speed), and the use or application to be made of the article.
In order that the PSA article have the desired heat or solvent r~si~t:ln~e for aparticular application, the PSA can be cured or crosslinked. For example, where the PSA article is a m~king tape to be used in paint spraying operations and has to undergo the paint stoving process, a cros~linked PSA is particularly useful.
However, crosclinking processes which involve heating may be detrimental to preserving the orientation and crystallinity in the PSA.

BT~IEF DESC~IPTTON OF THE I~RAWINGS
The invention will be more fully appreciated with respect to the following non-limiting drawings in which:
FIG. 1 is a schem~tic representation of one embodiment of a continuous compounding and coating line of equipment or appalal~ls which can be used to carry out the above-described solvent-free, hot-melt process for making PSA
articles according to this invention;
3û FIG. 2 is a ~.h~m~tic representation of one embodiment of an extruder screw design or compounding device shown in FIG. l;

CA 02238617 1998-0~-2~

FIG. 3 is a sr~he~m~fic cross-section in elevation of one embodiment of a PSA
article of this inve~tion in the form of a tape or sheet;
FIGs. 4 and 5 are schem~tic isometric views of an embodiment of a PSA
article of this invention which is used as a graphic arts application tape or sheet for the transfer of letters from one substrate to another substrate;
FIGs. 6 and 7 are schematic cross-sectional views in elevation of FIGs. 4 and 5, respectively; and ~IGs. 8-11 are schem~tic top or plan views illustrating PSA products ofthis invention and in which FIGs. 9-11 have patterns of spatially-variable regions ofdi~e~ L pressure-sensitive taclc.

DETAILED DES~R~PTION OF THE PREFERRED EMBODIMENTS
Referring now to the dra~,vings, and initially to FIG. 1, reference number 20 generally decign~fes a device or al~pal ~lus which can be a single unit or a series of units interco~n~cted so as to contin-lo-l~ly compound or process the elastomer component of the PSA used in this invention. Device 20 can be a twin-screw extruder, such as a Werner-Pfleiderer~M co-rotating, twin-screw extruder, e.g., Model ZSK-30 or ZSK-60. Device 20 can have a sequence of alternating and interconnecting conveying and processing sections or zones. A plurality of metering hoppers 21, 22, 23, connected to a corresponding plurality of inlet openings, are provided to feed the PSA components to device 20 at controlled rates. K-TronTM automatic loss-in-weight feeders or liquid addition devices, such as heated pail unloaders or liquid metering pumps, can be used to obtain these rates.
A vent 24 can be provided at the do~~ ;anl or di~chal~ ~ end of device 20 to release volatile substances therefrom. A melt pump 26, such as a Zenith-NicholsTM
gear pump, is connected to the discharge end of device 20 to convey therefrom at a controlled rate a hot melt of the compounded PSA (i.e., molten, compounded PSA). A filter 27 can be disposed downstream of pump 26 to filter the metered hot melt and remove unwanted Col~tz~ s therefrom. Alternatively, the filter 27 can ~ 30 be disposed upstream of pump 26.

CA 02238617 1998-0~-2~

The molten PSA is shaped by extruding it from an opening or slot in a direct-contact coating die 32, such as a flexible blade coater with a silicone rubber wiping blade affixed to the upper side of the die slot. The die can also be a rotary rod contact die. The die deposits, coats, smears, or wipes the mo}ten PSA
extrudate as a continuous coating or film with desired thickness, e.g. 20-75 ~m,onto one surface of a moving web 34. However, the PSA need not be a continuous coating on the web. .It can also be provided as a longitudinally or transverselydiscontinuous coating or film. Web 34 provides the backing for the PSA article and may be made of any material desired, inrlu~1ing those commonly employed as b~c~ing.~ for pressure sensitive adhesive tapes such as biaxially-oriented polyester or polypropylene, vinyl, cloth, paper, metal foil, etc. Additionally, the web can be a release surface such as a release liner.
Shaping and straining of the elastomer component of the PSA melt occurs as it flows out of die 32 and is wiped onto web 34. Web 34 passes over a guide roll 30 and is conveyed to and from the orifice of die 32 by a cooled coating roll ordrum 35. The relative positions of die 32 and coating roll 35 can be such that the PSA extrudate is deposited as shown on the surface of the roll. Roll 35 can be achromed steel coating roll (particularly useful with the flexible blade coater) or a rubber-covered coating roll (particularly useful with the rotary rod contact die).
The interior of the roll 35 can be supplied with a temperature-controiled cooling medium (e.g., circ~ ting water) to m~int~in the roll temperature to effect rapidcooling or q~enching of the molten of PSA extrudate to obtain the desired degrees of orientation and cryst~lli7~tion of the elastomer component. Cooling of the molten PSA extrudate is caused by the transfer of heat from the extrudate to thebacking which is cooled by roll 35. Alternatively, when roll 35 is rubber-covered, an additional cooled roll 36 can be used for cooling the surface of roll 35 to provide the requisite quick cooling of the PSA extrudate. Alternatively, or in addition,cooling can be provided by a spray device 37 mounted or disposed above coating die 32 to spray a cooling mç~ m, such as a mist of water or a curtain of chillednitrogen gas, onto the surface of the molten PSA extrudate as it exits the die. A

CA 02238617 1998-0~-2~

further alternative is to precool web 34 and to coat the PSA onto the cooled web(which acts as a heat sink). Another alternative is to cool the PSA-coated web 38.
The PSA-coated web 38 may be wound up and slit or otherwise cut to the desired size or configuration. As shown in FIG. 1 it may first be conveyed to a croc~linking station 39 where the PSA layer on the web is exposed to r~ tion from a radiation source 41. Radiation source 41 may be an electron beam (e.g., an ElectrocurtainTM unit) or ultraviolet radiation. Radiation provides cro~linkin~ of the elastomer component of the PSA and produces a cross-linlced PSA-coated web 42 which may be wound up and cut to size. A release coating and/or low-adhesion b~cL ci7~, such as that conventionally used on PSA tapes, may also be applied to the web, either before or after the molten PSA extrudate is deposited thereon. Otherdetails of the compounding and coating equipment illustrated will be omitted in the interest of brevity, such details being set forth in the aforementioned PCT
application WO 94/11175.
When coating on relatively thin backings ~e.g., appluxill~ately 25 ~m thick), an effective qll~nching rate to produce the PSA elastomer component in the desired oriented, crystallized state can be achieved simply by controlling the te~.pe~LLIre of the coating roll. With thicker b~cl~ing~ however, it may be nece~s~ry to employ additional cooling means, such as pre-chilling the backing prior to coating it with the PSA extrudate or applying cooling in the form of a chilled liquid or gas stream directed at the surface of the extrudate immediately downstream of the coating die.
Other means can be employed, however. The important thing is that the cooling rate be sufficiently fast that cryst~lli7~tion occurs in the elastomer before the orientation in~llced by the shaping and/or coating operation has relaxed.
FIG. 2 illustrates the design of a screw extruder that can be used for compounding device 20 in FIG. 1. Also shown are hoppers 21, 22 and 23 which dispense the elastomer, tackifying resin, and antioxidant components of the PSA,respectively, into different extruder sections 1, 5, and 7, respectively, via inlet openings. The elastomer is kne~cled or masticated in section 2, conveyed and further masticated in section 3, mixed with tackifying resin and/or other adjuvants in section 5, and mixed with antioxidant in section 7. Further mixing and mastication CA 022386 17 1 998 - 0~ - 2~

takes place in sections 6 and 8. The extruder screw has apl)rol)liate flights or turns to convey the PSA components from one section to a s~Ccee~iin~ section in the direction indicated by the arrows in the upstream and do~ll.,l,ealll zones 1 and 9, respectively. The extruder screw also kneads and m~tic~tes the ~ tQ~nçr The elastomer can be supplied to device 20 as a warrn mass from an external processing device. Alternatively, it can be fed in a pelletized or ground form and coated or dusted with powdered talc or other common parting agents to prevent ornl;ll;l~ e the sticking ofthe elastomer to the screw or interior wall ofthe extruder.
If aerobic processing is desired, an oXygen-cont~ining gas, such as COnlpl essed air, can be injected (e.g., at a pressure of 5-100 psig, 30-700 kPa~ into the extruder, for example, in section 3, to aid in the controlled reduction of the elastomer molecular weight and to ease processing of the PSA. During processing of the PSA and its components in the extruder, the various extruder sections are heated, e.g., to 1 60~C, and, optionally, other adjuvants can be added to the extruder and compounded with the elastomer and tackifying resin.
FIG. 3 illustrates the cross-section of a PSA article 43 of this invention, suchas that cut from web 38 or 42 of FIG. 1. Article 43 comprises the PSA coating 44derived from the hot PSA extrudate, and web or backing 46 such as biaxially-oriented polyester or polypropylene.
As mentioned abovet in one embodiment of the PSA article of this invention, the degrees of orientation and crystallinity of the PSA elastomer aresufficient to impart anisotropic peel force to the article. An article having anisotropic peel force may be used as a graphics application tape (inçl~lfiing both premask and prespace tapes), which is useful in graphic arts work. For example, die-cut graphics often take the form of such vinyl decals. Typically, the decal is formed by cutting it from a sheet of colored, adhesive-coated vinyl film which has been i~min~ted to a release liner. The waste or weed is peeled away and then a graphics application tape is appiied to the top of the die-cut decals to lift them from the release liner while keeping them in register. The decals are then transferred to the desired target substrate and the graphics application tape is peeled away. Such graphics application tapes need to be aggressive enough to reliably lift all of the CA 022386l7 l998-0~-2~

components of the graphic (i.e., the decals ;n this example) from the release liner, but still should be easily removed after transferring the graphic to the target substrate and should not pull any ofthe graphic offthe target. This is often a difficult balance to achieve. Using the PSA tape of the present invention as thegraphics application tape, one could pull in the high adhesion direction to remove the graphic from the liner, apply it to the target substrate, and then remove the graphics application tape by pulling in the low adhesion direction. Other graphics application tapes do not involve die-cut components but there would still be an advantage to having graphics application tapes with a very easy removal direction because the graphics can be very wide and difflcult to pull offwith conventionaladhesives. When a conventional adhesive is form~ ted to have a low removal force, the ability to hold onto the graphic is impaired. The anisotropic PSA tapes of the present invention can have high holding ability but still have a low removalforce.
An embodiment of a graphics application article of this invention is illustrated in FIGs. 4-7. It comprises a tape or sheet generally de~ign~ted 43 (a cross-sectional portion of which is also shown in FIG. 3) CO~ hlg a PSA coating 44 with anisotropic peel force on a backing 46. In FIG. 4, graphics application article 43 is shown placed on top of a release liner 51 which functioned as a substrate for PSA-coated die-cut letter 52 in the form of "E". The lower surface of - graphic application article 43 is defined by the exposed surface of the PSA coating 44. By placing the article over the release liner 51 and then peeling or lifting the tape up in the direction shown in FIG. 4 by the vertical arrow (that is, the high adhesion direction or the cross direction shown by the horizontal arrow designated "CD"), the die-cut letter 52 is removed from the substrate because it adheres toPSA coating 44. This use of the graphic application article 43 is further illustrated in FIG. 6, wllere release liner 51 has removably mounted thereon in a desired pattern an array of PSA-coated die-cut letters 52a, 52b, 52c, 52d, 52e, and 52f,each comprising a baçl~inp 53 coated with a conventional isotropic PSA 54. FIGs.5 and 7 illustrate how the die-cut letters 52a, etc., loaded on anisotropic graphic application article 43 of FIGs. 4 and 6, respectively, can be removed therefrom and CA 02238617 1998-0~-2~

I,~n~re,,ed to a target substrate 56. The letter-loaded graphic application article is placed on the target substrate and the graphic application article is peeled the.~r~u.l.
in the direction shown in FIG. 5 by the vertical arrow, (the machine direction shown by the arrow d~cign~ted "MD"3. The letter 52, "E", is thus transferred to the target substrate 56, as shown in FIG. 5, and the array of letters 52a, etc., are l-~"~re"t;d in a desired pattern to the target substrate 56 as shown in FIG. 7.
Another application in which the anisotropic peeling properties of the invention can be used is in the m~n--f~cture of diaper f~st~ning tape. The low peel force of such a tape in the m~chine direction would allow a large stock roll of the tape to be unwound for converting without the aid of a release material. In the process of converting the stock roll to individual tapes, the tape could be cut so the cross direction of the stock roll, which is the high adhesion direction, becomes the direction of peel on the fini~hed diaper product.
Yet another application of the PSA article would be in wall decoration films.
One can produce a graphic wall decoration with the anisotropic PSA article in such a way that the high adhesion direction is vertical or down the wall to prevent failure due to gravity, while the low adhesion direction is horizontal to provide an easy removal direction avoiding any damage to the wall.
Another use for an anisotropic PSA article of the invention is in m~Qt~ing applications that use a m~Q~nt sheet or drape adhesively fixed to a substrate inorder to mask a large area of the substrate. Maskant sheets or drapes are used in automotive painting or r~?finiching and in commercial and reQid.~nti~l wall painting wherein a paper or plastic film is taped to the autobody part or the wall in order to prevent overspraying of a coating onto the area that is m~Qtred If the m~Ql~nt sheet is relatively long and heavy it will induce a constant peel force in the direction ofthe drape that may cause the tape to pull away from the ~ul)sL~Le. The adhesive can be form~ ted to be more aggressive and overcome the stress induced by the weight of the drape, but the tape may then be difficult to remove completely from the substrate after the painting operation is completed. An anisotropic PSA tape of the present invention that exhibits low peel force in the m~-~.hine direction and high peel force in the cross direction is useful in such m~Qking applications. The tape can -CA 02238617 1998-0~-2S
W O 97/22675 PCT~US96/18090 be made to have high peel resistance or holding ability in the cross direction to overcome the peel stress induced by the weight of the drape, but have only a very low peel or removal force in the lengthwise direction to remove the tape withoutdamage to the substrate. Since heating the PSA tape could detrim~nt~lly affect its anisotropic characteristics, it is not recommended to pass the tape through a paint baking oven.
Another use for an anisotropic PSA article of this invention is as an adhesively bonded wall hook or wall hanger, e.g., for a picture frame. Such an article would have its anisotropic PSA laye~ positioned such that its high adhesion direction would be down the wall to prevent adhesion failure due to gravity or the weight of the picture frame. The wall hanger can be easily repositioned if desired by removing it from the wall by pulling it therefrom in the horizontal direction (in which adhesion of the PSA layer is low), and then, when the hanger is in the new, desired position, heating it, for example, with a hot air gun or dryer, to fix the hanger in position.
Another embodiment of this invention is a PSA article comprising a PSA
layer of a partially oriented and partially crystalline elastomer, where the degrees of orientation and crystallinity of the elastomer are sufficient to impart tack and peel resi~t~nce which are relatively low in both directions (and much lower than that of a product of the same formulation in which the elastomer in the adhesive layer wasnon-oriented and non-crystalline).
An application of the above-described low-tack PSA article of the invention is as a pressure sensitive tape that does not need a low adhesion backsize (LAB) on the back side of the adhesive-coated tape backing. Such a tape is useful, for example, where it is desirable to print directly on the back side of the tape. Printing on many commercially available tapes ~iullellLly involves a multi-step process wherein the LAB coating is partially or completely removed, the printing is applied to the back side of the tape using standard flexographic methods, and then an LAB
is again applied over the printed surface. Since the PSA tape of the present ~ 30 invention can be made to have very low tack, the LAB can be lolimin~te~1 and indicia can be printed directly on the tape backing. The tape can then be wound up again CA 02238617 1998-0~-2~

into a roll having low tack, or an LA~ can be applied over the printed backing and the tape heated up to provide a printed tape having normal tack and peel. Similarly, the low-tack PSA tape of this invention may be used to produce linerless labels that can be printed in the low-tack state and then heated immetli~tely before application S to restore the tack and peel resistance. For example, a tape or label stock having low tack could be (1) fed to a station that would print the desired indicia on the backing by any conventional printing technique, (2) advanced past a heated roller or wire to increase the tack of the adhesive, (3) be cut offto form a label of the desired length, and (4) be directly applied to a substrate. If the printing in this process is accomplished by thermal printing, and it is desired to store the resulting product before use, then one must be sure that the temperature needed for printing should be less than that needed to melt the crystalline regions of the elastomer component of the PSA and relax orientation in the adhesive.
Another application ofthe low-tack PSA ofthe invention is in the m~n-lf~r.tllre of a PSA tape having tack so low that the surface of its adh~sive layer will not stick to most other surfaces, but wherein the surfaces of the tape stick to each other. Surprisingly, the low-tack adhesive surface of this embodiment of the invention adheres aggressively to itself or another similar low-tack adhesive surface even though the adhesive surfaces are not tacky to the touch. Such a taRe would be useful for a variety off~ctening and sealing applications, such as, for example,diaper closures, sealing strips on envelopes and packages, clothing fasteners, and other applications where hook and loop fasteners are commonly used.
Another application of the low-tack PSA of the invention is in bundling operations where a number of elemrntc are bound together by wrapping with adhesive tape, but wherein the bundling tape initially has low tack to allow some slip during the blln-lling, and the bundle is then heated to increase the holding ability so that slip is ~Timin~ted Such a tape would be useful in wrapping cables, fiT~m~nt~
reinforcing fibers, and other elongate members.
The PSA article having low-tack oriented adhesive may also be treated by a zone heating ter.hniq~le to modify the PSA layer and impart a desired pattern thereto of spatially-variable tacky and nontacky regions or to impart di~lel~L adhesive CA 02238617 1998-0~-2~

properties to di~re"L regions such as varying regular, random, or patterned zones of high and low tack. This modification (illustrated in FIGs. 9-11, described hereinafter) can be accomplished, for example, by placing a mask, such as clear polyethylene terephth~l~te film, on the exposed adhesive surface of a PSA article of S this invention having low anisotropic peel force in the rn~hine direction and directing infrared (IR) radiation toward the exposed face of the so-placed mask.The mask will have a desired array or pattern of laser-printed bl~r~ned features or zones which absorb the IR radiation, and transmit or reflect IR radiation through the non-blackened zones of the mask. The temperature of that portion of the PSA
layer that lies beneath and in registry with the blackened zones of the mask is raised, e.g., to temperatures of 50 to 1 50~C. This causes thermal relaxation of the oriented, cryst~lli7ed PSA elastomer component with a consequent increase in thetack of the so-heated portions of the PSA layer. The unwind noise of a PSA tape can be altered by spatially varying the tack of the adhesive. A PSA tape having such a patterned adhesive may also be used in security and tamper-evident applications wherein a predetermined pattern of adhesive could be left on the substrate when the tape is removed.
Additionally, selectively heating regions of the PSA layer to increase the tack could be an alternative to pattern coating an adhesive or selectively det~ckifying areas of an adhesive with varnishes or cover films. For example, "pouch tapes" used to form pockets that contain invoices or other docllm.ont~ onshipping cartons are currently made by coating the entire surface of the backingwith adhesive, and then coating the center section with a varnish to deaden the adhesive everywhere except at the periphery of the pouch. Documents can then be placed in the center region, so that they do not contact the active adhesive at the periphery, and then the pouch is pressure-sealed to the shipping container by the exposed tacky adhesive at the edges of the pouch.
Alternatively, a pouch may be made from a low-tack PSA tape of the present invention. Doc~ments can be placed directly against the low tack adhesive ~ 30 surface of the tape and positioned as desired on the shipping carton. The periphery CA 02238617 1998-0~-2~
WO 97122675 PCT/UC,96/18090 of the pouch can then be heated, for example by a heated iron that limits heating to the peripheral edge where it is desired to increase the tack and peel of the adhesive.
Similarly, the low-tack PSA article of the present invention may be used as an alternative to pattern coating an adhesive, which often requires precise registration of the adhesive application. This is used, for example, in cover tapes for surface-mount component carrier tapes wherein it is desired that adhesive bepresent only at the outer edges of the cover tape so that it contacts only the side rails of the carrier tape and not the components which are held in the pockets of the carrier tape by the cover tape. It is difficult eo obtain the precise registration of adhesive needed for this application, and often a blocker film is used down the center of the adhesive coated cover tape to ensure that the tacky surface of theadhesive does not contact electronic components that are held in the pockets of the carrier tape by the cover tape. Alternatively, the low-tack PSA of the present invention can be used on the entire surface of the cover tape, but then activated only at the edges by heat-sealing the cover tape to the side rails of the carrier tape.
Similarly, a low-tack PSA of the present invention can be used in applications where pattern coating of the adhesive is needed by simply heat activating only those areas of the adhesive where sealing is desired.
Any of the natural rubbers which have heretofore been used or proposed for use as the elastomer component of natural rubber-based PSAs can be used to make the PSAs used in the practice of this invention. Uncured natural rubber is chemically unsaturated and an amorphous material in the unstressed or un~ elclled state and is subject to strain-ind~lced orientation and cryst~lli7~tion (at least partially) of its molecules upon stretching. Natural rubber hydrocarbon is a 1,4-polyisoprene having eee~onti~lly 100% cis structure and has little inherent tack (thus, it is preferably compounded with tackifying resin for PSA use). Commercial natural rubber products which can be used in making the PSAs of this invention are the visually graded rubbers known as ribbed smoked sheets and pale crepes, the technically specified rubbers, such as the SIR or SMR, and the controlled viscosity grades such as the ~V60 version (which are described in Kirk-Othmer, -CA 02238617 1998-0~-2~
.

Encyclopedia of Polymer Sci. and Eng.. Vol. 14, p. 692, Johll Wi'ey ~. Sons, Islc.
1988/~lhich dcGcription i9 incorpor~tcd hcrcin by rc~r~flc~).
Polyisobutylene, also useful as the non-therrnoplastic el~ctorn~or component of the PSAs of this invention, has little tendency to crystallize in the unoriented state but likewise is subject to orientation and strain-induced crystallization upon stretching. This elastomer has only terminal unsaturation. It has inherent tack at low molecular weight, though it is often compounded with tackifying resins to obtain the b~l~nced PSA properties. Co-lul.e~-;ialiy available polyisobutylene products which can be used in this invention include those high molecular weight, normally solid products, such as Vistanex~ M L-80. Low molecular weight polyisobutylene, such as Vistanex~M LMMS, can be used along with the high molecular weight version to contribute tack (see the description of Vistanex~) Polyisobutylene in product bulletin SYN-76 1434 published by Exxon Chem. Co.
U.S.A.¦which dc3cription i3 incorpor~tcd hcrcin by rcfcrcnc~).
Tackifying resins useful as components of the PSAs of this invention include those normally liquid or solid resins known to tackify natural rubber- and polyisobutylene-based PSAs. Those resins preferably have molecular weights that are relatively lower than the elastomer component and glass transition temperatures higher that the elastomer component. The main classes of tackifying resins useful herein inciude the known classes: wood rosin ar~d its der.vatives; petro!eum based resins; and terpenes. The amount of the tackifying resin to be used will be thatsufficient to impart the desired tack to the PSA, and that amount generally will be 10 to 400 parts, preferably 20 to 150 parts, by weight, per 100 parts by weight of elastomer. Particularly useful cornmercially available tackifying resins for tackifying natural rubber are PiccolyteTM S-l 15 terpene and Escorez~M 1310. Particularly usefill commercial petroleum-based resins useful in tac3cifying polyisobutylene-based PSAs are Escorez~ 1310 tackifiers.
Other adjuvants cornrnonly used in rubber-based PSAs can also be incl~ded in the PSAs of this invention, such as antioxidants, e.g., IrganoxTM 1010 tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)-propionate]methane, plasticizer oils, e.g., white mineral oil, elastomer oligomers, waxes, and inorganic AMENDED SHEET

CA 02238617 1998-0~-2~

fillers, e.g., talc, anc oxide, titanium dioxide, ~lumin~lm oxide, ~r.d sil ca (seo Sat~, ~ ' supra. Chap. II for a description of such adjuvants~. Typically, the amount (on a weight basis, per 100 parts by weight of elastomer) of antioxidant to be used will be up to 5 parts, the amount of plasticizer will be up to 50 par~ts, preferably up to 20 S parts, and the amount of filler will be up to S0 parts.
The materials which can be used as a backing or substrate for the PSA
articles of this invention include those heretofore used for rubber-based PSA
articles, incluriin~ polymeric films, e.g., flexible polypropylene and polyester films, metallic foils, paper, ceramic films, and the like. Such backings can also comprise a plurality of fibers in a woven or nonwoven mat-like construction. The other side of the backing can be coated with a release coating or low adhesion backsize and the PSA layer can be covered with a release liner. Backings and release co~tin~c or liners are described in Satas, ~3, pp. 208-211, 585-600~which d~scription is incorporatod hcr0in by rcf0r0n~
EXAMPLES
The invention is illustrated in the following examples, but the particular materials and forms and amounts thereof, and the equipment and process conditions which are set forth in these e.Yamples, should not be construed to unduly limit this invention. In preparing the PSA articies of these examples', equipment iike thatillustrated in FIG. 1 was used. In these examples, the orientation and cryst~ 7~tion of the elastomer PSA components were measured at room temperature with a combination of techniques. The molecular weight of the natural rubber after processing in the mastication section of the extruder was rneasured in terms of inherent viscosity (IV). The tack and peel force of the PSA products were also measured. The techniques or methods of these measurements are as follows.
The optical birefringence measurements of the PSA showed evidence of orientation in that the PSA had different refractive indices for light polarized parallel to the machine direction compared to that for light polarized perpendicular to the machine direction.

A1'~F~O,~) SH~E~

CA 02238617 1998 - 0 ~ - 2 ~
wo 97/22675 PCT/US96/18090 The crystallinity of the elastomer in the PSA was detected by x-ray diffraction analysis. The degree of crystallinity was estim~ted from (li~ iai sc~nnin~ calorimetry analysis and was determined to be low in these ~mrles~ viz., on the order of a few percent by weight of the elastomer.
Direct measurement ofthe PSA orientation was made using samples of PSA
which were coated on the release side of a film which had been previously treated with a silicone release coating. Multiple layers ofthe adhesive were transferredfrom the release film to a clean glass slide (of microscope quality but larger in dimension) by applying the glass slide to the adhesive surface, trimrning the adhesive around the edge of the slide with a razor blade, and lifting the slide. This process was repeated as many times as necess~ry to obtain the desired number of adhesive layers, m~i..l~;..;.~g the relative orientation ofthe slide and the coated adhesive each time. The slide was mounted on a sample holder on an optical bench.
The birefringence of the PSA samples was determined by ~ ting the Babinet compensator so that its birefringence was equal and opposite to that of the sample, as indicated by the black line appeal illg in the center of the crosshairs of the compensator eyepiece. The birefringence of the sample was determined by the compensator setting, the wavelength of the light ~546nm), and the sample thic~n~following standard methods, such as described by White, J.L. et al. in Encyclopedia of Polymer Science. John Wiley & Sons, Vol. 10, p. 605, 1987. The definition o~
birefringence is the difference in refractive index of the sample for light polarized in two mutually perpendicular directions. In this patent specification, the birefringence value is the refractive index difference for light polarized parallel and perpendicular to the direction of p, t;~e, ~ ~d orientation.
Fourier transforrn att~m-~ted total reflectance infrared (FT ATR-IR) dichroism measurements were performed on some of the PSA articles of this invention to measure the molecular orientation in the plane of the co~ting The method is more fully described by F. Mirabella in J. Applied Spectroscop~ 42(7),1258-1265 (1988), and J. Polymer Science. Polymer Physics Edition 22, 1283-1304 (1984). The Nicollet 10-DX Fourier Transform infrared spectrometer that was used was fitted with an ATR ~tt~chment and a germanium (Ge) single diamond -CA 02238617 1998-0~-25 W O 97t22675 PCT~US96/18090 polarizer (Harrick, PSD-JIR). ~ Ge internal reflection element cut ~or a 45~
incidence angle was placed at 22~ from the normal to the beam after the polarizing element and before the detector. The crystal measured 50 mm x 20 mm x 3 mm thick. The actual incjdçnce angle into the Ge crs~stal was c~lc~ tecl to be 39~ due to refraction, corresponding to a l micron thick penetration depth of the infrared ener~3y into the pressure-sensitive adhesive coating. We found that an a~sorption at 1130 cm~l was sensitive to orientation in the sample such that its absorption intensity was higher when the IR beam was polarized along the m~chine (or web) direction compared to when the beam was polarized aiong tlle transverse direction for samples having anisotropic peel adhesion and molecular orientation. The tapesamples were directly adhered to both sides of the Ge crystal. The polarization of the incident IR beam was selected to be parallel to the plane of the adhesive coating. When a PSA sample was mounted with the electric field vector of the radiation parallel to the m~chine direction, the machine direction absorption spectrum was obtained. Conversely, when a sample was mounted with the electric field vector parallel to the cross-web direction, the cross-web absorption spectrum was obtained. The intensity of the 1130 cm~l band was measured as the peak height minus the baseline signal. This value was normalized by dividing this intensity by the intensity ofthe 1095 cm~l absorption (also having baseline signal subtracted) which is independent of orientation so that sample contact area artifacts for the MD
and CD spectra could be factored out. For each spectrum, 50 scans for both background and sample were averaged. For each sample, the relative absorptance ofthe 1130 cm~' band for both machine and cross-web directions was measured.
The "IR anisotropy" is defined as the ratio of the norm~li7ed absorptance of the1130 cm~l band for IR radiation polarized in the machine direction to the absorptance for radiation polarized in the cross direction.
The resistance of a PSA tape to peeling under a constant load was measured by the test referred to as adhesion at constant angle and stress (ACAS) which is a variation of PSTC 14 (Pressure Sensitive Tape Council, Glenview, IL). The staticload peel resict~nce of the tapes was tested in the following manner. A strip of tape 0.75 inch (1.9 cm) wide was cut with a razor cutter and applied to a polished CA 02238617 1998-0~-2~

stainless steel panel. For some of the testing, a quartz substrate was used instead of stainless steel. The panels were cleaned between uses ~y washing once with diacetone alcohol and then three times with heptane, wiping with KimwipeTM sheets each time. The tape was rolled down onto the panel with a 4.5 Ib (2 kg) rubber-coated roller 4 inches (10 cm) in diameter using two passes at appluxl--lately 12 in/min(30.5 cm/min). A wire hook was affixed to one end of the tape strip. The panel was mounted horizontally with the tape on the bottom side. A 200 g weight was hung from the hook and the peel rate was determined by measuring the time topeel the 3-inch (7.6 cm) length ofthe panel. The peel recict~n~e was c~c~ ted asthe inverse peel rate in min/in. Replicate measurements were made and the peel resistance values averaged. The results using this test method are ~ e- I ed to herein as ACAS 1. Alternatively, the aforementioned test was run using ~uartz plate as a substrate instead of stainless steel and the altemative test results are referred to herein as ACAS2.
The peel strength at fixed peeling speed was also measured using an InstronTM universal test machine. A l-inch (2.54 cm) wide strip oftape was cut and applied to a flat glass plate. The strip was rolled down with two passes of a 4.5 Ib (2 kg) rubber covered roller as in the holding power measurements described above.
The glass plate with attached sample was mounted ho~ o~lLally in a sliding jig on the Instron machine. A cord ~tt~hed to the front edge of the sliding plate was threaded through a pulley and attached to the crosshead. The tape tab was clamped in the grips attached to the force tr~nsd-1cçr in the moving crosshead. The tape was peeled by moving the crosshead up at a constant speed of 12 in/min (3.5 crn/min).
This arrangement allowed for 90~ peel of the tape while ~ ;";,~ the peel front directly below the crosch~d The average peel force during the peeling was determined. The ~eel strength is expressed as the force divided by the width of the tape. The results of this test are referred to herein as PLl.
Another peel strength test was used for some of the testing. In this further test, a piece of biaxially-oriented polypropylene (BOPP~ film was applied to a stainless steel test panel with double-sided PSA tape. The PSA tape product of this invention to be tested was slit to a l-inch (2.54 cm) width and then applied to the CA 02238617 1998-0~-2~
wo 97/22675 PCT/US96/1 8090 BOPP film and rolled down as described in the above-described PL1 test. The tapewas peeled by the Instron machine with a 180~ peel angle with a crosshead speed of 12 in/min (30.5 cm/min). The average peel force was measured and the peel strength calculated as the peel force divided by the tape width. The results of this test are referred to herein as PL2.
A third type of peel test was cond-lcted by applying a 1 inch (2.54 cm~ wid strip of the PSA tape of this invention to a glass substrate, rolling and peeling at a peel angle of 180~ and a peeling speed of 90 inches/min (228.6 cm/min). The results of the test are referred to herein as PL3. The same test method was run at a peel rate of 12 inches/min (30.48 cm/min) and the results are referred to herein as PL4.
Tack was measured by the rolling ball test method described in PSTC 6. A
strip of adhesive tape was mounted, adhesive side up, at the base of an inclinedplane. A stainless steel ball was released from the top of the inclined plane and the ~liet~nce it traveled on the adhesive surface before stopping was measured. Results are averages of two measurements. The results of this test are I t;f~l led to herein as RBT.
The molecular weight of the natural rubber after processing in the m~ctic~tion zone of the extruder was sometimes characterized using inherent viscosity (IV) measurements. This technique is well known in the polymer scienceart. A sample of the rubber was removed from the extruder at the tackifier addition port with the tackifier addition turned off. This sample was dissolved in toluene and diluted to a concentration of 0.15 gldl + 0.02 gldl. The diluted solution was centrifuged to remove insoluble components. A 10 ml portion of the solution was transferred to a Cannon-Fenske glass capillary viscometer. The viscol"eler and solution were equilibrated for 5 min in a water bath m~int~ined at 25~C. The solution was then drawn up in the viscometer to the indicated mark with a squeeze bulb and allowed to flow through the capillary of the viscometer. The time for the solution to flow through was measured with a stopwatch. This procedure was repeated for a sample ofthe pure solvent in the same viscometer. The precise polymer concentration was determined by delivering 20 ml of solution with a CA 02238617 1998-0=,-2=, W O 97/22675 PCT~US96/18090 pipette to a preweighed all-mimlm drying dish. The solution was placed in an oven at 100~C for 2 hours. The Ir~ g polymer weight was then determined. All weights were determined using an analytical balance with 0.1 mg resolution. The IV (inherent viscosity) was calculated by the following relation:
.

IV = In (tsolution / tsolvent) S wherein: tSolution is ef~lux time for the polymer solution t,olv"" is efflux time for the solvent c is polymer concentration (g /dl) In is natural logarithm.

E~amples 1-4 and Comparison Esample A
All of these exampies were produced with a single adhesive formulation and fixed extruder conditions. The formulation consisted ofthe following components:
Component Parts bv weight Natural rubber (ribbed smoked sheet) 100 Piccolyte~ S-1 15 tackifier 65 IrganoxTM 1010 antioxidant The natural rubber, supplied by Goodyear Chernical Plantation Division, was ground and fed to the extruder at a rate of 68.4 g/min. The PiccolyteTM S-115 tackifier was ground and d~y blended with IrganoxTM 1010 antioxidant at a weightratio of 65/1 PiccolyteTM S-l 15/IrganoxTM 1010, and this blend was fed at a rate of 4~.1 g/min to the extruder at a second addition port downstream of the rubber addition. The extmder screw configuration shown in FIG. 2 was used along with air injection to the rubber mastication zone. The screw speed was 475 rpm and temperature in the m~tic~tion zone was 1 72~C. Under these conditions, the rubber IV was 2.0 dl/g. The line speed was 60 ~/min (18.3 m/min) and the adhesive melt temperature at the die was 100~C. A contact type die was used with a rubber lip in conjunction with a chromed steel backup roll as shown in FIG. 1.
The quick cooling of the PSA extrudate was effected with a backup roll having a ~ meter of 30 cm and a circumference of 94 cm. The roll interior was -W O 97I22675 PCT~US96/18090 m~int~ined in Examples 1-4 at temperatures of 15 to 50"C using circulating water.
In Comparison Example A, the backup roll interior temperature was 70~C. In all examples, a biaxially oriented polyethylene tereph~h~l~te film (30 llm in thickness) was used as a backing and was coated with the PSA extrudate at a thickness of 40~m. For each example the same conditions were also used to make a second sample by coating the same PSA extrudate on a backing of ~0 ~lm thick polyester film having a silicone release coating on the side to which the adhesive was applied.
This second sample was produced so that the adhesive could be transferred to a glass slide for measurements of the elastomer orientation by birefringence. Testresults on the adhesive and tape prepared in this way are shown below in Table 1.

Table I
Ex. Co~ng Bir~ Rolling ACASl ACAS2 PL2 AJ~
No. roll fnng- ball s~/cm sec/cm N/cm -~opy temp., ence ~ck,RBT, (nu~in) (nu~in) (Ib/~n) DR
~C ~nx103 cm MD CD MD CD ~DD C~
1 15 1.4 6.2 0.7 43 0.2 66 0.11 1.05 2.3 (0.03) (1.8)(0.01)~2.8)(0.06)(0.60) 2 30 1.9 2.2 0.7 83 -* - - - 2.2 (0.03) (3.5) 3 40 0.32 2.1 1.9 40 1.4 54 0.12 2.50 l.X
(0.08) (1.7~(0.06~(2.3)(0.07)(1.43) 4 50 0.22 1.5 28 52 - - - - 1.1 (1.2) (2.2) A 70 0.02 1 499 135 118 139 2.50 2.45 1.0 (4.2) (5.7) ~5.0) (5.9)(1.43)(1.40) *The dashes in Table 1 mean the values were not measured.
Both the birefringence and infra-red dichroism data of Table 1 show that there is significant molecular orientation ofthe elastomer in the PSAs ofthis invention, Examples 1-4, which were prepared by cooling the PSA extrudate at 15-50~C. The peel resistance data of Table 1 (under the headings ACAS 1, ACAS2, and PL2) for the PSA articles of Examples 1-4 are values that are greater by significant amounts in the cross direction (CD) than in the m~chine direction (MD~, the higher anisotropy correlating with greater orientation. In contrast, in preparing the PSA of Comparison Example A, using a higher backup roll temperature, 70~C, the consequent, relativeiy slow cooling of the PSA extrudate resulted in little or no CA 02238617 1998-0~-2~

orientation and crystallization of the elastomer, as shown by the bh~r~ ence andinfra-red dichroism data of Table 1. The peel resistance values for the m~.hine and cross directions for the Comparative Example A do not appreciably differ or are nearly the same, indicating very low or essentially no adhesion anisotropy. The rolling ball tack data demonstrate that, at high degrees of orientation, the taclc is reduced substantially.
The PSA prepared under the conditions for Example 2 was coated on a release liner and transferred to glass for x-ray diffraction analysis. The results showed two diffraction peaks (which were not present in the spectrum from Co,l,pal~ e Example A) which were at diffraction angies m~tçhin~ those reported in the literature for c~st~ ed natural mbber. Differential sc~nnin~ calorimetry (DSC) analysis of this adhesive showed an endothermic peak at 52~C with a heat of fusion of 0.2 cal/g of adhesive. With the literature value of the heat of melting of rubber crystals given as 16.1 caUg crystals, applu~imalely 2% ofthe elastomer inthe PSA of Example 2 was calculated to be crystalline.

E~ample 5 A sample of the PSA article prepared in Example 1, affixed to a glass slide, was mounted in the birefringence setup described earlier. The PSA layer of the article was heated with a heat gun to a temperature of about 80~C for I rninute and the birefringence fell to less than O.Olx10-3. The sample felt substantially tackier to the touch after heat tre~trnçnt than it did before he~tin~ demonstrating that the oriented, crystallized state of the elastomer of the PSA can be çlimin~ted by heating to a temperature above the melting point of the oriented, crystalline phase of the elastomer.

E~ample 6 A portion of the PSA tape of Example 2 was applied to a release liner and aged in an oven at 65~C for 5 min. Another portion of the same tape was applied to the same release liner and kept at room temperature ~ca 20~C). The two portions CA 02238617 1998-0~-2~
WO g7/22675 PCT/~JS96tl8090 were then tested for peel reci~t~nce by the ACAS } method. The two portions of so-treated tapes were then tested and the results are shown in Table 2.

Tnble 2 ACAS 1, sec/c-n (min/in) Tl t;a~n~ell~ MD CD
Kept at room temperature, ca 23~C 0.7 (0.033 83 (3.5) Heated at 65~C 1800 (75)* 1800 (75)*
*tape cohesively split The data of Table 2 show that the oriented, crystallized state of the elastomer of the anisotropic PSA of this invention can be eliminated by heat treatment, resulting in an increase in peel resistance and loss of the anisotropic peel I 0 properties.

E~amples 7 and 8 For these examples, the extruder screw configuration used was the same as illustrated in FIG. 2. The screw speed was 400 rpm and the air injection port was closed. For these examples a controlled viscosity grade of natural rubber, SMR
CV60, available from Goodyear Chemical Plantation Division, was used.
PiccolyteTM S-115 tackifying resin was fed to extruder zones 5 and 7 and, in Example 7, white mineral oil was added to the vent port in zone 9. The rubber IVunder the operating conditions of this experiment was measured to be 3.5 dllg.
For Example 7, natural rubber CV-60 was pelletized with a Moriyama extrusion pelletizer and dusted with talc. The rubber pellets were fed to zone I of the twin screw extruder at a rate of 68.4 g/min. Ground PiccolyteTM S-115 tackifying resin which had been preblended with IrganoxTM 1010 antioxidant at a ratio of 15/1 PiccolyteTM/IrganoxTM was added at a rate of 10.9 g/min to zone 5.Un~ utecl PiccolyteTM S-l 15 was added at a rate of 44.5 g/min to zone 7. White mineral otl was added at a rate of 13.7 g/min to zone 9. The resllltin~ formulation was as follows.

WO 97/22675 rCT/US96/18090 Component Parts by wei~ht Natural rubber CV-60100 PiccolyteTM S-l 15 tackifier 80 Mineral Oil 20 S IrganoxTM 1010 antioxidant The PSA temperature at the coating die was 100~C. The same coating die and roll were used as in Examples 1-4. The fluid circ~ tin~ through the backup roll was controlled at 40~C. The line speed was 60 ft/min. (18.3m/min). The adhesive was coated at a thickness of 50 !lm onto the same polyester ~lm as used in Examples 1-4. The properties of the tape are shown in Table 3 .
For Example 8, the same conditions were used as in Example 7 except that the feed rate of PiccolyteTM S-l lS to zone 7 was 34.2 g/min and no oil was added in zone 9. The fonnula for the PSA of Example 8 was as follows.

Component Parts Natural Rubber CV-60 100 PiccolyteTM S-l 15 tackifier 65 IrganoxTM 1010 antioxidant~0 The line speed was 30 ft/min. (9.1 m/min). The fluid circ~ tin~ to the backup roll was controlled at 40~C. The adhesive was coated at 50 ,~lm onto a crepe paper m~kin~ tape backing approxi~a~ely 100 ~m thick. The tape test results are shown in Table 3.
Table 3 Example PLl (MD), PLl (CD), ACAS1 (MD), ACAS1 (CD), N/cm N/cm sec/cm sec/cm (Ib/in) (Ib/in) (min/in) (min/in) 7 0.5 2.8 2 45 (0.3) (1 6) (0.1) (1.9) 8 0.9 2. 1 0.7 4.2 (0.5) (1.2) (0.03) (0.18) The data of Table 3 show that the anisotropic peel properties can be achieved with these alternate formulations and b~cking~

CA 022386 17 1 998 - 0~ - 2~
wO 97/2267s PCT/US96/1 8090 E~amples 9-}3 For these examples, the extruder configuration shown in FIG. 2 was used along with a rotary rod die and a rubber-covered backup roll. The air injection port of the extruder was closed and the screw speed was 300 rpm. The rubber surface of the backup roll was cooled by contact with a chill roll and the surface of the adhesive was further cooled using either a water spray or a stream of cold nitrogen gas and liquid as shown in Figure 1. The nitrogen cooling was provided by supplying liquid nitrogen to a copper manifold with holes drilled in it. The liquid nitrogen partially evaporated in the transfer hose and the manifold, producing astream of cold nitrogen gas accompanied by a slow drip of liquid nitrogen onto the contact point between the die and the web. The water spray was produced by supplying water at a metered rate to a set of needles arranged in line approximately 0.25 in. (0.67 cm) apart. Compressed air was used to direct two impinging air streams from a manifold such that they met at the line of needle tips, atomizing the water and carrying the spray toward the web imme~ tely downstream of the die.
The adhesive was coated at a thickness of 40 ,um on polyester film b~ in,g~ of various thic,knçs~es. The line speed was 30 ft/min. (9.1 m/min). The adhesive temperature at the die was 1 50~C.
For Example 9, the adhesive formulation was as follows.

Component Parts by wei~ht Natural rubber CV-60 100 PiccolyteTM S-115 tackifier 65 IrganoxTM 1010 antioxidant The natural rubber was added at 68.4 g/min to extruder zone 1, ~In~ilnted PiccolyteTM S-l 15 was added at 13.7 g/min to zone 5, and a blend consisting of 45/1 PiccolyteTM S-1 15/IrganoxTM 1010 was added at 31.5 g/min to zone 7.
Chilled water at a temperature of 15~C was circulated to the chilled nip roll. The water circ ~l~tin~ through the rubber covered backup roll was at 25~C. No chilled nitrogen gas or water spray was used for this example. The adhesive was coated onto a 100 ~m thick biaxially-oriented polyethylene terephth~l~te (PET) film.

CA 02238617 1998-0~-2~

For Example 10, the same conditions were used as for Example 9 except that the liquid nitrogen cooling system was used for quickly cooling the P~A
extrudate.
For Example 11 the same conditions were used as for Example 9 except that EscorezTM 1310 tackifying resin was substituted for Piccolyte~ S-l 15 product and the adhesive was coated on 50 !lm thick PET film.
For Example 12 the same conditions were used as for Example 11 except that the liquid nitrogen cooling system was used to effect the quick cooling.
For Example 13 the same conditions were used as for Example 11 except that the water spray cooling system was used to effect the quick cooling.
The tape properties of Examples 9-13 are set forth in Table 4.

Table 4 Example NoPL3 (~), N/cm (Ib/in)PL3 (CD), N/cm (Ib/in) 9 1.42 (0.81) 2.05 (1.17) 0.26 (0.15) 1.56 (0.89) 1 1 2.40 (1 .37) 3. 12 (1.78) 12 0.19 (0.11) 3.59 (2.05) 13 0.18 (0.10) 3.01 (1.72) The data of Table 4 show that in making PSA tapes with relatively thick b~cking~ on the rubber-covered bac~up roll, cooling from the backup roll alone did not provide a high degree of anisotropy. However, the use of liquid nitrogen or water cooling can provide the desired degree of orientation and anisotropy.

E~ample 14 For Example 14 and Conlpa~ e Example B, the extruder and coating station setups of Examples 9-13 were used. The fluid circ~ ting through the rubber-covered backup roll was controlled at 20~C. The chilled roll cooling the - surface of the backup roll was cooled with water at 1 5~C. The liquid nitrogen cooling system was used with the addition of a second manifold to cool the web prior to coating. The adhesive had the following formulation.

CA 02238617 1998 - 0 ~ - 2 ~
WO 97/22675 PCT/US96/1809û

Component Parts by weight VistanexTM MM L-80 polyisobutylene 62.8 VistanexTM LMMS polyisobutylene20.0 EscorezTM 1310 tackifying resin33.7 White mineral oil 10.0 IrganoxTM 1010 antioxidant 0.6 The VistanexTM MM L-80 polyisobutylene was pelletized in the same way as the CV60 natural rubber for the earlier examples and fed to extruder zone 1. The VistanexTM LMMS polyisobutylene is a low molecular weight product which is a very viscous liquid. This material was heated and pumped to zone 5 of the compounding device using and heated pail unloader. The Escorez~U 1310 resin was fed to zone 7 and the mineral oil was metered into zone 9 using a gear pump.The antioxidant ~vas preblended with the tackifying resin and fed along with it. The adhesive was coated at a thickness of 40 ,um onto a PET backing 50 um in thickness. The line speed was 30 ~ctmin. (9.1 m/min). The resulting tape properties are listed in Table 5.

Comparative E~cample B
The same conditions were used as in Example 14 except that Exxon Butyl 077 rubber was substituted in the adhesive formulation for VistanexTM MM L80 polyisobutylene. The tape properties of this comparative example are also set forth in Table 5.

Table 5 Example No.PL4 (MD) N/cm (Ib/in)PL4 (CD) N/cm (Ib/in) 14 0.18 (0.10) 4.89 (2.79) Col"pal~iveB 6.78(3.87) 6.31 (3.60) The data of Table 5 show that the polyisobutylene-based adhesive had strong peel anisotropy in that the MD peel force was less than 4% of the CD peelforce, but the butyl rubber-based material produced under id~ntic~l conditions did not. The CD peel force is slightly lower than the MD peel force in this case at 93%
ofthe MD value. The di~erence between Example 14 and Co~ a,~i~e Example B

CA 02238617 1998-0~-2~

may be attributed to the fact that the small amount of isoprene comonomer in theButyl 077 rubber prevents cryst~lli7~fion of the rubber.

Example 15 ~ tape made according to Example lO was cut to applo,.inlately six inches (15.2 cm) in length. Approximately one-half of the width of the tape was masked to allow heating of only a portion of the adhesive so as to selectively melt thecrystallinity and relax the orientation of the elastomer and thereby selectively alter the tack of the adhesive. The rolling ball tack (RBT) of the tape sample prior to any m~king or selective heating was 68 mm.
A mask was then prepared. More specifically, a pattern was laser printed on paper such that one-half of the paper was printed black and one-half remained unprinted. The paper was then fed through a TherrnofaxTM photocopying m~r.hine with an infrared transparency film, which darkens by absorbing infrared energy in the machine selectively in those areas which are dark on the paper. This resulted in a patterned transparency film mask which was half dark and half transparent.
The PSA tape (comprising an elastomer having a partially oriented and partially crystalline component) was than applied to the patterned transparency film mask so that one-half of the tape in the longitu-lin~l direction overlapped the dark patterned region of the transparency, and one-half overlapped the clear l-npattPrned region. In order to further protect the unrnasked area of the PSA tape from the effects of infrared absorption, a white tape that did not significantly absorb infrared energy was l~min~ted over the clear unpatterned area of the transparency film mask and to the back of the PSA tape in the area which overlapped the clear unpatterned region of the transparency film mask. The l~min~te was fed through the TherrnofaxTM machine again, with the m~chine at a setting of 6, causing local heating of the adhesive in the area that overlapped the dark pattern on the transparency film.
The rolling ball tack (RBT) of each side of the tape sample was measured and found to be 38 rnm for the unmasked side, and 11 mm for the masked, heated side of the tape. From these data, it appears that some heating and concurrent CA 02238617 1998-0~-2~

melting of the oriented crystalline component of the elastomer occurs even in the ~np~tt~rned regions due to generalized heating within the ThermofaxTM m~hine Example 16 A second six inch (15.2 cm) tape sample made according to Example 10 was masked to allow heating in a spatially varying pattern to give a pattern of alternating high and low tack. Prior to any masking or selective heating the rolling ball tack (RBT) of the tape sample was measured at 68 mm. A pattern as shown in FIG. 10 was produced using a computer drawing program and printed on paper with a laser printer. The paper was then fed through a ThermofaxTM photocopying m~.hine with an infrared transparency film as described in Example 15 to forrn atransparency film mask patterned with alternating dark and transparent lines as shown in FIG. 10. The PSA tape (comprising an elastomer having a partially oriented and partially crystalline component) was than applied to the patterned transparency film mask with the m~ nt lines perpendicular to the longitl--lin~l direction of the tape. The l~min~te was fed through the TherrnofaxTM m~rhine again, with the machine at a setting of 4, causing local heating of the adhesive in the areas that overlapped the dark lines on the transparency film. The rolling ball tack (RBT) of the selectively heated tape sample was measured at 1 Omm, with the tackmeasured across (perpendicular to) the alternating heated and unheated regions of the elastomer.

Examples 17-20 A PSA tape was prepared using the same extruder screw configuration, coating roll, and die setup used in Examples 1-4. The rubber used was SMR CV60 natural rubber, and the PSA formulation of Examples 17-20 was as follows:

Component Parts by weight Natural rubber 100 PiccolyteTM S-115 50 Irganox~ 1010 CA 02238617 1998-0~-2~

The coating roll temperature was controlled at 30~C, and the tape produced had relatively low tack and high peel anisotropy.
The PSA tapes of Examples 17-20 were exposed to heat in a spatially-varying pattern to selectively melt the crystallinity and relax the orientation of the elastomer. By varying the shape of the heating pattern, the unwind characteristics of the tape could be varied. To accomplish the h~tinç~, the desired pattern was produced as described in Example 16, except using the patterns shown in FIGs. 9-11 and in Table 6 below. FIG. 9 shows a tape sample made from a m~ nt having alternating dark and transparent regions which run parallel to the m~chine direction of the tape, and FIG. 10 shows a tape sample made from a m~k~nt having alternating dark and transparent regions which run perpendicular to the m~l~.hine direction of the tape. FIG. 8 is a control sample which corresponds to an unpatterned, relatively low tack tape sample that was not selectively heated to vary its unwind characteristics.
The tapes were peeled at a speed of 100 in/min (254 cm/min) to characterize the noise levels of the tapes during unwind. The characteristics are shown in Table 6.
Table 6 Example No. PatternNoise characteristics 17 FIG. 8low peel adhesion, raspy 18 FIG. 9smooth peel, quiet 19 FIG. 10shocky peel, raspy ~IG. 11smooth peel, quiet From these data, it is apparent that the peel characteristics and unwind noise levels can be altered by spatially varying the tack of the adhesive.

Example 21 An anisotropic PSA tape was made by the same conditions as in Example 10 with the exception that the PSA was coated on 50 ,um thick polyester film. The adhesion of the PSA tape measured by the PL3 method was found to be 0.15 N/cm when peeled in the machine direction and 4.40 N/cm in the cross direction. A sheet of this tape was used as an application tape to transfer die cut letters from a silicone CA 02238617 1998-0~-2~

7~ PCT/US96/18090 release liner~ sirnilar to that illustrated in FIGs. 4-7. Letters applc),d.-.ately 1.2 cm in height were die cut from a vinyl graphic Controltac~ film and the waste vinyl material removed from the space between the letters. The tape was applied to thesurface of the die cut letters on the release liner and rubbed down. The application tape was then peeled in the cross direction (the high-adhesion direction). The high adhesion exhibited by the application tape in this direction ensured that all of the letters would be lifLed from the release liner and held securely to the application tape. The application tape and its attached die cut letters were then applied to the target substrate and rubbed down. The application tape was then removed by peeling in the m~rhin~ direction (the low-adhesion direction). The low peel force of the tape when peeling in this direction ensured that all of the letters rern~ined bonded to the target substrate and the application tape was easy to remove.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this 1 5 invention.

Claims (15)

What is claimed is:

1. A pressure-sensitive adhesive article comprising a substrate and pressure-sensitive adhesive layer thereon, wherein the pressure-sensitive adhesive comprises a partially oriented and partially crystallized elastomer in which the extent of orientation and crystallinity is sufficient to permit the pressure sensitive adhesive layer to display orientation when measured by optical birefringence, infrared dichroism or x-ray diffraction and to display crystallinity when measured by differential scanning calorimetry or x-ray diffraction.

2. The pressure-sensitive adhesive article of claim 1 wherein said elastomer comprises natural rubber.

3. The pressure-sensitive adhesive article of claim 1 wherein said elastomer comprises polyisobutylene.

4. The pressure-sensitive adhesive article of claim 1 wherein said substrate is a release liner.

5. The pressure-sensitive adhesive article of claim 1 wherein said adhesive layer has anisotropic peel force.

6. The pressure-sensitive adhesive article of claim 1 wherein said adhesive layer has relatively lower tack and lower peel force which are irreversibly convertible to relatively higher tack and higher peel force upon heating said elastomer above the melting point of the partially oriented, partially crystalline elastomer.

7. The pressure-sensitive adhesive article of claim 1 in the form of a tape, wherein said substrate is a backing and said pressure-sensitive adhesive layer is coated on said backing.

8. The pressure-sensitive adhesive article of claim 7 wherein said backing is selected from the group consisting of polyethylene terephthalate, polypropylene and paper.

9. The pressure-sensitive adhesive article of claim 1 further comprising a second substrate, said pressure sensitive adhesive layer being attached to said substrate and said second substrate.

10. The pressure-sensitive adhesive article of claim 9 wherein said surface is a graphic arts application film.

11. The pressure-sensitive article of claim 7 wherein said pressure-sensitive adhesive layer has spatially-varying regions of relatively high and low tack.

12. A process for preparing the pressure-sensitive adhesive article of claim 4, which process comprises providing an elastomer capable of strain-induced crystallization masticating said elastomer, optionally, blending said masticated elastomer with a tack-inducing additive, heating said masticated elastomer, shaping said masticated and heated elastomer to induce partial orientation therein, depositing said shaped elastomer on a substrate, and cooling said shaped elastomer to a temperature below the melt temperature of the partially oriented elastomer at a rate so as to induce partial crystallization and maintain said partial orientation in said elastomer induced by the strain of said shaping.

13. The process according to claim 12 wherein said substrate is a backing, and said shaping is accomplished by extruding and depositing said elastomer onto said backing.

14. A process of bonding one or more substrates or objects, which process comprises applying to the surfaces thereof the pressure-sensitive adhesive article of claim 1.

15. A process of transferring one or more objects from one location to another location, which process comprises applying to the surfaces of said objects the pressure-sensitive adhesive article of claim 7, and transferring the resulting loaded product to the other location.