CA2196169A1 - Acrylic syrup curable to a crosslinked viscoelastomeric material - Google Patents

Acrylic syrup curable to a crosslinked viscoelastomeric material

Info

Publication number
CA2196169A1
CA2196169A1 CA002196169A CA2196169A CA2196169A1 CA 2196169 A1 CA2196169 A1 CA 2196169A1 CA 002196169 A CA002196169 A CA 002196169A CA 2196169 A CA2196169 A CA 2196169A CA 2196169 A1 CA2196169 A1 CA 2196169A1
Authority
CA
Canada
Prior art keywords
group
syrup
radiation
sensitive
unsaturated monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002196169A
Other languages
French (fr)
Inventor
Greggory S. Bennett
Gaddam N. Babu
Kejian Chen
Louis E. Winslow
George F. Vesley
Patrick G. Zimmerman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2196169A1 publication Critical patent/CA2196169A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S522/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S522/904Monomer or polymer contains initiating group
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S522/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S522/904Monomer or polymer contains initiating group
    • Y10S522/905Benzophenone group

Abstract

Solute polymers in solvent monomers form a coatable syrup that can be cured to a viscoelastomeric material when radiation-sensitive .alpha.-cleaving groups in either the polymer or one of the monomers are exposed to ultraviolet radiation. The solute polymers can be formed from the solvent monomers or be added thereto to form the syrup.

Description

~v0 96/04346 2 1 9 6 1 6 9 P~ QI

ACRYLIC SYRUP CURABLE TO A
CROSSLINKED VISCOELASTOMERIC MATERIAL

~ This application is a Crmfin~ tir~ n-part of U.S. Serial No. 08/282,058 filed July 29, 1994, currently pending.

BACKGROUND OF THE INVENTION
1. Field of the Invention This invention describes a ~ o~l~Cu~ - ;r, material with high shear at ambientandelevatedLtl--y~dLul~preparedfromablendof~Lh~
ulla~lu~ dled monomers. A process for making this material is also described.
2. Background l- ru-ulc,LiDl~
Pressure sensitive adhesives (PSAs) made by phu~upol.~ an alicyi acrylate and a polar ~,uyu~ le monomer are known in the art. See, e.g., U.S. Patent Nos. RB 24,906, 4,181,755; 4,364,972; and 4,243,5û0. Acrylic-based PSAs exhibit good adherence to high energy (i.e., polar) substrates such as metai and painted steel surfaces but generally exhibit lower adhesion to low energy (i.e., nonpolar) substrates such as yul.~,.hjl~,..e and pGl~Jluyjlu..~,.
Solvent-processed acrylic PSA r"~ :y~J~- 'r' - can be crosslinked by adding 20 a polyrullcLiul~al .,. uaalhlkillg agent that reacts with a reactive group present in the polymer. See, e.g., Japanese Kokoku 58[1983]-046236 in which is described a solvent-processed crosslinked acrylic PSA with excellent cohesion that is the reaction product of (a) a polyisocyanate, prepared by reacting (I ) an acrylic copolymer having a molecular weight between 1,000 and 30,000 and from 1.7 to 25 5.0 functional groups that can react with an isocyanate group with (2) a diisocyanate, so that the ratio of isocyanate groups per coreactive functional group is about 2: 1, and (b) an adherent copolymer comprising functional groups that can react with an isocyanate group. Like any solvent processing technique, however, the preparation of thick adhesives is difficult because the solvent causes SUSSTITUTE SHEET (RULE 26) 2 1 q6 1 69 w096/04346 r~uJ,~.v5~

bubbling in the adhesive and the emission of solvent vapors into the atmosphere is undesirable.
To avoid environmental pollution, mllmlf~ntllring processes that do not require the use of volatile solvents have become of great interest. An early step in this direction for the manufacture of PSA tape was the process described in Belgium Patent No. 675,420. In this process, flexible carriers are coated with acrylic monomers, or mixtures of such monomers with uupOlr~ ,.;~Llt compounds, with the possible addition of a thickening and/or initiating agent, and the monomers are polymerized directly on the carrier using ultraviolet radiation.
o Hot melt coating a PSA cnmpocitinn eliminates the necessity of solvent processing. To hot melt process an adhesive uo~ n~ the c...I n- ~ ;.... must be u~ uaalhlLt:l during the coating process; however, to achieve a PSA with balanced properties (i.e., peel and shear adhesion), the .,..".~ ;.... must be crosslinked. In hot melt coating processes, this is usually done by exposure to 15 high energy radiation (e.g., E-beam or high intensity ultraviolet radiation). When high intensity ultraviolet radiation is used, a phuloal,live uluaal;llillg species such as t, .,.,~,h.... ~.f'. is generally added to the .,u,.,~ ,., However, this often results in PSAs that display cure gradients. Additionally, thicker sections of PSA
compositions cannot be cured this way.
A more eficient method of pllvlu~,luaal;llLillg involves ;ncu-~
hydrogen abstracting moieties into the polymer backbone prior to coating. Such polymers can be hot melt coated and 'il 'I.'f qU ~ ~ly cured by uù..~. ' irradiation techniques. This process is typified by U.S. Patent No. 4,737,599 where a PSA with good adhesion to skin is described; That process is much more 25 efficient than the high intensity irradiation method described ' '~, above, but the preparation Or a thick PSA section that does not display a cure gradient is not described.
The cohesive strength of an acrylic PSA can be increased without unduly affecting its compiiance by utilizing a photoactive ~,- ua~l;.d~i..s agent in ~ nnl~ with a phntniniti~tnr See, e.g., U.S. PatentNos. 4,181,752, 4,329,384; 4,330,590, 4,391,687, and 5,202,361. Useful photoactive Cluaa~ illg SUBSTlTUTE SHEET (RULE 26) 21 l~ar~ lSS6 VO~Sll~S & P~TNE
PCT/US 95L09601 p~T~;4~ AL R
~iNl~SO ~IN}~G ~ M~NUFACTURING 2 1 9 6 1 6 9 slL~E~rs~R ~
cnlr Re~: A 1124 PCT ~ 75 ~\s. ~

agentS include various aldehydes, quinones, and particularly certain ~,LIulllupllu~e-substituted ' ' h; s triazines (because they provide desirably shortened reaction times and somewhat greater tolerance to oxygen over the non-hdlv.r.~ht: . ~ g agents), although their use can result in evolution of HCI
5 during pGl~.,~".i~liu~.
An ultraviolet (UV) radiation-curable ~ n~ that includes 20 to 99%
(by wt.) of a copolymer of eLL~ un ~a~UI al~d monûmers, I to 80% (by wt.) elhJ' ~ n~tllrrted monomers, and 0 to 20% (by wt.) of one or more pol~ u~ co~ ~l ollllll~ is described in U.S. Patent No.
0 5,180,~56.
cuL~ alJlc 1 ' ' "' ' such as 2-[4-~2-hydroxy-2,2-dimethyl-l-oxopropyl~, ' y]ulllyl 2-propenoate and their use in the pGl~ .i~liu.. of c~ u~a~lu~alcd Cnmrûl~ iS disclosed in U.S. Patent No. 4,922,004.
Japanese Kokai 2[1990]-248482 describes a l)l -~ .hk PSA obtained 15 by reacting (a) 30 to 50 parts by weight (pbw) of a copolymer of an acrylic acid alkyl ester, a coL~ulyl~ iLable ..li.J' ' "~, unsaturated monomer having a polargroup, and a copû' 7,,.~ abie monomer with a pL~tG$r ~ group (such as 2-ac-~lu,!v..~L )~ ' - or l-a~.yloylv,.y-2-[4-(4-, ' ' u~ uJ:)benzoyl-oxy]ethane); (b) 40 to 60 pbw of an aryloxy acrylic monomer such as 20 pll~,.u,.~lh~l acrylate or ..u.., !~ ,II.J: acrylate; and (c) a tackifying resin.
The ~ u~ is cured using a total dose of energy of 300 to 800 mJlcml from a high pressure mercury lamp. Such high intensity ultraviolet radiation is likely to produce an adhesive that has a shear value less than IOO minutes.
Similarly, DE 4~ 03 183 Cl (Germany) discloses a method for producing 25 PSA layers comprising the steps of thickening a monomer mixture that includes a u~ t; ~ with a separately made, solvent-free saturated W-reactive polyacrylate; coating the thickened mixture onto a substrate; and irradiating the coated substrate. The separately made polymer comprises side chains that, when irradiated, participate in .-~ reactions. The sole example involves the 30 addition of a .,u.n...~ avaiiable polymer having a molecular weight of about 200,000 to a monomer mixture that is then pol~..._.i~,d.

AMENDED SHEET
... ............ . , . ,,, , ,,,,,, .,, . , .. ,, . . ,, , ,, . , _ _ , .. ,, . ,,, . , . , .,,, _,,,, . , , . _, .
. ... .......

~0 96/04346 ~ ,3 V,~

The shear values of PSAs prepared by actinically irradiating acrylic monomers can be enhanced by the addition of polyacrylic crosslinking agents.
See, e.g., U.S. Patent No. 4,3~9,201. Such PSAs involve networks and are sensitive to processing conditions.
A l,.,.,.~o~;liuu that can be radiation cured to provide thick, high molecular weight PSA ~ .~ " "~ ; ~~"~ with ~ V properties has not been previously described.

SU~ARY OF TH~ INVENTION
lo Briefy, the present invention provides a syrup, preferably a syrup of a coatable viscosity, curable to a crosslinked ~ o" . ;~ material ~,u...~,. i~;..~.
a) about 85 to 99.9 weight percent, preferably about 90 to 99.9 weight percent, of a solvent monomer mixture comprising 95 to 100 pbw, preferably 97 to 100 pbw, of at least one free radically-poly.l.~,~i~l,lc ~Lhrl~,l..vall~ u~ lu~dltid 15 monomer and O to 5 pbw, preferably O to 3 pbw, of an ~Lllr' "~ nll~llrd monomer comprising a radiation-sensitive a-cleaving group;
b) about 0.1 to 15 weight percent, preferably about 0.1 to 10 weight percent, of a solute polymer, preferably a polymer having a molecular weight of at least 500,000, comprising about 95 to 100 weight percent mer units derived from 20 one or more free radically-pol~".~,.;~l,lc ~ J1~ u~ tu-~ d monomers and about O to S weight percent mer units derived from an ~lhr~ lly .,.,- -n..,.lrd monomer comprising a radiation-sensitive a-cleaving group, with the proviso thatthe weight percent of the second component of the polymer cannot be zero when the monomer mixture comprises zero parts by weight of the ethylenically 25 u~ Lu~lLed monomer comprising a radiation-sensitive a-cleaving group;
c) from O to 5 pbw, preferably 0.01 to 0.30 pbw, of a free radically-puly~ ,.i~ble polyethylenically unsaturated monomer; and d) from O to 3 pbw, preferably 0.001 to 1.0 pbw of a saturated energy-activated initiator of polymerization (i.e., an energy-activated initiator of 30 polyl"~,.;~Li.,ll that is free of ethylenic unsaturation).

SUESTITU ï E Sl lEET (RULÇ~ 2~

~ 2 1 q6 ~ 69 os6/04346 r~ a3 In another aspect, the present invention provides a process for making a crosslinked viscoelastomeric material comprising the steps:
a) providing a ~ o~ comprising a solvent monomer mixture comprising at least one free radically-poly..~ ,l,le ethylenically ~ d 5 monomer and 0 to 5 pbw, preferabiy 0 to 3 pbw, of an ethylenically ~.-- -~ inrrl monomer comprising a radiation-sensitive ~-cleaving group and 0 to 3 pbw, preferably 0.001 to 0.5 pbw, of a saturated energy-activated initiator of polyll~ ;~Livll, preferably a saturated radiation-activated initiator of pulylllc~ Liull, with the proviso that the amount of saturated initiator must beo greater than zero when the amount of ethylenically u..,~LuldLr i monomer comprising a radiation-sensitive a-cleaving group is zero;
b) exposing the cnmpncitinn to energy, preferably radiative energy, so as to partially polymerize the monomer mixture and form a coatable syrup;
c) adding to the syrup, based on the total amount of monomer initiaily present in said monomer mixture, 0 to 3 pbw, preferably 0.001 to 0.5 pbw, of a saturated energy-activated initiator of polymerization, preferably a saturated radiation-activated initiator of polyl~ ivn, 0 to 3 pbw of an c~
ull~aLu~dkd monomer comprising a radiation-sensitive a-cleaving group, with the provisothattheamountofethylenically~"~--mlillrdmonomercomprisinga 20 radiation-sensitive a-cleaving group added to the syrup must be greater than zero when the amount of ethylenically u~ uld~d monomer comprising a radiation-sensitive a-cleaving group in the monomer mixture is zero; and/or 0 to 5 pbw, preferably 0.01 to 0.30 pbw, of a polyethylenically u~ Lul ~t~d monomer; and d) exposing the syrup to energy that activates the initiator and the radiation-sensitive a-cleaving group so as to form the crosslinked .",.. l_~l.. i~ material.
The vis~orl~ctnmrric material produced from the above syrup is aiso described. The syrup optionally can be coated on a substrate prior to being irradiated, and such articles are also described.
The coatable syrup of the present invention is p~lylll~,li~iJle to a 30 ~ v~ rl ic material that can be crosslinked directly. The ~;~ v IA~I'III.. ~ i.
material is preferably a PSA having high shear at both ambient and elevated SU3STlTUTE S"lEET \n.iEE 2~j WO 96/1~4346 ~ ,,,5.'C, ,~

Lelu~u.,. GLul ~s. This syrup comprises a solute polymer in a solvent monomer mixture. The polymer preferably has a very high molecular weight, preferably at least 500t000, more preferably at least 750,000, even more preferably at least 1,000,000, most pr~eferably at least 1,500,000. One or both of the polymer and 5 monomer contains at least one radiation-sensitive a~-cleaving group that, uponexposure to W radiation, is activated to enable curing. The cured product is a v;,~ orl~ctuln . ;c material.
Where the polymer of the syrup of the present invention contains side chains that comprise radiation-sensitive a-cleaving groups activatable by W
10 radiation, free radicals are formed that allow for growth of the side chain by addition of ethylenically unsaturated monomer(s). These growing side chains become entangled with other such side chains, or react with other such side chains, to produce a crosslinked Y;~ o~ l ~ crl ., .... ;G material . Where the polymer does not include radiation-sensitive a-cleaving group-containing side chains, the IS monomer mixture contains enough ethylenically ull:~alul dLt;d monomer comprising a radiation-sensitive a-cleaving group to form, upon exposure to W radiation, a polymer that includes radiation-sensitive a-cleaving groups in side chains. In this ~,l.bG'd;.l.~.lt, the original polymer chains become entangled with the newly formed polymer chains to form a crosslinked network.
Where no ethylenically unsaturated monomer comprising a radiation-sensitive a-cleaving group is present in the initial monomer mixture, some polymer that includes side chains comprising the Gr~ uLiu~e;l radiation-sensitive a-cleaving groups or some monomer that cQntains a radiation-sensitive a-cleaving group must be added to the syrup prior to formation of the v;~uelG ,Loll~ , material therefrom (i.e., poly~ GLiun ofthe monomer(s) ofthe monomer mixture). Preferably, however, the solute polymer is prepared in situ, i.e., directly from the solvent monomer mixture. This eliminates the need for solubilizing a separately made polymer in a monomer mixture and allows very highmolecular weight polymers to be formed and solubilized.

SU13STITUTE SHEET (RULE 26) ... . . . . ..

219616q ~o 96/04346 ~ c,s ~ n Vi, of l~cr, ." ,~, ;c materials produced from the syrup of the present invention can be used as PSAs, vibration damping materials, transfer adhesives, structural adhesives, protective coatings, and the like. Advallta~,~,uualy, the syrup of the present invention can have a coatable viscosity and can therefore be applied 5 to a substrate prior to curing, thus allowing for the simple production of articles comprising one or more layers of the ~rul~ d v;, u~ material.
Unless otherwise indicated, the following definitions apply in this d~
"group" or "compound" or "monomer" or "polymer" means, unless 10 otherwise noted, a chemical species that can be substituted by co..~, ~b~ul~ that do not interfere with the desired product; and "(meth)acrylic" refers to acrylate, ~ ,.La.,l~laLe, acrylamide, and methacrylamide comrounrlc~ as well as alkyl and aryl ~.u...l~u~ that have been substituted with an acrylate omll~lla~ laLe group.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The syrup of the present invention comprises from about 85 to 99.9 weight percent, preferably from about 9û to 99.9 weight percent, of a solvent monomer mixture and from about 0.1 to 15 weight percent, preferably from about 0.1 to 1020 weight percent, of a solute polymer.
In the syrup of the present invention, the solute polymers and the solvent monomer mixtures are based, in substantial part, on free radically-pGly...~,liLal,lc ethylenically ull ,alul aLed monomers. Ethylenically ull ,aLul aLtd monomers that do not contain a radiation-sensitive a-cleaving group comprise from about 95 to 100~5 pbw, preferably 97 to 100 pbw, of the monomer mixture. From 95 to 100% ~by wt.) of the mer units of the polymer are also derived from such monomers.
Preferred free radically-polymerizable ethylenically ull~aLul dL~d monomers are (meth)acrylic acid and its numerous well known derivatives.
Particularly preferred among such monomers are IIIUIIU~
30 ull~a~uld~d monomers that are hUIIIUPOIYII~ IIC to a polymer with a glass transition L~ n:latul~ (T6) less than about 0~C (hereinafter "A monomers").
SUBSTITUTE SHEET (RULE 26) 21 q61 69 WO 96/04346 P~llu,, .'C, .~1 These monomers preferably constitute from about 50 to 100 pbw, more preferably from about 60 to 95 pbw, of the solvent monomer mixture of the syrup of the present invention. Common examples of A monomers include (meth)acrylic acid esters of ~ul~oL~ J~;c alcohols. Preferred among these are ."~ .". .n. InAI esters 5 of non-tertiary alcohols, particularly primary alcohols. Those (meth)acrylic acid esters wherein the alkyl portion of the ester contains from 4 to about 12 carbonatoms have been found to be especially useful. Such monomers include, but are not limited to, isooctyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, decyl acrylate, and dodecyl acrylate.
Monethylenically ullsalul~Led monomers that are hollloyoly.,,~;~le to a polymer with a T greater than about 50~C (hereinafter "B monomers") can also be included in the free radically-polymerizable cLh~' ~y ullaaiul~lLcd portion of the monomer mixture of the composition of the present invention. B monomers, when present, preferably constitute from about 0.1 to about 50 pbw, more 15 preferably from about 5 to about 40 pbw of the monomer mixture. Examples of useful B monomers include, but are not limited to, (meth)acrylic acid, itaconic acid, substituted (meth)acrylamides such as N,N-J;Ill~nl.yla.,.yla~;de and N-o~,Lyla-,lyla",;le, N-vinyl I~Y~ N-vinyl ~,a~JIula~,La~" a~aylulf~Ll;le~
lcnallyJIu~ul~ulyl acrylate, isobomyl acrylate, abitol acrylate, and 20 dicyrloppnfn~ nyl acrylate.
Elhyl~ ally Ulla~tUI alti monûmers that compnse a radiation-sensitive a-cleaving group and that are copolyll,cii al~lc with the arùltlll~,llLiùllC~ freeradically-polymerizable ethylenically u~a~lulaled monomers (hereinafter "C
monomers") constitute from 0 to about 5 pbw, preferably 0 to 3 pbw, ofthe 25 solvent monomer mixture of the syrup of the present invention. Preferred C
monomers include ethylenically unsaturated compounds having the general formula SUBSTITUTE S,~IELT (RULE 26J

~0 96/04346 CH=C CX~ )b--(M~)c~G Z
R n wherein R is H or a C, to C3 alkyl group, preferably H or a methyl group;
X is O or NE~;
n is 0 or I ;
m is 0 or an integer from I to 5;
a, b, and c are in~lPpf-n~;~ntly O or l;
M' is CH2 or SiRIR2;
M2 is CR3R4 or SiR'R2;
M3 is O, NH, C(O), C(O)O, C(O)NH, or OC(O)NH;
R~ and R2 are; ~ lly H or a Cl to C4 alkyl group;
R3 and R4 are i~ IJ' ~ y H, an alkyl group having I to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 S, N, and nonperoxidic O l.~L~I u~ltullla, or R3 and R4 taken together with the carbon to which they are attached form a carbocyclic ring containing 4 to 12 ring atoms;
G is a covalent bond, (CH2)d, or (CH2)dO where d is an integer from 1 to 4, preferably from I to 2;
Z is a radiation-sensitive o~-cleaving group having the formula ~ 5 --Ar-C--R

20in which Ar is a substituted arene having 6 to 12 carbon atoms, preferably a ben2ene group;
R is hydrogen, a C, to C,2 alkyl group, a C, to C,2 alkoxy group, or a phenyl group; and SUBSTITUTE SHEET (RULE 26) wo 96/04346 10 r~.,u~ ~ ~ol--R is selected from the group consisting of 18 ~ N~

in which R is hydrogen, a Cl to Cl2 alkyl group, a Cl to Cl2 alkoxy group, or a phenyl group, with the proviso that, when R and R4 are both ortho to the carbonyl group of Z, together they can be one of --O-- --C-- --S-- and --CH2--and R, R, and R are i~ ly a hydroxyl group, a phenyl group, a Cl to C6 alkyl group, a C, to C6 alkoxy group, or a --NR R group, whereinR andR are; ~ ly hydrogenor o a Cl to C6 alkyl group, with the proviso that, when R is CR R R, one of the following must be true:
(I) at least one of R, R, and R is selected from the class consisting of hydroxyl, alkoxy, and--NRI~Rll groups, (2) any two of R, R, and R together are one of--C H2--and ~CpH2p~ wherein p is either 2 or 3 so that they, together witll the carbon atoms to which they are attached, form a 5- or 6-membered ring; and (3) any two of R, R, and R together are a carbonyl group, provided that the remaining one of R, R, and R is selected SUBSTITUTE S,~E~, (ri~ L 2u ~wos6/04346 11 r~l~u- ~ "~1 from the class consisting of hydroxy, alkoxy,--NR R , and phenyl groups.
Preferably, where m is not 0, M~ and M2 are not both SiRIR2. Preferred a-cleaving type C monomers are those compounds described i.,.",e.l;aLtly above 5 where R is and/or Ar (from Z) being a b~ iyl group.
Particularly preferred C monomers include O O CH~
H2C=CH--CO~C--COH PIA #l CHJ

o CH~
H2C=CI I CocH2cH2o{~c--COH PIA #2 H2C=CII COCH2CH20--O C--CH PIA #3 OCH~

H,C=CH--co~ ~) PIA #4 SUEiSTlTUTE SHEET (RULE 26) W0 96/0~346 12 P~ "'u' ~ql--o O OCH3 H2c=CH--co~cH2cH20~ 0~ PIA #5 o fH3 C--COH
H2C= lC--COCH2CH20--0 CH~ PIA #6 H2C--C--CO~}C--I H PIA #7 A variety of C monomers can be made by reacting an t,LI,~
ullaa~ul~Led monomer comprising a first functional group (hereinafter "D
c..~ .ltlC~) with a compound that comprises a radiation-sensitive ~-cleaving group and a second functional group (hereinafter "E ~,u~ Jullda"), the two functional groups behlg coreactive with each other. Preferred D and E
cnmpo-lntl~ are ethylenically unsaturated aliphatic, cy~ ., and aromatic lo t~nmpo~ having up to 36 carbon atoms, optionally one or more oxygen and/or nitrogen atoms, and at least one reactive functional group. When the first and second functional groups react, they form a covalent bond and link the D and E
compounds.
Examples of useful functional groups include hydroxyl, secondary amino, azlactyl, oxazolinyl, acetyl acetonyl, carboxyl, isocyanato, epoxy, aziridinyl, acyl SJEsT! ru .TE ~1 IEFT /RULE 26) ~wos6/04346 13 r.l~U..-/U' halide, vinyloxy, and cyclic anhydride groups. Preferred among these are isocyanato, hydroxyl, carboxyl, and vinyloxy g}oups. Where the D or E
compound comprises an isocyanato group, the other preferably comprises a secondary amino or hydroxyl group; where the D or E compound comprises a 5 hydroxyl group, the other preferably comprises a carboxyl, isocyanato, epoxy, anhydride, or azlactyl group; where the D or E compound comprises a carboxyl group, the other preferably comprises a hydroxyl, amino, epoxy, vinyloxy, or oxazolinyl group; and where the D or E compound comprises a vinyloxy group, the other preferably comprises a carboxyl group.
Representative examples of useful D cnmpQlln~lc include hydlu~. " yl (meth)acrylates such as 2-hydl u~,~..;hyl (meth)acrylate and 2-(2-hyd~ ,;llu~y)ethyl (meth)acrylate; aminoalicyl (meth)acrylates such as 3-an~ u~Jlu~Jyl (meth)acrylate and 4-alll;llo~Lylcll~, azlactyl-substituted c~
such as 2-ethenyl-1,3-oxazolin-S-one and 2-propenyl-4,4-dimethyl-1,3-oxazolin-5-one; carboxy-substituted compounds such as (meth)acrylic acid and 4-carboxybenzyl (meth)acrylate; isocyanato-substituted ccn~ u~ such as isu~,yallaLu~Lllyl (meth)acrylate and 4-isûcyanatocyclohexyl (meth)acryiate, epoxy-substituted çomrçlln~lc such as glycidyl (meth)acrylate; aziridinyl-substituted Cul~l,uuu~l;is such as N-acrylaziridine and 1-(2-propenyl)-aziridine; and acyl halides such as (meth)acryl chloride.
Representative examples of E rnmpçllnrlc include functional group-substituted a-cleaving compounds such as 1-(4-hy hu~y~ ly;)-2,2-dil~ Lu~ hal~ùne, 1-[4-(2-hydroxyethyl)phenyl]-2,2-~lhll~ u~y~ ' , (4-isu~,yanaLupll~"lyl)-2,2-dimethoxy-2-pL.l~ l.d.lull~, 1-{4-[2-(2,3-e~u~y}~l u~Ju~y)phenyl] }-2,2-dimethyl-2-hydl U~J ~,;Lal'ulle~ 1-[4-(2-aminoethoxy)phenyl]-2,2-di,l,~ u,~,;llanulle, and 1-[4-(~,albulll~,;llu~.y)~ .JI]-2,2-dimethoxyethanone.
If desired, a saturated energy-activated initiator of polyul.,li~alic/n (i.e., asource of free radicals other than a C monomer) can be used in forming the 30 polymer component of the syrup of the present invention from the monomer çomrnnPnt These energy-activated sources can be either heat- or W radiation wo 96/04346 14 ~ v~

activated. Examples of heat-activated sources include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, azobis(isobutyronitrile), and methyl ethyl k~iu~ u~dllf . Useful W radiation-activated initiators include the benzoin ethers such as benzoin methyl ether and benzoin ispropyl ether, substituted 5 ~,-f rophf nnrPc such as 2,2-diethoxy~r f trphf n~nf available as IrgacureTM 651 rh-~tniniri~tnr (Ciba-Geigy Corp.; Ardsley, NY), 2,2-diméthoxy-2-phenyl-1-phenylethanone commonly available as EsacureTM KB-I rh~ u-, (Sartomer Co.; West Chester, PA), and J;~ illu~yll~JIu~G~ f-.~orl, ~.nf, substituted a-ketols such as 2-methyl-2-hydroxy ~ul~iul~l.e~ollc; aromatic sulfonyl chlorides lo such as 2- , ' ' ~ yl chloride; and photoactive oximes such as 1-phenyl-1,2-propanedione-2-(O-~ll,u,.y~G.l,u,,yl)oxime~ Particularly preferred among these are the substituted a~ h f ,.. "'~ i A saturated energy-activated source of free radicals can be present in an amount from about 0 to 3 pbw, preferably from0.001 to about 1.0 pbw, more preferably from 0.005 to 0.5 pbw, per 100 pbw of 15 the solvent monomer mixture.
When present and upon activation through introduction of appropriate energy, the saturated energy-activated initiator of polymerization initiates poly~ Giiùn ofthe free radically-polymerizable L~h.yh~;cGlly ull~GlulalLd monomers (i.e., the A and B monomers). When LLI~yL". ~ally ~ U~
20 monomers comprising a radiation-sensitive a-clcaving group (i.e., C monomers)are also present, they also can be i.,cu~ old~Ld into the backbone chain of the polymer, resulting in radiation-sensitive a-cleaving groups pendent from the backbone chain.
Where a saturated heat-activated initiator is used with a monomer mixture 25 that includes at least one C monomer, the syrup can be exposed to heat only or to heat and W-radiation so as to initiate pol.~"..,.i~alion of the monomer mixture.Where a saturated I JV radiation-activated initiator is used with a monomer mixture that includes at least one C monomer, the saturated Pl~ r can have an absorption spectum with an onset of absorption (?~A) that is at least 25 nm 30 apart from the onset of absorption of the radiation-sensitive a-cleaving group of ~V0 96/04346 15 P.~

the C monomer (~B). This allows fom,~v~al;llhillg, through activation of the a-cleaving group, to occur after the saturated phntninifi~tor has initiated polymerization .
Inclusion of unsaturated hydrogen abstracting monomers and/or s polyu,laaluldLtd monomers will provide a polymer with pendent groups that include hydrogen abstracting or unsaturated groups, respectively. Those groups can then be activated by means known in the art to allow for further pOly.l~.,,i~aliul" normally after the monomer-polymer ~nlllpn~:l;u~ (i.e., syrup) has been coated onto a substrate.
0 One or more free radically-pulyll.~ dl,lc polyethylenically u ,--m~ d monomers can be included in the monomer mixture or, preferably, added to the syrup. Use of such monomer(s) allows for a reduction in the amount of elh~ .ally unsaturated monomer comprising a radiation-sensitive a-cleaving group necessary to produce the ~i~l .Of 1~ ~1.. ;. material of the present invention.
15 Examples of polyethylenically ulu~aLul altd monomers that can be used include, but are not limited to, polyacrylic-functional monomers such as ethylene glycol diacrylate, propyiene glycol dimethacrylate, trimethylolpropane triacrylate, 1,6-hexamethylrnerlirlrli~ rylate, p~ .yllllilul di-, tri-, and Ltl~aal,l~lale, and 1,12-dnrk ,...r-~linl.l;,,. ~y61e; olefinic-acrylic-functional monomers such as allyl20 methacrylate, 2-allylù,-y~,all,ollrL..Il;do~ yl methacrylate, and 2 ~'ylal,u~lu~L
acrylate; allyl 2-acrylamido-2,2-dh.l~,;ilyla-,l,lale, dh,i,ljCu"~ ,, and the like.
If desired, Inh,l u~Jhr,l ta can be added to the syrup of the present invention.When 1ll;.,lu~lh~,lt~ are used, the resultant v;~ u~ 1 n~ . material has a foarn-like appearance. These nl;.,l U .~h~,. t, can be made from materials such as glass 2s and polymers.
Glass microspheres, as described in U.S. Patent No. 4,223,û67, can have an average diameter of from about 5 to 200 ,um, preferably from about 20 to about 80 um. Such microspheres can comprise from S to 65~/c (by vol.) ofthe viscor-l~c~nml~ric material ofthe present invention. Preferably, a coated layer of 30 the ~ U~id:~tUIII~I ic, material is at least three times as thick, preferably at least seven times thick, as the diameter of the glass III;~,IU~IJL~,l c~.

r ~ -lrL f ~ iE 26) 21 ~61 6q wo s6/04346 ~ G ~

Alternatively, hollow polymeric ul;-,lua~)llcl~s having average diameters of from 5 to 200 um-are blended into the syrup of the present invention in amounts of from about 15 to about 75~/O (by vol.) prior to coating. Where such polymeric,l./a~Jh..ua are used, they can be added into the syrup in an u ~ d form 5 and ~l ~b,~ ~lu . ll ly heated to cause expansion. However, expanding them prior to addition is generally preferred because this helps to ensure that the hollow lll;ulua~h~.~a are aubs(~llL;dlly surrounded by at least a thin layer of viscoPl~ctr~mpric material in the final article. Useful polymeric ll~ uatJL~.~a are described in U S. Patent Nos. 3,615,972, 4,075,238, and 4,287,308. Hollow 10 polymeric nl;cl ~JalJh~ a are available under the tradename ExpancelTM (Eka Nobel Inc; Marietta, GA). In expanded form, they have a specific density of approximately 0.02 to 0.036 g/cm .
A particularly usefiul adjuvant is fumed silica, especially h~d.ul,Lbb;., silicaas disclosed in U.S. Patent Nos. 4,710,536 and 4,749,590. In another 15 PmhculimPnt ofthe present invention, a layer ofthe ~;s~o. l~cl(,;n material can contain from about 2 to about l S pbw of hydrophobic silica having a surface area of at least 10 m /g.
Other useful adjuvants that can be blended into the syrup of the present invention include fillers, dyes, pigments, plasticizers, fibrous reinforcing agents, ~o woven and nonwoven fabrics, foaming agents, A"~ , stabilizers, fire retardants, tackifiers, electrically conductive particles, and viscosity adjusting agents. For some ~ L;una, the use of chain transfer agents might be desirable to keep the molecular weight of the solute polymer below a desired value. The amount of such adjuvants can vary froln about 0. I to 50% (by wt.), depending onthe desired end use.
Although viscoplA~tompric films can be prepared directly from the solvent monomer mixture (by quickly polymerizing a coated layer of the monomer to a polymer-monomer mixture), increasing the viscosity to a level more suitable for coating is preferred. This is readily ;~ C ~ pl; ~I d by exposing the monomer(s) to a source of energy until about 0.1 to l 5~/O (by wt.), preferably about 0.1 to 10%

SUBSTlTUTE Si-iEET (RULE 26) ~vo 96/04346 r~

(by wt.), more preferably about 3 to 7% (by wt.), of the monomers have poly.,.c. i~cd. If the source of energy is heat, a heat-activated initiator of free radicals can be included in the ~ ''J~ n If the source of energy is W
radiation, a radiation-activated source of free radicals can be used (but is not~, 5 required where the C monomer contains a radiation-sensitive group that produces free radicals on exposure to suitable radiation). Use of a radiation-activated source of free radicals is preferred in such situations, however.
The compo~ition (i.e., syrup) ofthe present invention is preferably prepared i~7 situ by mixing one or more free radically-polymerizable ~LIl,~' ' 'i~, 0 l ~,u ~ ed monomers and 0 to 5 pbw of one or more of the above-described C
monomers and then polymerizing the monomer(s) to form a solute polymer. The monomers can be added in any order. Where no C monomer is present in the monomer mixture from which the syrup is formed (i.e., no radiation-sensitive a-cleaving groups are present in either the solute polymer or the solvent monomer mixture), some of these groups must be introduced into the syrup prior to formation of the vis~ ~F ~ l ic material. This can be done by adding C
monomer to the syrup after formation of the solute polymer or by adding to the syrup a second polymer (made separately from the syrup) that contains mer units with the above-described radiation-sensitive o~-cleaving groups pendent therefrom.
Adjuvants, when desired, can thereafter be blended into the mixture.
The in situ preparation of the ~" ~. . ,l.. .~.l ;' ,.~ just described allows for the production and ~lnhili7~ion of very high molecular weight polymers. Such polymers preferably have a molecular weight of at least 500,000, more preferablyat least 750,000, even more preferably at least 1,000,000, most preferably at least 1,500,000. The solllh 1 7~ti~m of a separately made polymer of such a high molecuiar weight is very difficult. Therefore, the above-described in situ ylc~Ja~ iull method is the preferred manner of maicing the UUIIIIJO~ iUll ofthe present inver~tion.
A syrup of a coatable viscosity can be applied to a substrate, preferably a f exible carrier web, using any conventional coating means such as roller coating, dip coating, knife coating, and extrusion coating. The substrate can further SUBS~lTUTESrlE.l (~ULE26) wos6/04346 18 r~ "~

comprise a release coating between the substrate and the syrup or on the side ofthe substrate opposite the side on which the syrup is coated.
Once a syrup has been prepared, a crosslinked visco~ ctom~ ric material can be prepared therefrom in a variety of ways. In each method, the remaining s monomer(s) in the syrup are polymeri~ed by exposure to radiation that activates the a-cleaving groups and facilitates pol~uu~iLaLioll~ However, this process canbe carried out in a variety of ways.
One way to make the v;a~u.,lasLu~ , iu material from the remaining monomer(s) is to irradiate the syrup with both high and low intensity W
10 radiation. Low intensity radiation is defined as 10 mW/cm or less (as measured in accordance with procedures approved by the United States National Institute of Standards and Technology as, for example, with a WIMAPTM UM 365 L-S
radiometer lllauurG~,lulcl by Electronic L~l~u..,~,uLdLion & Technology, Inc., in Sterling, VA), preferably in the wavelength region of 200 to 600 nm, more preferably 280 to 400 nm. High intensity radiation is defined as anything greater than 10 mW/cm2, preferably between 15 and 450 mW/cm . When such radiation is used, the vi~.u ~ ", .., ic material is formed directly from the syrup.
Other ways of making the v;~uFl~cuJ". i.. material involve initially exposing the syrup to only low intensity radiation. Syrup ru~u~ulGLioll~ that 20 producehighp~ru,~Gn~ ;s~oFl~c~n~F~icmaterialswilldependontheparticular crosslinker (i.e., C monomer) and its ability to be activated by the particular radiation used. Generally, where the percentage (by wt.) of mer units derived from the C monomer(s) is about 0.4% or greater and no poly~
ull~aLulatFIi monomer is present and curing is performed in an ~llV;lUlUll~llt that is 25 bub ~all~ free of oxygen, this low intensity exposure is sufficient to make aviscoelà~ " iC material that is a PSA with balanced properties. Where curing occurs between radiaiion transparent release liners, the amount of C monomer(s) can be about O.04~~O (by wt.) and, yet, a ~ u l ~l nl ll~ dc material with balanced PSA properties can be obtained. Where the percentage (by wt.) of mer units 30 derived from the C monomer(s) is less than about 0.4%, however, further SU~S T !Ti~', L ~l~. T ~RULE 26) ~vo g6/04346 1,0 r~l",~,u~ J~

processing is preferable. Specifically, exposure to low intensity light followed by exposure to high intensity radiation can produce a crosslinked vi,~.u material with balanced PSA properties, About 0,05~/~ (by wt.) of a m~lltifimrtioscrylate (e.g., hexanediol diacrylate) is preferably added to the syrup to aid in the ~, 5 formationofthe~ u '~c~ ;material.
Polymerization is preferably performed in an inert (i.e., oxygen firee) dLnlu~lJh.,. ~, such as a nitrogen dLIllua~ll.,. ~. Tolerance to oxygen can be increased by including in the syrup an oxidizable tin compound, as is taught in U.S, Patent No, 4,303,485, the teaching of which is in~,ù~l~oldled herein by reference, o The syrup of the present invention can be cured in air by covering a layer ofthe photoactive coating with a plastic film that is Cllh ' " ~Iy transparent to W radiation but impervious to oxygen and irradiating the nf)rnrocitir~n through that film using UV lamps that emit light in the wavelength range ~UIIt~ /U..d;llg to the absorption maximum of any saturated ~ 3;~ll,, used, Several drfferent 15 cul.ull~ ,;dlly available lamps, including medium pressure mercury lamps and low-intensity fluorescent lamps, can be used. The radiation intensity of these lamps is preferably adjusted so that the radiation intensity at the surface of the coating is less than 20 mW/cm, preferably 0,5 to 6 mW/cm, each having emission maxima between 200 and 600 nm, preferably between 280 and 400 nm, Maximum ~o efticiency and rate of polymerization is dictated by the . ~,laliull~L~J between emission properties of the radiation source and the absorption properties of thephotoactive ~ "~I)o"",li employed, Where the saturated energy-activated initiator in the syrup of the present invention is heat-activated, the syrup preferably is exposed to a heat source either 25 before or 5imnlt~neo-lcly with exposure to radiation of a wavelength that activates the o~-cleaving groups present in the monomer and/or the polymer of the syrup.
Where saturated the energy-activated initiator in the syrup of the present invention is a W radiation-activated initiator, the syrup preferably is exposed first to a wavelength of radiation that activates the saturated initiator until the 30 monomers polymerize to a coatable viscosity so that the syrup can be coated on a substrate, This coated çomroQitil-r is exposed to radiation of a wavelength to SU.,~ L~ iLr ~) 2 1 q6 1 69 WO 96/04346 1 ~,l/U~ J~

which the a-cleaving group of the C monomer is sensitive at an intensity of less than 10 mW/cm (for a total dose of 30 to 800 mJ/cm2) so as to further polymerize the monomers as well as crosslink the polymer chains. The I.ng~l.s used to activate the saturated initiator and the a-cleaving group can 5 be the same as long as the wavelength is one at which the saturated initiator is more sensitive than the a-cleaving group. For example, a ~ ;f~l\ comprising PIA #2 (which has an absorption spectrum with an absorption maximum at a ~va~ 5 Lh of about 300 nm) as the C monomer and 2,2-dimethoxy-2-phenyl-1-pl,.,..~ l,anolle (which is activated by radiation having a wavelength maximum at 10 about 35û nm) as the saturated initiator.
Extent of polymerization can be monitored by measuring the refractive index of the adhesive layer. Refractive index is a sensitive measure of the extent of polyll,~,liLalivl- This method is commonly applied in pol~"~ LaLivn kinetics work. See, for example, discussions about the method in ~olJ . i~ ". ai 15 Advanced Degrees of ComJrArsiol7~ G.P. Gladyshev and K.M. Gibov, Keter Press,Jerusalem (1970). Change in refractive index occurs linearly with conversion of (meth)acrvlate unsaturation.
Where the crosslinked vi~ ~FI~c~v~ .ie material ofthe present invention is a PSA, it displays balanced PSA properties (i.e., a good ef~mb~ ti~n of adhesion, ~0 cohesion, ~IGl.,h...~,aa, and elasticity). This is believed to result from the crosslinked nature of the vi,~ vf ~ material. Crosslinking in the present invention is quite different from the ~un ~,ulivllal mechanism of ~,lvDalh~ g provided by diacrylates where a similar increase in ~Vn~GIII~OI;VII of diacrylates results in a ~ I reduction in peel adhesion strength without an increase in ~5 static shear strength.
A ululLilaj~"Gd tape that includes at least one cured layer derived from the syrup of the present hlvention is also within the scope of the present invention.
Such tapes can have a thin layer of a different PSA laminated thereto, so that the adhesive of the invention is being used as a backing or core layer. The additional 30 layer(s) can be any conventional adhesive known in the art; however, (meth)acrylic adhesives are preferred. Such ulullila,~" Gd ~OIIDII u~,livlla can be i.Lt~) . , . ., . .. .. . _ . ... . . . ... . _ _ _ . _ _ _ 21 q61 69 6/04346 21 P.

prepared by processes disclosed in U.S. Patent Nos. 4,818,610,4,894,259, and 4,895,738, the teachings of which are h-cul~,v-dL~d herein by reference. More preferably, additional adhesive layers include polymers of at least one alkyl (meth)acrylate monomer and a copolymerizable monomer ho..ll,oly.,.~,.;~l,le to a polymer with a T& above about 50~C.
Multilayered tapes where a layer of a polyurethane, poly.,l.lu, u~
polyacrylic foam, or polyethylene foam on which is coated a layer of the ~ ,~ url~cn ~ dc material of the present invention are also possible. Such tapesare often used to attain very high bond strengths. Further information about such 0 constructions can be found in, for example, U.S. Patent Nos. 3,565,247, 3,993,833,and4,415,615,theteachingsofwhicharehl~,ullJuldledhereinby reference.
When the coated films of the present invention are cured, they preferably have a percent gel (corrected for any soluble tackifying resins and other additives) in the range of from 2 to 95% (by wt.), more preferably from 30 to 90% (by wt.),and most preferably from 50 to 80% (by wt.).
The cr~mpo~itiron~ of the present invention can also be used to make a cellular PSA membrane as is described in U.S. Patent No. 4,415,615, the teachingof which is i,..,u,},o,dLed herein by reference.
Objects and advantages of this invention are further illustrated by the following examples. The particular materials and amounts thereof, as well as other conditions and details, recited in these examples should not be used to unduly limit this invention.

EXAMPLES
A. Static Shear Value The adhesive films described in the examples were cut into strips 1.27 cm in width. One of the release liners was removed and the strip was placed, with the adhesive side down, onto a piece of aluminum foil 125 ,um thick and 1.6 cm wide.The remaining release liner film was removed from each of the strips to form a "test adhesive tape" and adhered by its adhesive to a flat, rigid stainless steel plate SUBSTITUTE S'~EET (RULE 26) wo96/04346 21 9 6 1 6 9 r l~.JL ~.o ~

with exactly 1.2~ cm length of tape in contact with the plate. Before testing, a1000 g weight at 25~C was placed over the bonded area for about 15 minutes.
The plate with the adhered tape was placed either at room L~ ld~UI= (RT) or in an air-circulating oven which had been preheated to 70~C. A weight was hung 5 from the free end of the tape, with the panel tilted 2~ from vertical to eliminate any peel forces. The time (in minutes) at which the weight fell was designated the static shear RT (1000 g) or 70~C (500 g). The test was .~ ...o.,,l~d after 10,000 minutes if no failure occurred and the result given as " 10,000+".

o B. Peel Strength Each measurement was made using a 90~ peel mode at 30.5 cm/min. In the Examples below, results are reported in N/dm.
Pieces of stainless steel were washed once with acetone and three times with a 50:50 water-isopropanol solution. Each adhesive film was adhered to a stainless steel backing for three days prior to being tested. Each sample was about 1.3 cm wide and had a 0.13 mm anodized aluminum backing (about 1.6 cm wide).
Examples 1-5 A number of compositions including the following ~ were prepared: ~
90 pbw isooctyl acrylate (prepared according to processes available in the literature) 10 pbw acrylic acid 0.04 pbw 2,2-dimethoxy-2-phenyl-1-pl~ ,yl~.il,dno..e (Ciba Geigy).

To each mixture was added the amount of PIA #2 (available as ZLI 3331 25 from Ciba-Geigy), shown in Table II. Each mixture was degassed in a vacuum desiccator. The degassed mixture was partially poly.,.~ .l by exposure for about 10 seconds to SylvaniaTM Fl ST81350 BL 15-watt fluorescent black lamps.
The resulting syrup was knife coated onto a 50 llm biaxially-oriented poly(ethylene terephthalate) (PET) film at a thickness of 125 mm for Examples I
30 to 5. The coated films were passed through a coating device maintained underN2.

SUBSTITUTE SHEET (RULE 26) 0 96/04346 P~ 3 The films were exposed to radiation from black iamps having a peak output at 350nm and an intensity of'4.0 mW/cm . Each coated tape was aged 72 hours at 25~C
and 50% relative humidity. Measured peel adhesion and shear strengths and are listed in Table 11.
~, 5 Table 11 Peel Adhesion (N/dm) Shear Strength (min) Ex. Wt. % StainlessPolypropylene 25~C, 70~C, No. PIA#2 Steel I kgload 0.5 kgload 0.0 181.5 71.5 366 366 2 0.1 163.3 71.8 612 34 3 0.2 185.7 52.8 7440 199 4 0.3 177.3 58.9 10,000+ 5399 0.4 154.5 57.5 10,000+ 10,000+

Those skilled in the art will readily observe that the vonc~lLIdliu~ of C
lo monûmer (i.e., PIA #2) over the range from 0 to 0.4% (by wt ) has very littleeffect on the peel adhesion of the tapes ~I.e., the peel adhesion remained within 154 to 186 N/dm for stainless steel and 52 to 72 N/dm for polr~u~jlu~ A
concentration of C monomer of 0.2% (by wt.) or more in the adhesive is helpful in obtaining shear strengths of more than 5000 minutes at room Lclll~ Lul t:, and 0.3% (by wt.) or more is helpful in obtaining shear strengths of more than 5000 minutes at 70~C.

Examples 6-9 Syrups were prepared as described in Examples I to 5 using mixtures of 20 monomers as shown in Table III. (In Example 9, the monomer mixture aiso included a polystyrene macromer with a number average molecular weight of about 13,000.) The weight percentage of 2,2-dimethoxy-2-phenyl-1-~,h~,..yl.,l.~..lolle and PIA #2 used in each syrup was 0.04%.

SllrSl~T~vT~ rL~

W0 96/04346 P~ S )~l --The syrups of Examples 6 and 7 were coated at a thickness of 250 llm and those of Examples 8 and 9 at 125 ~Lm. A 25 ,um thick release-coated sheet of PETwas laminated to the syrup-coated side of each tape, and the laminate exposed toradiation as described in Examples I to 5. Each PSA tape was then aged for 72 hours at 25~C and a relative humidity of 50%. The peel adhesion and shear , strength of each is shown in Table III

Table III

Amounts of mollomer Peel Adhesion (N/drn)Shear Strength (n~in), (pb~) 25 mm x 125 n rn Ex. IOA AA Poly- Stainless Poly~acrylo-25~C, 1 kg 70~C,0.5 No. styrene steel lI;Il;k,lJUt~load kg load st~rene) 6 95 5 0 65.5 133.0 10,000+ 10,000+
7 90 10 0 177.4 142.1 10,000+ 10,000+
8 80 20 0 131.2 45.9 10,000+ 10,000+
9 90 10 4 139.7 59.9 10,000+ 10,000+

Example 10 To a series of glass jars purged with nitrogen were added 90 pbw IOA, 10 pbw AA 0.04 pph 2,2-dimethoxy-2-phenyl-l-pll.,.lyl~ o~e~ and varying amounts of PIA #2. Each mixture was exposed to low intensity W radiation so as to partially polymerize the monomers to a coatable viscosity. An additional 0.16 pph 2,2-dimethoxy-2-phenyl-1-phenylethanone was added after the syrup was made. Varying amounts of HDDA were also added to the syrup.
The mixtures were cured on a solvent-free silicone paper release liner at a thickness of 0.13 mm. The samples were exposed to low intensity radiation for 145 seconds, the first third of the time at an intensity of 1.9 mWlcm2 and the remainder ofthe time at an intensity of 4.2 mW/cm2. The oxygen level was 250 i 20 ppm. The samples were exposed to high intensity radiation at an average intensity of 112 mW/cm2 for about five seconds. The conversion of all the polymers was greater than 98%.

SUBSTITUTE SHEET (RULE 26) .. . _ ... . . ..... . ..

2 1 96 ~ 6~
~wos6/04346 5 F.~ 03cr Peel strength values were determined after the peel samples were adhered to the stainless steel substrates for three days.
Static shear strength values were measured using stainless steel substrates cleaned once with acetone and three times with a 50:50 isopropanol/water mixture. 2.54 cm x 1.27 cm samples were prepared and a 1000 g load was used at room ItUl~ lLUlt~ and a 500 g load was used at 70~C. The shear samples were adhered to stainless steel for four hours prior to hanging. (0.13 mm anodized aluminum backings were used for all ofthe samples.) The time until failure is the average oftwo samples (in minutes).

Table IV
Ex.Amt. of Amt. of Shear Strength (min)Peel No.PIA (pph)HDDA (pph) Strength (N/dm) RT 70~C
C1 0 O.l 10,000+ 141 203 C2 0.02g 0.05 10,000+ 265 200 10 0.125 0.05 10,000+ lO,000+ 196 Example C 1 shows that, when using HDDA by itself, balanced properties (i.e., a PSA with high room le~ ,.alulc shear, high 70~C shear, and high peel 15 strength) are not obtained. Example C2 shows that too low of a loading level of PIA, when used with HDDA, also does not provide balanced static shear strength properties. However, at loading levels of about 0.1 pph of PIA used in ~.n,l,~ ;nl~ with high intensity radiation and about 0.05 pph HDDA, balanced shear properties can be achieved.
Various mn~ifir~rinnc and alterations that do not depart from the scope and spirit of this invention will become apparent to those skilled in the art. This invention is not to be unduly limited to the illustrative rll~l~od; ~ set forth therein.

SUBSTITUTE S~IEET (RULE 26)

Claims (16)

We claim:
1. A syrup curable to a crosslinked viscoelastomeric material comprising:
a) about 85 to 99.9 weight percent of a solvent monomer mixture comprising 1 ) 95 to 100 parts by weight of at least one free radically-polymerizable ethylenically unsaturated monomer, and 2) 0 to 5 parts by weight of an ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group;
b) about 0.1 to 15 weight percent of a solute polymer comprising 1 ) 95 to 100 weight percent mer units derived from one or more free radically-polymerizable ethylenically unsaturated monomers, and 2) 0 to 5 weight percent mer units derived from an ethylenically-unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group;
with the proviso that the weight percent of the second component of said polymer cannot be zero when said monomer mixture comprises zero parts by weight of said ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group;
c) from 0 to 5 parts by weight of a free radically-polymerizable polyethylenically unsaturated monomer; and d) from 0 to 3 parts by weight of a saturated energy-activated initiator of polymerization.
2. The syrup of claim 1 wherein said at least one free radically-polymerizable ethylenically unsaturated monomer of said monomer mixture comprises a monoethylenically unsaturated monomer homopolymerizable to a polymer having a glass transition temperature of less than about 0°C.
3 . The syrup of claim 2 wherein said selected from the group consisting of isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, decyl acrylate, dodecyl acrylate, hexyl acrylate, and butyl acrylate.
4. The syrup of claim 2 wherein said at least one free radically-polymerizable unsaturated monomer further comprises a monoethylenically unsaturated monomer homopolymerizable to a polymer having a glass transition temperature of greater than about 50°C.
5. The syrup of claim 4 wherein said second monoethylenically unsaturated monomer is selected from the group consisting of (meth)acrylic acid,itaconic acid, N,N-dimethylacrylamide, N-octylacrylamide,2-hydroxyethyl acrylate, N-vinyl pyrroline, N-vinyl caprolactam, acrylonitrile, tetrahydrofurfuryl acrylate, and isobornyl acrylate.
6. The syrup of claim 1 wherein said ethylenically unsaturated monomer comprising a radiation-sensitive group has the formula wherein R is H or a C1 to C3 alkyl group, preferably H or a methyl group;
X is O or NH;
n is 0 or 1 ;
m is 0 or an integer from 1 to 5;
a, b, and c are independently 0 or 1;
M1 is CH2 or SiR1R2;
M2 is CR3R4 or SiR1R2;
M3 is O, NH, C(O), C(O)O, C(O)NH, or OC(O)NH;

R1 and R2 are independently H or a C1 to C4 alkyl group;
R3 and R4 are independently H, an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R3 and R4 taken together with the carbon to which they are attached form a carbocyclic ring containing 4 to 12 ring atoms;
G is a covalent bond, (CH2)d, or (CH2)d O where d is an integer from 1 to 4, preferably from 1 to 2;
Z is a radiation-sensitive .alpha.-cleaving group having the formula in which Ar is a substituted arene having 6 to 12 carbon atoms;
R is hydrogen, a C1 to C12 alkyl group, a C1 to C12 alkoxy group, or a phenyl group; and R is selected from the group consisting of in which R is selected from the class consisting of hydrogen, C1 to C12 alkyl groups, C1 to C12 alkoxy groups, and phenyl groups, with the proviso that, when R 3 and R 5 are both ortho to the carbonyl group of Z, together they can be one of and -CH2-and R6, R7, and R8 are independently selected from the class consisting of hydroxyl, phenyl, C1 to C6 alkyl, C1 to C6 alkoxy, and -NR10 R11 groups, wherein R10 and R11 are independently hydrogen or a C1 to C6 alkyl group, with the proviso that, when R9 is-CR6 R7 R8, one of the following must be true:
(1) at least one of R6, R7, and R8 is selected from the class consisting of hydroxyl, alkoxy, and -NR10 R11 ;
(2) any two of R6, R7, and R8 together are one of -CpH2p-and -OCpH2pO- wherein p is either 2 or 3 so that they, together with the carbon atoms to which they are attached, form a 5- or 6-membered ring; and (3) any two of R6, R7, and R8 together are a carbonyl group, provided that the remaining one of R6, R7, and R8 is selected from the class consisting of hydroxy, alkoxy,-NR10 R11, and phenyl groups.
7. The syrup of claim 6 wherein R9 of said ethylenically unsaturated monomer comprising a radiation-sensitive group is
8. The syrup of claim 6 wherein X is O, m is 0, and G is (CH2)dO with d being 2.
9. The syrup of claim 6 wherein Ar of said ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group is a benzene group.
10. The syrup of claim 1 wherein said saturated energy-activated initiator of polymerization is present in an amount of 0.001 to 1.0 parts by weight.
11. The syrup of claim 10 wherein said energy is ultraviolet radiation.
12. The syrup of claim 1 wherein said syrup is of a coatable viscosity.
13. A process for making a viscoelastomeric material comprising the steps:
a) providing a composition comprising 1) a solvent monomer mixture comprising (a) at least one free radically-polymerizable ethylenically unsaturated monomer, and (b) 0 to 5 parts by weight of an ethylenically unsaturated monomer comprising a radiation-sensitive group, and 2) 0 to 3 parts by weight of a saturated energy-activated initiator of polymerization, with the proviso that the amount of said saturated initiator must be greater than zero when the amount of said ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group is zero;
b) exposing said composition to energy so as to partially polymerize said monomer mixture to form a coatable syrup;
c) adding to said syrup, based on the total amount of monomer initially present in said monomer mixture, 1) 0 to 3 parts by weight of a saturated energy-activated initiator of polymerization, 2) 0 to 3 parts by weight of an ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group, with the proviso that the amount of ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group added to said syrup must be greater than zero when the amount of said ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group in said monomer mixture is zero, and 3) 0 to 5 parts by weight of a free radically-polymerizable polyethylenically unsaturated monomer; and d) exposing said syrup to energy that activates said saturated initiator and said radiation-sensitive .alpha.-cleaving group of said ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group so as to form said viscoelastomeric material.
14. The process of claim 13 wherein said ethylenically unsaturated monomer comprising a radiation-sensitive .alpha.-cleaving group has the formula wherein R is H or a C1 to C3 alkyl group, preferably H or a methyl group;
X is O or NH;
n is or 1;
m is 0 or an integer from 1 to 5;
a, b, and c are independently 0 or 1;
M1 is CH2 or SiR1R2;
M2 is CR3R4 or SiR1R2;
M3 is O, NH, C(O), C(O)O, C(O)NH, or OC(O)NH;
R1 and R2 are independently H or a C1 to C4 alkyl group;
R3 and R4 are independently H, an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R3 and R4 taken together with the carbon to which they are attached form a carbocyclic ring containing 4 to 12 ring atoms;
G is a covalent bond, (CH2)d, or (CH2)dO where d is an integer from 1 to 4, preferably from 1 to 2;
Z is a radiation-sensitive .alpha.-cleaving group having the formula in which Ar is a substituted arene group having 6 to 12 carbon atoms;
R 5 is hydrogen, a C1 to C12 alkyl group, a C1 to C12 alkoxy group, or a phenyl group; and R9 is selected from the group consisting of in which R 4 is selected from the class consisting of hydrogen, C1 to C12 alkyl groups, C1 to C12 alkoxy groups, and phenyl groups, with the proviso that, when R 3 and R 5 are both ortho to the carbonyl group of Z, together they can be one of and -CH2-and R6, R7, and R8 are independently selected from the class consisting of hydroxyl, phenyl, C1 to C6 alkyl, C1 to C6 alkoxy, and -NR10 R11 groups, wherein R10 and R11 are independently hydrogen or a C1 to C6 alkyl group, with the proviso that, when R9 is -CR6 R7 R8, one of the following must be true:
(1) at least one of R6, R7, and R8 is selected from the class consisting of hydroxyl, alkoxy, and -NR10 R11;
(2) any two of R6, R7, and R8 together are one of -CpH2p-and -OCpH2pO- wherein p is either 2 or 3 so that they, together with the carbon atoms to which they are attached, form a 5- or 6-membered ring; and (3) any two of R6, R7, and R8 together are a carbonyl group, provided that the remaining one of R6, R7, and R8 is selected from the class consisting of hydroxy, alkoxy, -NR10 R11, and phenyl groups.
15. The process of claim 14 further comprising the step:
e) prior to irradiating said syrup, coating said syrup on a substrate.
16. The process of claim 15 wherein said substrate is a flexible web.
CA002196169A 1994-07-29 1995-07-28 Acrylic syrup curable to a crosslinked viscoelastomeric material Abandoned CA2196169A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28205894A 1994-07-29 1994-07-29
US08/282,058 1994-07-29

Publications (1)

Publication Number Publication Date
CA2196169A1 true CA2196169A1 (en) 1996-02-15

Family

ID=23079927

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002196169A Abandoned CA2196169A1 (en) 1994-07-29 1995-07-28 Acrylic syrup curable to a crosslinked viscoelastomeric material

Country Status (8)

Country Link
US (3) US5773485A (en)
EP (2) EP0772656B1 (en)
JP (2) JP3548933B2 (en)
KR (1) KR970704849A (en)
CA (1) CA2196169A1 (en)
DE (2) DE69520434T2 (en)
ES (1) ES2142489T3 (en)
WO (2) WO1996004346A1 (en)

Families Citing this family (147)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5538774A (en) * 1994-07-29 1996-07-23 Minnesota Mining And Manufacturing Company Internally damped rotatable storage article
US5773485A (en) 1994-07-29 1998-06-30 Minnesota Mining And Manufacturing Company Acrylic syrup curable to a crosslinked viscoelastomeric material
EP0837844B1 (en) * 1995-07-28 2000-04-05 Minnesota Mining And Manufacturing Company Acrylamide derivatives as chromophoric photocrosslinking compound
DE19653631A1 (en) * 1996-12-20 1998-06-25 Basf Coatings Ag Process for producing radiation-crosslinkable polymeric acrylic or methacrylic acid esters
US6628040B2 (en) * 2000-02-23 2003-09-30 Sri International Electroactive polymer thermal electric generators
US7320457B2 (en) * 1997-02-07 2008-01-22 Sri International Electroactive polymer devices for controlling fluid flow
US6376971B1 (en) 1997-02-07 2002-04-23 Sri International Electroactive polymer electrodes
US6812624B1 (en) * 1999-07-20 2004-11-02 Sri International Electroactive polymers
US6781284B1 (en) 1997-02-07 2004-08-24 Sri International Electroactive polymer transducers and actuators
US6545384B1 (en) 1997-02-07 2003-04-08 Sri International Electroactive polymer devices
CN1121421C (en) * 1997-02-19 2003-09-17 西巴特殊化学品控股有限公司 (CO) polymers by photopolymerization
US5879759A (en) * 1997-12-22 1999-03-09 Adhesives Research, Inc. Two-step method for the production of pressure sensitive adhesive by radiation curing
US6599602B2 (en) 1999-06-02 2003-07-29 3M Innovative Properties Company Polycarbonate articles and adhesive composition therefor
ES2165768B1 (en) 1999-07-14 2003-04-01 Almirall Prodesfarma Sa NEW DERIVATIVES OF QUINUCLIDINE AND PHARMACEUTICAL COMPOSITIONS THAT CONTAIN THEM.
US7537197B2 (en) * 1999-07-20 2009-05-26 Sri International Electroactive polymer devices for controlling fluid flow
DE60037433T2 (en) * 1999-07-20 2008-12-04 Sri International, Menlo Park Electroactive polymer generators
US6448337B1 (en) 1999-10-07 2002-09-10 3M Innovative Properties Company Pressure sensitive adhesives possessing high load bearing capability
US6340719B1 (en) 1999-12-29 2002-01-22 3M-Innovative Properties Company Crosslinking process
US6911764B2 (en) 2000-02-09 2005-06-28 Sri International Energy efficient electroactive polymers and electroactive polymer devices
EP1259992B1 (en) * 2000-02-23 2011-10-05 SRI International Biologically powered electroactive polymer generators
DE10008842C1 (en) * 2000-02-25 2001-06-28 Beiersdorf Ag Method of reducing flow viscosity of polyacrylate composition, used as adhesive, involves mixing (co)polyacrylate(s) with (co)polyacrylate(s) with lower molecular weight and ultraviolet-curable functional groups
US20020004130A1 (en) * 2000-07-07 2002-01-10 Ramesh Lhila Acrylic foam-like tape
US6841234B2 (en) 2000-08-04 2005-01-11 Scapa Tapes North America Inc. Heat-activated adhesive tape having an acrylic foam-like backing
US6448301B1 (en) 2000-09-08 2002-09-10 3M Innovative Properties Company Crosslinkable polymeric compositions and use thereof
US6709716B2 (en) 2001-04-27 2004-03-23 3M Innovative Properties Company Microemulsion compositions and methods of making and using same
US6949297B2 (en) * 2001-11-02 2005-09-27 3M Innovative Properties Company Hybrid adhesives, articles, and methods
DE10295498D2 (en) * 2001-11-24 2004-11-11 Tesa Ag 2-component crosslinking of end-functionalized polyacrylates
EP2317639A1 (en) * 2002-03-18 2011-05-04 SRI International Electroactive polymer devices for moving fluid
US7157535B2 (en) * 2002-06-19 2007-01-02 National Starch And Chemical Investment Holding Corporation Polymeric photoinitiators
AU2002953099A0 (en) * 2002-12-04 2002-12-19 Australian Composites Pty Ltd Reinforced polymer composition
US7927703B2 (en) * 2003-04-11 2011-04-19 3M Innovative Properties Company Adhesive blends, articles, and methods
WO2004101678A1 (en) 2003-05-19 2004-11-25 Nippon Shokubai Co., Ltd. Resin composition for thermally conductive material and thermally conductive material
WO2005007819A2 (en) 2003-07-09 2005-01-27 Wisconsin Alumni Research Foundation Charge-dynamic polymers and delivery of anionic compounds
US20050070688A1 (en) * 2003-09-26 2005-03-31 3M Innovative Properties Company Reactive hydrophilic oligomers
US7691437B2 (en) * 2003-10-31 2010-04-06 3M Innovative Properties Company Method for preparing a pressure-sensitive adhesive
US7384984B2 (en) * 2003-12-10 2008-06-10 3M Innovative Properties Company Reactive hydrophilic oligomers
US7074839B2 (en) * 2004-03-01 2006-07-11 3M Innovative Properties Company Crosslinkable hydrophilic materials from reactive oligomers having pendent photoinitiator groups
US7342047B2 (en) * 2004-03-02 2008-03-11 3M Innovative Properties Company Crosslinkable hydrophilic materials from reactive oligomers having pendent unsaturated groups
JP4543140B2 (en) * 2004-08-16 2010-09-15 綜研化学株式会社 Circuit board protecting adhesive sheet and method for producing the same
US7332546B2 (en) * 2004-10-01 2008-02-19 3M Innovative Properties Company Ring-opened azlactone telechelic polymer
US7304112B2 (en) * 2004-10-01 2007-12-04 3M Innovative Properties Company Azlactone telechelic polymer
US7307106B2 (en) * 2004-12-10 2007-12-11 3M Innovative Properties Company Photocurable Michael addition polymers
US20060234014A1 (en) * 2005-04-14 2006-10-19 Liu Yaoqi J Patterned adhesives for tamper evident feature
US20060234040A1 (en) * 2005-04-14 2006-10-19 Liu Yaoqi J Patterned adhesives for color shifting effect
US7981988B2 (en) * 2006-05-25 2011-07-19 3M Innovative Properties Company Ultraviolet radiation-polymerizable compositions
US8834918B2 (en) * 2007-01-22 2014-09-16 Wisconsin Alumni Research Foundation Modified multilayered film
WO2009006318A1 (en) 2007-06-29 2009-01-08 Artificial Muscle, Inc. Electroactive polymer transducers for sensory feedback applications
US7842762B2 (en) * 2007-08-08 2010-11-30 Ppg Industries Ohio, Inc. Electrodepositable coating composition containing a cyclic guanidine
WO2009049092A1 (en) * 2007-10-09 2009-04-16 Wisconsin Alumni Research Foundation Covalent assembly of ultrathin polymeric films
US20090098359A1 (en) 2007-10-11 2009-04-16 Waller Jr Clinton P Hydrophilic porous substrates
US7652103B2 (en) * 2008-02-14 2010-01-26 3M Innovative Properties Company Acrylic pressure-sensitive adhesives with aziridine crosslinking agents
EP2100599A1 (en) 2008-03-13 2009-09-16 Laboratorios Almirall, S.A. Inhalation composition containing aclidinium for treatment of asthma and chronic obstructive pulmonary disease
EP2100598A1 (en) 2008-03-13 2009-09-16 Laboratorios Almirall, S.A. Inhalation composition containing aclidinium for treatment of asthma and chronic obstructive pulmonary disease
US7714076B2 (en) * 2008-03-27 2010-05-11 3M Innovative Properties Company Acrylic pressure-sensitive adhesives with aziridine crosslinking agents
EP2294118B1 (en) * 2008-05-30 2012-07-04 3M Innovative Properties Company Method of making ligand functionalized substrates
JP2011523965A (en) 2008-05-30 2011-08-25 スリーエム イノベイティブ プロパティズ カンパニー Ligand functionalized substrate
EP2291478B1 (en) * 2008-06-09 2012-08-01 3M Innovative Properties Company Acrylic pressure-sensitive adhesives with aziridine crosslinking agents
WO2010033807A1 (en) * 2008-09-19 2010-03-25 3M Innovative Properties Company Ligand graft functionalized substrates
US8765217B2 (en) 2008-11-04 2014-07-01 Entrotech, Inc. Method for continuous production of (meth)acrylate syrup and adhesives therefrom
US7838110B2 (en) * 2008-12-02 2010-11-23 3M Innovative Properties Company Aziridine-functional photoactive crosslinking compounds
JP5595413B2 (en) * 2008-12-12 2014-09-24 ビーエーエスエフ ソシエタス・ヨーロピア Modified polyvinyl lactam
WO2010077435A1 (en) * 2008-12-31 2010-07-08 3M Innovative Properties Company Stretch releasable pressure-sensitive adhesives
EP2406338B1 (en) 2009-03-09 2012-11-28 3M Innovative Properties Company Aziridine crosslinking agents for acrylic adhesives
EP2239793A1 (en) 2009-04-11 2010-10-13 Bayer MaterialScience AG Electrically switchable polymer film structure and use thereof
US8329079B2 (en) 2009-04-20 2012-12-11 Entrochem, Inc. Method and apparatus for continuous production of partially polymerized compositions and polymers therefrom
BRPI1011747A2 (en) 2009-06-23 2018-02-27 3M Innovative Properties Co functionalized nonwoven article.
US8067504B2 (en) 2009-08-25 2011-11-29 3M Innovative Properties Company Acrylic pressure-sensitive adhesives with acylaziridine crosslinking agents
US8148471B2 (en) * 2009-11-23 2012-04-03 3M Innovative Properties Company Acrylic pressure-sensitive adhesives with aziridinyl-epoxy crosslinking system
CN102108133B (en) * 2009-12-23 2014-12-10 3M创新有限公司 (Methyl) acrylyl-aziridine crosslinking agent and adhesive polymer
CN102127183B (en) 2010-01-20 2014-08-20 3M创新有限公司 Crosslinkable acrylate adhesive polymer composite
US8712559B2 (en) * 2010-02-10 2014-04-29 The Board Of Trustees Of The University Of Illionois Adaptive control for uncertain nonlinear multi-input multi-output systems
US8377672B2 (en) 2010-02-18 2013-02-19 3M Innovative Properties Company Ligand functionalized polymers
EP2889625B1 (en) 2010-03-03 2016-09-14 3M Innovative Properties Company Ligand guanidinyl functionalized polymers
US8222340B2 (en) 2010-04-05 2012-07-17 3M Innovative Properties Company Crosslinkable syrup copolymers with aminoalkyl (meth)acryloyl solvent monomers
WO2012077720A1 (en) * 2010-12-09 2012-06-14 協立化学産業株式会社 Compound suitable for photopolymerization initiator, photopolymerization initiator, and photocurable resin composition
CN103282429B (en) 2010-12-29 2015-11-25 3M创新有限公司 There is the pressure sensitive adhesive of triazine-epoxy cross-linking system
US8563560B2 (en) 2011-02-25 2013-10-22 Ppg Industries Ohio, Inc. Preparation of bicyclic guanidine salts in an aqueous media
EP2681748B1 (en) 2011-03-01 2016-06-08 Parker-Hannifin Corp Automated manufacturing processes for producing deformable polymer devices and films
US9195058B2 (en) 2011-03-22 2015-11-24 Parker-Hannifin Corporation Electroactive polymer actuator lenticular system
EP2510928A1 (en) 2011-04-15 2012-10-17 Almirall, S.A. Aclidinium for use in improving the quality of sleep in respiratory patients
US8785517B2 (en) 2011-05-25 2014-07-22 3M Innovative Properties Company Pressure-sensitive adhesives with onium-epdxy crosslinking system
US8871827B2 (en) * 2011-06-07 2014-10-28 Basf Se Hotmelt adhesive comprising radiation-crosslinkable poly(meth)acrylate and oligo(meth)acrylate with nonacrylic C-C double bonds
WO2012177337A1 (en) 2011-06-23 2012-12-27 3M Innovative Properties Company Pressure-sensitive adhesives with onium-epoxy resin crosslinking system
WO2013052105A2 (en) 2011-10-03 2013-04-11 Biomimedica, Inc. Polymeric adhesive for anchoring compliant materials to another surface
US9876160B2 (en) 2012-03-21 2018-01-23 Parker-Hannifin Corporation Roll-to-roll manufacturing processes for producing self-healing electroactive polymer devices
US8715904B2 (en) * 2012-04-27 2014-05-06 3M Innovative Properties Company Photocurable composition
WO2013192143A1 (en) 2012-06-18 2013-12-27 Bayer Intellectual Property Gmbh Stretch frame for stretching process
CN104737018B (en) 2012-09-27 2017-06-30 3M创新有限公司 Part graft base
WO2014066576A1 (en) 2012-10-24 2014-05-01 Bayer Intellectual Property Gmbh Polymer diode
EP2970725A1 (en) 2013-03-13 2016-01-20 3M Innovative Properties Company Adhesives comprising epoxy-acid crosslinked groups and methods
US9068089B2 (en) 2013-03-15 2015-06-30 Ppg Industries Ohio, Inc. Phenolic admix for electrodepositable coating composition containing a cyclic guanidine
JP2016521306A (en) 2013-04-15 2016-07-21 スリーエム イノベイティブ プロパティズ カンパニー Adhesive and method comprising a crosslinking agent having a (meth) acrylate group and an olefin group
US9688874B2 (en) 2013-10-25 2017-06-27 Ppg Industries Ohio, Inc. Method of making a bicyclic guanidine-cured acrylic coating
EP2878606B1 (en) * 2013-11-29 2015-08-05 ICAP-SIRA S.p.A. UV-curable composition and pressure sensitive adhesive having breathability derived therefrom, as well as method for manufacturing the same
CN105814155A (en) 2013-12-09 2016-07-27 3M创新有限公司 Curable silsesquioxane polymers, compositions, articles, and methods
EP2886620B1 (en) 2013-12-18 2019-11-27 3M Innovative Properties Company Post-curable pressure-sensitive adhesive
WO2015157350A1 (en) 2014-04-11 2015-10-15 3M Innovative Properties Company Adhesives comprising (meth)allyl crosslinker and methods
WO2015164087A1 (en) * 2014-04-24 2015-10-29 3M Innovative Properties Company Compositions comprising cleavable crosslinker and methods
WO2015167819A1 (en) 2014-04-28 2015-11-05 3M Innovative Properties Company Physically crosslinkable adhesive copolymer
WO2015183782A1 (en) 2014-05-29 2015-12-03 3M Innovative Properties Company Acrylic adhesive composition with controlled molecular weight
EP2957577B1 (en) 2014-06-19 2019-11-27 3M Innovative Properties Company Curable pressure-sensitive adhesive compositions
US10370564B2 (en) 2014-06-20 2019-08-06 3M Innovative Properties Company Adhesive compositions comprising a silsesquioxane polymer crosslinker, articles and methods
WO2015195355A1 (en) 2014-06-20 2015-12-23 3M Innovative Properties Company Adhesive compositions comprising a silsesquioxane polymer crosslinker, articles and methods
JP2017519081A (en) 2014-06-20 2017-07-13 スリーエム イノベイティブ プロパティズ カンパニー Curable polymer and method comprising a silsesquioxane polymer core and a silsesquioxane polymer outer layer
WO2016036634A1 (en) 2014-09-02 2016-03-10 3M Innovative Properties Company Acrylate adhesive with vinylsilane crosslinking agents
CN106715495A (en) 2014-09-12 2017-05-24 3M创新有限公司 Allyl acrylate crosslinkers for PSAs
US9957358B2 (en) 2014-09-22 2018-05-01 3M Innovative Properties Company Curable polymers comprising silsesquioxane polymer core silsesquioxane polymer outer layer, and reactive groups
US9957416B2 (en) 2014-09-22 2018-05-01 3M Innovative Properties Company Curable end-capped silsesquioxane polymer comprising reactive groups
CN107001862A (en) 2014-12-05 2017-08-01 3M创新有限公司 Slurry polymerisation compositions and by its obtained adhesive
CN107108922B (en) 2014-12-08 2020-08-18 3M创新有限公司 Acrylic polyvinyl acetal films and compositions
CN107001761B (en) 2014-12-08 2020-06-16 3M创新有限公司 Acrylic polyvinyl acetal film, composition, and heat-bondable article
EP3298098A1 (en) 2015-05-18 2018-03-28 3M Innovative Properties Company Pressure sensitive adhesive comprising (meth)acrylic polymer comprising epoxy-functional groups and triazine crosslinker
US10350861B2 (en) * 2015-07-31 2019-07-16 Corning Incorporated Laminate structures with enhanced damping properties
US10768528B2 (en) 2015-09-28 2020-09-08 3M Innovative Properties Company Patterned film article comprising cleavable crosslinker and methods
EP3170876A1 (en) 2015-11-17 2017-05-24 3M Innovative Properties Company Post-curable precursor of an acrylic-based pressure-sensitive adhesive
US10493738B2 (en) 2015-12-22 2019-12-03 3M Innovative Properties Company Acrylic polyvinyl acetal graphic films
CN108472936B (en) 2015-12-22 2020-10-27 3M创新有限公司 Acrylic polyvinyl acetal film comprising an adhesive layer
US11167523B2 (en) 2015-12-22 2021-11-09 3M Innovative Properties Company Acrylic films comprising a structured layer
WO2017112453A2 (en) 2015-12-22 2017-06-29 3M Innovative Properties Company Acrylic polyvinyl acetal films comprising a second layer
US11397286B2 (en) 2016-06-07 2022-07-26 3M Innovative Properties Company Acrylic polyvinyl acetal film for a light directing article
EP3559062B1 (en) 2016-12-22 2020-12-02 3M Innovative Properties Company Crosslinkable and crosslinked polymeric materials
RU2019134405A (en) 2017-03-31 2021-04-30 Колопласт А/С ACRYLAMIDE PHOTO INITIATORS
US10640687B2 (en) 2017-03-31 2020-05-05 3M Innovative Properties Company Polymeric materials formed using controlled radical initiators
DE102017114266B9 (en) 2017-06-27 2020-09-17 Certoplast Technische Klebebänder Gmbh Process for the production of a wrapping tape
DE102017114256A1 (en) 2017-06-27 2018-12-27 Certoplast Technische Klebebänder Gmbh Process for producing an adhesive tape
US11752731B2 (en) 2017-06-30 2023-09-12 3M Innovative Properties Company Articles having adhesive layers including urethane acrylate polymer or acrylate copolymer
EP3668555B1 (en) * 2017-08-17 2021-10-06 Coloplast A/S Polymeric coatings
US20200199421A1 (en) 2017-09-13 2020-06-25 3M Innovative Properties Company Physically crosslinkable composition
CN111108154B (en) 2017-09-28 2022-01-28 3M创新有限公司 Silicone pressure-sensitive adhesive
CN111148795B (en) 2017-09-28 2023-06-23 3M创新有限公司 Photo radical curing of silicones
US11904031B2 (en) 2017-11-22 2024-02-20 3M Innovative Properties Company Orthodontic articles comprising polymerized composition comprising at least two free-radical initiators
US11492460B2 (en) 2017-12-19 2022-11-08 3M Innovative Properties Company Polymeric materials formed using initiators with two thiocarbonylthio-containing groups
WO2019123182A1 (en) 2017-12-21 2019-06-27 3M Innovative Properties Company Polymeric compositions prepared with a controlled radical initiator
EP3755728A1 (en) 2018-02-21 2020-12-30 3M Innovative Properties Company Polymeric materials formed using initiators with a ketone group and two thiocarbonylthio-containing groups
EP3755732A1 (en) 2018-02-21 2020-12-30 3M Innovative Properties Company Ketone-containing controlled radical initiators for polymerization reactions
WO2020003169A1 (en) 2018-06-29 2020-01-02 3M Innovative Properties Company Orthodontic articles comprising cured free-radically polymerizable composition with improved strength in aqueous environment
EP3841131A1 (en) 2018-08-22 2021-06-30 3M Innovative Properties Company Curable compositions for pressure-sensitive adhesives
EP3883999A1 (en) 2018-11-19 2021-09-29 3M Innovative Properties Company Composition including a polythiol, a polyepoxide, a polymeric catalyst, and a conductive filler and methods relating to the composition
WO2020104882A1 (en) 2018-11-19 2020-05-28 3M Innovative Properties Company Polymer comprising hydroxy groups and tertiary amine groups suitable for use as a catalyst
DE102019202569A1 (en) 2019-02-26 2020-08-27 Tesa Se Adhesive tape comprising at least two different adhesive compositions which are separated from one another by a barrier layer
JP7131504B2 (en) * 2019-08-02 2022-09-06 三菱ケミカル株式会社 Curable polymer composition, cured product, laminate
JP7167877B2 (en) * 2019-08-02 2022-11-09 三菱ケミカル株式会社 Cured material, laminate
US11787884B2 (en) * 2019-12-13 2023-10-17 Kj Chemicals Corporation Photopolymerization initiator
CN114929776A (en) 2019-12-20 2022-08-19 3M创新有限公司 Adhesive articles, adhesive compositions, and methods comprising polymer and polymerizable cyclic olefin
EP4200131A1 (en) 2020-10-29 2023-06-28 3M Innovative Properties Company Method of thermoforming multilayer polymer film and articles
WO2022123498A1 (en) 2020-12-10 2022-06-16 3M Innovative Properties Company Crosslinked polymer particles and related compositions and processes
WO2023111715A1 (en) 2021-12-16 2023-06-22 3M Innovative Properties Company Compositions comprising cleavable crosslinkers

Family Cites Families (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE24906E (en) * 1955-11-18 1960-12-13 Pressure-sensitive adhesive sheet material
DE1184034B (en) * 1963-03-13 1964-12-23 Hoechst Ag Process for dry cleaning of fiber material
FR1432713A (en) * 1965-02-10 1966-03-25 Novacel Sa New manufacturing process for pressure-adhering adhesive tapes and device therefor
US3615972A (en) * 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US3575925A (en) * 1968-06-17 1971-04-20 Nat Starch Chem Corp Photosensitive coating systems
US3565247A (en) * 1968-10-21 1971-02-23 Minnesota Mining & Mfg Pressure-sensitive adhesive tape product
US4075238A (en) * 1973-10-29 1978-02-21 Hooker Chemicals & Plastics Corporation Polyhalobenzylic disulfooxonium compounds
US4181752A (en) * 1974-09-03 1980-01-01 Minnesota Mining And Manufacturing Company Acrylic-type pressure sensitive adhesives by means of ultraviolet radiation curing
DE2443414C2 (en) * 1974-09-11 1983-05-19 Beiersdorf Ag, 2000 Hamburg Process for the manufacture of self-adhesive products
US3993833A (en) * 1976-01-19 1976-11-23 Minnesota Mining And Manufacturing Company Polyurethane foam-backed pressure-sensitive adhesive tape
US4223067A (en) * 1978-03-27 1980-09-16 Minnesota Mining And Manufacturing Company Foam-like pressure-sensitive adhesive tape
US4181755A (en) * 1978-11-21 1980-01-01 Rca Corporation Thin film pattern generation by an inverse self-lifting technique
US4243500A (en) * 1978-12-04 1981-01-06 International Coatings, Co., Inc. Pressure sensitive adhesives
US4303485A (en) * 1979-08-20 1981-12-01 Minnesota Mining And Manufacturing Company Ultraviolet polymerization of acrylate monomers using oxidizable tin compounds
US4304705A (en) 1980-01-02 1981-12-08 Minnesota Mining And Manufacturing Company Radiation-curable polymers containing pendant unsaturated peptide groups derived from azlactone polymers
US4329384A (en) * 1980-02-14 1982-05-11 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape produced from photoactive mixture of acrylic monomers and polynuclear-chromophore-substituted halomethyl-2-triazine
US4330590A (en) * 1980-02-14 1982-05-18 Minnesota Mining And Manufacturing Company Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-2-triazine
US4391687A (en) * 1980-02-14 1983-07-05 Minnesota Mining And Manufacturing Company Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-1-triazine
JPS6021770B2 (en) * 1980-02-14 1985-05-29 松本油脂製薬株式会社 Method for manufacturing thermally expandable microcapsules
JPS5846236B2 (en) * 1980-03-05 1983-10-14 日東電工株式会社 pressure sensitive adhesive composition
US4364972A (en) * 1981-01-16 1982-12-21 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive copolymers of acrylic acid ester and N-vinyl pyrrolidone
US4379201A (en) * 1981-03-30 1983-04-05 Minnesota Mining And Manufacturing Company Multiacrylate cross-linking agents in pressure-sensitive photoadhesives
JPS5846236A (en) * 1981-09-16 1983-03-17 Clarion Co Ltd Clutch
US4777276A (en) 1981-10-29 1988-10-11 Minnesota Mining And Manufacturing Company Acrylamidoacylated oligomers
GB2108487B (en) 1981-11-03 1985-07-31 Sericol Group Ltd Water soluble thioxanthone photoinitiators
US4415615A (en) * 1982-01-15 1983-11-15 Minnesota Mining And Manufacturing Co. Cellular pressure-sensitive adhesive product and method of making
JPS6183273A (en) * 1984-09-28 1986-04-26 Nitto Electric Ind Co Ltd Photo-setting self-adhesive molding
US4710536A (en) * 1985-08-07 1987-12-01 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape containing hydrophobic silica
US4749590A (en) * 1985-08-07 1988-06-07 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape containing hydrophobic silica
DE3534645A1 (en) * 1985-09-28 1987-04-02 Merck Patent Gmbh COPOLYMERIZABLE PHOTOINITIATORS
US4732808A (en) * 1985-11-14 1988-03-22 Minnesota Mining And Manufacturing Company Macromer reinforced pressure sensitive skin adhesive sheet material
US4737559A (en) * 1986-05-19 1988-04-12 Minnesota Mining And Manufacturing Co. Pressure-sensitive adhesive crosslinked by copolymerizable aromatic ketone monomers
US4818610A (en) * 1986-08-29 1989-04-04 Minnesota Mining And Manufacturing Company Unified pressure-sensitive adhesive tape
US4894259A (en) * 1986-08-29 1990-01-16 Minnesota Mining And Manufacturing Company Process of making a unified pressure-sensitive adhesive tape
US4895738A (en) * 1986-08-29 1990-01-23 Minnesota Mining And Manufacturing Company Method of making a unified pressure-sensitive adhesive tape
EP0258719A3 (en) * 1986-08-30 1989-07-05 Ciba-Geigy Ag Two-layer system
DE3738567A1 (en) * 1987-03-12 1988-09-22 Merck Patent Gmbh COREACTIVE PHOTOINITIATORS
DE3880920T2 (en) * 1987-08-05 1993-10-07 Ciba Geigy Links.
US4874822A (en) 1988-04-07 1989-10-17 Minnesota Mining And Manufacturing Company Process for the acrylamidoacylation of alcohols
US5264533A (en) * 1988-06-16 1993-11-23 Basf Aktiengesellschaft Benzophenone derivatives and their preparation
JPH089586B2 (en) * 1988-09-28 1996-01-31 昭和電工株式会社 Bifunctional acrylate compound and method for producing the same
DE3836968A1 (en) * 1988-10-31 1990-05-03 Basf Ag UV CROSSLINKABLE MASSES BASED ON ISOAMYL (METH) ACRYLATE COPOLYMERISATS
US4931582A (en) 1988-11-04 1990-06-05 Minnesota Mining And Manufacturing Company Fluorinated, acrylamide-functional monomers
JP2604453B2 (en) * 1988-12-14 1997-04-30 積水化学工業株式会社 Acrylic adhesive tape
DE3844445A1 (en) * 1988-12-31 1990-07-19 Basf Ag UV-CROSSLINKABLE MASSES BASED ON (METH) -ACRYLESTER POLYMERISATS
US5248805A (en) * 1988-12-31 1993-09-28 Basf Aktiengesellschaft Radiation-senstive, ethylenically unsaturated, copolymerizable compounds and their preparation
JP2744051B2 (en) * 1989-03-09 1998-04-28 積水化学工業株式会社 Acrylic adhesive and method for producing acrylic adhesive tape or sheet
JPH02248482A (en) * 1989-03-23 1990-10-04 Fujikura Kasei Co Ltd Photocurable pressure-sensitive adhesive composition
DE3914374A1 (en) * 1989-04-29 1990-10-31 Basf Ag THROUGH ULTRAVIOLET RADIATION UNDER AIR OXYGEN ATMOSPHERIC CROSSLINKABLE COPOLYMERS
DE3914375A1 (en) * 1989-04-29 1990-11-15 Basf Ag THANKS TO ULTRAVIOLET RADIATION
JP2974150B2 (en) * 1989-06-30 1999-11-08 王子製紙株式会社 Adhesive sheet
JP2777219B2 (en) * 1989-09-01 1998-07-16 東陶機器株式会社 Toilet flush water supply
JP2899346B2 (en) * 1990-02-27 1999-06-02 ユニチカ株式会社 Composite material with good laser marking properties
DE4037079A1 (en) 1990-11-22 1992-05-27 Basf Ag UNSATURATED PHENONE DERIVATIVES AND THEIR USE AS ADHESIVE ADHESIVES
AU1641492A (en) * 1991-02-28 1992-10-06 Minnesota Mining And Manufacturing Company Multi-stage irradiation process for production of acrylic based adhesives and adhesives made thereby
WO1993009152A1 (en) * 1991-11-05 1993-05-13 Avery Dennison Corporation Uv-cured hot melt pressure-sensitive adhesives
US5202361A (en) * 1991-12-23 1993-04-13 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive
EP0633918A1 (en) * 1992-03-31 1995-01-18 Minnesota Mining And Manufacturing Company Ultraviolet radiation curable acrylate pressure-sensitive adhesive compositions
US5302629A (en) * 1992-05-15 1994-04-12 Berejka Anthony J Hydrophilic acrylic pressure sensitive adhesives
JPH0819392B2 (en) * 1992-11-30 1996-02-28 日東電工株式会社 Pressure-sensitive adhesives and their adhesive sheets
SG49755A1 (en) * 1992-12-07 1998-06-15 Minnesota Mining & Mfg Adhesive for polycarbonate
JPH0819393B2 (en) * 1992-12-09 1996-02-28 日東電工株式会社 Pressure-sensitive adhesives and their adhesive sheets
JP2795366B2 (en) * 1992-12-09 1998-09-10 日東電工株式会社 Adhesive sheets with foam base
DE4243270A1 (en) * 1992-12-21 1994-06-23 Lohmann Gmbh & Co Kg Process for crosslinking pressure sensitive adhesives using lasers
JPH06200225A (en) * 1992-12-29 1994-07-19 Nitto Denko Corp Pressure-sensitive adhesive for coating material and adhesive sheet using the same
DE4303183C1 (en) * 1993-02-04 1994-07-21 Lohmann Gmbh & Co Kg Process for the production of thick pressure-sensitive adhesive layers, in particular for the production of self-adhesive high-performance adhesive articles
US5506279A (en) * 1993-10-13 1996-04-09 Minnesota Mining And Manufacturing Company Acrylamido functional disubstituted acetyl aryl ketone photoinitiators
US5773485A (en) 1994-07-29 1998-06-30 Minnesota Mining And Manufacturing Company Acrylic syrup curable to a crosslinked viscoelastomeric material
WO1997005100A1 (en) 1995-07-28 1997-02-13 Minnesota Mining And Manufacturing Company Chromophoric photocrosslinking compound

Also Published As

Publication number Publication date
KR970704849A (en) 1997-09-06
WO1996004346A1 (en) 1996-02-15
US6245922B1 (en) 2001-06-12
DE69515310T2 (en) 2000-07-27
EP0772656B1 (en) 2001-03-21
JP3545414B2 (en) 2004-07-21
JPH10503548A (en) 1998-03-31
EP0772656A2 (en) 1997-05-14
WO1996005249A3 (en) 1996-03-28
DE69520434T2 (en) 2001-10-18
JP3548933B2 (en) 2004-08-04
US5773485A (en) 1998-06-30
EP0772655B1 (en) 2000-03-01
US5902836A (en) 1999-05-11
DE69515310D1 (en) 2000-04-06
EP0772655A1 (en) 1997-05-14
ES2142489T3 (en) 2000-04-16
JPH10503802A (en) 1998-04-07
DE69520434D1 (en) 2001-04-26
WO1996005249A2 (en) 1996-02-22

Similar Documents

Publication Publication Date Title
CA2196169A1 (en) Acrylic syrup curable to a crosslinked viscoelastomeric material
US5741543A (en) Process for the production of an article coated with a crosslinked pressure sensitive adhesive
JP3231772B2 (en) Pressure sensitive adhesive
CA1145294A (en) Pressure-sensitive adhesive tape produced from photoactive mixture or acrylic monomers and polynuclear-chromophore-substituted halomethyl-s- triazine
US6339111B1 (en) Multi-stage irradiation process for production of acrylic based adhesives and adhesives made thereby
US5416127A (en) Radiation curable hot melt pressure sensitive adhesives
EP1375617A1 (en) Radiation-curable, solvent-free and printable precursor of a pressure-sensitive adhesive
US6884848B2 (en) Benzocyclobutenone-functional fluoropolymers
JP2016505668A (en) Liquid optical adhesive composition
CN102292317A (en) Aziridine-functional photoactive crosslinking compounds
JPH08507563A (en) Permanent re-release of radiation-curable acrylate / silicone Releaseable pressure-sensitive adhesive
JP2000509089A (en) Method for radiation-crosslinking polymer and radiation-crosslinkable composition
JPH08209083A (en) Acrylic tacky agent and acrylic tacky tape
JP2596707B2 (en) Radiation curable hot melt pressure sensitive adhesive
JP4606078B2 (en) Acrylic viscoelastic material
JP3091783B2 (en) Photopolymerizable adhesive composition, pressure-sensitive adhesive using the same, and adhesive sheet
TW202219202A (en) Release coating compositions for pressure sensitive adhesive articles and methods
JP2000026805A (en) Pressure sensitive adhesive composition and preparation thereof
CA2196173A1 (en) Acrylic syrup curable to a crosslinked viscoelastomeric material
AU6780481A (en) Pressure-sensitive adhesive tape produced from photoactive mixture of acrylic monomers and polynuclear-chromophore- substituted halomethyl-s-triazine

Legal Events

Date Code Title Description
FZDE Discontinued