CA2173228A1 - Acrylamido functional disubstituted acetyl aryl ketone photoinitiators - Google Patents

Acrylamido functional disubstituted acetyl aryl ketone photoinitiators

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Publication number
CA2173228A1
CA2173228A1 CA002173228A CA2173228A CA2173228A1 CA 2173228 A1 CA2173228 A1 CA 2173228A1 CA 002173228 A CA002173228 A CA 002173228A CA 2173228 A CA2173228 A CA 2173228A CA 2173228 A1 CA2173228 A1 CA 2173228A1
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Prior art keywords
group
groups
aryl ketone
pbw
photoinitiator
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Abandoned
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CA002173228A
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French (fr)
Inventor
Gaddam N. Babu
Steven M. Heilmann
Howell K. Ii Smith
Louis E. Winslow
Kejian Chen
Greggory S. Bennett
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3M Co
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/49—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/52—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/22—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/28—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S522/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S522/904—Monomer or polymer contains initiating group

Abstract

The invention provides novel acrylamide functional disubstituted acetyl aryl ketones and a process for their preparation in high yields uncontaminated by difunctional material. The invention further provides photo-cross-linkable compositions comprising one or more ethylenically-unsaturated monomers and as photoinitiator the acrylamide functional disubstituted acetyl aryl ketone of the invention. The compositions are useful for the preparation of films and coatings, particularly pressure- sensitive adhesive coatings.

Description

~ WO 95/10552 2 ~ 7 ~ 2 2 8 PCTIUS94110620 AC~Y~ DO ~ UNC;.1ONAL DISUB~ U~ ACETYL ARYL
~.GN~S PHOTO1N1,1ATOR8 .

15 FIEI,D OF TXE ~NV ~ 1ON
This invention relates to novel compounds useful as photoinitiators for the polymerization of free radically polymerizable ethylenically-unsaturated compounds. The invention further relates to 2 0 photoinitiators that are copolymerizable with ethylenically-unsaturated compounds and to polymerizable compositions contA; n; ng the photoinitiators. The invention also relates to a process for the production of the photoinitiators. In 25 addition, the invention relates to pressure-sensitive adhesives and tape articles prepared using the photoinitiators of the invention.

B~C~G12OIJ~7D OF THE 1NV~ 1ON

The use of photoinitiators to bring about the polymerization of free radically polymerizable compounds and compositions is well known and many photoinitiators are commercially available. The selection of a particular photoinitiator for use in a 35 composition is generally made on the basis of the solubility, rate of reaction, activating wavelength, and inte~ use of the photoinitiator (e.g., use as protective coatings, viscoelastic products, and the like).
Until recently, photoinitiators have been radiation sensitive compounds that, on exposure to WO95110552 PCT~S94/10620 2~32~
~ - 2 -activating radiation of monomer compositions cont~;n;ng them, will in the absence of polyfunctional monomers in the composition induce polymerization of the monomers in a composition to essentially linear thermoplastic 5 polymers. Included among ~hese initiators are acyloin and derivatives thereof, e.g., benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, aF~ ~-methylbenzoin, organic sulfides e.g., diphenyl s~ ide, diphenyl disulfide, lO decyl phj-nyl sulfide, and tetramethylthiuram monosulfide, S-acyl dithiocarbamates, e.g., S-benzoyl-~,N-dimethyldithiocarbamate, and ~-substituted acetophenones, e.g. ~,~-dimethyl-~-hydroxy acetophenone, ~,~-diethoxy acetophenone. The initiator 15 is generally used in amounts ranging from about O.Ol to 5.0% by weight of the total polymerizable composition.
Photosensitive compounds are known that when incorporated into pho~opolymerizable compositions bring about the crosslinking of the composition with 20 att~n~t enhancement of the cohesive strength of the composition. Examples of these photoactive compounds include: sulfonyl halides, such as ~-naphthalene sulfonyl chloride; halogenated aromatic compounds, such as ~-chloromethylnaphthalene; and trichloromethyl-s-25 triazines, such as 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine. These photosensitive compounds, although very effective for use in the polymerization and photocrosslinking of monomer containing compositions liberate hydrogen chloride as a 30 by-product, following hydrogen abstraction by chlorine radicals which are responsible for initiating the polymerization and crosslinking. The corrosiveness of the liberated hydrogen chloride makes these photosensitive crosslinkers unsatisfactory for some 35 purposes.
Photosensitive compounds that can bring about the crosslinking of monomer containing compositions without ~ WO95/10552 2 1 7 3 2 2 8 PCT~S94/10620 the liberation of hydrogen chloride are disclosed in European Patent Application No. 0 281 941. In this application, coreactive photoinitiators are disclosed that have the general formula:

RG - A - IN

in which IN denotes a photoinitiator structure, A
denotes a spacer group, and RG denotes a functional 10 group. This extremely broad Formula I includes acryloyloxy functional photosensitive compounds and acrylamidoacyl functional photosensitive compounds such as CH2=CH-C-O-CH2CH2-O ~ ~ > C-C-OH ll 2-propenoic acid, 2-[4-(2-hydroxy-2-15 methylpropanoyl)phenoxy]ethyl ester II, also called 2-hydroxy-1-[4-(2-acryloyloxyethoxy)phenyl]-2-methyl-1-propanone) and C~ =CH-C-N~-CH2-C-O-CH2C~-O ~ C-CI-OH lll 2-propenoylaminoethanoic acid, 2-[4-(2-hydroxy-2-methylpropanoyl)phenoxy]ethyl ester, III.
Acryloyloxy functional photosensitive compound II
is also disclosed in RADCURE '86, Conf. Proc., 10th, 4/43-4/55 (September 8-11, 1986); and its preparation in U.S. Patent No. 4,922,004, among other patents in which it is taught that Compound II is prepared in a 25 calculated 60% yield from 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure~

WO95/10552 PCT~S94/10620 ~

2959, Ciba-Geigy, Chicago, IL) by reaction with acryloyl chloride.
Acrylamidoacetyl functional photosensitive compounds such as Compound III are included in the EP
5 application 281,941 formula RG-A-IN only by proper combination of groups from among the many groups disclosed as useful in the formula; the formula discloses for spacer group "A" only unsubstituted (CH2) units.
Japanese KOKAI Patent HEI 2tl990]-248482 describes a photocurable pressure sensitive adhesive (PSA) suitable for screen printing enabling a high rate of production of printed circuit boards using as photoinitiator l-acryloyloxy-2-[4-(4-15 chlorobenzoyl)benzoyloxy]ethane, a hydrogen abstracting photocrosslinker. Such a composition would yield an adhesive having a shear value of less than~l00 minutes.
Japanese KOKAI Patent HEI 2[1990]-235908 discloses pressure sensitive adhesives by use of a composition of 20 ethylenically-unsaturated cleavage type photopoly-merization initiator such as 2-hydroxy-1-[4-(2-acryloyloxyethoxy)phenyl]-2-methyl-1-propanone [Formula II], a conventional photopolymerization initiator and a polyfunctional crosslinking agent such as hexanediol 25 diacrylate. The PSA would have good shear primarily because of the conventional polyfunctional crosslinking agent. In the absence of such a conventional polyfunctional crosslinking agent the PSA would be expected to exhibit poor shear.
8UMMARY OF THE lNv~ ON
The present invention provides novel acrylamide functional disubstituted acetyl aryl ketones useful as photoinitiators which in polymerizable ethylenically 35 unsaturated compositions, preferably acrylic compositions such as pressure-sensitive adhesive compositions, are more hydrolytically stable and have a ~ WO9S/lOS52 217 3 ~ 2 ~ PCT~S94/10620 higher rate of free radical homopropagation than that of corresponding acryloyloxy functional photoinitiators. In addition, use of these photoinitiators results in compositions possessing 5 excellent shear strength whether polymerized in the presence or absence of conventional polyfunctional crosslinkers.
The invention also provides a process for the preparation of the acrylamide functional disubstituted 10 acetyl aryl ketones in greater than 70% theoretical yield comprising the steps of (a) providing a hydroxyl, thiol, or primary amine functional aryl ketone and (b) reacting the hydroxyl, thiol, or primary amine functional aryl ketone with an alkenyl azlactone.
The invention further provides photocrosslinkable compositions comprising (a) one or more photopolymerizable ethylenically-unsaturated compounds, (b) an acrylamide functional disubstituted acetyl aryl ketone photoinitiator, and (c) optionally, a 20 photoinitiator not having an ethylenically unsaturated functional group. These compositions provide "PSAs"
with higher molecular weights between crosslinks than conventional crosslinked PSAs. The photocrosslinkable and photocrosslinked compositions provide pressure-25 sensitive adhesives which can be used in tape andlaminate constructions.
The invention also provides pressure-sensitive adhesives and products prepared therefrom comprising the polymerization product of the acrylamide functional 30 disubstituted acetyl aryl ketone photoinitiator, at least one acrylic acid ester of a monohydric alcohol having an average of 4 to 12 carbon atoms, and at least one ethylenically unsaturated monomer whose homopolymer has a glass transition temperature greater than 50C.
In this application:
"acrylamido" and "acrylamide" are used interchangeably;

wossllo5s2 PCT~S94110620 2~7322~

"alkyl" means the monovalent group remaining after removal of a hydrogen atom from a linear, cyclic, or branched chain hydrocarbon containing 1 to 20 carbon atoms;
"lower alkyl" or "lower alkoxy" means C~ to C6 alkyl or alkoxy;
"aryl" means the monovalent group remaining after removal of one hydrogen atom from an aromatic hydrocarbon having 6 to 12 carbon atoms and optionally 10 up to 3 heteroatoms selected from S, N, and nonperoxidic O, and includes substituted aromatic compounds in which the substituents can be up to three groups selected from lower alkyl (Cl to C6) and lower alkoxy (C1 to C6) groups;
"acrylamido functional disubstituted acetyl aryl ketone compounds" mean any of 2-(N-acrylamido)-2,2-disubstituted acetoxy-functional aryl ketones, 2-(N-acrylamido)-2,2-disubstituted thiolacetoxy-functional aryl ketones, 2-(N-acrylamido)-2,2-disubstituted 20 acetamido-functional ary ketones;
"arenyl" means the monovalent residue remaining after the removal of a hydrogen atom from an aromatic hydrocarbon containing both alkyl and aryl groups;
"arylene" means the divalent group remaining after 25 removal of two hydrogens from an aromatic hydrocarbon having 6 to 12 carbon atoms and optionally up to 3 heteroatoms selected from S, N, and nonperoxidic O, and includes substituted aromatic compounds in which the substituents can be up to three groups selected from 30 lower alkyl and lower alkoxy groups;
"acryl", "acryloyl", "acryloyloxy", "acrylamido", and "acrylamidoacyl" are int~n~e~ to include also the corresponding "methacryl", "methacryloyl", "methacryloyloxy", "methacrylamido" and 35 "methacrylamidoacyl";
"disubstituted acetyl" means an acetyl group in which the carbon atom between the amide and carbonyl ~ woss/l~ss2 2 1 f 3 ~ 2 ~ PCT1594/l0620 groups is substituted by two alkyl groups or by one alkyl group and one aryl group;
"group" means a chemical species that allows for substitution or which may be substituted by 5 conventional substituents which do not interfere with the desired product, e.g., substituents can be alkoxy, phenyl, halo (F, Cl, Br, I), cyano, nitro, etc.
The novel ketones contain ethylenically unsaturated substituents such that they participate 10 directly in the polymerization reaction and their residues become incorporated into the polymer structure, which then retains the photoinitiating properties.
No art of which Applicants are aware disclose 15 acrylamidoacetyl functional photoinitiators, which in acrylic pressure-sensitive adhesive compositions have a higher rate of free radical propogation than that of the corresponding acryloyloxy functional photoinitiators.
DET~T~Rn DB~CRIPTION
The novel acrylamide functional disubstituted acetyl aryl ketones of the invention have the general formula IV

o pt2 o Il 1 11 Cl~2=C--C--NH--C--C--W~ IV
F21 ~3 25 wherein R1 is hydrogen or methyl;
R2 and R3 are independently an alkyl group of 1 to 14 carbon atoms, a cycloalkyl group of 3 to 14 carbon atoms, an aryl group of 5 to 12 ring atoms, an arenyl group having 6 to 16 carbon atoms and up to 3 heteroatoms selected from S, N, and nonperoxidic O, or R2 and R3 wosslloss2 - PCT~S94/10620 ~i ~3228 taken together with the carbon atom to which they are joined form a carbocyclic ring of 4 to 12 ring atoms;
W is -X- or a divalent connecting group joining the carbonyl group of the acrylamidoacetyl functional group to a photosensitive aryl ketone group, P; W is preferably selected from the class of connecting groups consisting of X- (CH2~ d X (C~H2 R4 n ~ R4 n in which n is a number having a value of one to four, R4 is hydrogen or methyl group, X is -O-, -S-, or -NH-, and Y is Q Q
O . S , NH- , lo--, OCNH
Q o ollo , o~ 0-- ;

P can be a radiation sensitive aryl ketone group capable of Norrish Type I cleavage. (Basic photochemistry of aryl ketones is discussed in a text by J. G. Calvert and J. N. Pitts, Jr., "Photochemistry", John Wiley & Sons, Inc., New York (1966) pp 377-38g.) Preferably P is selected from radiation sensitive groups having the formula:

WOgS/105S2 ~ 2 2 8 PCT~S94/10620 , ,, i,, 1 i i _ 9 in which Ar is an arylene group having 6 to 12 carbon atoms that can be substituted by a lower alkyl group having one to six carbon atoms, Ar preferably is selected from phenylene, naphthalenylene, and biphenylene; and R5 is selected from the group consisting of hydrogen, C1 to C12 alkyl groups, Cl to C12 alkoxy groups, and phenyl groups;
R6, R7, and R8 independently are selected from the group consisting of hydroxyl, C1 to C12 alkyl groups, C1 to C12 alkoxy groups, di(C1 to C12) amino groups, and aryl groups, provided that at least one of R6, R7 and R8 is selected from the group consisting of hydroxyl, C1 to C12 alkoxy groups, or C1 to C12 amino groups, or that any two of R6, R7, and R8 together can be an alkylene group, -(Cp H2p)-, or an alkylene-dioxy group, -O-(Cp H2p)-O-, in which p is an integer having a value of two or three, that together with the carbon atoms to which they are attached to form a 5- or 6-membered ring, or any two of R6, R7, and R8 taken together with the carbon atom to which they are attached can form a carbonyl o group, -C-, provided that the remaining R6, R7, or R8 is selected from the group consisting of hydroxyl, C1 to C12 alkoxy Wo95/10552 21 7 3 2 2 8 PCTMS94/10620 groups, Cl to Cl2 amino groups, and aryl groups.
Examples of acrylamido functional disubstituted acetyl aryl ketone photoinitiators of Formula IV
5 according to the invention include:

1.

CH2=CH--C NH C~--CH2cH2~o CH3 2.

CH~ C--NH ~--o--C~,C~,_o~(C~--~33 OH
3.

O C~3 C--~--OC2H5 ~3 CHb 217 3 2 2 8 ~ PCTIUS94110620 ~ WO 95/10552 CH2=CH--C--N~:~CH2CH2~ CccH--OH

5 6.

C~CH2CH~H

0 CH=CH--C NH--C--C--o~l CH3 WO 95/lOS52 ~:L73~2~
8. -- 12 --CH2=C,--C--NH--C--C--O CHzcHzo~ ~CHs CM, ~ M, -xa 10 .

CH=CH~--NH--~4--1--S (~.~2~ --~2~3 14H9 ~ 1H3 10 11.

CH9 CH3 ~c~cHc5H5 WO95/10552 ~ 7 3 ~ 2 8 PcT~ss4/l062n , . ;.. . . .

12.

CH2- - ~CH -~- NH - 1- C- O - CH2cH2 - o~ll IH3 13.

CH2~H~ NE~ O--CH2CH2--0~--C~ N~ ~O

The acrylamido functional disubstituted acetyl aryl ketone photoinitiators of the invention preferably are prepared by reaction of a hydroxy, thiol, or amine 10 functional aryl photoinitiator having the formula H-W-P, wherein W and P are as previously defined, with an equivalent amount of a 4,4-disubstituted alkenyl azlactone in accordance with the reaction scheme:

WO95/10552 PCT~S94/10620 21~3~28 ~R2 N~3 CHz=C~ 'H W P
Rl ~o Hydroxy I thiol, or anmine Alken~ ~o"e fu~n;tiGI~alary ketone (Formula V) (Formula Vl) R2 o CH2~--~ ~H--~W--P

Acrylamido fu, 1~ G~ ,al ~isubstitl ~te~
acety ary ketone photoin~tiator (Formula Vll) wherein R1, R2, R3, W, and P are the same as defined above.
One class of the acrylamide functional disubstituted acetyl aryl ketones is prepared by the reaction of an azlactone with a hydroxy, thiol or amine functional aryl ketone according to the reaction scheme:

WO95/10552 ~7 3 2 2 8 PCT~S94110620 CHz=C~ llW [~--R' alkenyl ~1~1~n~ hydra~y, thiol, or arnine A fl",clional a~3t~ rone (Fonnula \~J photoTn tiator (Forrnula Vlll) O ~2 11 ~ R~

wrylarnidoacyl fl,- dio~al acatoph~none photoTnitiator (Forrnula 1~

wherein R1, R2, R3, R5, R6, R7, R8, and W are the same as defined above.
The reaction of the alkenyl azlactone with the hydroxy, thiol, or amine functional aryl ketone is 5 preferably carried out in the presence of an effective amount of a catalyst selected from:
(a) bicyclic amidines such as, for example, 1,5-diazabicyclo[4.3.0~non-5-ene (DBN), 1,8-diazabicyclot5.4.0]undec-7-ene (DBU), and l~s~7-triazabicyclo[4.4.o]dec-5-ene (TBD).
Additional information relating to these compounds is given in U.S. Patent No.
4,874,822, and (b) compounds comprising trivalent phosphorous, such as trimethylphosphine, triethylphosphine, tributylphosphine, Wo95110552 PCT~S94/10620 ~ 3~28 trioctylphosphine, tris(dimethylamino)phosphine, dimethylphenylphosphine, diphenylmethyl-phosphine, 1,2-bis(di-n-propyl-phosphino)ethane, 1,3-bis(diphenylphosphino)propane, diethylmethoxyphosphine, and triphenylphosphine.
The amount of the initiator utilized in the 10 instant process may vary from about 0.05 mole percent (based on alkenyl azlactone) to about 10 mole percent or more. In most cases, however, 0.5 to 5 mole percent are sufficient to provide a reasonable reaction rate.
Alkenyl azlactones of Formula V of use in the 15 preparation of the photoinitiators of the invention are well known in the art, and include: 4,4-dimethyl-2-ethenyl-2-oxazolin-5-one (also known as 2-vinyl-4,4-dimethylazlactone), 4,4-dimethyl-2-isopropenyl-2-oxazolin-5-one, 2-ethenyl-4-methyl-4-phenyl-2-oxazolin-20 5-one, 2-ethenyl-4,4-pentamethylene-2-oxazolin-5-one, 4,4-diphenyl-2-isopropenyl-2-oxazolin-5-one, and 2-ethenyl-4-ethyl-4-methyl-2-oxazolin-5-one. Others are disclosed in assignee's U.S. Patent No. 4,777,276, and in U.S. Patent No. 4,304,705.
The hydroxy, thiol, and amine functional aryl ketones of Formula VI from which the acrylamidoacetyl functional ketones of the invention can be prepared by methods known to those in the art such as are described in Krepski, et al., Tetrahedron Letters 24,(38) pp 30 4075-4078 (1983). Some of the aryl photoinitiators of Formula VI are available commercially, such as 2-hydroxy-l-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (available as Irgacure~ 2959 from Ciba-Geigy, Chicago, IL).
The preferred conditions for carrying out the process of the invention are to mix the reactants and catalyst in the absence of solvent and to allow the Wo95/10552 ~ 7 3 2~ 8 PCT~S94/10620 reaction to proceed at room temperature (about 22C).
These conditions, howev~x, may be modified in certain instances as is clear to one skilled in the art. For example, reaction temperatures below (in the case of 5 exothermic reactions) or above room temperature (for very slow reactions or in the~case of solid reactants) may be advantageous. In general, reaction temperatures from about 0C to about 100C or so may be utilized to carry out the process of the instant invention. Also, 10 in certain cases nonreactive solvents or diluents may be utilized to facilitate or mediate the reaction. By "nonreactive" is meant that the solvents do not contain functional groups which can react with either the azlactone, the hydroxy, thiol, or amine functional 15 molecule, or the catalyst under the conditions utilized. Suitable nonreactive organic solvents include, for example, ethyl acetate, toluene, xylene, acetone, methyl ethyl ketone, acetonitrile, tetrahydrofuran, hexane, heptane, dimethylformamide, 20 dimethylacetamide, and the like, or combinations thereof. In many instances, it may also be advantageous to add an effective amount of an antioxidant or free radical inhibitor (e.g. 0.00005 to 5.0 weight percent based on the combined weight of 25 azlactone and hydroxy, thiol, or amine functional photoinitiator) such as a hindered phenol, to the reaction mixture or the final acrylamide functional product.
While in most instances it may be preferable to 30 carry out the process of the invention so as to have a 1:1 stoichiometric balance of alkenyl azlactone to hydroxy, thiol, or amine functional groups, thus converting all of these groups into acrylamide groups, it is also considered to be within the scope of the 35 invention to utilize more or less (e.g. from 50 to 150 mole %) than an equivalent amount of azlactone based upon the hydroxy, thiol, or amine equivalent weight.

WO95/10552 PCT~S9411062Q
~ 7 322~ 18 -As should be obvious to one skilled in the art, the reaction time required to convert the hydroxy, thiol, or amine functional compounds of Formula VI to the acrylamido functional disubstituted acetyl aryl 5 ketones of Formula IV will vary widely. Reaction times will depend upon several factors, including the nature of the functional group of Formula VI, the substituents of the azlactone, the type of catalyst used, the amount of catalyst, the concentration of reactants and the lO temperature of the reaction. ~10~r ess of the reaction of the alkenyl azlactone with the hydroxy, thiol or amine functional molecule is readily monitored by infrared spectroscopy by following the disappearance of the azlactone carbonyl stretching absorption near 1800 15 cm~l (about 5.5 micrometers). The absence of competing side reactions and estimation of acrylamide equivalent weights may be determined conveniently by lH-NMR
analysis.
The photopolymerizable compositions of the 20 invention comprise one or more photopolymerizable ethylenically unsaturated monomers and the acrylamido functional disubstituted acetyl aryl ~etone photoinitiators. The compositions are useful for the preparation of films and coatings for use on various 25 substrates including paper, plastics, wood, metal, glass and ceramics. Suitable photopolymerizable monomers for use in the compositions are selected from any of the free radically polymerizable ethylenically-unsaturated monomers, examples of which include one or 30 more of the vinyl aromatic monomers such as styrene, ~-methylstyrene, 2- and 4-vinyl pyridine, and the like;
a,~-unsaturated carboxylic acids and their derivatives such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, methyl 35 methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, ethyl acrylate, butyl acrylate, iso-octyl acrylate, octadecyl acrylate, cyclohexyl acrylate, WO9S/I~552 2 ~ 73 2 2 8 ~CT~594/ln~o tetrahydrofurfuryl methacrylate, phenyl acrylate, phenethyl acrylate, benzyl methacrylate, ~-cyanoethyl acrylate, maleic anhydride, diethyl itaconate, acrylamide, methacrylonitrile, N-butylacrylamide, and 5 the like; vinyl esters of carboxylic acids such as vinyl acetate, vinyl 2-ethylhexanoate, and the like;
vinyl halides such as vinyl chloride, vinylidene chloride, and the like; vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl 10 ether, and the like; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcarbazole, and the like; vinyl ketones such as methyl vinyl ketone and the like; and vinyl aldehydes such as acrolein, methacrolein, and the like; hydroxy functional vinyl mononers such as 2-15 hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl maleimide, 4-hydroxybutyl vinyl ether, glycerol monoacrylate or methacrylate, and diethyleneglycol monomethacrylate.
Polyunsaturated monomers can also be used to 20 provide additional cohesive strength, if desired, in the acrylamide functional disubstituted acetyl aryl photoinitiator-containing compositions of the invention such as polyfunctional acrylates, for example, ethylene glycol diacrylàte, 1,6-hexanediol diacrylate, 25 propoxylated bisphenol A diacrylate and dimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. Also useful in the compositions are unsaturated oligomers and polymers including, for example, acrylated polyesters, polyethers, and silicone 30 polymers. A preferred polyunsaturated monomer is hexanediol diacrylate. Copolymerizable polyunsaturated monomers can be present in the polymerizable composition in the range of 0 to 5.0 pbw (parts by weight), preferably 0.01 to 5.0 pbw, more preferably 35 0.01 to 2.0 pbw, and most preferably 0.01 to 0.5 pbw.
In preferred crosslinkable compositions of the invention, the use of as little as 0.05 part by weight WO95/10552 ~ 7 ~ ~ 2 ~ PCT~S94/10620 of polyunsaturated monomer will reduce the amount of acrylamide functional disubstituted acetyl aryl photoinitiator required to obtain high shear values to no more than about 0.05 part by weight.
The photopolymerizable compositions of the invention can be stabilized by adding known thermal inhibitors and antioxidants, such as, for example, hydroquinone or hydroquinone derivatives, pyrogallol, thiophenols, nitro compounds, or ~-napthols, in the 10 customary amounts without significantly impairing the initiating action of the photoinitiators according to the invention. The main purpose of such additions is to prevent premature polymerization during the preparation of the systems.
Depending on its intended use, the composition of the invention can contain, for example, plasticizers, viscosifiers, flatting agents, bacteriocides, fillers, lubricants, surfactants, pigments, dyes, and other agents. The amounts of these materials used is 20 selected to provide the characteristics desired in the final cured composition. The amounts to be added vary with the intended use.
The acrylamide functional disubstituted acetyl aryl ketone photoinitiator and ethylenically-25 unsaturated monomers of the invention can behomopolymerized or they can be copolymerized to linear products that can be crosslinked by exposure to actinic radiation. By the term "actinic radiation" is meant radiation having wavelengths in the 200 to 600 nm 30 range, preferably 280 to 450 nm, and more preferably 300-450 nm. Suitable sources include sunlight, carbon arcs, mercury vapor arcs, black light la~ps, fluorescent lamps, argon and xenon glow lamps, electronic flash units and flood lamps. Particularly 35 useful intensities include those in the range of 0.1 to 150 mW/cm2, preferably in the range of 0.5 to 100 mW/cm2 and more preferably in the range of 0.5 to 50 mW/cm2.

~3~2~
o95/10552 - PCT~S94110620 Depending on the concentration of photoinitiator, the particular acrylamide functional disubstituted acetyl aryl ketone photoinitiator and the depth of the composition, exposures necessary to polymerize (which 5 term includes polymerize and crosslink) the composition range from about l second or less to about lO minutes or longer.
In a first process, ethylenically unsaturated monomers and the novel photoinitiator(s) of the lO invention and preferably a conventional photoinitiator (such as those disclosed in the Background of the Invention, preferably Irgacure 2959 (Ciba-Geigy)) can be partially polymerized to provide a syrup having a coatable viscosity. Such a syrup comprises a linear 15 polymer having pendent photoinitiator groups. This can be accomplished by thermal teçhn; ques leading to linear polymer or by exposure to actinic radiation leading to branched polymer.
Such polymers can be used as polymeric 20 photoinitiators and can have the general formula:

Rl Rl (~H2C~)a (CH2pb R9 C- O R2 o X
H N I--C--W P

in which Rl, R2, R3, W, and P are the same as defined above; R9 is one or more organic groups as determined by the identity of the ethylenically-unsaturated 25 monomers in the polymerizable composition, preferably R9 is selected from alkoxy groups and alkoxy carbonyl .

WO95/10552 ~17 3 ~ 28 pcT~ss4llo62n groups having l to 20 carbon atoms, aryl, and arenyl groups (where these groups are as previously defined), and a and b are each numbers having a value sufficient to provide to the linear polymer a number average 5 molecular weight of from about lO00 to 5,000,000, the mole ratio, b/(a+b), having a value from about O.OOOl to 0.5.
In a second process, it is possible to polymerize the monomer composition containing an ethylenically lO unsaturated monomer and the novel photoinitiator of the invention to a linear polymer having pendent photoinitiator groups. This can be accomplished by including in the composition a conventional source of free radicals that contains no copolymerizable group 15 and is activated by heat or actinic radiation of a wavelength different from that of the acrylamide functional disubstituted acetyl aryl ketone photoinitiator.
A third process for the preparation of the 20 polymeric photoinitiator of formula X comprises the steps of polymerizing an alkenyl azlactone of formula V
with a copolymerizable ethylenically unsaturated monomer, and reacting the resulting copolymer with a hydroxy, thiol, or amino group-substituted 25 photoinitiator of formula VI to provide the polymeric photoinitiator of formula X.
Such a polymer of formula X cont~; n; ng pendent photoinitiator groups, preferably having a Tg in the range of -70 to 150C, can be added either to an 30 acrylic syrup (partially polymerized material prepared from one or more acrylic monomers) or to at least one ethylenically unsaturated monomer to provide a composition polymerizable to a crosslinkable pressure-sensitive adhesive having desirable high performance 35 properties.
The preferred photocrosslinkable composition of the invention comprises per lO0 parts by weight (pbw):

WO95/10552 ~ 7 3 2 2 8 PCT~Sg4/10620 (l) 60 to 99.95 pbw of one or more acrylic acid esters of monohydric aliphatic alcohols having an average of 4 to 12 carbon atoms;
(2) 0 to 39.95 pbw of ethylenically-unsaturated 5 monomers whose homopolymer has a glass transition temperature (Tg) greater than 50C, and (3) O.Ol to lO.0 pbw of acrylamide functional disubstituted acetyl aryl ketone photoinitiator, (4) 0 to 5.0 pbw of a polyfunctional acrylate, and (5) 0 to 5.0 pbw of a thermal or actinic radiation activated source of free radicals, the source being unsubstituted by ethylenic unsaturation.
A pressure-sensitive adhesive (PSA) is generally a component of a pressure-sensitive tape which in its 15 most simple configuration is comprised of the adhesive and a backing, and the overall construction is tacky and adherent at the use temperature (typically room temperature) and adheres to a variety of substrates using only moderate (typically fingertip) pressure to 20 form the bond. In this fashion, pressure-sensitive tapes constitute a complete, self-contained bonding system.
In the present invention, normally tacky and pressure-sensitive adhesive tapes represent a very 25 versatile family of products, performing such diverse functions as insulating, mounting, sealing, mending, holding, mask; ng, labeling, binding, joining, laminating, protecting, and reinforcing. The tapes can be single or double coated (i.e., PSA on both surfaces 30 of a substrate) and can be applied to a substrate.
When coated on a flexible backing, the photocrosslinkable or photocrosslinked compositions can provide pressure-sensitive adhesive tapes having desirable hydrolytic stability. A layer of a 35 conventional release material can be included in the tape construction which can then be provided as a roll of pressure-sensitive adhesive tape. In addition, a Wo95/1OS52 2 ~ 7 3 2 2 g PcT~sg4/l062n - 2~ -pressure-sensitive adhesive of the invention can be included between two substrates to provide a laminated construction. At least one of the substrates can be nonadhering or can be releasing to the PSA.

TEST Mh~nO~
The following tests may be used to evaluate the adhesive tapes of the invention.

Static Shear Value The adhesive films as described in the examples were cut into strips 1.27 cm in width and adhered by its adhesive to a flat, rigid stainless steel plate with exactly 1.27 cm length of tape in contact with the 15 plate. Before testing, a 1000 g weight at 25 C was placed over the bonded area for 15 minutes. Then the plate with the adhered tape was placed either at room temperature (RT) or in an air-circulating oven which had been preheated to 70C, and after 15 minutes a 20 500 g or 1000 g weight was hung from the free end of the tape, with the panel tilted 2 from the vertical to insure against any peeling forces. The time (in minutes) at which the weight fell was the "Static Shear RT (1000 g) or 700C (500 g)". The test was 25 discontinued at 10,000 minutes if there was no failure.
In the Tables, this was designated as 10,000+ minutes.

Peel Adhesion Peel adhesion was measured as in ASTM D-3330-78 30 except that the test tapes were 1.27 cm in width and were tested immediately after being adhered to a glass or stainless steel surface. Results were reported in Newtons per/decimeter (N/dm).

woss/10s52 ~ 17 3 2 2 8 PCT~S94ll0620 Percent Gel Test [ASTM D-3616-82]
The gel test was performed as described in U.S.
Patent No. 5,112,882, col. 10, line 18 to col. 11, line 2.

The objects and advantages of the invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and 10 details, should not be construed to unduly limit this invention. Unless stated otherwise, all parts are parts by weight and all temperatures are degree centigrade.

ExamPle 1. Preparation of the acrylamidoacetyl photoinitiator:

O CH9¦0~ C~H

Compound No. 1 Into a 200 ml round bottom flask fitted with a magnetic stirrer were placed 22.4 g (0.1 mole) of HO--(CH2CH2)--~ CH9 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone -WO9S/10552 ~1 7 3 2 2 g PCT~S94/10620 (available as Irgacure~ 2959 from Ciba-Geigy), 14.2 g (0.102 mole) of 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDM) (available from SNPE Inc., Princeton, NJ 08540), and 50 ml of amyl acetate. While stirring the mixture, 5 0.76 g of 1,8-diazabicyclo~5.4.0]undec-7-ene (DBU) (available from Aldrich Chemical Co., Milwaukee, WI) was added. Heat was evolved as the reaction components went into solution, and after complete solution was obtained, stirring was discontinued. The mixture was 10 allowed to cool to room temperature and the solid that had formed was collected by filtration. After drying the recovered solid in a vacuum oven at about 40 C, there was obtained 32.6 g of reaction product (89.8 %
of theory). The material had a melting point of 84.5-15 85.5C (uncorrected). Elemental Analysis, InfraredSpectral Analysis, and 1H and 13C Nuc`aar Magnetic Resonance confirmed that the material was the title compound.

20 Example 2. Preparation of the methacrylamidoacetyl photoinitiator H2C = C--C--NH--~ C-- O--CH2GH2_ ~ 1l--~-- OH

Compound No. 2 The procedure of example 1 was utilized except that 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one (IDM;
prepared as described by Taylor, et al., J. Polym. Sci.
Polym. Lett. Ed., 1971, 9, 187) was utilized instead of ~ wos~/10552 ~ 7 ~ 2 ~;8 pcT~s94llo62n VDM. The reaction was run on a 0.5 mole scale. After drying in a vacuum oven at about 40C there was obtained 141.6 g of reaction product (75% of theory).
The material had a melting point of 69-71C
(uncorrected)n 1H and 13C Nuclear Magnetic Resonance confirmed that the material was the title compound.

Example 3. Preparation of the acrylamidoacetyl photoinitiator:

CH2==CH ~ - NH ~C ~ -CH2cH2-~o ~ CH3 Compound No. 3 Step l. Preparation of 2-ethenyl-4,4-pentamethylene-2-oxazolin-5-one Into a 500 ml round bottom flask equipped with a 15 reflux condenser and a magnetic stirrer were placed 9.15 g (0.05 mole) 1-acrylamidocyclopentane carboxylic acid (prepared by the method described by Heilmann et al., SYnthetic Communications 17(7), 843-862(1987), 10.32 g (0.05 mole) of the dehydrating agent, N,N'-20 dicyclohexylcarbodiimide (available from Aldrich Chemical Co.) and 150 ml methylene chloride and the mixture was stirred for 18 hours. The resulting slurry was filtered to remove N,N'-dicyclohexylurea formed during the reaction, and the methylene chloride was 25 removed under reduced pressure at room temperature.
The azlactone obtained was used in Step 2 without further purification.

WO95/10552 2 1 7 3 2 2 g PCT~S94110620 Step 2. Condensation of Product from Step 1 and Irgacure~ 2959 The procedure of Example 1 was repeated using a) the a ~ctone of Step 1, b) 11.2g 0.05 mcl~ Irgacure~ 2959, c) 40 ml amyl ac-.;.. .:e, and d) 5 drops of DBU
There was obtained 17.5 g (90.0 % of theory) of the acrylamidoacetyl photoinitiator of the title. It 10 had an uncorrected ~elting point of 119-121C.
Infrared, Elementa. and 1H and 13C Nuclear Magnetic Resonance (NMR) s~ ral anr ies confirmed that the material was the t ~ mater , Compound No. 3.

15 Com~arative ExamPle 1.
Preparation of:

CH2=~CH----C--NH-~CH2 ~ -~ CH2cH2-~D ~ O CH3 Comparative Compound A

Into a 500 ml flask fitted with a magnetic stirrer 20 and reflux condenser were placed 6.46g (0.05 mole) N-acryloylglycine (prepared according to the procedure of Kulkarni and Morawetz, J. Polymer Sci., S4, 491 (1961)), 10.75 g (0.048 mole) Irgacure 2959, 9.90 g (0.048 mole) N,N-dicyclohexylcarbodiimide, 150 ml 25 methylene chloride, and 0.57 g (0.005 mole) trifluoroacetic acid. The mixture was stirred at room temperature (about ~2C) for 75 hours. The solid that had collected was removed by filtration and the filtrate was concentrated under reduced pressure to an WO9S/lOSS2 ~ 7 3 ~ 2 8 PCT~S94/10620 ,, ; ~.

oil. After st~n~ing at room temperature for 7 days the oil solidified. The solid was recrystallized from ethyl acetate and dried in a vacuum oven at 60C.
There was obtained 9.0 g (56.0 % of theory based on 5 Irgacure 2959) showing an uncorrected melting point of 93-94C. After a sample of this material was recrystallized from ethyl acetate/pentane, its uncorrected melting point was 94.5 - 95.5C.
Elemental analysis, lH and 13C NMR spectra confirmed 10 that the material was that of the title compound.

~xam~le 4: Preparation of isooctyl acrylate/acrylic acid, and acrylamidoacetyl photoinitiator (Compound 1) terpolymer (Polymer I):
Nine grams of (90/10 parts by weight) of isooctyl acrylate and acrylic acid, 1 gram of Compound 1, 100 grams of ethyl acetate, 0.1 gram of carbon tetrabromide (a chain transfer agent) an~ 0.1 gram of benzoyl peroxide were charged into a bottle. The bottle was 20 purged with nitrogen for 10 minutes. The bottle was capped, placed in a water bath at 600C and agitated for approximately 20-24 hours. The viscosity of the solution increased and the infrared spectrum of the polymer showed the disappearance of the vinyl monomer.
25 The solvent was removed on a rotary evaporator. The mixture was precipitated in methanol and dried under vacuum to constant weight.

~x~mple 5: Preparation of isobornyl acrylate/acrylic 30 acid and acryamidoacetyl photoinitiator (Compound 1) terpolymer (Polymer II) Nine grams of (90/10 parts by weight) of isobornyl acrylate and acrylic acid, 1 gram of Compound 1, 100 grams of ethyl acetate, 0.1 part of carbon tetrabromide (a chain transfer agent) and 0.1 gram of benzoyl peroxide were charged into a bottle. The bottle was purged with nitrogen for 10 minutes, capped, placed in WO95/10552 217 3 2 2 ~ PCT~S94/1062~ -a water bath at 60C and agitated for approximately 20-24 hours. The viscosity of the solution increased and the infrared spectrum of the polymer showed the disappearance of the vinyl monomer. The solvent was 5 removed on a rotary evaporator. The mixture was precipitated in methanol and dried under vacuum to constant weight.

Example 6. Preparation of copolymer of isooctyl 10 acrylate-acrylamido functional initiator (Polymer III) 92.5 g of isooctyl acrylate and 7.5 g of vinyldimethylazlactone, 100 g of ethyl acetate, o.l g of carbon tetrabromide (a chain transfer agent) and 0.1 g of benzoyl peroxide were charged to a bottle. The 15 bottle was purged with nitrogen for 10 minutes. The bottle was capped, placed in a water bath at 60C and agitated for approximately 20-24 hours. The viscosity of the solution increased and the infrared spectrum of the polymer showed the disappearance of the carbon-20 carbon double bonds. The reaction bottle was chargedwith 11.97 grams of Irgacure~ 2959 and 0.7 g of 1,8-diazabicyclo~5.4.0]undec-7-ene. The reaction mixture was heated at 60C under nitrogen. The progress of the reaction was followed by infrared spectroscopy. At the 25 end of the reaction, the solvent was removed on a rotary evaporator. The mixture was stirred in methanol and the precipitated polymer having pendent photoinitiator groups was dried under vacuum to constant weight.
ple 7. Preparation of isobornyl acrylate-acrylamido functional initiator (Polymer IV) 92.5 g of isobornyl acrylate and 7.5 g of vinyldimethylazlactone, 100 g of ethyl acetate, 0.1 g 35 of carbon tetrabromide (a chain transfer agent) and 0.1 g of benzoyl peroxide were charged to a bottle.
The bottle was purged with nitrogen for 10 minutes.

~ WO95/1055~ ~ ~ 7 3 2 2 8 . ~ PCT~S94/10620 The bottle was capped, placed in a water bath at 60C
and agitated for approximately 20-24 hours. The viscosity of the solution increased and the infrared spectrum of the polymer showed the disappearance of the 5 carbon-carbon double bonds. The reaction bottle was charged with 11.97 grams of Irgacure~ 2959 and 0.7 g of 1,8-diazabicyclo~5.4.0]undec-7-ene. The reaction mixture was heated at 60C under nitrogen. the progress of the reaction was followed by infrared 10 spectroscopy. At the end of the reaction, the solvent was removed on a rotary evaporator. The mixture was stirred in methanol and the precipitated polymer having pendent photoinitiator groups was dried under vacuum to constant weight.
Example 8. Preparation of pressure-sensitive adhesives A monomer mixture was prepared to contain:
90 pbw isooctyl acrylate (IOA) 10 pbw acrylic acid (AA) 0.04 pbw 2,2-dimethoxy-2-phenylacetophenone (KB-1~) (available from Sartomer) To portions of the monomer mixture was added 0.3 to 1.0~ by weight of Compound No. 1, dimethyl substituted acrylamidoacetyl functional photoinitiator 25 of Example 1 or 0.3 to 0.7% by weight of Comparative Compound A, the dihydroacrylamidoacyl functional photoinitiator of the Comparative Example. Each portion was partially (5 to 10~) photopolymerized in bulk in an inert (nitrogen) atmosphere using a bank of 30 40-watt fluorescent blacklights to provide coatable syrups of a viscosity (Brookfield) of about 1500 cps.
Each coating syrup was knife-coated onto 40 ~m poly(ethylene terephthalate)film (PET) at a thickness of 40~m. The coating was exposed to a bank of 35 blacklight bulbs (about 300-400 nm). The coating was exposed to an intensity of about 2.2 mW/cm2 for about 2.0 minutes. Each coating received an irradiated dose W095/10552 ~ 7 3 2 2 8 PCT~S94/10620 of about 250 mJ/cm2. Properties of the various pressure-sensitive tapes are recorded in Table I.

TABLE I

Peel Pho~o- adhesion( a) Shearb holding initiator Wt% N/dm 25C( ) min.
Compound No. 1 0.3 80 5gg7 0.7 66 6876 1.0 66 10,000+

Comparative A 0.3 67 384 0.4 66 2509 0.7 66 4303 (a) Peel adhesion was measured from glass at 180C
also using a 230 cm/minute peeling rate.
(b) Shear holding values were determined employing (1/2" x 1/2") 1.27 cm x 1.27 cm areas of adhesive adhered to stainless steel plates and a suspending load of lOOOg at 25C.
It can be seen from the data in Table I that pressure-sensitive adhesives prepared using the photoinitiator of the invention, Compound No. 1, have peel adhesions in the same range as the peel adhesions 30 of the adhesives prepared with dihydroacrylamidoacetyl photoinitiator, Comparative Compound A, and that the shear holding strengths of adhesives prepared using Compound No. 1 are greater than lO,OoO minutes at 25C
while the shear holding strengths of adhesives prepared 35 using Comparative Compound A are less than 4500 minutes at 25.

WO95/10552 2 ~ 7 3 2 2 8 PCT~S94/10620 ~m~le 9: A series of pressure-sensitive adhesive tapes were made by first partially polymerizing a mixture of, by weight, 90 pbw of isooctyl acrylate lO pbw of acrylic acid l.30 pbw of Compound No. l.
The partial photopolymerization was accomplished in an inert (nitrogen) atmosphere using a bank of 40-watt fluorescent blacklights to provide a coatable lO syrup. The mixture was knife coated onto 40 ~m poly(ethylene terephthalate) (PET) film to different thicknesses. The coating was exposed to a bank of blacklight bulbs. The coating was subjected to different irradiated doses. The reaction conditions 15 and properties of various pressure-sensitive tapes are recorded in Table II.

~7322~

a~ a o E~ Ul ~ U
o H ~ N ~ ~ ~ ~ ~ ~ N

U .~,~ , U~
a_ ~ ~ ~
''-- t~ _I ~ ~o ~ _I ~ ~ O
_ ~ o ~ o ~ o _~ o +++++++++ u~
~^ooooooo~o ~r ~ o o o o o o o . o a ~ o o o o o o o o o .~
H 'C El o O O C; ~ 3 .
o O ~ O o O

X Uu~ ~ ~ O t~ o~ t~ o co a~
O .
I
x 1:'3 k .C
~ a Ox ~ ~

.O ......... ~x,c) VJ ;C

~; ~, H
a ~ _ _ U. ~i ~a Q
1~ o Ir~ o ~1 ~1 C~

~ W095/lOS~2 2 i ~ 3 2 2 8 PCT~S94110620 The data in Table II show that increase in thickness of the adhesives gave increased peel adhesions. All adhesives of Table II gave 10,000+ shear values independent of oxygen concentration.
ExamPle 10: Pressure-sensitive adhesive prepared using both the photoinitiator of the invention and a polyfunctional acrylate.
A monomer mixture was prepared to contain 90 pbw isooctyl acrylate (IOA) 10 pbw acrylic acid (AA) 0.04 pbw KB-1.
To portions of the monomer mixture, as shown in Table III, was added O to 0.5 pbw of Compound No. 1. Each 15 portion was partially polymerized to a coating syrup as described in Example 8. To each syrup 0.16 pbw KB-1 and O
to 0.3 pbw of hexanediol diacrylate (HDDA) were added, as shown in Table III and each syrup was coated and cured by irradiation as follows:
All of the PSAs were cured on solvent free silicone paper release liner in a nitrogen-rich environment (250 ppm oxygen). 125 ~m thick (5 mil) PSAs were cured with ultraviolet irradiation using 355 mJ/cm2 of energy applied over 150 sec. Three average intensities for all samples 25 of Table III were utilized (in order given): 1.0 mW/cm2 for 50 sec., 2.1 mW/cm2 for 95 sec., and 36 mW/cm2 for 5 sec. Peel strength values were determined from stainless steel after it had been washed once with acetone and three times with a 50/50 isopropanol/water mixture. All peel 30 strengths were determined using a sOo peel mode at 30.5 cm/minute. 1.27 cm wide samples with 125 ~m thick (5 mil) anodized aluminum backings were used for all of the testing. The static shear strength values were measured from stainless steel substrates cleaned once with acetone 35 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 temperature and a 500 g load was used at WO95/10552 ~ 2 28 PcT~sg4/ln620 ~

70C. The time to bond failure was recorded. 125 ~m thick (5 mil) anodized aluminum backings were used for all of the static shear samples. The percent volatiles were gravimetrically determined after drying for three hours at 5 120C.

WO 95/10552 ~ 17 3 2 2 ~ PCTrUS94110620 ; r Table I-I
Compd. 70 72 hr.
Sample No. 1 HDDA R. T . Shear Peel Volatile~
No. phr phr Shear min min N/dm %
1 0.1 0 10,000+ 712 149 0.88 2 0.2 0 10,000+ 10,000+ 187 0.84 3 0.3 0 10,000+ 10,000+ 175 0.80 4 0.5 0 10,000+ 10,000+ 152 0.69 0.8 0 10,000+ 10,000+ 152 0.80 6 1.1 0 5,329 10,000+ 181 0.83 7 0 0.02 10,000+ 1,444 167 0.84 8 0 0.05 7,676 97 168 0.85 9 0 0.10 10,000+ 126 169 0.83 0 0.15 10,000+ 432 171 0.97 11 0 0.20 10,000+ 156 184 0.95 12 0 0.25 10,000+ 353 169 0.93 13 0 0.30 10,000+ 765 160 0.86 14 0.01 0.02 8986 40 189 1.17 0.01 0.05 10,000+ 144 206 1.15 16 0.01 0.10 10,000+ 107 183 1.14 17 0.05 0.02 10,000+ 380 167 1.08 18 0.05 0.05 10,000+ 10,000+ 194 1.13 19 0.05 0.10 10,000+ 10,000+ 199 1.04 0.10 0.02 10,000+ 10,000+ 200 0.87 21 0.10 0.05 10,000+ 10,000+ 159 0.88 22 0.10 0.10 10,000+ 10,000+ 166 0.74 23 0.20 0.02 10,000+ 10,000+ 210 0.79 24 0.20 0.05 10,000+ 10,000+ lS2 0.75 2S 0.20 0.10 10,000+ 10,000+ 160 0.76 26 O.S0 0.02 10,000+ 10,000+ 161 0.71 27 O.S0 O.OS 10,000+ 10,000+ 178 0.74 28 0.50 0.10 10,000+ 10,000+ 148 0.77 The data of Table III show that compositions cont~;n;ng 0.02 to 0.30 HDDA (Samples 7-13) and no Compound No. 1 did not provide adhesives having 70 shear values above 1,444 minutes. The data of Table III do show WO9S/10552 PCT~S94/10620 ~73228 that without HDDA, pressure-sensitive adhesives having 70 shear values of lO,oOo minutes or more were not obtained with compositions containing 0.1 pbw or less of Compound No. 1 (Sample 1), however, with as little as 0.05 pbw of 5 HDDA, compositions cont~;n; ng only 0.05 pbw of Compound No. 1 (Sample 18) gave an adhesive that had a 70O shear value of greater than 10,000 minutes. The adhesive of Sample 18 also had an excellent 72 hour peel value.
10 Example 11: A series of pressure-sensitive adhesive tapes were made by first partially polymerizing (according to the method of Example 8) a mixture of, by weight, 90 pbw of isooctyl acrylate 10 pbw of acrylic acid 0.04 pbw of 2,2-dimethoxy-2-phenylacetophenone (KB-l) (available from Sartomer) into a syrup.
Five grams of polymeric photoinitiator (Polymer I of Example 4 or Polymer II of Example 5) were added to each syrup and thoroughly mixed. The mixture was knife coated 20 onto 40 ~m poly(ethylene terephthalate) (PET) film at a thickness of 50 ~m. The coating was exposed to a bank of blacklight bulbs. Each coating received an irradiated dose of 250 mJ/cm2, 2.4 mW/cm2 for 104 seconds at an oxygen level of 193 ppm. The properties of various 25 pressure-sensitive tapes are recorded in Table IV. Peel adhesion and shear holding values were measured as described in Example 8.

Table IV
Peel Polymeric adhesion Shear holding photoinitiator Wt% N/dm 25C 70C
Polymer I 5 68 10,000+ 4890 Polymer II 5 58 10,000+ 6810 WO95/10552 2 ~ ~ ~ 2 2 8 PCT~S94/10620 The data of Table IV show that the addition of polymeric photoinitiators to partially polymerized acrylic syrups, followed by photochemically curing, provided pressure-sensitive adhesives having high performance properties.

Example 12: Preparation of pressure-sensitive adhesives A series of pressure-sensitive adhesive tapes was made by partially photopolymerizing a mixture of:
90 pbw isooctyl acrylate (IOA) 10 pbw acrylic acid (AA) 0.04 pbw 2,2-dimethoxy-2-phenylacetophenone The partial photopolymerization was accomplished in an inert (nitrogen) atmosphere using a bank of 40-watt fluorescent black lights to provide a coatable syrup of a 15 viscosity of about 1500 cps. A polymeric photoinitiator (polymer III of Example 6 or polymer IV of Example 7) was added to each syrup. Each mixture was coated at a thickness of 50 ~m using a conventional knife coater onto biaxially-oriented polyethylene terephthalate film. The 20 coated film was cured using the procedure of Example 11.

Table V
Oxygen Parts in the Peel by chamber adhesion Shear values Polymer wt (g) (ppm) N/dm (min) 35 Each of the tapes had a peel adhesion in the range of 68 to 74 N/dm (measured from glass at 180) and a peeling WO95/10552 PCT~S~/1062~

rate of 230 cm/min) and a 25C shear value of up to 8426 minutes.

~mple 13:
This example teaches the use of a methacrylamidoacetyl photoinitiator (Compound No. 2 of Example 2) in combination with a conventional photoinitiator (KB-l) and with a diacrylate additive (HDDA). Each of the following trials was prepared using 10 partially polymerized syrups described in Example 10;
additional KB-1 photoinitiator (0.12 wt. %) was then dissolved in each syrup. Coating and polymerizations to high conversions, i.e., greater than 98%, were also conducted as described in Example 10, and two irradiation 15 conditions were utilized- Blacklight alone (in Trials 1-3; 250 mJ/cm2 using an -~ensity of 2.4 mW/cm2 for 147 seconds at an oxygen lev~ of 200 ppm) and Blacklight followed by exposure t~ ~ medium pressure mercury lamp (in Trials 4-6; 70 mJ/cm2 u ~g an intensity of 16.9 mW/cm2 20 for 8 seconds). The shear holding data recorded in Table VI below was obtained using 2.54 cm x 1.27 cm (1.0" x 0.5") adhesive areas and a 500 gram load at 70C.; the values serve as a means of differentiating the effectiveness of Compound 2 in the presence and absence of 25 diacrylate additives.

WO 95/10552 ~ ~ 7 ~ 2 2 8 PCTrUS94110620 Table VI

Rl ' li~ ' R~ lig~t + Mercury Lamp Alone C . ' Shear T~ne Shear Times Peel A&esion T~ No. No. 2 FDDDA (n~nu~) (n~nu~ /dm) 1 0.40 142 10,000+ 158 2 0.80 -- 7584 10,000.+ 144 3 1.20 -- 10,000+ 51 p.o.* 139 1 0 4 0.05 0.10 17 434 157 0.10 0.10 27 10,000+ 148 6 0.20 0.10 ~3 10,000+ 157 15 * p.o. = pop-off failure The data of trials 1-3 show that a concentration of about 1.20% Compound No. 2 is required for high 20 performance shear holding capability, while the data of trials 4-6 show that the conc~tration of Compound No. 2 can be substantially reduced, i.e., to as little as 0.10%, when HDDA and post-Blacklight exposure to high intensity are utilized.
Exam~le 14:
This example teaches that a high performance pressure sensitive adhesive with low percentage volatiles can result from use of Compound No. 2 of Example 2 and high 30 intensity exposure only.
The following trials were conducted by adding 1.3 weight percent of Compound No. 2 to the monomer solution of Example 8 and exposing the solutions to Blacklight until a coatable viscosity was achieved. Resulting syrups 35 were knife-coated onto polyester, and the coated syrups were covered with a polyester cover sheet (50 micrometers in thickness) prior to exposure to the high intensity light from a medium pressure Hg lamp.

WO95/10552 pcT~ss4lln62o ~73228 Table vm To~ Shear Peel E~s~le % Time Adhesion I(.) Time 5Tn~(ni~ Vola~les (;n~es) ~/dm) m W/cm2 sec.
1 408 11.6 -- -- 16.9 24 2 816 1.2 10,000+ 108 . 16.9 48 3 l æ 4 1.1 10,000+ 105 16.9 72 4 1632 1.0 10,000+ 107 16.9 96 ( a ) I = intensity Trial l produced an unacceptable pressure sensitive lS tape because of an excessive level of percent volatiles in the form of unpolymerized monomers. When the amount of high intensity radiation was increased, however, in trials 2-4 very acceptable percent volatiles and tape performances were observed.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention 25 is not to be unduly limited to the illustrative embodiments set forth herein.

Claims (12)

We claim:
1. An acrylamide functional disubstituted acetyl aryl ketone.
2. The acrylamide functional disubstituted acetyl aryl ketone of claim 1 having the formula:

IV

wherein R1 is hydrogen or methyl;
R2 and R3 independently are an alkyl group of 1 to 14 carbon atoms, a cycloalkyl group of 3 to 14 carbon atoms, an aryl group of 5 to 12 ring atoms, an arenyl group having 6 to 16 carbon atoms, the aryl and arenyl groups up to 3 heteroatoms selected from S, N, and nonperoxidic O, or R2 and R3 taken together with the carbon atom to which they are joined form a carbocyclic ring of 4 to 12 ring atoms;
W is -O-, -S-, or -NH- or a divalent connecting group joining the carbonyl group of the acrylamidoacetyl functional group to the photosensitive group, P; and P is a radiation sensitive aryl ketone group capable of Norrish Type I cleavage.
3. The acrylamide functional disubstituted acetyl aryl ketone according to claim 2 wherein W is selected from the class of connecting groups consisting of and in which n is a number having a value of one to four, R4 is hydrogen or methyl group, X is -O-, -S-, or -NH-, and Y
is selected from the group consisting of , , , , , , or ;

wherein the radiation sensitive group P has the formula:

in which Ar is an arylene group having 6 to 12 carbon atoms that can be substituted by a lower alkyl group having one to six carbon atoms; and R5 is selected from the group consisting of hydrogen, C1 to C12 alkyl groups, C1 to C12 alkoxy groups, and phenyl groups;
each R6, R7, and R8 independently are selected from the group consisting of hydroxyl, C1 to C12 alkyl groups, C1 to C12 alkoxy groups, di(C1 to C12) amino groups, and phenyl groups, provided that at least one of R6, R7, and R8 is selected from the group consisting of hydroxyl, C1 to C12 alkoxy groups, or C1 to C12 amino groups, or that any two of R6, R7, R8 together is an alkylene group, -(CpH2p)-, or an alkylene-dioxy group, -O-(CpH2p)-O-, in which p is an integer having a value of two or three, that together with the carbon atoms to which they are attached form a 5- or 6- membered ring, or any two of R6, R7, and R8 taken together with the carbon atom to which they are attached form a carbonyl group, provided that the remaining R6, R7, or R8 is selected from the group consisting of hydroxyl, C1 to C12 alkoxy groups, C1 to C2 amino groups, and aryl groups; and wherein Ar is selected from the group consisting of phenylene, naphthylenylene, and biphenylene.
4. A photopolymerizable composition comprising one or more ethylenically-unsaturated monomers and an acrylamide functional disubstituted acetyl aryl ketone photoinitiator according to any of claims 1 to 3, said composition optionally being polymerized.
5. The photopolymerized composition according to claim 4 which includes a polymeric photoinitiator comprising units having the formula in which R1, R2, R3, W, and P are the same as defined above; R9 is one or more groups as determined by the identity of the ethylenically-unsaturated monomers in the polymerizable composition; and a and b are each numbers having a value sufficient to provide to the linear polymer a number average molecular weight of from about 1000 to 5,000,000, the mole ratio, b/(a+b), having a value from about 0.0001 to 0.5.
6. A photopolymerizable composition comprising one or more ethylenically unsaturated monomers and the polymeric photoinitiator having units according to claim 5, said photopolymerizable composition optionally being a coatable syrup.
7. A composition photopolymerizable to a pressure-sensitive adhesive comprising per 100 parts by weight (pbw) of (1) 60 to 99.95 pbw of one or more acrylic acid esters of monohydric aliphatic alcohols, said alcohols having an average of 4 to 12 carbon atoms;
(2) 0 to 39.95 pbw of ethylenically-unsaturated monomers whose homopolymer has a glass transition temperature (Tg) greater than 50°C, and (3) 0.01 to 10.0 pbw, preferably 0.01 to 2.0 pbw of acrylamide functional disubstituted acetyl aryl ketone photoinitiator according to any of claims 1 to 3, (4) 0 to 5.0 pbw, preferably 0.01 to 5.0 pbw of a polyfunctional unsaturated monomer, which preferably is hexanediol diacrylate, and (5) 0 to 5.0 pbw of a thermal or actinic radiation activated source of free radicals, the source being free of ethylenic unsaturation;
said composition optionally being polymerized.
8. A substrate bearing a layer of the composition according to any of claims 1 to 7.
9. A pressure sensitive adhesive tape comprising a flexible backing and on at least one surface thereof a layer of the photopolymerized composition according to any of claims 4 to 7, said pressure sensitive adhesive tape optionally further comprising a layer of a release coating.
10. A laminated article comprising the pressure-sensitive adhesive according to claim 7 applied between two substrates, wherein optionally at least one substrate is nonadherent to the pressure sensitive adhesive.
11. The process for preparing an acrylamide functional disubstituted acetyl aryl ketone according to any of claims 1 to 3 comprising the steps of (a) providing an admixture of 100 mole percent of a hydroxyl, thiol, or amine functional aryl ketone with from 50 to 150 mole percent of one or more disubstituted alkenyl azlactones;
(b) maintaining the admixture at 0°C to 100°C for a sufficient time to convert the hydroxyl, thiol, or amine functional aryl ketone to an acrylamide functional disubstituted acetyl aryl ketone;

(c) optionally, isolating the resulting acrylamide functional disubstituted acetyl aryl ketone;
said aryl ketone optionally having the formula H-W-P, wherein W and P are as defined above and the alkenyl azlactone has the formula wherein R1, R2, and R3 are defined above;
said process optionally further comprising the step of polymerizing said acrylamide functional disubstituted acetyl aryl ketone with at least one ethylenically unsaturated monomer to provide a crosslinked polymer.
12. A process for preparing the polymeric photoinitiator according to claims 5 or 6 comprising the steps of:
a) polymerizing an alkenyl azlactone with a copolymerizable ethylenically unsaturated monomer, and b) reacting the resulting copolymer with a hydroxy, thiol, or amino group-substituted photoinitiator to yield said polymeric photoinitiator.
CA002173228A 1993-10-13 1994-09-16 Acrylamido functional disubstituted acetyl aryl ketone photoinitiators Abandoned CA2173228A1 (en)

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