CA2185121A1

CA2185121A1 - Microparticle-containing pressure sensitive adhesive tape

Info

Publication number: CA2185121A1
Application number: CA002185121A
Authority: CA
Inventors: Richard J. Goetz; Daniel P. Pohl; Mary L. Brown
Original assignee: Richard J. Goetz; Daniel P. Pohl; Mary L. Brown; Minnesota Mining And Manufacturing Company
Current assignee: 3M Co
Priority date: 1994-04-04
Filing date: 1995-02-24
Publication date: 1995-10-12
Also published as: BR9507272A; AU1930895A; EP0754212A1; US5626955A; JP3547751B2; CN1144532A; DE69527056T2; JPH09511771A; WO1995027014A1; US5609932A; EP0754212B1; DE69527056D1

Abstract

A pressure sensitive adhesive tape that employs a water-absorptive backing, a microparticle-containing pressure sensitive adhesive and a water-dispersible component is provided. A method of bonding close fitting parts is also disclosed. In the method, a microparticle-containing pressure-sensitive adhesive tape (with or without the water-dispersible component in the adhesive) is employed. Articles made using the tape and/or by the method are also disclosed.

Description

2 ~ 85 1 2 1 ~O 95/27014 ~ v~ 4 - MICROPARTICLE,CONTi~lN'ING
pRF,CS~ . SENSITIVE ADHESIVE TAPE
S
Field of the InventiQn This invention relates to a microparticle-containing pressure sensitive adhesive tape, articles made with the tape, and a method of bonding close fitting parts together using the tape.

There are many products and cu.,~LI u~Liu~s in which close-fitting parts must be joined together. These all involve fitting one piece partially or wholly within a second piece. Examples include joining two pieces of piping, 15 and attaching grips to a variety of types of equipment such as fishing rods, golf clubs, I~u~u~ s, tools, and the like.
For the attachment of grips to various types of equipment, it has been recently customary to secure a strip of pressure sensitive adhesive tape about the shaft, remove the tape's release liner to expose the adhesive, render 20 the adhesive temporarily slippery by applying an organic solvent, such as, for example, mineral spirits or a related petroleum distillate, or trichlu-u~l,y~...~,, and slide the grip over the adhesive. The solvent gradually evaporates to provide a strong adhesive bond between the grip and the shaft. The process is ~ d~ dble due to release of organic solvent vapors into the ~ U~ IL, 25 personal exposure to liquid organic solvents, and hazards posed by flammable solvents. Alternative approaches include the use of solvent-based adhesives;
two part structural adhesives; and hot melt adhesives which are applied to the shaft, followed by slipping the resilient grip over the "wet~ or flowable adhesive In yet another approach, heat moldable adhesives are employed.
One disadvantage of these methods is that adhesive is "squeezedr out when the close-fitting grip is slid onto the shah and positioned. This is messy ~ 2185121 and timc c~nsuming :o clean up. Additionally, the adhesive that is sciucezed out is wastcd. ru~ tL.~ u~- ~ non-uniform bond lines n result, which can r~ducs adhesive strength. Moreo~cr, vhcn solvcnt-base~i a~ihesiYes arc empioyed, there is still unr~esirable exposure to tlamtnable oreanic liquids and5 organic vapon as desCribed aboYe. Further, ~hen hol melt ûr hea~ moldable a~ihesiYw are employed, the use oF heat is reciuired.
Examplcs of llût mdt adhesives fûr use in joining t~vo parts togethcr include those disclosed by De~lis in U.S. Patent No. 41785~495; and Stobbie ct ai. in U.S. Patent No. 5,288,359 Stobbie also disclûses that when at~
rJ apccit ily bght fittin~ joint is desired it is help~l tû applr a lubrica~ing aid, such as water ûr hydroxy c- ~i ' to ~he interior-fitting part. A hcat molda~ie adhesive for use in applying motorcyc~e hand grips is described by Dellis in U.S. Patent No. 5,155,878.
Use of a water activi~ted s~stell~ would be dcsirable from thc perspective 15 tllat tile use of ~le~t or organic solvonts could be avûidcd. Howcvcr, typicai wi~ter activate~i adhe5ives hare their own ' ~vall~gw. Once a grip is 5iip~
on, ~vater is trapped ~etwn thc twû parts and long dryin~ tim~s, e.g., ~reater than ~4 hou#, are thus re4uired b~fore harldling strength is reached. Scc, ror eYamplel U.S. Patent 5,~81 ,28B. When water soluble adhesives ilre used there 2 0 is an obserYed puddlin~ or co~lection of liqu~d ol' ;he adhesivc ~ . - when the grip is slid on. ~his "puddl~ng" retarr~s dryi~g, and can result in i bond strength ~ dcscrioed above.
" there e~dsts a need for an adhesive tapc that can be used lo bond close fitting parts together without thc necd to apply and remo~re 25 organic solYen~s or w;~hout the need to ~pply heat tû ~etivate the adhesiv~.

S ~f' I -Briefly, in one aspect of the invention, a .~,;~ ,. . ' i ' ' _ ~r~s~ire sensitivc ildhcsivc tape is provided that comprises a watcr-absorptivc, , AMENDED SHEET

.. 21~5121 prcfcrsbly ~ , bacicin7, having firsl and sccond opposed surfaces with a ilrst , ' eontaininS pressure sensitive adh~siYe on at IeasL a por~ion of the first ~urface of the backin~. Tile second surfa¢e may have a second pressurescn~itive a~ih~sive on at least a portion thercor. Ir a second pres~ure sensitive is s e~nploYeli, it may hnYe the same or a djfferent , than the first n~h,..)~ ' containing ~ hesiYe.
The .r\;.,.u~.li.~c ~ pr ~ aiL;~C adhe~ive eomprises a) . from about 90 ~o 99.75 parts i~y weight of a ll~;t ~v~Jal l;CIL-containing eûmponent; and cu-- r b) frem abeut lO to about 0.2S parts by wei~7h~ of a - ~ , t, that can be dispersed, solYated, or swoi~en in wat~r.
In another aspect of th~ inYention, an article is pr~ided tllat colllprises at least part~aily hollow first member arid a seeend memi~er that is ~eceived inte~iorly ûf Ihe ffrst memi~er and bond~d there~o by nneiins of the pressure 15 rensitive adhesive upe of the invention.
In YCl another aspect of the invention, a rnethod of bonding e~ose filting ~ts is pruvide~i. The method corripi ises the steps of.
(a) se~uring ~lle lape aceording to th~ invention to the second member such that the ";l-us, .liJ~ . ~ adtiesive layer is cxpostxi;
~b) activating Ihe ~ adhesive to ren,ier it rlippery;
(c) ,oosilioning the first men~oer in a fnanner such that the second r~ember i~ at least partially rec-~ived in the fir~t mûmt~er; and ~d) causing the - ,vt - ~ contsining adhesivc- to dry and adhesively secure the fir~t 2nd second m~mbers together.
The h~ of the inv~ntion are ~/alLi~ ally use~ul for bondirg close fitting ~ r ' together. For e catnple, il is userul in bonding pipin~, ~nd the place nent of a handgrip on the shan of items sueh as ~ools, b~cycl~ or rnotorcye~e handle bars, ~,olf elubs and the like. By "ciose fitting parts' it is .

- AMEI\ DED SHE~

11 t`~-S~ 3--~3~ :31: , 3~ +~ s) `'.iSiS~ :II1.>
. ~ . 2185121 ~ncant that even in the abs~r3csz of the adhe5ive t~3?e ~here would be somc yhysical contact betwcen the firs~ and second mt3mbers when they arc s~sernb3e~3, As us~id hcr~3in, th~ ~erm ~wat~s-dispersible" means a comyoncnt that un b~ dis~crsed, sol~ated, or swolll3n in water.

AMENDED SHEET

WO 9,C~Z701~ PCTIUS95/0231 Detailed l)escriptiQn The tape of the invention comprises a water-absorptive backing, a first up~uticlc containing pressure sensitive adhesive layer and, optionally, a second pressure sensitive adhesive layer. While not intending to be bound by 5 theory, it is believed that the water-absorptiYe backing enables water used toactivate the ~ u~kuLiclc containing pressure sensitive adhesive to be removed from the activated adhesive layer, thereby facilitating the drying of the adhesive and shortening the time necessary to attain a suitable level of shear holding properties.
While the microparticle-containing adhesive layer is water-activated, it is not dissolved during activation. This is because the amount of water needed for activation is not suMcient to dissolve the layer.
The Water-Absorptive R:~ kin.~
A wide variety of materials are useful as the backing. Although certain of these materiais may not be inherently water-absorptive, it is sometimes possible to make them so by ill~lUdUU;I~; porosity; applying various treatments,or including additives, modifiers, etc. or any ~u.,.l.,..-l;.," thereof. Such methods are described in U.S. Patent Nos. 4,539,256; 4,833,172; 4,861,644;
20 4,867,881; 4,957,943; and WO 92/07899. The backing preferably comprises a microporous matrix.
Examples of materials suitable for use as the water-absorptive baci~ing include, but are not limited to, kraft paper (available from Mnno~nn~k Paper, Inc.); cellophane (available from Flexel Corp.); spun-bond poly(ethylene) and 25 poly(ylu~ such as Tyvek~ and Typarn' (available from DuPont, Inc.);
and porous films obtained from poly(ethylene) and ~uly(~ u.~ .), such as Accurer (available from Ak70na); Teslin~ (available from PPG Industries, Inc.), and Cellguard~ (available from Hoechst-Celanese~.
While a variety of water-absorptive backing materials are useful in the 30 invention, it has been found that pûrous films of, for example, polyolefin are preferred when there is a close tolerance between the parts to be fitted together WO 9~/27014 PCT/US9~/02314 and/or when the first member must be slid a significant distance onto the second member. An especially useful backing of this type is an ultrahigh molecular weight polyolefin.
As disclosed above, a material that is useful as the backing material is a 5 Illi~,lUlJU~UU~ ultrahigh molecular weight polyolefin material, commercially available as "TESLIN" film. This material is flexible, stretchable, and heat andwater resistant as described in U.S. 4,~61,644. The film is a Ill;~,lUpUlU~
matrix cûmposed essentially of ultrahigh molecular weight, high density polyethylene having a network of i..t~..,o,~..c~ g pores that:
10 throughout the matrix. The density of ultrahigh molecular weight pul~
is greater than 0.94 g/cm3. The intrinsic viscosity of the ultrahigh molecular weight polyethylene is at least 18 deciliters/gram, typically 18 to 39 deciliters per gram (col. 2, lines 46-54 of U.S. 4,861,644). The average diameter of the pores within the matrix is in the range of from û.02 to about 50 Illil,lUlllCt~
(col. 6, lines 54-59). The matrix can be filled with siliceous materials such assilica, mica, mnntmnTillOnit~', kaolinite, asbestos, talc, sodium aluminum silicate, alumina silicate, alumina silica gels, and glass particles.
The Mi~-u~ .licle-C-!ntAinin~ Pressure Sensitive A~h~cive The ~ u~ulicle-containing pressure sensitive adhesive useful in the first pressure sensitive adhesive layer comprises a l~ lup~ cnmrnnPt~ and preferably, a water-dispersible romrtm~nt Optionally, one or more modifiers may be included in the adhesive.
The water-dispersible component suitable for use in the ~ lu~)~liCI-, 25 containing adhesive is a material that comprises sufficient lly.llu~Jllili~ units to render it capable of being water-dispersible. Preferably the water-dispersible component contains functional groups, such as hydroxyl, carboxyl, amino, sulfonyl, and the like. l~ upluliclc containing adhesives which employ these types of water-dispersible ~ u~f ,l~ have been found to exhibit improved 30 shear strength.

2 1 ~5 ~ 2 1 WO95127014 ,~_117J..,5~ 'l4 Examples of suitable water-dispersible .~....I.u ~ include, but are not limited to, materials selected frûm the group cûnsisting of surfactants such as poly(ethylene ûxide) llu~ ,'"~.iyl ethers such as those sold under the name IGEPAL CO (available from Rhone-Poulenc, Inc.); poly(ethylene oxide) 5 octylphenyl ether; poly(ethylene oxide) lauryl, cetyl, and oleyl ethers such as those sold under the name Brij (available from ICI Americas, Inc.);
poly(ethylene oxide) laurate; poly(ethylene oxide) oleate; sorbitan oleate;
ethylene u~idc/~,.u~,~L..., oxide block copolymers such as those sold under the name PLURONIC and TETRONIC (available from BASF Corporation);
10 metal salts ~such as the sodium sa',t) of dodecyl benzene sulfonate, available as Siponate~ DS-lû (Rhone-Poulenc); poly(sodium styrene sulfonate); alkylaryl ether sulfates, such as sodium alkylarylether sulfate, sold under the name Triton"' (available from Rohm and Haas, Inc.); cetyl trimethyl z7mm~nillm bromide; and ammonium lauryl sulfate.
Other water-dispersible ~,,,.1....... ,.. 1~ useful in the invention include those disclosed in U.S. 2,g38,421, U.S. 3,441,430, U.S. 4,442,258, U.S. 3,890,292, and U.S. 5,196,504, U.S~ 4,92,501, U.S. 4,518,745, U.S.
4,4~2,675, U.S. 4,442,258, U.S. 4,413,080, and DE C 23 11 76. Examples of such Cu~ 7ull~ 5 include but are not limited to those selected from the group 20 consisting of poly(acrylic acid); poly(vinyl a,cohol); po ly(N-v;nyl pyrrolidone); poly(vinyl methyl e~her); poly(ethylene imine);
poly(acr~vlamide); poly(alkoxyalkyl (meth)acrylates), such as 2-ethoxy ethyl acrylate, 2-ethoxy ethyl .~ y' , 2-(2-,~ o~ u~y) ethyl acrylate, and 2-methoxy ethyl acrylate (available from SARTOMER Company, Inc.);
25 poly(vinyl methyl ether); poly(vinyl methyl ether:maleic anhydride), sûld under the name Gantrez~ (available from l~ lla7iull~1 Specia'ity Products); poly~etherpolyols), such as poly(propylene glycol) and the like, such as those sold under the name Sannixn' (available from Sanyo Chemical Industries); cùpol~
thereof, and the like. Copolymers of these and alkyl (meth)acrylate esters or 30 vinyl esters are a',so suitable. Gums such as those derived from okra and guar may also be used.

2 ~ 8 5 1 2 1 WO 95/~7~14 PCTIU~ 5102314 An example of a pressure sensitiYe adhesive polymer that may be used as the water-dispersible component is an emulsion polymer that comprises the pOl.~ i~liu-~ product of a water-dispersible poly(alkoxyalkyl) acr~Ylate (preferably from about 50 to 98 parts by weight), and a carboxylic acid 5 (preferably from about S0 to 2 parts by weight). Additionally, an essentially water-insoluble alkyl acrylate and a copolymerizable emulsifier monomer may be included in the pol~,.,.,;~liu~ The alk~Y~ acrylate typically comprise from 0 to 40 parts by weight, preferably 0 parts by weight, of the ~ilylll.,i~ion mixture. The emulsifier monomer typically comprises from 0 to 10 6 parts by weight, preferably 0 to 4 parts by weight, of the pOIyll~.li~lliU
mixture.
~ xamples of poly(alkoxyalkyl) acrylates useful in preparing the emulsion polymer include but are not limited to those selected from 2-(2-ethoxyethoxy) ethyl acrylate, 2-ethoxyethyl acrylate, 2-~ ù~y~llu~Lllyl acrylate, 15 2-~ llu~.lllyl li,.llld~ly' , polyethylene glycol l~ul~ù~yl~ and yl~t~s, and the like.
Examples of carboxylic acids useful in preparing the emulsion polymer include but are not limited to those selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, beta-~ubu,~
20 acry~ate, and the like.
Examples of alkyl acrylates useful in preparing the emulsion polymer include but are not limited to those selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acr,Ylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acr,Ylate, isooctyl acrylate, 2-ethylhexyl acrylate,25 isononyl acrylate, isodecyl acrylate, and the like.
Examples of culJùlyll~.;~bl~ surfactant monomers useful in preparing the emulsion polymer include but are not limited to those which are anionic vinyl functionai clirf~t~ c such as sodium vinyl sulfonate, sodium st~Yrene sulfonate, alkylene polyalkoxy sulfates, and the like.
30 Yet another pressure sensitive adhesive polymer that may be used as the water ~i ~ersible component in th~ inv,n[ on is ~escribed in copending wo 9512701~ Pcrlus9~102 application Senal Number 08/093,080. This pressure sensitive adhesive polymer comprises a polymer of AA, BB, and CC monomers. The AA
monomer is a llydlu,uhvl);c monomer se~ected fron~ the group consisting of an acrylic or a methacrylic ester of a non-tertiary alcohol having from 2 to 14 5 carbon atoms. The AA monomer comprises from 50 to 80% by weight of the AA plus BB plus CC monomers. The BB monomer is selected from ,~-~bU~.r. il~y~ acrylate (BCEA) or a salt thereof, and mixtures of BCEA or a salt thereof, and other vinyl carboxylic acids or a salt thereof. The BB monomer comprises from about lO to about 30% by weight of the AA plus BB plus CC
10 monomers. If a mixture of BCEA and the vinyl carboxylic acid or its salt is used, the BCEA must comprise at least 10% by weight of the polymer.
Additionally, the carboxylic acid groups of the polymer have been neutralized with an alkali metal hydroxide. The quantity of the hydroxide used to neutral;ze the acid groups is from about 0.5 to 2 equivalents of the hydroxide 15 per acid group. The CC monomer is a water-dispersible 1111~
monomer which has the formula X-Y-Z. In the CC monomer, X is a moiety copolymerizab]e with AA and BB, Y is a divalent linking group which joins X
to Z and Z is a water-dispersible group which contains at least two units which are essentially unreactive under free radical initiated copolymerization 20 conditions which can be used to form the polymer. CC comprises from 10 to 30% by weight of the AA plus BB plus CC monomers. The X, Y, and Z
monomers are described in more detail below with respect to the ~ of the ~ U~1 Licl~ ~.
This pressure sensitive polymer typically has an inherent viscosity (IV) 25 at 27.5C in 2-butanone of from about 0.2 to over 2 dl/g. Preferably the IV is in the range from about 0.7 to 1.5 dl/g. Most preferably the IV is in the range of from about 0.9 to 1.4 dl/g.
The ~iwup~icl~ component useful in the adhesive of the first pressure sensitive adhesive layer is comprised of polymeric, el ~l .. ;c, solvent 30 insoluble but solvent dispersible ~ icl~. These spheres may be inherently pressure sensitive if desired, although they need not be so.

-WO9S12701~ r~
Additionally, they may be crosslinked if desired. They are ge~erally spheroidal . in shape, although they need not be perfectly spheroidal. They typically have ~ari average diameter in the range of from I to 300 (preferably from 1 to 50) f~.
The ~ ic~s used in the invention may be solid or hollow. Hollow 5 I~ lvp~licl-,J may contain more than one void. Typically, the hollow or void portion of the ~ lv~ s is less than 100 11 in average diameter.
The In;~lv~ may be prepared by various ~ml~lcifi~ari~n processes.
For example the I~ U~ may be obtained via suspension pOIyl~ iu such as the following "two-step" emlllcifi~arirm poly,..~li~liu" process 0 comprising the steps of:
a) forming (i) forrning a water-in-oil emulsion by mixing an aqueous solution of polar monomer(s) with oil phase monomer(s), the oil phase monomer(s) being selected from alkyl (meth)acrylate esters and vinyl esters; and (ii) forming a water-in-oil-in-water emulsion by dispersing the water-in-oil emulsion into an aqueous phase; and b) initiating polymeri2ation, preferably by application of heal or radiation.
In this process, the first step preferably invo]ves forming a water-in-oil emulsion of an aqueous solution of monomer(s) (at least some of which is a polar monomer) in an oil phase monomer, i.e., at least one (meth)acrylate or vinyl ester monomer, with optional free radically reactive hydrophilic oligomersandlor polymers, using an emulsifier having a low hydrophilic-lipophilic 25 balance (HLB) value. Suitable emulsifiers are those having an HLB value below about 7, preferably in the range of about 2 to about 7. Examples of such emulsifiers include sorbitan " - ~ , sorbitan trioleate, and ethoxylated oleyl alcohol such as Brijn' 93, available from Atlas Chemical Industries, Inc.
In the first phase of the first step, oil phase monomer(s), emulsifier, a 30 free radical initiator, and, optionally, free radically reactive lly~lupllilic oligomer and/or polymer, and, optionally, a crosslinking monomer or g WQ 9S127014 PCTlUS9~/023t'~
monomers as defined below are combined, and an aqueous solution of all or a portion of the polar monomer(s) is agitated and poured into the oil phase mixture to form a water-in-oil emulsion. The free radically reactive hydrophilicoligomer amd/or polymer, may be added to either the oil phase or the water 5 phase. A thickening agent, e.g., methyl cellulose may also be included in the aqueous phase of the water-in-oil emulsion. In the second phase of the first step, a water-in-oil-in-water emulsion is formed by dispersing the water-in-oil emulsion of the first step into an aqueous phase containing an emulsifier havingan HLB value above about 6. The aqueous phase may also contain any portion 10 of the polar monomer(s) which was not added in step one. Examples of such emulsifiers include ethoxylated sorbitan ."~ c,~ r ethoxylated lauryl alcohol, and alkyl sulfates. In both steps. when an emulsifier is utilized, its ~),., ....I.,.~;n.~ should be greater than its critical micelle ~llAc~ ;..."which is herein defined as the minimum u unc~ a~iu~l of emulsifier necessary for the 15 formation of micelles, i.e., ~ub~ lu~ul~ic a~y.cy~.~iull~ of emulsifier molecules. Critical micelle c-- ~ .II...~;.~n is slightly different for each emulsifier, usable ~ ~ ranging from about 1.0 x lû4 to about 3.0 moles/liter. Additional detail concerning the ~UIC~J~dLiO~I of water-in-oil-in-water emulsions, i.e., multiple cemulsions~ may be found in various literature 20 references, e.g., Surfactant Systems: Their Chemistry. Pharmacy. & Biolo~v.
(D. Attwood and A. T. Florence, Chapman & Hall Limited, New York, 1983).
If the water-in-oil-in-water emulsion is stable, then hollow or multi-void h lu~ku~icl~s will be formed The second, or final process step of this method involves the application 2S of heat or radiation to initiate poly,.l~,iL~Liu., of the monomers. Useful initiators are those which are normally suitable for free radical pOl~ iLaLiull of acrylate or vinyl ester monomers and which are oil soluble and of very low solubility in water. Howeve}, when the polar monomer is N-vinyl ~lll ' ' o, the use of benzoyl peroxide as the initiator is 1~ Examples of such 30 initiators include azo comrCl~ln~ dlu~ uAides~ peroxides, and the like, and 2 1 ~51 21 WO gS~27014 I ~ "'C~14 such as b~ u~ ,u-,c, benzoin ethyl ether, and 2,2-dimethoxy-2-phenyl ~
Use of a water soluble pu~ d~iull initiator causes formation of substantial amounts of latex. The extremely small particle size of latex particles renders any significant formation of latex ~ F The initiator is generally used in an amount ranging from about û.01 percent up to abûut 10 percent by weight of the total polymerizable ~ ù~ ., preferably up to about ~i percent.
lu~Jdlti~1~.7 may also be prepared by a simpler ("one-step") 10 pmlllcifi~tir~n process comprising aqueous suspension poly~ iul~ of at least one alkyl (meth)acrylate ester monomer or vinyl ester monomer and, optionally.
at ]east one polar monomer in the presence of at least one emulsifier which is capable of producing a water-in-oil emulsion inside the droplets, which is cllhct~n~ y stable during ~ ul~;rlcdliOn and pol~." ;,-~ . In this process ~i the aqueous suspension optionally, and preferably, also includes a free radically reactive hydrophilic oligomer and/or polymer.
As in the two-step Pn -llcifi~ir)n process, the emulsifier is utilized in c..-- ..1..~ greater than its critical micelle cun~ dliùll~ Examples of such emulsifiers include alkylaryl ether sulfates such as sodium alkylaryl ether 20 sulfate, e.g., Tritonn' W130, available from Rohm and Haas; alkylaryl poly(ether) sulfates such as alkylaryl poly(ethylene oxide) sulfates, preferablythose having up to about 4 ethoxy repeat units; and alkyl sulfates, such as sodium lauryl sulfate, ~mm~ lm lauryl sulfate, t-;- 11~ ;"-~ lauryl sulfate, and sodium hexadecyl sulfate; alkyl ether sulfates such as ~nnr~tnillnn lauryl 25 ether sulfate; and alkyl poly~ether) sulfates, such as alkyl poly(ethylene oxide) sulfates, preferably those having up to about 4 ethoxy units. Alkyl sulfates;
alkyl ether sulfates; alkylaryl Pther sulfates; and mixtures thereof are preferred as they provide a maximum void volume per ~ u~udulicle for a minimum amount of surfactant. Nonionic Pml~l~ifi~rc e.g., Siponicn' Y-~00-70 30 (~llu~y~d~d oleyl alcohol, available from Alcolac, lnc.); and PLURONIC
P103 (a block copolymer of poly(propylene oxide) and poly(ethylene oxide), -Il-21~5121 v~o ss/270l4 r~ 4 --available from BASF Corporation) can be utilized alone or in ~OI~jUll~ Liull with anionic emulsifiers. Polymeric stabili~ers may also be present but are not necessary. . ; -Both the "two-step" and "one-step" methods produce an aqueous S suspension of monomer droplets. Upon poly,,l~ .i~Liu,, the droplets become microparticles. The majority of the DliwulJcu~ have interior cavities that, upon drying, become voids.
Another process which may be used to prepare the ~ ul~ulicl~.~ forms an oil-in-water emulsion and then disperses the emulsion into an aqueous phase.
10 The aqueous phase comprises at least one alkyl (meth)acrylate ester monomer or vinyl ester monomer, and optionally a free radically reactive hydrophilic oligomer and/or polymer. This process employs a suspension stabilizer rather than an emulsifier. As a result, this process forms monomer droplets which have no interior cavities. Upon poly-n n7~ion~ these droplets become solid 15 ~ u~
Discrete polymeric microparticles may also be prepared via suspension pol~ ;.,"c as disclosed in U.S.Patent Nos. 3,691,140; 4,166,152;
4,636,432; 4,656,218; and 5,045,569 which all describe adhesive ~ ,c,~
Preparation of the ~ "u~-Licl~s of this invention may be modified by 20 withholding the addition of all or pan of the optional free radically reactive hydrophilic oligomer and/or polymer, and optionally polar monomers until after polymeri2ation of the oil phase is initiated; however, the ~ must be added to the polymerizing mixture prior to 100% conversion.
The ~liclu~J~uLicl~ may be prepared from a number of materials. For 25 example, alkyl acrylate and l,.~ LII~,Iyl~ltl_ monomers may be used tû prepare the spheres. These monomers are ., -- ,~r, ,~ , J acrylate and y' esters of non-tertiary alkyl alcohols. The alkyl groups of these alcohols preferably contain from 4 to 14 carbon atoms. These acrylate monomers are oleophilic, water emllicifi~l-lr~, have restricted water solubility, 30 and as homopolymers, generally have glass transition ~ IU~ U~r~ below about -IOGC. Examples of such monomers include but are not limited to those WO~5127014 I~ Jv,51~7~il4 .
selected from the group consisting of isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isodecyl ~ ld~yld~, isononyl acrylate, isodecyl acrylate, and mixtures thereof.
S Preferred acrylate monomers include those selected from the group consisting of isooctyl acrylate, isononyl acrylate, isoamyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, sec-butyl acrylate, and mixtu~es thereof.
Acry]ate or methacry]ate or other vinyl monomers which, as 10 hù~l~upùly~l~ers, have glass transition ~ ul~a higher than about -10 to 0C, e.g., tert-butyl acrylate, isobornyl acrylate, butyl ~II.;,hd.,l~ " Yinyl acetate, acrylonitrile, mixtures thereof, and the like, may optionally be utilized in .U~ljLllC~iOII with one or more of the acrylate, Ill~tll~l~lyldl~ and vinyl ester monome~s provided that the glass transition ~CI~ Ul~ of the resultant 15 polymer is below about -10C.
Vinyl este~ monomers suitable for use in the microparticles include but are not limited to those selected from the group consisting of vinyl 2-yl~ , vinyl caprate, vinyl laurate, vinyl ~I~u~ul~t~ viny~ hexanoate, vinyl propionate, vinyl decanoate, vinyl octanoate, and other ~l~u~uru,'~Lional - ~ vinyl esters of linear or branched carboxylic acids comprising I to 14 carbon atoms which as homopolymers have glass transition t~l~lp~ldLul~a below about -10C. Preferred vinyl ester monomers include those selected from the consisting of vinyl laurate, vinyl caprate, vinyl 2-~ ylll ~ , and mixtures thereof.
The polar monomers useful in preparing the ll~icluudlLicl~ are both somewhat oil soluble and water soluble, resulting in a diallib.~ of the polar monomer between the aqueous and oil phases. R~ acl.L~ivc examples of suitable polar monomers include but are not limited to those selected from the group consisting of acrylic acid; Il,~Lll~lclylic acid; itaconic acid; crotonic acid;
30 ~naleic acid; fumaric acid; sulfoethyl lli~lld~lyl.~t~, and ionic monomers such as sodium ~ d~ly~t~, ammonium acrylate; sodium acrylate; trimethy~amine p-WO 95127014 PC~T/US95102314 vinyl benzimide; N,N-dimethyl-N-(beta-methoxy-ethyl) ammonium propionate betaine; trimethylamine ~ Llld~lyla,llide; 1,1-dimethyl-1-(2,3-dillyd~u~.yp~ yl)amine If,~ a~lyL~ ;d~, N-vinyl Fyrrolidone; N-vinyl ~IuLl~L~ ; a.lyl~"idt, t-butyl ~yl.llllidc, dimethylamino ethyl acrylamide;
S N-octyl d~lyLII~I;dt, mixtures thereof, and the like. Preferred polar monomersinclude those selected from the group consisting of .,,..,..~..1. r...;..
...~,.,o.,~ul,u,.ylic acids; ,.... ~r.1. r, ,;- dicarboxylic acids; acrylamides; N-substituted a~lyl~",id~j salts thereof, and mixtures thereof. Examples of such monomers include but are not limited to those selected from the group 10 consisting of acrylic acid; sodium acrylate; N-vinyl pylluliJull." and mixtures thereof.
Optionally there may be included free radically reactive hydrophilic oligomers and/or polymers in the microparticles. These include but are not limited to those selected from the group consisting of poly(alkylene oxides) 15 such as poly(ethylene oxide); po]y(vinyl methyl ether); poly(acrylamide);
poly(N-vinyl pyrrolidone); poly(vinyl alcohol); and mixtures thereof.
Fl-n~tinr~li7,-~l derivatives of free radically reactive hydrophilic oligomers and polymers useful in the ll,i~lu~ icl~i include those selected from the group consisting of macromers of the general formula:
X~(Y)n~Z
wherein X is a group that is free radically copulyl"c.i~l,lc with the free radically poly,l.~.i~l,k, monomer~s) and polar monomer(s);
Y is a diYalent linking group;
n is an integer of 0 to 1;
Z is a mûnovalent hydrophilic polymeric or oligomeric moiety having a degree of polylll~,iLa~iull greater than or equal to 2.
Examples of such ~ldclull~ollunl~ls include but are not limited to those selected from the group consisting of acrylate and methacrylate functional 30 oligomers and polymers, where X represents H2C=CRI-, where Rl represents H or CH3; Y is a divalent carboxyl group; n = I; and Z is a ;~ydlu~Jllilic WO 0~/27014 ~ / U rN~
oligomeric or polymeric moiety having a degree of po]y~ iu" greater than or equal to 2. Such I~ UIIIUIIV~ also include but are not limited to p-styryl - functional materials, X represents H2C=CRI-, where Rl represents H or CH3; Y represents ~CH2 n = l; and Z is a hydrophilic oligomeric or polymeric moiety having a degroe 10 of pv~yl~ iull greater than or equal to 2. Difunctional or r,.ultiru,,~liullal oligomers and polymers having more than one X group radically copolymerizable with the free radically ~ul~vlr~ le monomers and polar monomers of the microparticles used in the present invention, such X groups either pendant from or ~.Il.i..~Lil~g hydrophilic polymeric or oligomeric moiety15 Z, are also useful in the microparticles of the present invention.
Preferred macromonomers include those selected from the group consisting of acrylate terminated poly(ethylene oxide); I~l..,llavly' terminatedpoly(ethylene oxide); methoxy poly(ethylene oxide) Ill~,lld~-yl~t~, butoxy poly(ethylene oxide) methacrylate; p-viny] benzyl terminated poly(ethylene 2û oxide); acrylate terminated poly(ethylene glycol); ,~ Iy' terminated poly(ethylene glycol); methoxy poly(ethylene glycol) I--~ ,-y' , butoxy poly(ethylene glycol) methacrylate, p-vinyl benzyl terminated poly(ethylene glycol); poly(ethylene oxide) diacrylate; poly(ethylene ûxide) dilll~lla~,ly' and mixtures thereof. These f~lnr~inn~li7~ materials are preferred because they 25 are easily prepared through well known ionic pol~ iu,l techniques and are also highly effective in providing grafted hydrophilic segments along froe radically poly.~ i, ~ acrylate polymer backbones.
Preferred ,n~",u.~U.. u,.,~l, also include those selected from the group consisting of p-vinyl benzyl terminated poly(N-vinyl pyrrolidûne); p-vinyl 30 benzyl terminated poly(acrylamide); methacrylate terminated poly(N-vinyl pyrrolidone); and mixtures thereof. These III~ J~ may be prepared WO 9~12701~ PCTIUS95102314 through the P5tPT jfi~`~tj~n reaction of a carboxy terminated N-vinyl pyrrolidone or acrylamide, beta-~ au~ul~,ul,;o~lic acid chain transfer agent, and chlc~romethyl styrene or methacryloyl chloride as described in a series of papers by M. Akashi et al. [Angew. Makromol. Chem., 132, 81 (1985); J. Appl.
5 Polym. Sci., ~, 2027 (1990); J. Polym. Sci., Part A: Polym. Chem., j~, 3521 (1989] all i..~o.uu. ' by reference herein.
Preferably at least one po~ar monomer is included in the ~
but ~ V~ ,b,~ may also be prepared using alkyl acrylate, alkyl methacrylate and/or vinyl ester monomer(s) alone or in . ."n~ .., only with other vinyl ~û free radically pùly~ .iLdble monomers, e.g., vinyl acetate. Hûwever~ when a nl~ ~lla~lylalc monomer alone is utilized, a crûsslinking agent, infra must be included unless the hydrûphilic component comprises more than one radically ]ylll.liL_~IC group X as defined in ~ormula 1. Most preferably at least abûut I part to about 10 parts by weight polar monomer is included as this ratio15 prûvides ll~ u,ual Li- L i with balanced PSA properties.
The cû~ ù~;l;l~n from which the ~ lullalLiCl~ ~ are made may also contain a multifunctional crosslinking agent. The term ~T ll;r~ " as used herein refers to crosslinking agents which possess two or more free radically pOlylllcliLalJlc ethylenically ' groups. Useful 20 Illullirull~liullal crosslinking agents include those selected from the groupconsisting of acrylic of methacrylic esters of diols such as butanediol diacrylate, triols such as glycerol, and tetrols such as p.nLa~ly~ iLul~ Other useful u~ ' ;ne agents include those selected from the group consisting of polymeric I~lulLirulluLiunal acrylates and l"~Lll~cly' , e.g., poly(ethylene 25 oxide) diacrylate or poly(ethylene oxide) dilllcil~a~.~y , polyvinylic crosslinking agents, such as substituted and .~ ;l"t ~ d;V;IIYIIJI~IIL~ and .~;r..l. 1;..,,-l urethane acrylates, such as Ebecryr 270 and Ebecryl 230n' (1500 weight average molecular weight and 5000 weight average molecular weight acrylated urethanes, respectively - both available from Radcure Specialties), and 30 mixtures thereof.

2 1 ~51 2 1 WO 9512701-1 PCT/U~i9.'5/02314 The ~ P~L;CIC~ useful in this invention are preferably comprised, based on 100 parts by weight total, of 100 parts or less of at least one free radically pOlyll...i~tl. monomer se]ected from the group consisting of alkyl acrylate esters, alkyl methacrylate esters, vinyl esters, and mixtures thereof;
S and optionally about 0 to about 30 parts by weight of one or more polar monomers; and optionally about 0 to about 40 parts by weight of at least one l~ydlu~llilic oligomer or polymer cf mr~nl~nf Preferably the pressure sensitive "~ u~ licl., comprise about 80 to about 98 parts of free radically pOly~ lc monomer selected from the group 10 consisting of alkyl acrylate esters, alkyl l~ lyldte esters, vinyl esters, and mixtures thereof; and optiona~ly about I to 17 parts of at least one polar monomer; and optionally about I to 18 parts of a hydrophilic oli~omer or polymer component, based on 100 parts by weigh~ total. Most preferably the pressure sensitive microparLicles comprise about 87 to about 98 parts of free 15 radically polyll,.li~l,lc monomer; and optionally about I to 8 parts of a polar monomer; and optionally about 1 to 5 parts of a hydrophilic oligomer or polymer comrl~n~nf~ based on 100 parts by weight total.
When a crosslinker is employed, it is typically employed at a level of up to about 10 equivalent weight percent. Above about 0.15 equivalent weight 20 percent, of the total pulylll~ ab]c Ill;~uy~LiClf; G. ~ v~ , the l~ uu~uLi~ sbecome tack-free. The Uequivalent weight percent" of a given compound is defined as the number of equivalents of that compound divided by the toLa number of equivalents in the total (l~h,lU~)alliclC) ~ '`, wherein an equivalent is the number of grams divided by the equivalent weight. The 25 equivalent weight is defined as the molecular weight divided by Lhe number off~ùlylll~liLalJI~ groups in the monomer (in the case of those monomers with onlyone poly ' '. group, equivalent weight = molecular weight). The crosslinker can be added at any time before 100% conversion to polymer of the monomers of said microparticle ~u..l~o~;L;ull. Preferably it is added before 30 initiation occurs.

l 851 21 WO ~5/2701~1 . PCI`/US9~/0231-1 In one ~ o~ , the hydrophilic component may be absent from the u~auLicle cu ,~ Preferably the said hydrophilic component is included in the microparticle ~ While not wishing to be bound by theory, it is believed that the pendant hydrophilic moieties, when employed, areS located near to or at the surface of the microparticles. In this manner their presence cûntributes to the "~ u~ " of the adhesive when comes in contact with water, thus facilitating joining of the inner and outer parts. Further, thepresence of the l.,i.lu,u~Li~l~ containing adhesive is re,-iuired to ensure that the adhesive does not completely dissolve, or degrade in some other way, when lû exposed to humid or moist conditions and result in the joined parts sliding or slipping if exposed to force after drying. The presence of illi.,u,ua,Li~ with hydrophilic groups improves the slippery ~ ( vhen wet) of the adhesive blend. Conse~iuently, the method of the invention does not re~iuire thepresence of a water-dispersible c~mr~n~ nt However, the presence of such a 15 component does improve ~ Increasing the amount of the water-dispersible component will provide increased ~ at the expense of longer drying times~
The relative amounts of the above cul~ u..~ are important to the properties of the resultant microparticle~ Use of higher levels of a 20 Il~uliiru~l~Liul~ai crossiinker will result in tack-free ~ lu~auLiclc:~. In such cases the water soluble, or tii~rPr~ihll- po]ymeric component must be tacky. In those cases where the water soluble, or dispersible, polymeric component is not itself tacky, it is necessary for the Illiclui~al~ adhesive to be so.
The Illi~luya~ containing adhesive may optionaily contain one, or 25 more, modifying agents to impart or enhance desired ~ rl ;~ related to the iul~;iu~ua~iull of the adhesive or to its ~rr~ fi~-n Examples of useful modifying agents include, but are not limited to, thickening agents such as those selected from the group consisting of aikali swellable, associative polymers, such as those sold under the names UCAR POLYPHOBE (available frûm 30 Union Carbide, Inc.); Alcogumsu (available from Alco Chemical); Rheolate~

WO gS/27014 PCT/11595/0231~1 (available from Rheox); AcrysolT" (available from Rohm & Haas); and Carbopor (available from B. F. Goodrich).
r~ lizin~ agents, which are often employed in ~""1.~ ", with thickening agents or carboxylic acid functional polymers, may also be used in 5 the present invention. Such neutralizers include, but are not limited to, those selected from the group consisting of metal ions, such as sodium, potassium, calcium, n~r ~ m copper, aluminum, or zinc; and amines, such as ammonia, n h_AyLI-ll..lc, 1~ lol amine, II~;Ad~ ";...
Other modifying agents which may be used to alter the properties of the 10 adhesive blend include, but are not limited to, those selected from the groupconsisting of tackifying resins, plasticizers, pigments, fillers, flow control agents, and stabilizers.
The water-dispersible component used in the adhesive blend of the present invention is provided in quantity to sufficient to result in the rcquired IS degree of cli~ U~ L~ to the joining operation being enabled.
Preferably it comprises from about 0.25 and 10%, more preferably from about 0.~ and 5% based on 100 parts total weight of the adhesive. Cul~ u~di~ly, the ~,.;clul,~lLicles used in the adhesive preferably are tacky and comprise about 99.75% or less, preferably from 99.75 to 95%, based on lû0 parts total weight 20 of the adhesive blend.
The second pressure sensitive adhesive layer useful in the present invention may be a ~ -u~ le-containing pressure sensitive adhesive if desired. If the second pressure sensitive adhesive contains ~ lul~licles, it may have the same or a different ~ ,u~ n ~ than the first adhesive layer.
25 Altematively, the second pressure sensitive adhesive may be some other ty~pe of adhesive (i.e., heat activated, paste, pressure sensitive, aerosol, liquid, etc.).
~ xamples of various materials and ~ useful as a pressure sensitive adhesive in the second adhesive layer include those discussed in the literature (e.g, Houwink and Salomon, Ad~7esion and Adhesives, Elsevier 30 Publishing Co, Amsterdam, r~l~ , 1967; Handbook of Pressure-Sensitive Adhesive Technology, Donates Satas, Ed., Van Nostrand Reinhold Co., N.Y., WO !151Z7014 PCTIIIS95/02314 l9g2). These non-microparticle pressure sensitive adhesives generally comprise lUbb~,./lC:~;II mixtures, acrylic resins, polyu.~ resins, silicone resins, and the like. Among the various patent literature describing C and il~ U~ in pressure sensitive adhesive rull..ul.lliùlls are 5 U.S. Patent Nos. RE 24,906; 2,652,351; 3,740,366; 3,299,010; 3,770,708;

3,701,758; 3,922,464; 3,931,087; 4,012,560; 4,077,926; 4,387,172;

4,418,120; 4,629,663; and the like. These classes of IL.bl,~ , acrylic, silicone, and polyurethane pressure sensitive adhesives as well as any other pressure sensitive adhesives are generally useful in the present invention as the 10 second pressure sensitive adhesive layer.
Specific examples of pressure sensitive adhesives useful as the sccond adhesive layer include, but are not limited, to those selected from the group consisting of urethanes, block copolymer rubber, siiicones, styrene block copolymers; natural rubber with a tackifier; copolymers of isooctyl 15 a..y' 'd~ylic acid, isooctyl acrylate~acrylamide, isooctyl acrylatelN-vinyl uli~iunc, and t~ vlylll. .~ of isooctyl a..yl~l~. /a..ylic acid/~uly~ly.c.lc IIICCIUIIIUIIUIII~,I, and isooctyl a -y- 'a -ylic acid/(meth)acrylate ester.
When the IJI .rullll~ of the present invention is compared to that of a conventional water activated, repulpable adhesive, such as those disclosed in 20 U.S. Patent Nos. 3,865,77û; 4,413,080; or 4,442,258; or DE-C 2 311 746, on a water absorbing backing, the present invention provides ill~lllU~ in terms of elimination of "puddling'`.
The pressure sensitive Illi.lu,u~ containing adhesive sheet of the invention may be prepared in a number of ways. For example, The adhesive 25 layers may be applicd to the backing by sequential coating followed by any necessary drying and/or cooling between the individual coating steps.
Altematively, the adhesive layers may be applied ~ v ~ly followed by any necessary drying or cooling. A number of coating techniques may be used to apply the adhesive to the backing. These include knife coating, Meyer Bar 0 coating, curtain coating, and extrusion coating. Additionaily, the adhesive may be sprayed onto a support if so desired.

2 1 ~51 21 WO '~5127014 PCTIUS95102314 The method of the invention will now be discussed with reference to the application of a resilient hand grip to a golf club. In this discussion, the resilient grip constitutes the first membet and the shaft of the club constitutes the second member.
In the prefetred embodiment of the present invention, a tape having a porous, water absorbing film and first and second pressure sensitive adhesive layers is employed. The tape is applied to the golf club shaft such that the second pressure sensitive adhesive layer holds the tape to the shaft. This may be ~ h~ by Inr~itll~in~lly applying a strip of the tape to the shaft.
10 Alternatively, the tape may be applied atound the circumff r~7nre of the shaft.
When this technique is used, the tape may be applied so that it does not overlapitself. Alternative]y, the tape may be spirally wrapped atound the shaft .so that each succeeding wrap of the tape ovei~laps a portion of the preceding wrap of the tape. Whatever application technique is employed, the first ~ U~;.,IC-15 containing pressure sensitive adhesive layer is left exposed.
After being applied to the shaft, the exposed ~ ",a,Licle adhesivelayer is activated by water so as to render it slippery. The water may contain a surfactant or a detergent, if desired. A number of techniques can be used to apply the water. These include dipping the wrapped shaft in the fluid, spraying 20 the fluid onto the wrapped tape, or wiping the wtapped shaft with an applicator holding the water.
Once the microparticle-containing pressure sensitive adhesive has been rendered slippery, the resilient grip can be slid onto the shaft to its final position. The resulting assembly is then allowed to dty so as to essentially 25 p. .~ Lly bond the resilient grip to the shaft. The drying time required to reach handling strength ranges from 10 to 30 minutes. In this way the advantages of ~1;",;-, l;"~ exposure to solvent, .'limir~tio~ of "puddling", andreduced drying times are realized. A further advantage of the present invention is that the outer part does not need to be wetted ptior to the joining opetation.
30 Still another advantage provided is the ease with which the outer part may be~ub~u~lllly removed from the inner part. This is ~,`~,,..,l,l;~l,.`.~ by simply 2 1 851 2~
WO 95/27014 PCI`/US95~231.1 reversing the process, that is, water may be injected between the two parts causing the outer adhesive layer to become Uslippery once again, allowing for their separation.
Although this method has been described with regard to the placement of

5 a resilient grip on a golf club, the method is not so limited. It is generallyuseful in the bonding of an at least partially open, hollow, or tubular first member, such as a sheath, sleeve, cover or grip over a second member such as a core, rod, shaft or the like, wherein the second member is received interiorlyof the first member. The second member may be hollow or solid, elongated or 10 not, and may have a circular, oval, triangular or other polygonal shape, or an asymmetrical shape in cross-section. It is also useful in bonding a grooved member, such as weather stripping, over the edge of a door or window. It may be made from metal, p3astic, ceramic, glass or cellulosic material. Similarly, the first member may have a wide variety of shapes and ,~.,.1~.", l;.. ~ and may1~ be formed from most any material. While it is preferred that the first memberhave a shape that ~ that of the second member, such is not required.
By necessity, the first member must be at least partially hollow such that the second member may be received interiorly thereof, although the first member need not be ~ u~ Li~lly C~-ntinl.,-llc The present invention is further illustrated in the following examples which should not be viewed as limiting in scope.
Emulsion MS-A
2~i 4.8 g of acrylic acid (AA), 2.4 g of poly(ethylene oxide)l7acrylate, 0.24 g of 1,6 hexanediol diacrylate and 1.13 g lucidol-70 (70% benzoyl peroxide) were dissolved in 232.4 g of iso-octylacrylate (IOA). 0.75 g of sodium dodecyl benzene sulfonate was dissolved in 360 g of water. The IOA
mixture was then added to the surfactant solution, then emulsified using an 30 OmnPU Mixer until the droplet size was less than 5 ~. The emulsion was then charged to a l-liter indented resin flask, heated to 6~DC, degassed with argon 21~5121 WO~5/27014 F.ll~,, ln7~14 and allowed to react for 8 hours. The mi. lul .l,Licl~s had an average diameter of 3 microns as determined by optical microscop~.
MS-B
4.2 g of acrylic acid (AA), 4.2 g of 1,6 HDDA and 1.13 lucidol-70 (70% benzoyl peroxide) were dissolved in 230 g of iso-o~Lyl~ly~ (IOA).
0.75 g of sodium dodecyl benzene sulfonate was dissolved in 360 g of water.
The IOA mixture was then added to the surfactant solution, then emulsified using an OmniTK Mixer until the droplet size was less than 5 y. The emulsion 10 was then charged to a l-liter indented resin flask, heated to 65C, degassed with argon and allowed to react for 12 hours. The ~ u~cuLicl~ 5 had an average diameter of 3 ~ as determined by optical microscopy.
~IS-C
l.S 4.8 g of acrylic acid (AA), 2.4 g of poly(ethylene oxide)l7acrylate, 0.24 g of 1,6 hexanediol diacrylate and 1.13 g lucidol-7û (70% benzoyl peroxide) were dissolved in 232.4 g of iso-octylacrylate (IOA). 0.75 g of sodium dodecyl benzene sulfonate was dissolved in 360 g of water. The IOA
mixture was then added to the surfactant solution, then charged to a 1-liter indented resin flask, stirred at 400 RPM, heated to 65C, degassed with argon and allowed to react for 8 hours. The Ill;.lU~,~lLicl~s had an average diameter of approximately 4511 as determined by optical ll~iCIu~-_v~uy.
MS-D
Mil u~uLiclcs that had an average diameter of 3 lll;Clulll~,t~ ) as rrin~l by optical III;- JU~CU~y were prepared as follows:
4.8 g of acrylic acid (AA), 2.4 g of poly(ethylene oxide)l7acrylate, 0.24 g of 1,6 hexanediol diacrylate and 1.13 g lucidol-70 (70% benzoyl peroxide) were dissolved in 232.4 g of iso-octylacrylate (IOA). 0.75 g of 30 sodium dodecyl benzene sulfonate was dissolved in 360 g of water. The IOA
mixture was added to the surfactant solution and emulsified using an Omn 21 ~51 21 wo 9~12701~ PcT/usssm23l4 Mixer until the ~roplet size was less than 5 ~L. The emulsion was then charged to a l-liter indented resin flask, heated to 65C, degassed with argon and allowed to react for 8 hours. 2.4 g of poly(acryiic acid) and 3.6 g of PolyJl bc,~ 104 (Union Carbide) were added to the resulting dispersion. The 5 pH of the dispersion was adjusted to 7 with the addition of NH40H. The op~u Li~ a had an average particle size of 3 ~ as determined by optical ua~
F ' I
The MS-A emulsion was thickened with Poly~ ,b~'~ 104 (Union Carbide 1.5% by weight of the MS-A emulsion) and then neutralized with NH40H to a pH of 7. Various additives were then added to the thickened emulsion and the resulting mixtures were coated onto separate "TESLIN" films at a wet coating thickness of 101.6 ~ (4 mils). The coated films were dried at 15 80C for 3 min.
The ali~ a of the film was then tested. A section of the film was secured to a table by double-coated tape to leave the ,lli~lu~Li~ adhesive surface exposed. The adhesive surface was wet with about 10 g of water and a section of a rubber golf grip was slid back and forth across the film. The 20 ~ of the wetted film was subjectively rated between 0 and 5 where 0 means that the film was not siippery and 5 means that the film had excellent sli~ s. The resu~ts are listed in Table 1.

21~5121 WO!)5/27014 F~.l/U
TABI~ I
Water-Dispersible Component .~lirpl~ c Example Type Amt. Rating (Wgt. %) laSodium dodecyl benzene 3 5 sulfonate 5 lb Pluronicn' F108 3 5 IcPoly(acrylic acid) 1 5 IdPoly(vinyl alcohol) 3 5 leSodium dodecyl ben2ene 1 4 sulfonate lfPoly(sodium styrene sulfonate) 1 4 10lg Ammonium lauryl sulfonate 1 4 lhPoly(N-vinyl pyrrolidone) 1 3 liCetyl trimethyl ~mmnnillm 1 3 bromide ljNone - 2 lkPoly(vinyl alcohol) 1 2 1511 Po]y(ethylene oxide) l I
(MW=400) ImPoly(ethylene imine) l 0 Exam~le 2 The MS-A, B, and C emulsions were thickened with rul~ ob~ 104 as 20 described in Example 1. The thickened material was then admixed with either 2% by weight poly(acrylic acid) or 3% by weight sodium dodecyl benzene sulfonate. The resulting adhesive ~ v~ o~;liull~ were coated onto TESLIN film, dried and tested for ~1;1,l,~,;... ~ as described in Example 1. The results of the tests are listed in Table 2.

2 1 851 2 t wo 9~/271~1~ . r~

Water-Dispersjble ~`omr~n~n~
Ex.
T Amt. Mi~luud Lic~ lirpPrinPcc Yre (Wgt.9G) Rating 2a Poly(acrylic acid) 2 MS-A 5 5 2b Poly(acrylic acid) 2 MS-B 5 2c Sodium dodecyl benzene 3 MS-B 4 sulfonate 2d Sodium dodecyl benzene 3 MS-A 4 sulfonate 2e Poly (acrylic acid) 2 MS-C 3 2f Sodium dodecyl benzene 3 MS-C 2 sulfonate 102g None - MS-B 2 2h None - MS-A
2i None - MS-C 0 Example 3 MS-D was coated at 152.4 ~ (6 mils) wet onto a 50.8 ~ (2 mil) polyester, then oven dried at 80C for 3 min. An acrylic adhesive was coated at approximately 101.6 ~ (4 mils) wet on the opposite side, then oven dried at 80C for 3 min.
S cm (2 inch) wide strips of the tape ~~ 'y 30.5 cm (12 inches) 20 long were applied l~n~irll~in~lly to the end of a golf club with the .u~d.~i~lc-containing pressure sensitive adhesive facing outwards. The taped end of the golf club was then submerged in water for ~J,UII ' ' ~y 10 seconds. After the 10 second soak, the golf club was removed and a rubber grip was applied. The resulting assembly was air dried at room t~ L~Lu 25 Time for the tape to dry exceeded 60 minutes.

Claims

WHAT IS CLAIMED IS:

1. A microparticle-containing pressure sensitive adhesive tape comprising a water absorbing backing having first and second opposed surfaces, and a first microparticle-containing pressure sensitive adhesive on at least a portion of the first surface of the backing, wherein the first microparticle-containing pressure sensitive adhesive comprisesa) from about 90 to 99.75 parts by weight of a microparticle-containing component; and correspondingly b) from about 10 to about 0.25 parts by weight of a component, that can be dispersed, solvated, or swollen in water.

2. A microparticle-containing pressure sensitive adhesive tape according to claim 1 wherein said water absorbing backing is microporous.

3. A microparticle-containing pressure sensitive adhesive tape according to claim 2 wherein said backing has an average pore diameter of from 1 to 300µ.

4. A pressure sensitive microporous adhesive tape according to claim 1 wherein said water-absorbing backing is selected from the group consisting of kraft paper, cellophane, film, or microporous films of polyolefin, polyester, poly(caprolactam), poly(N-vinylidene fluoride), nylon, cellulose acetate.

5. A pressure sensitive microporous adhesive tape according to claim 4 wherein said water-absorbing backing is a microporous film of ultrahigh molecular weight polyolefin.

6. A microparticle-containing pressure sensitive adhesive tape according to claim 5 wherein said polyolefin is polyethylene.

7. A microparticle-containing pressure sensitive adhesive tape according to claim 6 wherein the pores of said water-absorbing ultrahigh molecular weight backing have an average diameter in the range of from 0.2 to 50µ.

8. A microparticle-containing pressure sensitive adhesive tape according to claim 1 wherein said microparticle-containing pressure sensitive adhesive comprises:
a) from about 95 to 99.75 parts by weight of said microparticle-containing component; and correspondingly b) from about 5 to 0.25 parts by weight of said component, that can be dispersed, solvated, or swollen in water.

9. A microparticle-containing pressure sensitive adhesive tape according to claim 1 wherein said microparticle-containing component comprises (1) 100 parts by weight or less of at least one free radically polymerizable monomer selected from the group consisting of alkyl acrylate esters, alkyl methacrylate esters, vinyl esters and mixtures thereof;
(2) 0 to 30 parts by weight of at least one polar monomer copolymerizable with the free radically polymerizable monomer of part (1); and (3) 0 to 40 parts by weight of at least one hydrophilic oligomer or polymer copolymerizable with either of the free radically polymerizable monomer of part (1) and the polar monomer of part (2).

10. A microparticle-containing pressure sensitive adhesive tape according to claim 9 wherein the microparticle-containing component comprises from about 80 to 98 parts of the free radically polymerizable monomer, from about 1 to 17 parts by weight of the polar monomer and from about 1 to 18 parts by weight of the hydrophilic oligomer or polymer.

11. A microparticle-containing pressure sensitive adhesive tape according to claim 10 wherein the hydrophilic component of said microparticle-containing comprises macromonomers of the general formula X-(Y)n-Z
wherein X is a group that is free radically copolymerizable with the free radically polymerizable monomer and optional polar monomer(s);
Y is a divalent linking group;
n is an integer of 0 to 1; and Z is a monovalent hydrophilic polymeric or oligomeric moiety having a degree of polymerization greater than or equal to 2.

12. A microparticle-containing pressure sensitive adhesive tape according to claim 11 wherein said component, that can be dispersed, solvated, or swollen in water is a surfactant.

13. A microparticle-containing pressure sensitive adhesive tape according to claim 12 wherein said surfactant is selected from the group consisting of poly(ethylene oxide) nonylphenyl ethers; poly(ethylene oxide) octylphenyl ether; poly(ethylene oxide) lauryl, cetyl, and oleyl ethers; poly(ethylene oxide) laurate; poly(ethylene oxide) oleate; sorbitan oleate;
ethylene oxide/propylene oxide block copolymers; metal salts of dodecyl benzene sulfonate;
poly(sodium styrene sulfonate); alkylaryl ether sulfates; cetyl trimethyl ammonium bromide;
and ammonium lauryl sulfate.

14. A microparticle-containing pressure sensitive adhesive tape according to claim 13 wherein said surfactant is a metal salt of dodecyl benzene sulfonate.

15. A microparticle-containing pressure sensitive adhesive tape according to claim 14 wherein said metal salt is sodium dodecyl benzene sulfonate.

10. A microparticle-containing pressure sensitive adhesive tape according to claim 15 wherein said component, that can be dispersed, solvated, or swollen in water is a polymer selected from the group consisting of poly(acrylic acid), poly(vinyl alcohol); poly(N-vinyl pyrrolidone); poly(vinyl methyl ether); poly(ethylene imine), poly(acrylamide); poly(alkoxyalkyl (meth)acrylates); poly(vinyl methyl ether); poly(vinyl methyl ether:maleic anhydride);
poly(ether polyols); copolymers thereof; and copolymers of thereof and alkyl (meth)acrylate esters or vinyl esters.

17. An article comprising an at least partially hollow first member and a secondmember that is received in said first member and adhesively bonded to said first member by means of the microparticle-containing pressure sensitive adhesive tape of claim 1.

18. An article according to claim 17 wherein said first member is substantially circular in cross-section and said first member is circumferentially continuous.

19. An article according to claim 18 wherein the first member is a resilient hand grip.

20. An article according to claim 19 wherein the second member is an item of sports equipment.

21. An article according to claim 20 wherein said second member is at least a portion of the shaft of a golf club.

22. A method of adhesively bonding an at least partially hollow first member to a second member received interiorly of said first member, which method comprises the steps of:
(a) securing a pressure sensitive adhesive tape according to claim 1 to the second member such that the microparticle-containing adhesive is exposed;
(b) activating the microparticle-containing adhesive to render it slippery by moistening it with water;
(c) positioning the first member in a manner such that the second member is at least partially received in the first member;
(d) allowing said water to be absorbed by said backing; and (e) allowing the microparticle-containing adhesive to dry to adhesively secure the first and second members together.