PHOTOCURABLE ADHESIVE OR SEALANT COMPOSITION

Abstract

The present invention is directed to a photo-curable adhesive or sealant composition comprising, based on the weight of the composition: from 1 to 10 wt. %, of a) at least one oxetane compound according to Formula (I) below:

##STR00001## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 are independently selected from H and C.sub.1-C.sub.6 alkyl; R.sup.4 is —(CH.sub.2).sub.mX; m is 0 or 1; X is C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.6-C.sub.18 aryl, C.sub.6-C.sub.18 aryloxy, C.sub.7-C.sub.18 aralkyl, C.sub.7-C.sub.18 aralkoxy or is represented by the formula:

##STR00002## each R.sup.7 is independently a C.sub.1-C.sub.12 alkylene group, C.sub.2-C.sub.12 alkenylene group, C.sub.6-C.sub.18 arylene, C.sub.7-C.sub.18 alkarylene, C.sub.7-C.sub.18 aralkylene or a poly(C.sub.1-C.sub.6alkyleneoxy) group; R.sup.8 is H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.18 aralkyl; and, n is an integer of from 1 to 3; from 5 to 20 wt. % of b) at least one epoxide compound, wherein part b) is characterized in that at least 50 wt. % of the total weight of epoxide compounds is constituted by b1) at one cycloaliphatic epoxide; from 0.1 to 5 wt. % of c) at least one ionic photoacid generator; from 0.1 to 5 wt. % of d) at least one free radical photoinitiator; and, from 50 to 90 wt. % of e) particulate filler.

Claims

1. A photo-curable adhesive or sealant composition comprising, based on the weight of the composition: from 1 to 10 wt. %, of a) at least one oxetane compound according to Formula (I) below: ##STR00012## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 are independently selected from H and C.sub.1-C.sub.6 alkyl; R.sup.4 is —(CH.sub.2).sub.mX; m is 0 or 1; X is C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.6-C.sub.18 aryl, C.sub.6-C.sub.18 aryloxy, C.sub.7-C.sub.18 aralkyl, C.sub.7-C.sub.18 aralkoxy or is represented by the formula: ##STR00013## each R.sup.7 is independently a C.sub.1-C.sub.12 alkylene group, C.sub.2-C.sub.12 alkenylene group, C.sub.6-C.sub.18 arylene, C.sub.7-C.sub.18 alkarylene, C.sub.7-C.sub.18 aralkylene or a poly(C.sub.1-C.sub.6 alkyleneoxy) group; R.sup.8 is H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.18 aralkyl; and, n is an integer of from 1 to 3; from 5 to 20 wt. % of b) at least one epoxide compound, wherein part b) is characterized in that at least 50 wt. % of the total weight of epoxide compounds is constituted by b1) at one cycloaliphatic epoxide; from 0.1 to 5 wt. % of c) at least one ionic photoacid generator; from 0.1 to 5 wt. % of d) at least one free radical photoinitiator; and, from 50 to 90 wt. % of e) particulate filler.

2. The composition according to claim 1 comprising, based on the weight of the composition: from 5 to 10 wt. % of a) said at least one oxetane compound according to Formula (I); from 5 to 15 wt. % of b) said least one epoxide compound; from 0.1 to 5 wt. %, of c) said at least one ionic photoacid generator (PAG); from 0.1 to 5 wt. % of d) said at least one free radical photoinitiator; from 50 to 80 wt. % of e) particulate filler.

3. The composition according to claim 1, wherein part a) comprises or consists of a monofunctional oxetane compound of Formula (I) wherein: R.sup.1 and R.sup.3 are independently selected from H and C.sub.1-4 alkyl; R.sup.2, R.sup.5 and R.sup.6 are all H; R.sup.4 is —(CH.sub.2).sub.mX; m is 1; and X is C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.6-C.sub.18 aryl, C.sub.6-C.sub.18 aryloxy, C.sub.7-C.sub.18 aralkyl, C.sub.7-C.sub.18 aralkoxy.

4. The composition according to claim 3, wherein X is C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 hydroxyalkyl or phenyl(C.sub.1-C.sub.4)alkoxy.

5. The composition according to claim 3, wherein part a) comprises or consists of a monofunctional oxetane compound selected from the group consisting of: 3-ethyl-3-oxetanemethanol; 3-methyl-3-oxetanemethanol; 3,3-dimethyloxetane; 3-ethyl-3-[(phenylmethoxy)methyl]-oxetane; and, mixtures thereof.

6. The composition according to claim 1, wherein part a) comprises or consists of a difunctional oxetane compound of Formula (IA): ##STR00014## wherein: R.sup.3 and R.sup.8 are independently selected from H and C.sub.1-C.sub.6 alkyl; each R.sup.7 is independently a C.sub.1-C.sub.12 alkylene group, C.sub.2-C.sub.12 alkenylene group, C.sub.6-C.sub.18 arylene, C.sub.7-C.sub.18 alkarylene, C.sub.7-C.sub.18 aralkylene or a poly(C.sub.1-C.sub.6 alkyleneoxy) group; and, n is an integer of from 1 to 3.

7. The composition according to claim 6, wherein part a) comprises or consists of a difunctional oxetane compound of Formula (IAA): ##STR00015## wherein: R.sup.3 and R.sup.8 are independently selected from H and C.sub.1-C.sub.6 alkyl; R.sup.7 is a C.sub.1-C.sub.12 alkylene group, C.sub.2-C.sub.12 alkenylene group, C.sub.6-C.sub.18 arylene, C.sub.7-C.sub.18 alkarylene, C.sub.7-C.sub.18 aralkylene or a poly(C.sub.1-C.sub.6 alkyleneoxy) group.

8. The composition according to claim 7, wherein: R.sup.3 and R.sup.8 are C.sub.1-C.sub.4 alkyl; and, R.sup.7 is a C.sub.1-C.sub.6 alkylene, C.sub.6-C.sub.18 arylene or C.sub.7-C.sub.18 aralkylene.

9. The composition according to claim 8, wherein part a) comprises 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene.

10. The composition according to claim 1, wherein b1) said at least one cycloaliphatic epoxide compound constitutes at least 65 wt. % of said part b).

11. The composition according to claim 1, wherein said cycloaliphatic epoxide is selected from the group consisting of bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl) ether, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate and mixtures thereof.

12. The composition according to claim 1, wherein part b) comprise at least one glycidoxy alkyl alkoxy silane having the formula: ##STR00016## wherein: each R is independently selected from methyl or ethyl; and, n is from 1-10.

13. The composition according to claim 1, wherein part e) comprises or consists of amorphous silica particles having an average particle diameter (d50) of from 5 to 100 μmas measured by laser diffraction.

14. A bonded structure comprising: a first material layer; and, a second material layer; wherein a cured adhesive composition as defined in claim 1 is disposed between and contacts said first and second material layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

a) Oxetane Compounds

[0070] The composition of the present invention comprises from 1 to 10 wt. %, based on the weight of the composition of a) at least one oxetane compound according to Formula (I) below:

##STR00005##

wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 are independently selected from H and C.sub.1-C.sub.6 alkyl; [0071] R.sup.4 is —(CH.sub.2).sub.mX; [0072] m is 0 or 1; [0073] X is C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.6-C.sub.18 aryl, C.sub.6-C.sub.18 aryloxy, C.sub.7-C.sub.18 aralkyl, C.sub.7-C.sub.18 aralkoxy or is represented by the formula:

##STR00006## [0074] each R.sup.7 is independently a C.sub.1-C.sub.12 alkylene group, C.sub.2-C.sub.12 alkenylene group, C.sub.6-C.sub.18 arylene, C.sub.7-C.sub.18 alkarylene, C.sub.7-C.sub.18 aralkylene or a poly(C.sub.1-C.sub.6 alkyleneoxy) group; [0075] R.sup.8 is H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.18 aralkyl; and, n is an integer of from 1 to 3.

[0076] The composition may, for example, comprise from 5 to 10 wt. %, based on the weight of the composition of a) said at least oxetane compound according to Formula (I).

[0077] In one embodiment, the composition comprises a monofunctional oxetane compound in which: [0078] R.sup.1 and R.sup.3 are independently selected from H and C.sub.1-4alkyl; [0079] R.sup.2, R.sup.5 and Re are all H; [0080] R.sup.4 is —(CH.sub.2).sub.mX; [0081] m is 1; and [0082] X is C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.6-C.sub.18 aryl, C.sub.6-C.sub.18 aryloxy, C.sub.7-C.sub.18 aralkyl, C.sub.7-C.sub.18 aralkoxy.

[0083] It is particularly preferred in this embodiment that: X is C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 hydroxyalkyl or phenyl(C.sub.1-C.sub.4)alkoxy. Exemplary oxetanes in accordance with this embodiment are: 3-ethyl-3-oxetanemethanol; 3-methyl-3-oxetanemethanol; 3,3-dimethyloxetane; and, 3-ethyl-3-[(phenylmethoxy)methyl]-oxetane.

[0084] In an embodiment of the invention, which is not intended to be mutually exclusive of that given above, the composition may comprise a di-functional oxetane of Formula (IA):

##STR00007##

wherein: R.sup.3 and R.sup.7 are independently selected from H and C.sub.1-C.sub.6 alkyl; [0085] each R.sup.7 is independently a C.sub.1-C.sub.12 alkylene group, C.sub.2-C.sub.12 alkenylene group, C.sub.6-C.sub.18 arylene, C.sub.7-C.sub.18 alkarylene, C.sub.7-C.sub.18 aralkylene or a poly(C.sub.1-C.sub.6 alkyleneoxy) group; and, [0086] n is an integer of from 1 to 3.

[0087] For example, the composition may comprise an oxetane meeting the Formula IAA below:

##STR00008##

wherein: R.sup.3, R.sup.7 and R.sup.8 are as defined above.

[0088] Within this embodiment it is preferred that: R.sup.3 and R.sup.8 are C.sub.1-C.sub.4 alkyl; and, R.sup.7 is a C.sub.1-C.sub.6 alkylene, C.sub.6-C.sub.18 arylene or C.sub.7-C.sub.18 aralkylene. An exemplary compound in accordance with Formula (IAA) is 1,4-Bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene.

[0089] In another embodiment of the invention, which is again not mutually exclusive of those mentioned above, the composition may comprise a di-functional oxetane of Formula (IB):

##STR00009##

wherein: R.sup.3 and R.sup.8 are as defined above.

[0090] Within this embodiment, a preference may be noted for R.sup.3 and R.sup.8 being a C.sub.1-C.sub.4 alkyl. Whilst R.sup.3 and R.sup.8 may be the same or different, it is preferred that they are the same. An exemplary compound in accordance with Formula (IB) is bis[1-ethyl-3-oxetanyl)methyl]ether.

b) Epoxide Compounds

[0091] The composition of the present invention comprises from 5 to 20 wt. %, based on the weight of the composition of b) at least one epoxide compound. The composition may, for example, comprise from 5 to 15 wt. %, based on the weight of the composition, of b) said least one epoxide compound. As noted above, at least 50 wt. %, based on the total weight of epoxide compounds in the composition is constituted by b1) at one cycloaliphatic epoxide. It is considered that b1) said at least one cycloaliphatic epoxide compound may reasonably constitute at least 65 wt. % and even 100 wt. % of said part b).

b1) Cycloaliphatic Epoxide Compounds

[0092] The or each cycloaliphatic epoxide compound included in the composition comprises at least one epoxy group which may be in the form of: a terminal epoxy group; a glycidyl ether (e.g. —O—CH.sub.2-epoxide); or, an epoxide fused to a C.sub.5-7 cycloakyl group.

[0093] Exemplary cycloaliphatic epoxide compounds include: mono-epoxy-substituted cycloaliphatic hydrocarbons, such as cyclohexene oxide, vinylcyclohexene monoxide, (+)-cis-limonene oxide, (+)-cis,trans-limonene oxide, (−)-cis,trans-limonene oxide, cyclooctene oxide, cyclododecene oxide and α-pinene oxide; vinylcyclohexene diepoxide; limonene diepoxide; glycidyl ethers of cycloaliphatic alcohols; glycidyl esters of cycloaliphatic monocarboxylic acids; diglycidyl ethers of cycloaliphatic diols, such as cyclopentane diol and cyclohexane diol; and, glycidyl esters of cycloaliphatic polycarboxylic acids, which acids contain at least two carboxylic acid groups and no other groups reactive with epoxide groups.

[0094] Without intention to limit the present invention, suitable cycloaliphatic epoxy resins include: cyclohexanedimethanol diglycidyl ether; bis(3,4-epoxycyclohexylmethyl) adipate; bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; bis(2,3-epoxycyclopentyl) ether; 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate; 1,4-cyclohexanedimethanol diglycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; bis(2,3-epoxypropyl)cyclohexane-1,2-dicarboxylate; and, cycloaliphatic epoxy resins obtained by the hydrogenation of aromatic bisphenol A diglycidyl ether (BADGE) epoxy resins.

[0095] Preferably the cycloaliphatic epoxy comprises two C.sub.5-6 cycloalkyl groups wherein each are independently fused to an epoxide such as bis(3,4-epoxycyclohexylmethyl) adipate, bis(3 4-epoxy-6-methylcyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl) ether, or 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate.

[0096] As commercial cycloaliphatic epoxide compounds mention may be made of: Cyracure® UVR6105, UVR6107, UVR6110 and UVR6128 available from Dow Chemical; Syna Epoxy S-06E available from Synasia; and, Celloxide 2021P, available from Daicel Corporation.

b2) Aliphatic and Aromatic Epoxide Compounds

[0097] The composition of the present invention may optionally comprise, in addition to the cycloaliphatic resins necessarily present, b2) at least one further epoxide compound. Said further epoxide compounds as used herein may include monofunctional epoxy resins, multi- or poly-functional epoxy resins, and combinations thereof. The epoxy resins may be pure compounds but equally may be mixtures of epoxy functional compounds, including mixtures of compounds having different numbers of epoxy groups per molecule. Said further epoxy resin may be saturated or unsaturated, aliphatic, aromatic or heterocyclic and may be substituted. Further, the epoxy resin may also be monomeric or polymeric.

[0098] Without intention to limit the present invention, illustrative non-cycloaliphatic monoepoxide compounds include: alkylene oxides; epoxy-substituted aromatic hydrocarbons; monoepoxy substituted alkyl ethers of monohydric alcohols or phenols, such as the glycidyl ethers of aliphatic and aromatic alcohols; monoepoxy-substituted alkyl esters of monocarboxylic acids, such as glycidyl esters of aliphatic and aromatic monocarboxylic acids; monoepoxy-substituted alkyl esters of polycarboxylic acids wherein the other carboxy group(s) are esterified with alkanols; alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxyalkyl ethers of polyhydric alcohols wherein the other OH group(s) are esterified or etherified with carboxylic acids or alcohols; and, monoesters of polyhydric alcohols and epoxy monocarboxylic acids, wherein the other OH group(s) are esterified or etherified with carboxylic acids or alcohols.

[0099] By way of example, the following glycidyl ethers might be mentioned as being particularly suitable monoepoxide compounds for use herein: methyl glycidyl ether; ethyl glycidyl ether; propyl glycidyl ether; butyl glycidyl ether; pentyl glycidyl ether; hexyl glycidyl ether; octyl glycidyl ether; 2-ethylhexyl glycidyl ether; allyl glycidyl ether; benzyl glycidyl ether: phenyl glycidyl ether; 4-tert-butylphenyl glycidyl ether; 1-naphthyl glycidyl ether; 2-naphthyl glycidyl ether, 2-chlorophenyl glycidyl ether; 4-chlorophenyl glycidyl ether; 4-bromophenyl glycidyl ether; 2,4,6-trichlorophenyl glycidyl ether; 2,4,6-tribromophenyl glycidyl ether; pentafluorophenyl glycidyl ether; o-cresyl glycidyl ether; m-cresyl glycidyl ether; and, p-cresyl glycidyl ether.

[0100] In an embodiment, the monoepoxide compound conforms to Formula (II) herein below:

##STR00010##

wherein: R.sup.9, R.sup.10, R.sup.11 and R.sup.12 may be the same or different and are independently selected from hydrogen, a halogen atom, a C.sub.1-C.sub.8 alkyl group, a C.sub.2-C.sub.12 alkenyl, a C.sub.6-C.sub.18 aryl group or a C.sub.7-C.sub.18 aralkyl group, with the proviso that at least one of R.sup.10 and R.sup.11 is not hydrogen.

[0101] It is preferred that R.sup.9, R.sup.10 and R.sup.12 are hydrogen and R.sup.11 is either a phenyl group or a C.sub.1-C.sub.8 alkyl group and, more preferably, a C.sub.1-C.sub.4 alkyl group.

[0102] Having regard to this embodiment, exemplary monoepoxides include: ethylene oxide; 1,2-propylene oxide (propylene oxide); 1,2-butylene oxide; cis-2,3-epoxybutane; trans-2,3-epoxybutane; 1,2-epoxypentane; 1,2-epoxyhexane; 1,2-heptylene oxide; decene oxide; butadiene oxide; isoprene oxide; and, styrene oxide.

[0103] Again, without intention to limit the present invention, suitable polyepoxide compounds useful as part b2) may be liquid, solid or in solution in solvent. Further, such polyepoxide compounds should have an epoxide equivalent weight of from 100 to 700 g/eq, for example from 120 to 320 g/eq. And generally, diepoxide compounds having epoxide equivalent weights of less than 500 g/eq. or even less than 400 g/eq. are preferred: this is predominantly from a costs standpoint, as in their production, lower molecular weight epoxy resins require more limited processing in purification.

[0104] As examples of types or groups of polyepoxide compounds which may be polymerized in present invention, mention may be made of: glycidyl ethers of polyhydric alcohols and polyhydric phenols; glycidyl esters of polycarboxylic acids; and, epoxidized polyethylenically unsaturated hydrocarbons, esters, ethers and amides.

[0105] Suitable diglycidyl ether compounds may be aromatic or aliphatic in nature and, as such, can be derivable from dihydric phenols and dihydric alcohols. And useful classes of such diglycidyl ethers are: diglycidyl ethers of aliphatic diols, such as 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and 1,12-dodecanediol; bisphenol A based diglycidylethers; bisphenol F diglycidyl ethers; diglycidyl o-phthalate, diglycidyl isophthalate and diglycidyl terephthalate; polyalkyleneglycol based diglycidyl ethers, in particular polypropyleneglycol diglycidyl ethers; and, polycarbonatediol based glycidyl ethers. Other suitable diepoxides which might also be mentioned include: diepoxides of double unsaturated fatty acid C1-C18 alkyl esters; butadiene diepoxide; and, polybutadiene diglycidyl ether.

[0106] Further illustrative polyepoxide compounds include but are not limited to: glycerol polyglycidyl ether; trimethylolpropane polyglycidyl ether; pentaerythritol polyglycidyl ether; digylcerol polyglycidyl ether; polyglycerol polyglycidyl ether; and, sorbitol polyglycidyl ether.

[0107] Glycidyl esters of polycarboxylic acids having utility in the present invention are derived from polycarboxylic acids which contain at least two carboxylic acid groups and no other groups reactive with epoxide groups. The polycarboxylic acids can be aliphatic, aromatic and heterocyclic. The preferred polycarboxylic acids are those which contain not more than 18 carbon atoms per carboxylic acid group of which suitable examples include but are not limited to: oxalic acid; sebacic acid; adipic acid; succinic acid; pimelic acid; suberic acid; glutaric acid; dimer and trimer acids of unsaturated fatty acids, such as dimer and trimer acids of linseed fatty acids; phthalic acid; isophthalic acid; terephthalic acid; trimellitic acid; trimesic acid; phenylene-diacetic acid; chlorendic acid; diphenic acid; naphthalic acid; polyacid terminated esters of di-basic acids and aliphatic polyols; polymers and co-polymers of (meth)acrylic acid; and, crotonic acid.

[0108] And examples of highly preferred polyepoxide compounds include: bisphenol-A epoxy resins, such as DER™ 331, DER™ 332, DER™ 383, JER™ 828 and Epotec YD 128; bisphenol-F epoxy resins, such as DER™ 354; bisphenol-A/F epoxy resin blends, such as DER™ 353; aliphatic glycidyl ethers, such as DER™ 736; polypropylene glycol diglycidyl ethers, such as DER™ 732; solid bisphenol-A epoxy resins, such as DER™ 661 and DER™ 664 UE; solutions of bisphenol-A solid epoxy resins, such as DER™ 671-X75; epoxy novolac resins, such as DEN™ 438; epoxidized phenol novolac resins, such as Epalloy 2850; brominated epoxy resins such as DER™ 542; castor oil triglycidyl ether, such as ERISYS™ GE-35H; polyglycerol-3-polyglycidyl ether, such as ERISYS™ GE-38; and, sorbitol glycidyl ether, such as ERISYS™ GE-60.

[0109] The above aside, part b) of the composition can in certain embodiments comprise glycidoxy alkyl alkoxy silanes having the formula:

##STR00011##

wherein: each R is independently selected from methyl or ethyl; and, [0110] n is from 1-10.

[0111] Exemplary silanes include but are not limited to: γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy ethyl trimethoxy silane, γ-glycidoxy methyl trimethoxy silane, γ-glycidoxy methyl triethoxy silane, γ-glycidoxy ethyl triethoxy silane, γ-glycidoxy propyl triethoxy silane; and, 8-glycidooxyoctyl trimethoxysilane. When present, the epoxide functional silanes should constitute less than less than 20 wt. %, preferably less than 10 wt. % or less than 5 wt. %, based on the total weight of the epoxide compounds.

[0112] The present invention also does not preclude the curable compositions from further comprising one or more cyclic monomers selected from the group consisting of: cyclic carbonates; cyclic anhydrides; and, lactones. The disclosures of the following citations may be instructive in disclosing suitable cyclic carbonate functional compounds: U.S. Pat. Nos. 3,535,342; 4,835,289; 4,892,954; UK Patent No. GB-A-1,485,925; and, EP-A-0 119 840. However, such cyclic co-monomers should constitute less than 20 wt. %, preferably less than 10 wt. % or less than 5 wt. %, based on the total weight of the epoxide compounds b).

c) Ionic Photoacid Generator

[0113] The compositions of the present invention include from 0.1 to 5 wt. %, based on the weight of the composition, of c) at least one ionic photoacid generator (PAG). Upon irradiation with light energy, ionic photoacid generators undergo a fragmentation reaction and release one or more molecules of Lewis or Bronsted acid that catalyze the ring opening and addition of the pendent oxetane and epoxide groups to form a crosslink. Useful photoacid generators are thermally stable, do not undergo thermally induced reactions with the forming copolymer and are readily dissolved or dispersed in the curable compositions.

[0114] Exemplary cations which may be used as the cationic portion of the ionic PAG of the invention include organic onium cations such as those described in U.S. Pat. Nos. 4,250,311, 3,113,708, 4,069,055, 4,216,288, 5,084,586, 5,124,417, and, U.S. Pat. No. 5,554,664. The references specifically encompass aliphatic or aromatic Group IVA and VIIA (CAS version) centered onium salts, with a preference being noted for I-, S-, P-, Se- N- and C-centered onium salts, such as those selected from sulfoxonium, iodonium, sulfonium, selenonium, pyridinium, carbonium and phosphonium.

[0115] As is known in the art, the nature of the counter-anion in the ionic photoacid generator (PAG) can influence the rate and extent of cationic addition polymerization of the epoxide groups with, for illustration, the order of reactivity among commonly used nucleophilic anions being SbF.sub.6>AsF.sub.6>PF.sub.6>BF.sub.4. The influence of the anion on reactivity has been ascribed to three principle factors which the skilled artisan should compensate for in the present invention: (1) the acidity of the protonic or Lewis acid generated; (2) the degree of ion-pair separation in the propagating cationic chain; and, (3) the susceptibility of the anions to fluoride abstraction and consequent chain termination.

[0116] As exemplary ionic photoacid generators which have utility in the present composition, there may be mentioned: Irgacure™ 250, Irgacure™ PAG 290 and GSID26-1 available from BASF SE; Cyracure™ UVI-6990 and Cyracure™ UVI-6974 available from Union Carbide; Degacure™ KI 85 available from Degussa; Optomer™ SP-55, Optomer™ SP-150, and Optomer™ SP-170 available from Adeka; GE UVE 1014 available from General Electric; and, SarCat™ CD 1012, SarCat™ KI-85, SarCat™ CD 1010 and CD SarCat™ 1011 available from Sartomer.

d) Free Radical Photoinitiator

[0117] The compositions of the present invention include from 0.1 to 5 wt. %, based on the weight of the composition, of d) at least one free radical photoinitiator, which compound initiates the polymerization or hardening of the compositions upon irradiation with actinic radiation.

[0118] Typically, free radical photoinitiators are divided into those that form radicals by cleavage, known as “Norrish Type I”, and those that form radicals by hydrogen abstraction, known as “Norrish Type II”. The Norrish Type II photoinitiators require a hydrogen donor, which serves as the free radical source: as the initiation is based on a bimolecular reaction, the Norrish Type II photoinitiators are generally slower than Norrish Type I photoinitiators which are based on the unimolecular formation of radicals. On the other hand, Norrish Type II photoinitiators possess better optical absorption properties in the near-UV spectroscopic region. The skilled artisan should be able to select an appropriate free radical photoinitiator based on the actinic radiation being employed in curing and the sensitivity of the photoinitiator(s) at that wavelength.

[0119] Preferred free radical photoinitiators are those selected from the group consisting of: benzoylphosphine oxides; aryl ketones; benzophenones; hydroxylated ketones; 1-hydroxyphenyl ketones; ketals; and, metallocenes. For completeness, the combination of two or more of these photoinitiators is not precluded in the present invention.

[0120] Particularly preferred free radical photoinitiators are those selected from the group consisting of benzoin dimethyl ether; 1-hydroxycyclohexyl phenyl ketone; benzophenone; 4-chlorobenzophenone; 4-methylbenzophenone; 4-phenylbenzophenone; 4,4′-bis(diethylamino) benzophenone; 4,4′-bis(N,N′-dimethylamino) benzophenone (Michler's ketone); isopropylthioxanthone; 2-hydroxy-2-methylpropiophenone (Daracur 1173); 2-methyl-4-(methylthio)-2-morpholinopropiophenone; methyl phenylglyoxylate; methyl 2-benzoylbenzoate; 2-ethylhexyl 4-(dimethylamino)benzoate; ethyl 4-(N,N-dimethylamino)benzoate; phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; and, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. Again, for surety, the combination of two or more of these photoinitiators is not precluded in the present invention.

[0121] Given that the composition of the present invention comprises a free radical photoinitiator, irradiation of said curable compositions generates the active species from the photoinitiator(s) which initiates the cure reactions. Once that species is generated, the cure chemistry is subject to the same rules of thermodynamics as any chemical reaction: the reaction rate may be accelerated by heat. The practice of using thermal treatments to enhance the actinic-radiation cure of monomers is generally known in the art.

[0122] The use of the cationic and free radical photoinitiators in the present invention may produce residue compounds from the (photo)chemical reaction in the final cured product. The residues may be detected by conventional analytical techniques such as: infrared, ultraviolet and NMR spectroscopy; gas or liquid chromatography; and, mass spectroscopy. Thus, the present invention may comprise cured matrix (co-)polymers and detectable amounts of residues from the cationic and free radical photoinitiators. The residues are present in small amounts and do not normally interfere with the desired physiochemical properties of the final cured product.

[0123] As would be recognized by the skilled artisan, photosensitizers can be incorporated into the compositions to improve the efficiency with which photoinitiators—components c) and d) herein—use the energy delivered. The term “photosensitizer” is used in accordance with its standard meaning to represent any substance that either increases the rate of photoinitiated polymerization or shifts the wavelength at which polymerization occurs. Photosensitizers should be used in an amount of from 0 to 25 wt. %, based on the total weight of photoinitiators in the composition.

e) Particulate Filler

[0124] The composition of the present invention comprises from 50 to 90 wt. %, based on the weight of the composition, of e) particulate filler. The composition may, for instance, contain from 50 to 80 wt. % or from 55 to 80 wt. % of particulate filler, based on the weight of the composition.

[0125] The desired viscosity of the curable composition formed may be determinative of the amount of filler used. Having regard to that latter consideration, the total amount of fillers should not prevent the composition from being readily applicable by the elected method of application to the composition to a substrate. For example, photocurable compositions of the present invention which are intended to be applicable to a specific locus by printing or injection should possess a viscosity of from 1000 to 50,000, preferably from 10,000 to 20,000 mPas.

[0126] Broadly, there is no particular intention to limit the shape of the particles employed as fillers: particles that are acicular, spherical, ellipsoidal, cylindrical, bead-like, cubic or platelet-like may be used alone or in combination. Moreover, it is envisaged that agglomerates of more than one particle type may be used. Equally, there is no particular intention to limit the size of the particles employed as fillers. However, such fillers will conventionally have an average particle size (d50), as measured by laser diffraction/scattering methods, of from 0.1 to 1000 μm, for example from 1 to 500 μm.

[0127] Exemplary fillers include but are not limited to graphite, carbon black, calcium carbonate, calcium oxide, calcium chloride, calcium hydroxide (lime powder), calcium sulphate, fused silica, amorphous silica, precipitated and/or pyrogenic silicic acid, zeolites, bentonites, wollastonite, magnesium carbonate, magnesium sulphate, diatomite, barium sulfate, barium oxide, alumina, aluminium nitride, boron nitride, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass beads, glass powder, and other ground mineral substances. Organic fillers can also be used, in particular wood fibers, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, chaff, ground walnut shells, and other chopped fibers: poly(tetrachloroethylene), poly(chlorotrifluoroethylene) and poly(vinylidene chloride) powders may also be used. And short fibers such as glass fibers, glass filament, polyacrylonitrile, carbon fibers, Kevlar fibers, or polyethylene fibers can also be added.

[0128] Also suitable as fillers are hollow spheres having a mineral shell or a plastic shell. These can be, for example, hollow glass spheres that are obtainable commercially under the trade names Glass Bubbles®. Plastic-based hollow spheres, such as Expancel® or Dualite®, may be used and are described in EP 0 520 426 B1: they are made up of inorganic or organic substances and each have a diameter of 1 mm or less, preferably 500 μm or less.

[0129] The use of core-shell rubber particles as filler is also not precluded. The term “core shell rubber” or CSR is being employed in accordance with its standard meaning in the art as denoting a rubber particle core formed by a polymer comprising an elastomeric or rubbery polymer as a main ingredient and a shell layer formed by a polymer which is graft polymerized onto the core. The shell layer partially or entirely covers the surface of the rubber particle core in the graft polymerization process. By weight, the core should constitute at least 50 wt. % of the core-shell rubber particle.

[0130] The core-shell rubber may be selected from commercially available products, examples of which include: Paraloid TMS-2670J, EXL 2650A, EXL 2655 and EXL2691 A, available from The Dow Chemical Company; Clearstrength® XT100, available from Arkema Inc.; the Kane Ace® MX series available from Kaneka Corporation, and in particular MX 120, MX 125, MX 130, MX 136, MX 551, MX553; and, METABLEN SX-006 available from Mitsubishi Rayon.

[0131] Fillers which impart thixotropy to the composition may be preferred for many applications: such fillers are also described as rheological adjuvants, e.g. hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.

[0132] In an embodiment of the present invention, part e) of the composition comprises or consists of amorphous silica particles having an average particle diameter (d50) of from 5 to 100 μm, for instance from 5 to 50 μm, as measured by laser diffraction/scattering methods. For illustrative purposes, the use of the commercial grades of amorphous silica marketed under the tradename Denka FB may be mentioned.

Additives and Adjunct Ingredients

[0133] Said compositions obtained in the present invention will typically further comprise adjuvants and additives that can impart improved properties to these compositions. For instance, the adjuvants and additives may impart one or more of: improved elastic properties; improved elastic recovery; longer enabled processing time; faster curing time; and, lower residual tack. Included among such adjuvants and additives are: tougheners; plasticizers; stabilizers including UV stabilizers; antioxidants; reactive diluents; drying agents or moisture scavengers; adhesion promoters; fungicides; flame retardants; rheological adjuvants; color pigments or color pastes; and/or optionally also, to a small extent, non-reactive diluents.

[0134] Such adjuvants and additives can be used in such combination and proportions as desired, provided they do not adversely affect the nature and essential properties of the composition. While exceptions may exist in some cases, these adjuvants and additives should not in toto comprise more than 30 wt. % of the total composition and preferably should not comprise more than 15 wt. % of the composition.

[0135] A “plasticizer” for the purposes of this invention is a substance that decreases the viscosity of the composition and thus facilitates its processability. Herein the plasticizer may constitute up to 10 wt. % or up to 5 wt. %, based on the total weight of the composition, and is preferably selected from the group consisting of: diurethanes; ethers of monofunctional, linear or branched C4-C16 alcohols, such as Cetiol OE (obtainable from Cognis Deutschland GmbH, Düsseldorf); esters of abietic acid, adipic acid, sebacic acid, butyric acid, thiobutyric acid, acetic acid, propionic acid esters and citric acid; esters based on nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylic acid esters; esters of OH-group-carrying or epoxidized fatty acids; glycolic acid esters; benzoic acid esters; phosphoric acid esters; sulfonic acid esters; trimellitic acid esters; polyether plasticizers, such as end-capped polyethylene or polypropylene glycols; polystyrene; hydrocarbon plasticizers; chlorinated paraffin; and, mixtures thereof. It is noted that, in principle, phthalic acid esters can be used as the plasticizer but these are not preferred due to their toxicological potential.

[0136] “Stabilizes” for purposes of this invention are to be understood as antioxidants, UV stabilizers, thermal stabilizers or hydrolysis stabilizers. Herein stabilizers may constitute in toto up to 10 wt. % or up to 5 wt. %, based on the total weight of the composition. Standard commercial examples of stabilizers suitable for use herein include: sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; amines of the hindered amine light stabilizer (HALS) type; phosphorus; sulfur; and, mixtures thereof.

[0137] Whilst the use of epoxy functional silanes has been mentioned above, it is further noted that compounds having metal chelating properties may be used in the compositions of the present invention to help enhance the adhesion of the cured adhesive to a substrate surface. Further, also suitable for use as adhesion promoters are the acetoacetate-functionalized modifying resins sold by King Industries under the trade name K-FLEX XM-B301.

[0138] The presence of solvents and non-reactive diluents in the compositions of the present invention is also not precluded where this can usefully moderate the viscosities thereof. For instance, but for illustration only, the compositions may contain one or more of: xylene; 2-methoxyethanol; dimethoxyethanol; 2-ethoxyethanol; 2-propoxyethanol; 2-isopropoxyethanol; 2-butoxyethanol; 2-phenoxyethanol; 2-benzyloxyethanol; benzyl alcohol; ethylene glycol; ethylene glycol dimethyl ether; ethylene glycol diethyl ether; ethylene glycol dibutyl ether; ethylene glycol diphenyl ether; diethylene glycol; diethylene glycol-monomethyl ether; diethylene glycol-monoethyl ether; diethylene glycol-mono-n-butyl ether; diethylene glycol dimethyl ether; diethylene glycol diethyl ether; diethylene glycoldi-n-butylyl ether; propylene glycol butyl ether; propylene glycol phenyl ether; dipropylene glycol; dipropylene glycol monomethyl ether; dipropylene glycol dimethyl ether; dipropylene glycoldi-n-butyl ether; N-methylpyrrolidone; diphenylmethane; diisopropylnaphthalene; petroleum fractions such as Solvesso® products (available from Exxon); alkylphenols, such as tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-pentadecatrienylphenol; styrenated phenol; bisphenols; and, aromatic hydrocarbon resins especially those containing phenol groups, such as ethoxylated or propoxylated phenols.

[0139] The above aside, it is preferred that said non-reactive diluents constitute in toto less than 10 wt. %, in particular less than 5 wt. % or less than 2 wt. %, based on the total weight of the composition.

Methods and Applications

[0140] To form the defined curable compositions, the parts are brought together and mixed. It is important that the mixing homogenously distributes the ingredients within the adhesive composition: such thorough and effective mixing can be determinative of a homogeneous distribution of any constituent particulate filler or other adjunct material within the polymer matrix obtained following curing.

[0141] As is known in the art, to form the adhesive or sealant compositions, the elements of the composition are brought together and homogeneously mixed under conditions which inhibit or prevent the reactive components from reacting: such conditions would be readily comprehended by the skilled artisan. As such, it will often be preferred that the curative elements are not mixed by hand but are instead mixed by machine—a static or dynamic mixer, for example—in pre-determined amounts without intentional photo-irradiation.

[0142] In accordance with the broadest process aspects of the present invention, the above described compositions are applied to the material layer(s) and then cured in situ. Prior to applying the compositions, it is often advisable to pre-treat the relevant surfaces to remove foreign matter there from: this step can, if applicable, facilitate the subsequent adhesion of the compositions thereto. Such treatments are known in the art and can be performed in a single or multi-stage manner constituted by, for instance, the use of one or more of: an etching treatment with an acid suitable for the substrate and optionally an oxidizing agent; sonication; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric plasma treatment and flame plasma treatment; immersion in a waterborne alkaline degreasing bath; treatment with a waterborne cleaning emulsion; treatment with a cleaning solvent, such as acetone, carbon tetrachloride or trichloroethylene; and, water rinsing, preferably with deionized or demineralized water.

[0143] In some embodiments, the adhesion of the coating compositions of the present invention to the preferably pre-treated substrate may be facilitated by the application of a primer thereto. Indeed primer compositions may be necessary to ensure efficacious fixture and/or cure times of the adhesive compositions on inactive substrates. The skilled artisan will be able to select an appropriate primer.

[0144] The compositions are then applied to the optionally pre-treated, optionally primed surfaces of the substrate by conventional application methods such as: printing methods, including screen printing; pin transfer; and, syringe application, including by electro-pneumatically controlled syringes. It is recommended that the compositions be applied to a surface at a wet film thickness of from 10 to 700 μm. The application of thinner layers within this range is more economical and provides for a reduced likelihood of deleterious thick cured regions. However, great control must be exercised in applying thinner coatings or layers so as to avoid the formation of discontinuous cured films.

[0145] Given that the composition comprises photo-initiators, the energy source used to initiate the curing of the applied compositions will emit at least one of ultraviolet (UV) radiation, infrared (IR) radiation, visible light, X-rays, gamma rays, or electron beams (e-beam). Subsequent to their application, the photocurable adhesive compositions may typically be activated in less than 5 minutes, and commonly between 1 and 60 seconds—for instance between 3 and 12 seconds—when irradiated using commercial curing equipment.

[0146] Irradiating ultraviolet light should typically have a wavelength of from 150 to 600 nm and preferably a wavelength of from 200 to 450 nm. Useful sources of UV light include, for instance, extra high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low intensity fluorescent lamps, metal halide lamps, microwave powered lamps, xenon lamps, UV-LED lamps and laser beam sources such as excimer lasers and argon-ion lasers.

[0147] Where an e-beam is utilized to cure the applied coating(s), standard parameters for the operating device may be: an accelerating voltage of from 0.1 to 100 keV; a vacuum of from 10 to 10.sup.−3 Pa; an electron current of from 0.0001 to 1 ampere; and, power of from 0.1 watt to 1 kilowatt.

[0148] The amount of radiation necessary to satisfactorily cure an individual adhesive or sealant composition—such that said adhesive or sealant becomes fixed, for example—will depend on a variety of factors including the angle of exposure to the radiation and the thickness of the adhesive or sealant layer. Broadly, however, a curing dosage of from 5 to 10000 mJ/cm.sup.2 may be cited as being typical: curing dosages of from 500 to 5000 mJ/cm.sup.2, such as from 1000 to 4000 mJ/cm.sup.2 may be considered highly effective.

[0149] The purpose of irradiation is to generate the active species from the photoinitiator which initiates the cure reactions. Once that species is generated, the cure chemistry is subject to the same rules of thermodynamics as any chemical reaction: the reaction rate may be accelerated by heat or retarded by lower temperatures. Without intention to limit the present invention, the complete curing of the applied curable compositions should typically occur at temperatures in the range of from 20° C. to 50° C., preferably from 20° C. to 40° C. Where applicable, the temperature of the curable compositions may be raised above the mixing temperature and/or the application temperature using conventional means, including microwave induction.

[0150] There is no particular intention to limit the substrates to which the adhesive or sealant compositions of the present invention may be applied. The skilled artisan will, it is considered, be aware of those substrates conventionally found in opto-electronic devices or opto-mechanical devices. However, reference may be made to: polymers, such as polyvinylchloride, polyolefins and polycarbonates; carbon and nano-carbon substrates; metals, such as Al, Pb, Sn, Ge, Si, Ti, Bi, In, Ni and Fe; anodized metals, in particular anodized aluminium; alloys, such as brass and stainless steel; semiconductor materials, such as Si, GaAs, InP, GaP, GaSb, and InAs; ceramics including silica, zirconia, ceramic ferrules, piezoelectric ceramics and dielectric ceramics; and, glasses, including FTO/ITO glass, glass-polymer hybrid materials and glasses modified with conductive layers thereon.

[0151] The following examples are illustrative of the present invention and are not intended to limit the scope of the invention in any way.

Examples

[0152] The following commercial compounds are used in the Examples: [0153] Celloxide 2021P: 3,4-Epoxycyclohexylmethyl-3′,4′epoxycyclohexanecarboxylate, available from Daicel Corporation. [0154] Epalloy 8250: Epoxidized phenol novolac with an average functionality of 2.65, available from Huntsman Advanced Materials. [0155] Oxetane OXT-221: bis[1-Ethyl(3-oxetanyl)]methyl ether, available from Sanyo Corporation. [0156] Oxetane OXT-101 3-ethyl-3-Oxetanemethanol, available from Sanyo Corporation. [0157] Oxetane OXT-121 1,4-Bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, available from Sanyo Corporation. [0158] UviCure 140 3-Ethyl-3-[(phenylmethoxy)methyl]-oxetane, available from Lambson. [0159] UviCure 150 1,4-Bis[(3-ethyl-3-3-oxetanylmethoxy)methyl]benzene, available from Lambson. [0160] UviCure 160 4,4-Bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, available from Lambson. [0161] Bluesil PI 2074: (toluylcumyl) iodonium tetrakis (pentafluorophenyl) borate, available from Elkom Silicones. [0162] Denka FB 35: Fused silica, spherical, available from Denka Company Limited [0163] Silquest A-187: Epoxy functional silane, available from Momentive Performance Materials. [0164] Cab-O-Sil TS 720: Fumed silica, available from Cabot Corporation. [0165] Irgacure 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, available from Ciba Specialty Chemicals.

[0166] Exemplary formulations 1 to 4 and Comparative Formulations 1 to 4 were prepared in accordance with the compositional information provided in Table 1 below. The notation “Ex.” in Tables 1 and 2 denotes an Example in accordance with the present invention. The notation “CE” in Tables 1 and 2 denotes a Comparative Example.

TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 CE 1 CE 2 CE 3 CE 4 Ingredient Function (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) Celloxide Cyclo- 5.74 5.94 4.56 4.79 0.00 9.22 5.74 3.01 2021 P aliphatic epoxy OXT-221 Oxetane 1 5.74 5.31 6.55 4.79 3.69 7.38 0.00 5.49 (di- functional) OXT-101 Oxetane 2 5.74 4.83 4.08 4.79 7.38 3.69 5.74 10.46 (mono- functional) OXT-121 Oxetane 3 0.00 2.53 2.44 0.00 9.22 0.00 5.74 3.00 (aromatic) UviCure Oxetane 4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.78 140 (aromatic) UviCure Oxetane 5 0.00 0.00 0.00 2.87 0.00 0.00 0.00 2.90 150 (aromatic) UviCure Oxetane 6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.88 160 (aromatic) Bluesil Cationic 0.57 0.66 0.66 0.57 0.55 0.55 0.57 0.22 PI 2074 photoinitiator Irgacure Free-radical 0.38 0.68 0.62 0.38 0.37 0.37 0.38 0.39 1173 photoinitiator Silquest Adhesion 0.19 0.20 0.38 0.19 0.18 0.18 0.19 0.44 A-187 promoter DENKA Filler 79.47 77.82 78.44 79.47 76.54 76.54 79.47 59.67 FB 35 Cab-O-Sil Thickener 2.14 2.03 2.26 2.14 2.07 2.07 2.14 0.77 TS 720 Total 100 100 100 100 100 100 100 100

Methodology for Formulation Preparation:

[0167] The oxetane and, where applicable, the epoxide compounds were weighed into a speedmixer cup. The cup was held at 60° C. for 30 minutes after which was added A-187, Irgacure 1173 and 50% by weight of the Cab-O-Sil 720: the contents of the cup were mixed by hand and then subsequently speed-mixed for 2 minutes at 2800 rpm. The remainder of the Cab-O-Sil 720 was added and the contents again mixed by hand and speed-mixed for 2 minutes at 2800 rpm. In three doses, the Denka FB 35 was added, with each addition requiring both stirring by hand and stirring for 1 minute at 1800 rpm. The obtained mixture was permitted to cool down before the addition of P12074. The mixture was degassed and speed-mixed for 1 minute at 800 rpm to remove entrained air.

[0168] Curing Depth Test: Depth of cure was determined using a cylindrical stainless steel curing mold as the test fixture: the cylindrical cavity dimensions were 8 mm diameter and 20 mm depth. The test fixture was placed on a polyester film on a flat surface and the cylindrical cavity filled with the sample to be cured under irradiation. A doctor blade was used to smooth and level the sample surfaces. The filled test fixture was placed on a white background surface and the composition was treated by exposing the applied formulations to radiation of a wavelength of 365 nm for a 3 second duration at an intensity of 1000 mW/cm.sup.2. After irradiation, the sample was removed from the test fixture and any uncured sample was removed within 1 minute of irradiation by scraping uncured material from the bottom of the sample, opposite the side irradiated with the curing light. The thickness of the remaining cured material was measured. The reported cured depths (mm) are the actual cured sample thickness (mm) and are from a single measurement.

[0169] Measurement of Degree of Monomer Conversion: This was determined by comparison of the total enthalpy of the uncured material with the residual enthalpy of the cured material.

[0170] The results of the tests performed on the exemplary and comparative formulations are provided in Table 2 below. That Table also includes the further standard testing methodology where applicable. For completeness, the exemplary and comparative formulations were each cured by exposing the applied formulations to radiation of a wavelength of 365 nm for a 3 second duration at an intensity of 1000 mW/cm.sup.2.

TABLE-US-00002 TABLE 2 TEST Method Ex. 1 Ex. 2 Ex. 3 Ex. 4 CE 1 CE 2 CE 3 CE 4 Cure depth As Above 8.9 6.7 6.1 7.1 0 7.6 3.9 (mm) Total ISO 125.5 116.4 109.3 100.9 117 149.6 110 206 enthalpy 11357-5 (J/g) Residual ISO 10.4 8.2 8.2 11 103.7 19 6.8 69 enthalpy 11357-5 (J/g) Degree of As Above 91.7 93.0 92.5 89.1 11.4 87.3 93.8 66.5 conversion (%) Residual ISO 11.9 6.8 7.4 8.6 14.2 2.6 enthalpy 11357-5 after 24 hrs (J/g) Degree of As Above 90.5 94.2 93.2 91.5 90.5 97.6 conversion after 24 hrs (%) Tg DMA ISO 119 129 123 126 87/174 98 (° C.) 6721-1 Only one Yes Yes Yes Yes No Yes relaxation in DMA (Yes/No)

[0171] In view of the foregoing description and examples, it will be apparent to those skilled in the art that equivalent modifications thereof can be made without departing from the scope of the claims.