BACKGROUND

[0001] There are varieties of automotive sealing compositions on the market, the curing of all of which is triggered by curing mechanisms that depend on a catalyst, moisture and/or heat. It is well known that these curing mechanisms either provide the user with a limited amount of work time because the curing speed is relatively fast; or with a relatively long work time because the curing speed is relatively slow. For example, most one-part sealing compositions have long work time between 10-45 minutes, but cure slowly within hours. Under these circumstances, any sealed parts have to wait before they can be painted, resulting in a loss of efficiency and productivity for the user. In contrast, most two-part sealing compositions can cure as fast as 15 minutes, but have very short work time around 5-10 minutes. Under these circumstances, a user may not have enough time to work around on large piece. Moreover, the work time and cure speed of current sealing compositions also varies depending on the moisture level and temperature of the local environment. There is therefore a need for a sealing compositions that provide virtually unlimited work time and fast cure, thereby easing and accelerating sealing processes and substantially increasing a user's efficiency and productivity.

SUMMARY

[0002] The methods, compositions, and systems described herein solve the problems encountered with known sealing compositions by relying on an on-demand light-cure system for curing a sealing composition in less than five minutes even at relatively thick application and/or in highly filled opaque/colored sealing compositions.

[0003] Embodiment 1, therefore, is directed to a method comprising: applying a sealing composition to a substrate, the sealing composition comprising a urethane acrylate component; and a photoinitiator having an extinction coefficient of from about 10 to about 2000 L/mol cm at a wavelength from about 400 nm to about 500 nm in an amount of from about 0.5 wt.% to about 5 wt.%; and curing the sealing composition using a light-emitting curing device emitting light at a wavelength of from about 260 to about 550 nm; wherein the sealing composition cures to a depth of cure of up to about 10 mm within 0.5 seconds to 2 minutes per light exposure area.

[0004] Embodiment 2 is directed to the method of Embodiment 1, further comprising applying a primer and subsequently applying the sealing composition on the primer.

[0005] Embodiment 3 is directed to the method of Embodiments 1 -2, wherein the substrate is at least a portion of an automotive windshield assembly.

[0006] Embodiment 4 is directed to the method of Embodiments 1-3, wherein the light- emitting curing device comprises a light injection assembly optically coupled with an optical fiber. [0007] Embodiment 5 is directed to the method of Embodiments 1-4, wherein the light- emitting curing device is flexible.

[0008] Embodiment 6 is directed to the method of Embodiments 1-5, wherein the sealing composition is applied to the substrate at a thickness of about 10 mm.

[0009] Embodiment 7 is directed to the method of Embodiments 1-6, wherein the urethane acrylate component comprises an aliphatic urethane acrylate, an aromatic urethane acrylate, or a combination of an aliphatic urethane acrylate and an aromatic urethane acrylate.

[0010] Embodiment 8 is directed to the method of Embodiments 1-7, wherein the photoinitiator comprises a quinone, a phosphine oxide or a phosphinate.

[0011] Embodiment 9 is directed to the method of Embodiments 1-8, wherein the photoinitiator comprises camphor quinone.

[0012] Embodiment 10 is directed to the method of Embodiments 1-8, wherein the photoinitiator comprises:

[0013] Embodiment 11 is directed to the method of Embodiments 1-10, wherein the sealing composition further comprises at least one of photosensitizers, fillers, monothiols, polythiols, plasticizers, adhesion promoters, and diluents.

[0014] Embodiment 12 is directed to the method of Embodiment 11, wherein the adhesion promoter comprises an acid-functional monomer, a basic functional monomer or a silane.

[0015] Embodiment 13 is directed to the method of Embodiments 11-12, wherein the adhesion promoter comprises acrylic acid (AA), methacrylic acid (MAA), beta-carboxyethyl acrylate (B-CEA), 2-hydroxy ethyl methacrylate (HEMA) phosphate; (3- acryloxypropyl)trimethoxysilane, methacryloxypropyltrimethoxysilane, N-(3-acryloxy-2- hydropropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethylmethoxysilane, N-vinyl-caprolactam, N,N-dimethyl acrylamide, acrylamide, acrylonitrile, N-tert-butylacrylamide, 2-tert-butylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, N-isopropylacrylamide, methacrylonitrile, vinyl carbazole, 2-vinylpyridine, 4-vinylpyridine or l-vinyl-2-pyrrolidone or combinations thereof.

[0016] Embodiment 14 is directed to the method of Embodiments 1-13, wherein the light- emitting curing device is placed substantially in direct contact with the sealing composition. [0017] Embodiment 15 is directed to a method comprising: curing a sealing composition comprising a urethane acrylate component; and a photoinitiator having an extinction coefficient of from about 10 to about 2000 L/mol cm at a wavelength from about 400 nm to about 500 nm in an amount of from about 0.5 wt.% to about 5 wt.%; wherein the sealing composition cures to a depth of cure of up to about 10 mm within 0.5 seconds to 2 minutes per light exposure area.

[0018] These and other aspects of the invention will be apparent from the detailed description below. In no event, however, should the above summaries be construed as limitations on the claimed subject matter, which subject matter is defined solely by the attached claims, as may be amended during prosecution.

DESCRIPTION OF THE FIGURES

[0019] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.

[0020] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.

[0021] FIG. 1 is a schematic view of a sealing system including a curing head of the present disclosure including an air-cooled, light-emitting curing device.

[0022] FIG. 2 is a schematic cross-sectional view of an embodiment of the curing head of

FIG. 1 comprising a light "wand" including an array of light emitting diodes.

[0023] FIG. 3 is a schematic cross-sectional view of an embodiment of the curing head of

FIG. 1 comprising a light "wand" and a spotlight. The spotlight is optional.

[0024] FIG. 4 is a close-up view of a light emitting diode array having staggered LEDs.

Linear or other geometric LED arrangements (e.g., radial) are also contemplated.

[0025] FIG. 5 is a perspective view of an example heat sink that can be used in the curing heads of FIGS. 2 and 3.

[0026] FIG. 6 is a perspective view of a curing head of the present disclosure having a housing in which an array of light emitting diodes is located.

[0027] FIG. 7 is a perspective view of the curing head of FIG. 6 showing the housing partially exploded to expose fans positioned on opposite sides of a heat sink.

[0028] FIG. 8 is a block diagram of a system circuit architecture for an exemplary curing head of the present disclosure.

[0029] FIG. 9 is a cross-sectional view of an optical fiber illustrating the propagation of light through the fiber.

[0030] FIG. 10 is a perspective view of a segment of an optical fiber.

[0031] FIG. 11 is a plan view of the optical surface of the optical fiber depicted in FIG. 10.

[0032] FIG. 12 is a cross-sectional view, taken along a longitudinal axis, of a portion of an optical fiber depicted in FIG. 10. [0033] FIG. 13 is a cross-sectional view, taken perpendicular to a longitudinal axis, of a portion of the optical fiber depicted in FIG. 10.

[0034] FIG. 14 is a schematic view of an optical fiber illumination system in accordance with aspects of the present disclosure.

[0035] FIG. 15 is a cross-sectional view of an optical fiber illustrating shadowing effects in the fiber.

[0036] Repeated use of reference characters in the specification and drawings is intended to represent the same or analogous features or elements of the disclosure. It should be understood that numerous other modifications and examples can be devised by those skilled in the art, which fall within the scope and spirit of the principles of the disclosure. Figures may not be drawn to scale.

DESCRIPTION

[0037] One of the challenges with light-cure on demand sealing compositions is their cure speed at a given depth of application, especially when a highly filled opaque/colored system is used. To resolve this issue, the sealing compositions of the various embodiments described herein employ a light-emitting curing device that balances the depth of cure and cure speed. Theoretically, longer wavelength light, such as visible light, penetrates deeper than short wavelength light, such as UV. However, short wavelength light has higher energy and more efficiently trigger the initiator, compared with longer wavelength light. In this case, there is a fine balance between depth of cure and cure speed by designing the right wavelength lamp and sealing composition.

[0038] The various embodiments of the described herein employ "blue wavelength" because such light can cure significantly deep applications of the various compositions described herein, even when the compositions are highly filled opaque/colored. The light-emitting curing device of the various embodiments described herein provides a flexible assembly of different geometries and a high conversion efficiency from electricity to radiant energy, which enables the design of cordless battery rechargeable device.

[0039] In addition, the sealing compositions of the various embodiments described herein can accelerate productivity so that parts, such as vehicle parts and the vehicles into which they are incorporated, can be moved out of a body shop faster and bring more profit to shop owners; could reduce inventory due to the multiple use capability to potentially replace existing sealing compositions; and provide true global performance at all temperature ranges and humidity environments.

[0040] Various embodiments described herein are directed to a sealing composition comprising: a urethane aery late component; and a photoinitiator. In some embodiments, the sealing composition comprises a urethane aery late component in an amount of from about 30 wt.% to about 99.9 wt.% of the total weight of the sealing composition; and a photoinitiator having an extinction coefficient of from about 10 to about 2000 L/mol cm (e.g., about 50 to about 500 L/mol cm or about 100 to about 700 L/mol cm) at a wavelength from about 400 nm to about 500 nm in an amount of from about 0.1 wt.% to about 10 wt.%.

[0041] The sealing compositions can further comprise a filler component that makes up from about 1 wt.% to about 70 wt.% of the total weight of the sealing composition. The filler can be transparent, translucent, opaque or can comprise mixtures of fillers that are opaque and/or transparent such that a filler composition can span the entire spectrum from transparent to opaque and everywhere in between. The sealing compositions can further comprise at least one monothiol, polythiol or a combination of mono- and polythiol, in an amount of from about 0.5 wt.% to about 30 wt.% of the total weight of the sealing composition. In other embodiments, the sealing compositions can further comprise at least one plasticizer in an amount of from about 1 wt.% to about 40 wt.% of the total weight of the sealing composition. In yet other embodiments, the sealing composition can further comprise at least one adhesion promoter in an amount of from about 0.3 wt.% to about 20 wt.% (e.g., about 0.3 wt.% to about 10 wt.%) of the total weight of the sealing composition. The sealing compositions can further comprise at least one polymerizable or non- polymerizable diluent. In some embodiments, the sealing compositions comprise combinations of the foregoing urethane acrylate component and photoinitiator and at least one of the one or more fillers, one or more monothiols, polythiols or a combination of mono- and polythiols, one or more plasticizers, one or more adhesion promoters, and one or more diluents.

[0042] The sealing compositions of the various embodiments described herein advantageously, and unexpectedly, can be polymerized/cured to a depth of cure of up to about 30 mm within about 0.5 second to about two minutes; about 1 second to about 5 seconds; about 1 second to about 10 seconds; about 5 seconds to about 30 seconds; about 30 seconds to about two minutes; or about 45 seconds to about 1.5 minutes per exposure area when the sealing composition is irradiated with a light-emitting curing device (described in greater detail herein) emitting a wavelength of light of from about 260 nm to about 550 nm (e.g., from about 350 nm to about 550 nm, about 400 nm to about 500 nm; about 425 nm to about 475 nm; or about 440 nm to about 460 nm) and having a radiometric energy of about at least about 0.1 W/cm ² (e.g., about 0.5 W/cm ² to about 5 W/cm ² ; about 1 W/cm ² to about 3 W/cm ² ; about 1 W/cm ² to about 2 W/cm ² ; or about 0.5 W/cm ² to about 2 W/cm ² ).

[0043] It should be understood that the rate at which sealing compositions of the various embodiments described herein can be polymerized/cured can depend on the presence of certain components, when present, and the amount of those components. For example, the polymerization/cure rate of the sealing compositions of the various embodiments described herein can depend on the amount and/or type of filler contained in the sealing compositions, when a filler component is used. Thus, for example, if the sealing compositions are loaded with a relatively large amount of an opaque filler component (e.g., 70 wt.%), the curing time might be closer to 2 minutes per exposure area, even at a 30 mm depth, But if the filler component is transparent or translucent, the curing time might be closer to 1 second per exposure area, even if the sealing compositions are loaded with a relatively large amount of a filler component (e.g., 70 wt.%).

[0044] As used herein, the term "depth" generally refers to the thickness of a length of sealing composition of the various embodiments described herein applied to a substrate (e.g., an automotive part or body part, including a windshield assembly or at least a portion of an automotive windshield assembly, a truck, a door, a deck lid, a hood, a lift age, a tail gate, and a rear body panel), measured orthogonally to the surface of the substrate onto which the sealing composition is applied.

[0045] Light-curable aery late systems are particularly advantageous because they provide a robust fast cure feature that is not affected by humidity or other environmental conditions and have corrosion-prevention properties that are advantageous in applications in, among other areas, as sealing compositions in the automotive industry.

[0046] Suitable urethane acrylate components for use in the sealing compositions include aliphatic urethane acrylates and aromatic urethane acrylates. In some embodiments, the urethane acrylates can be mono-acrylates, di-acrylates, tri-acrylates or mixtures of mono-, di-, and/or tri- acrylates.

[0047] Examples of suitable urethane acrylates include, but are not limited to oligomers and prepolymers including aliphatic urethane acrylates, commercial examples of which include those from Cytec Surface Specialties under the trademark EBECRYL and designations 244, 264, 265, 284N, 1290, 4833, 4866, 8210, 8301, 8402, 8405, 8807, 5129 and 8411; those available from Sartomer under the designations CN 131, CN 704, CN 911, CN973H85, CN985B88, 964, 944B85, 963B80, CN 973J75, CN 973H85, CN 929, CN 996, CN 966J75, CN 968, CN 980, CN 981, CN 982B88, CN 982B90, CN 983, CN991; CN 2920, CN 2921, CN 2922, CN 9001, CN 9006, CN 9008, CN 9009, CN 9010, CN 9031, CN 9782; GENOMER 4302 and 4316 and UA 00-022 available from Rahn; PHOTOMER 6892 and 6008 available from Cognis; NK OLIGO U24A and U-15HA available from Kowa. Additional urethane acrylates include the BR series of aliphatic urethane acrylates such as BR 144 or 970 available from Bomar Specialties or the LAROMER series of aliphatic urethane acrylates such as LAROMER LR 8987 from BASF.

[0048] Suitable urethane acrylate components for use in the sealing compositions also include, but are not limited to those known by the trade designations: PHOTOMER (for example, PHOTOMER 6010 from Henkel Corp. of Hoboken, N.J.; EBECRYL (for example, EBECRYL 220 (a hexafunctional aromatic urethane acrylate of molecular weight 1000), EBECRYL 284 (aliphatic urethane diacrylate of 1200 grams/mole molecular weight diluted with 1,6-hexanediol diacrylate), EBECRYL 4827 (aromatic urethane diacrylate of 1600 grams/mole molecular weight), EBECRYL 4830 (aliphatic urethane diacrylate of 1200 grams/mole molecular weight diluted with tetraethylene glycol diacrylate), EBECRYL 6602 (trifunctional aromatic urethane acrylate of 1300 grams/mole molecular weight diluted with trimethylolpropane ethoxy triacrylate), and EBECRYL 840 (aliphatic urethane diacrylate of 1000 grams/mole molecular weight)) from UCB Radcure of Smyrna, Ga.; SARTOMER (for example, SARTOMER 9635, 9645, 9655, 963-B80, and 966-A80) from Sartomer Co., West Chester, Pa.; and UVITHANE (for example, UVITHANE 782) from Morton International, Chicago, 111.

[0049] Suitable urethane acrylate components for use in the sealing compositions also include, but are not limited to aliphatic urethane acrylates available from Soltech Ltd., Kyoungnam, Korea, such as SU 500 (aliphatic urethane diacrylate with isobornyl acrylate), SU 5020 (aliphatic urethane acrylate with butyl acetate), SU 5030 (aliphatic urethane acrylate with butyl acetate), SU 5039 (nona(9)-functional aliphatic urethane acrylate oligomer), SU 511 (aliphatic urethane diacrylate), SU 512 (aliphatic urethane diacrylate), SU 514 (aliphatic urethane diacrylate with hexane diol diacrylate (HDD A)), SU 591 (aliphatic urethane triacrylate with N-(2-hydroxypropyl) methacrylamide), SU 520 (deca(lO)-functional aliphatic urethane acrylate), SU 522 (hexa- functional aliphatic urethane acrylate), SU 5225 (aliphatic urethane diacrylate with isobornyl acrylate), SU 522B (hexa-functional aliphatic urethane acrylate), SU 5260 (aliphatic urethane triacrylate), SU 5270 (aliphatic urethane diacrylate), SU 530 (aliphatic urethane diacrylate), SU 5347 (aliphatic urethane diacrylate), SU 542 (low viscosity aliphatic urethane diacrylate), SU 543 (low viscosity aliphatic urethane diacrylate), SU 564 (aliphatic urethane triacrylate with HDD A), SU 565 (aliphatic urethane triacrylate with tripropylene glycol diacrylate), SU 570 (aliphatic urethane diacrylate), SU 571 (hexa functional aliphatic urethane diacrylate), SU 574 (aliphatic urethane triacrylate with HDD A), SU 574B (aliphatic urethane triacrylate with HDD A), SU 580 (aliphatic urethane diacrylate), SU 584 (aliphatic urethane triacrylate with HDD A), SU 588 (aliphatic urethane triacrylate with 2-(2-ethoxyethoxy)ethyl acrylate), and SU 594 (aliphatic urethane triacrylate with HDD A).

[0050] Suitable urethane acrylate components for use in the sealing compositions also include, but are not limited to aromatic urethane acrylates available from Soltech Ltd., Kyoungnam, Korea, such as SU 704 (aromatic urethane triacrylate with HDD A), SU 710 (aromatic urethane diacrylate), SU 720 (hexa-functional aromatic urethane acrylate), and SU 7206 (aromatic urethane triacrylate with trimethylolpropane triacrylate (TMPTA).

[0051] The urethane acrylate component is present in an amount of from about 30 wt.% to about 99.9 wt.%, from about 30 wt.% to about 65 wt.%, from about 40 wt.% to about 50 wt.%, from about 45 wt.% to about 55 wt.% or about from about 50 wt.% to about 60 wt.% of the total weight of the sealing composition.

[0052] Suitable photoinitiators for use in the sealing compositions include, photoinitiators having an extinction coefficient of from about 10 to about 2000 L/mol cm (e.g., about 50 to about 500 L/mol cm or about 100 to about 700 L/mol cm) at a wavelength from about 400 nm to about 500 nm.

Examples of suitable photoinitiators for use in the sealing compositions include, but are not limited to quinones, alpha aminoketones, benzophenones, phosphine oxides, phosphinates, alpha hydroxyketones, mixtures thereof and the like. Photoinitiators include camphorquinone (CPQ), 1- hydroxycyclohexyl-phenylketone available from Ciba Geigy under IRGACURE 184, oligomeric alpha hydroxyketones, such as ESACURE ONE or KIP 150 from Lamberti, 2-benzyl 2-N- dimethylamino-l-(4-moφholinophenyl)-l-butanone available from Ciba Geigy under IRGACURE 369, IRGACURE 379, and phosphine oxides available from BASF under LUCIRIN TPO, LUCIRIN TPO-L, LUCIRIN TPO-XL, or IRGACURE 819, IRGACURE 2100 from Ciba, mixtures thereof, such as SARCURE and SR 1135 from Sartomer or ESCACURE KTO 46 or TZT from Lamberti, which is a mixture of an alpha hydroxy ketone benzophenone derivatives and a phosphine oxide,

and the like. In some embodiments, the photoinitiator is

[0053] In some embodiments, the photoinitiator is present in an amount of about 0.1, about

1, about 2, about 4, about 6, about 8 or about 10 parts by weight or greater based on the weight of the sealing composition. In other embodiments, the photoinitiator(s) is (are) present in an amount of from about 0.1 wt.% to about 10 wt.%, about 2 wt.% to about 8 wt.%, from about 0.5 wt.% to about 10 wt.%, from about 0.5 wt.% to about 5 wt.%, from about 0.5 wt.% to about 2 wt.%, from about 1 wt.% to about 3 wt.% of the total weight of the sealing composition. In some embodiments, the photoinitiator(s) is (are) present in about 2 wt.%.

[0054] Suitable one or more fillers for use in the sealing compositions include, but are not limited to alumina (e.g., alpha alumina), silica (e.g., fumed, such as CAB-O-SIL TS-720 and TS- 710 or fused, Cabot Corp., Billerica, Ma.), mica, kaolin, talc, barium sulfate, carbides, potassium sulfate, calcium carbonate (including surface-modified calcium carbonate), zinc oxide, silicates, clay, titanium dioxide, zirconia, boron carbide, silicon carbide, cerium oxide, glass, wollastonite, diamond, aluminum nitride, silicon nitride, yttrium oxide, titanium diboride, metallic salts of fatty acids, or any combination thereof. Other fillers may be employed, such as those described in U.S. Pat. No. 7,781,493, which is incorporated by reference as if fully set forth herein. In some embodiments, fillers may contain surface hydroxy Is, have a particle size of about 10 microns or less or 5 microns or less, or both. The filler is present in an amount of from about 1 wt.% to about 70 wt.%, 1 wt.% to about 30 wt.%, from about 1 wt.% to about 25 wt.%, from about 1 wt.% to about 15 wt.%, from about 1 wt.% to about 10 wt.% or about from about 2 wt.% to about 6 wt.% of the total weight of the sealing composition.

[0055] Suitable one or more monothiols include, but are not limited to 1-ethanethiol, 1- propanethiol, 3-propanethiol, 3-butanethiol, 1-butanethiol, 2-butanethiol, 3-pentanethiol, 1- pentanethiol, 1-hexanethiol, l-mercapto-3-methylbutane, and a combination of any of the foregoing. A monothiol may have one or more pendant groups selected from an alkyl group, an alkoxy group, and a hydroxy 1 group. Other suitable monothiols include those of the formula (I):

R ¹ — SH

wherein R ¹ is (CH3)-(CH ₂ )r-X ¹ -(CH ₂ )r-, wherein r is an integer from 0 to 4 and X ¹ is -0-, -S- or C(R ² )2, wherein R ² is H or (Ci-Ce) alkyl. Examples of compounds encompassed by formula (I) include, for example, CH ₃ CH(-CH ₃ )-S-CH ₂ CH ₂ -SH, CH ₃ CH ₂ CH ₂ -SCH ₂ CH ₂ -SH, CH ₃ CH(-CH ₃ )-S- CH(CH ₃ )CH ₂ -SH and CH ₃ CH2CH2-S-CH2 CH(CH ₃ )-SH.

[0056] Suitable one or more polythiols include, but are not limited to dithiols, trithiols, and tetrathiols.

[0057] Examples of dithiols include, but are not limited to, 1,2-ethanedithiol, 1,2- propanedithiol, 1,3-propanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,3- pentanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, l,3-dimercapto-3-methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide, methyl- substituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane, l,5-dimercapto-3-oxapentane, and a combination of any of the foregoing. A polythiol may have one or more pendant groups selected from an alkyl group, an alkoxy group, and a hydroxy 1 group. Other suitable dithiols include those of the formula (II):

HS— R ³ — SH

wherein R ³ is -[(-CH2-)s-X ² -]q-(CH ₂ )r-, wherein s is an integer from 1 to 4, r is an integer from 1 to 4, q is an integer from 1 to 3, and X is -O- or -S-). Examples of compounds encompassed by formula (I) include dimercaptodiethylsulfide (DMDS); dimercaptodioxaoctane (DMDO); and 1,5- dimercapto-3-oxapentane. Other compounds encompassed by the formula (I) include, for example, methyl-substituted DMDS, such as HS-CH ₂ CH(-CH ₃ )-S-CH ₂ CH ₂ -SH, HS-CH(-CH ₃ )CH ₂ - SCH ₂ CH ₂ -SH and dimethyl substituted DMDS, such as HS-CH ₂ CH(-CH ₃ )-S-CH(CH3)CH ₂ -SH and HS-CH(CH ₃ )CH ₂ -S-CH ₂ CH(CH ₃ )-SH. It is also possible to use dithiols wherein X is -O- and -S- and pendant alkyl groups.

[0058] Examples of trithiols include, but are not limited to, 3,6-dimercaptomethyl-l,9- dimercapto-2,5,8-trithianonane, l,2,9-trimercapto-4,6,8-trithianonane, 3,7-dimercaptomethyl-l,9- dimercapto-2,5,8-trithianonane, 4,6-dimercaptomethyl-l,9-dimercapto-2,5,8-trithianonane, l,4,8,l l-tetramercapto-2,6,10-trithiaundecane, and combinations thereof. [0059] Examples of treatrathiols include, but are not limited to, 1, 4,9,12-tetramercapto-

2,6,7, 11-tetrathiadodecane, 1,4,9, 12-tetramercapto-2,6,7, 11-tetrathiadodecane, 2,3,5,6-tetrathia- 1,7-heptanedithiol, and combinations thereof.

[0060] Aromatic polythiols are also contemplated. Examples of aromatic polythiols include, but are not limited to, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4- dimercaptobenzene, l,2-bis(mercaptomethyl)benzene, l,3-bis(mercaptomethyl)benzene, 1,4- bis(mercaptomethyl)-benzene, l,2-bis(mercaptoethyl)benzene, l,3-bis(mercaptoethyl)benzene, 1,4- bis(mercaptoethyl)-benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5- trimercaptobenzene, l,2,3-tris(mercaptomethyl)benzene, l,2,4-tris(mercaptomethyl)benzene, 1,3,5- tris(mercaptomethyl)benzene, l,2,3-tris(mercaptoethyl)benzene, l,2,4-tris(mercaptoethyl)benzene, l,3,5-tris(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, l,3-di(p- methoxypheny l)propane-2,2-dithiol, 1 ,3 -dipheny lpropane-2,2-dithiol, pheny Imethane- 1 , 1 -dithiol and 2,4-di(p-mercaptophenyl)pentane, and combinations thereof.

[0061] In some embodiments, thiols are included in the sealing compositions of the various embodiments described herein in an amount such that the ratio of thiol functionality to acrylate functionality in the urethane acrylate component is 3: 10; 2: 10; or 1 : 10 thiol to acrylate.

[0062] Suitable one or more plasticizers for use in the sealing compositions include, but are not limited to plasticizers having a broad range of molecular weights and architectures. The plasticizers may be polymeric or monomeric. Small molecule plasticizers are typically derived from mono- or multi-functional, low molecular weight acids or alcohols that are esterified with a mono- functional alcohol or mono-functional acid, respectively. Common among these monomeric plasticizers are esters of mono- or di-basic acids such as myristate esters, phthalate esters, adipate esters, phosphate esters, citrates, trimellitates, glutarates, and sebacate esters (e.g., dialkyl phthalates, such as dibutyl phthalate, diisoctyl phthalate, dibutyl adipate, dioctyl adipate; 2-ethylhexyl diphenyl diphosphate; t-butylphenyl diphenyl phosphate; butyl benzylphthalates; dibutoxyethoxyethyl adipate; dibutoxypropoxypropyl adipate; acetyltri-n-butyl citrate; dibutylsebacate; etc.). Phosphate ester plasticizers are commercially sold under the trade designation SANTICIZER from Monsanto; St. Louis, Mo. Glutarate plasticizers are commercially sold under the trade designation PLASTHALL 7050 from Hallstar; Chicago, 111. Suitable plasticizers also include PLASTHALL 190.

[0063] Suitable one or more adhesion promoters for use in the sealing compositions include, but are not limited to acid-functional monomers such as acrylic acid (AA), methacrylic acid (MAA), beta-carboxy ethyl acrylate (B-CEA) and 2-hydroxy ethyl methacrylate (HEMA) phosphate. Suitable one or more adhesion promoters for use in the sealing compositions also include, but are not limited to (meth)acrylate functional silanes, including (3-acryloxypropyl)trimethoxysilane, methacryloxypropyltrimethoxysilane, N-(3-acryloxy-2-hydropropyl)-3- aminopropyltriethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, methacryloxypropyldimethylethoxysilane, and methacryloxypropyldimethylmethoxysilane, all of which are available from Gelest, Inc., Morrisville, Pa. Other suitable one or more adhesion promoters include basic functional monomers such as N-vinyl-caprolactam, N,N-dimethyl acrylamide, acrylamide, acrylonitrile, N-tert- butylacrylamide, 2-tert-butylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, N-isopropylacrylamide, methacrylonitrile, vinyl carbazole, 2- vinylpyridine, 4-vinylpyridine, and l-vinyl-2-pyrrolidone.

[0064] Suitable one or more diluents for use in the sealing compositions include, but are not limited to reactive and non-reactive diluents. Examples of reactive diluents include monomers including monoacrylates such as phenylthio ethyl(meth)acrylate, isooctyl acrylate (e.g., commercially available as SR-440 from Sartomer, Exton, Pa.), isodecyl acrylate (e.g., commercially available as SR-395 from Sartomer), isobornyl acrylate (e.g., commercially available as SR-506 from Sartomer), 2-phenoxyethyl acrylate (e.g., commercially available as SR-339 from Sartomer), alkoxylated tetrahydrofurfuryl acrylate (e.g., commercially available as CD-611 from Sartomer), and 2(2-ethoxyethoxy)ethylacrylate (e.g., commercially available as SR-256 from Sartomer); diacrylates such as 1,3-butylene glycol diacrylate (e.g., commercially available as SR-212 from Sartomer), 1,6-hexanediol diacrylate (e.g., commercially available as SR-238 from Sartomer), neopentyl glycol diacrylate (e.g., commercially available as SR-247 from Sartomer), and diethylene glycol diacrylate (e.g., commercially available as SR-230 from Sartomer). Other reactive diluent monomers include, for example, methyl styrene, styrene, divnyl benzene, and the like.

[0065] It should be understood that certain components described herein can act as non- reactive diluents, including plasticizers and fillers and combinations thereof. Tackifiers can also act as non-reactive diluents, including hydrogenated rosins and synthetic hydrocarbon resins.

[0066] The sealing compositions of the various embodiments described herein can further comprise any number of additives as desired. Examples of suitable additives include, photosensitizers (e.g., coumarin photosensitizers such as (7-ethoxy-4-methylcoumarin-3- yl)phenyliodonium hexafluoroantimonate, (7-ethoxy-4-methylcoumarin-6-yl)]phenyliodonium hexafluoroantimonate, (7-ethoxy-4-methylcoumarin-3-yl)phenyliodonium hexafluorophosphate, (7-ethoxy-4-methylcoumarin-6-yl)]phenyliodonium hexafluorophosphate, such as those described in Ortyl and Popielarz, Polimery 57: 510-517 (2012), which is incorporated by reference as if fully set forth herein; 1,3-dioxane methyl couramin, such as is described in Yin et al., Journal of Applied Polymer Science 125: 2371-2371 (2012), which is incorporated by reference as if fully set forth herein; coumarin dye; and ketocoumarin dye), pigments, surfactants, thixotropic agents, fire retardants, masking agents, and combinations of any of the foregoing. When used, the additives may be present in a composition in an amount ranging, for example, from about 0% to 20% by weight. In certain embodiments, additives may be present in a composition in an amount ranging from about 1% to 15% by weight. Photosensitizers, when present, can be present in an amount of from about 0.05 wt.% to about 5 wt.% (e.g., from about 0.5 wt.% to about 1 wt.%, about 1 wt.% to about 3 wt.% or about 0.05 wt.% to about 0.5 wt.%).

[0067] In some embodiments, the automotive parts that are sealed with the sealing compositions of the various embodiments described herein are optionally treated with a suitable primer, such as 8682 (a single step primer) or AP-111, both available from 3M, St. Paul, Mn. And the sealing composition is, in turn, applied as a layer on the primer, in some embodiments a layer that substantially covers the primer.

[0068] The sealing compositions of the various embodiments described herein can be polymerized/cured by any suitable method, including photochemically. In one embodiment, the sealing compositions of the various embodiments described herein can be polymerized/cured using a light-emitting curing device emitting light at a wavelength of from about 260 nm to about 550 nm (e.g., from about 400 nm to about 500 nm; about 425 nm to about 475 nm; or about 440 nm to about 460 nm) and having a radiometric energy of about at least about 0.1 W/cm ² (e.g., about 0.5 W/cm ² to about 5 W/cm ² ; about 1 W/cm ² to about 3 W/cm ² ; about 1 W/cm ² to about 2 W/cm ² ; or about 0.5 W/cm ² to about 2 W/cm ² ).

[0069] It should be understood that any suitable light-emitting curing device emitting light at a wavelength of from about 260 nm to about 550 nm and having a radiometric energy of about at least about 0.1 W/cm ² can be used to polymerize/cure the sealing compositions of the various embodiments described herein. In some embodiments, a suitable light-emitting curing device can use light emitting diodes (LEDs), but need not be limited to light-emitting curing devices based on LEDs. But any suitable source of light of wavelength of from about 260 nm to about 550 nm and having a radiometric energy of about at least about 0.1 W/cm ² can be used.

[0070] FIG. 1 is a schematic view of a sealing system 10 including curing head 12 of the present disclosure including an air-cooled, light-emitting curing device 14. Sealant system 10 can also include system controller 16, dispensing device 18 and jig 20. Curing head 12 can also include controller 22 and sensor system 24 (optional). Light-emitting curing device 14 can also include light- emitter 26, heat sink 28, fans 30A and 30B and lens 32. Dispensing device 18 can include first nozzle 40A, first container 42A, second nozzle 40B, second container 40B and controller 44. Sealing system 10 can be used to apply and cure a sealing composition on object 46.

[0071] Jig 20 can be used to support object 46 during dispensing and curing operations.

Dispensing device 18 can be used to apply a liquid material to object 46. Subsequently, curing device 14 can be used to cure the liquid material dispensed by dispensing device 18. System controller 16 can be connected to curing controller 22 and dispenser controller 44 in order to coordinate operations of curing device 14 and dispensing device 18.

[0072] Jig 20 can comprise any suitable device for holding object 46. Jig 20 can be configured to hold object 46 in a stationary manner with a side or sides of object 46 facing toward dispensing device 18 and curing device 14. In various examples, jig 20 can be configured to rotate or move object 46 in multiple directions to orient object 46 relative to dispensing device 18 and curing device 14 using any suitable means. In additional examples, dispensing device 18 and curing device 14 can be attached to robotic arms and can be configured to move relative to jig 20 and object 46 to provide complete sealant and curing coverage to object 46. Also, dispensing device 18 and curing device 14 can be manually positioned and operated devices.

[0073] The light-emitting curing device 14 can be held at any suitable distance from object

46, even in direct contact with a sealing composition that is dispensed onto the object 46. In some embodiments, the distance between the light-emitting curing device 14 and a sealing composition that is dispensed onto the object 46 can be optimized such that the intensity of light that is dispensed from light-emitting curing device 14 is maximized and/or the curing time of a sealing composition that is dispensed onto the object 46 is minimized (e.g., minimized to from about 0.5 second to about two minutes).

[0074] In an example, object 46 can comprise a substrate, such as an automotive body part requiring sealing, and dispensing device 18 can be configured to apply a multi-component sealing composition to the part. Although, system 10 can be used to apply any of the compositions of the various embodiments described herein to any object. In an example, the material dispensed by dispensing device 18 can comprise sealing composition of the various embodiments described herein, including one or more fillers, one or more thiols, one or more plasticizers, one or more one or more adhesion promoters, and one or more diluents.

[0075] In an example, components of the sealing composition can be individually loaded into containers 40A and 40B and dispensed from nozzles 42 A and 42B, respectively. Thus, the components can become mixed and entrained while in transit from nozzles 42A and 42B to object 46. In other examples, the components of the sealing composition can be pre-mixed and dispensed using only a single storage container and nozzle. In embodiments, dispensing device 18 can be automatically controlled. That is, nozzles 40A and 40B can be configured to open on demand by a signal generated from controller 44. Controller 44 can be configured to open and close valves within dispensing device 18. In other examples, dispensing device 18 can comprise a hand-held, manually operated device, such as something akin to a caulking gun or a syringe-type device.

[0076] Curing device 14 can be used to treat material dispensed by dispensing device 18.

In an example, curing device 14 can be used to cure a sealing composition by subjecting the composition to light of a particular wavelength and intensity using emitter 26. In an example, emitter 26 can comprise one or more light emitting diodes (LEDs). Specifically, emitter 26 can comprise an array of LEDs arranged to provide a wide swath of light in a consistent or uniform manner while also providing spacing that permits effective cooling. Lens 32 can be positioned in front of emitter 26, e.g., between object 46 and emitter 26, in order to condition or alter light waves emanating from emitter 26, as discussed herein. However, lens 32 can be configured as a transparent plate so as to not alter light waves from emitter 26. [0077] In order to dissipate heat generated by emitter 26, heat sink 28 can be positioned adjacent emitter 26. In an example, heat sink 28 can be positioned behind emitter 26, e.g., away from the direction of object 46. In an example, heat sink 28 can comprise a plurality of fins to draw heat away from emitter 26 and increase a surface area from which the heat can dissipate. Fans 30A and 30B can be used to further remove heat from emitter 26. For example, fans 30A and 30B can be used to push air past fins of heat sink 28.

[0078] Curing head 12 can include sensor system 24 that can be used to control operation of curing device 14. In various examples, sensor system 24 can comprise a temperature sensor to monitor the temperature of emitter 26. Controller 22 can monitor an output signal of sensor system 24 to, for example, adjust the operation of fans 3 OA and 30B to increase or decrease the amount of airflow applied to emitter 26 and/or the 28. Other cooling methods are contemplated, including heat pipes, or liquid cooling technology. Controller 22 can also adjust the intensity or brightness of light originating from emitter 26, such as by controlling power delivered to emitter 26. Heat sink 28, sensor system 24 and other components and accessories of curing head 12 can be configured in different arrangements and combinations in other embodiments, such as those shown in FIGS. 2 and 3.

[0079] FIG. 2 is a schematic cross-sectional view of an embodiment of curing head 12 of

FIG. 1 configured as a hand-held "wand" wherein emitter 26 comprises an elongate bank of light emitting diodes. Curing head 12 can include chassis 48 and housing 50 having upper housing component 50A and lower housing component 50B. Sensor system 24 can include lens sensor 24A and heat sink sensor 24B. Heat sink 28 can include heat sink banks 28A, 28B and 28C, and cross slots 52A and 52B.

[0080] Housing 50 can be configured to contain elements of curing head 12 in a self- contained package that can, for example, be a hand-held device. Housing 50 can be configured to open such as by separating upper housing component 50 A from lower housing component 50B. Housing components 50A and 50B can be held together by any suitable means, such as by means that permit components 5 OA and 50B to be releasably coupled together for repeated opening and closing. Lower housing component 50B can comprise opening 54. Lens 32 can be positioned adjacent opening 54. Chassis 48 can be mounted to lower housing component 50B, and emitter 26 can be mounted to chassis 48 to face toward opening 54. Gaps can be positioned between opening 54 and lens 32, and emitter 26 can be positioned back a distance from opening 54 so that cooling channel 56 can be positioned through housing 50.

[0081] Heat sink banks 28 A, 28B and 28C can be mounted to chassis 48 opposite emitter

26. More specifically, heat sink banks 28A - 28C can be positioned on chassis 48 to be in direct or indirect thermal communication with emitter 26. As such, heat sink banks 28 A - 28C can draw heat away from emitter 26 either directly or indirectly through chassis 48. As discussed in greater detail with reference to FIG. 5, each of heat sink banks 28 A - 28C can comprise a plurality of plate-like fins. The fins can be oriented in a common direction through housing 50, such as the direction extending between fans 30A and 30B. Fans 30A and 30B can be positioned to push and or pull air through the fins to increase thermal transfer of heat away from emitter 26. As shown in FIG. 7, housing 50 can include vents to facilitate airflow through curing head 12.

[0082] In some embodiments, fans 30A and 30B can be mounted on chassis 48. Cross slots

52A and 52B can be positioned between heat sink bank 28A and 28B and 28B and 28C, respectively, to help reduce resistance of the airflow through heat sink 28. Cross slots 52A and 52B can comprise gaps in heat sink 28, such as between banks of plate-like fins. Sensor 24A can be positioned in cross slot 52A to sense the temperature in heat sink 28. Sensor 24B can be positioned in channel 56 to sense the temperature of emitter 26. Emitter 26, fans 3 OA and 30B and sensors 24A and 24B can be connected to controller 22 (FIG. 1), which can be located within housing 50. Fans 30A and 30B and sensors 24A and 24B can comprise any suitable type of fan device or sensor device, respectively, as is known in the art.

[0083] In operation, controller 22 can activate, or a button on controller 22 can be activated by an operator, to energize emitter 26 in order to generate light beams 60. In example embodiments, emitter 26 can comprise an array of LEDs. More specifically, emitter 26 can comprise a 5 x 5 array of LEDs emitting light at a wavelength of from about 260 nm to about 550 nm (e.g., from about 400 nm to about 500 nm; about 425 nm to about 475 nm; or about 440 nm to about 460 nm) and having a radiometric energy of about at least about 0.1 W/cm ² (e.g., about 0.5 W/cm ² to about 5 W/cm ² ; about 1 W/cm ² to about 3 W/cm ² ; about 1 W/cm ² to about 2 W/cm ² ; or about 0.5 W/cm ² to about 2 W/cm ² ). Such an emitter can be used with a sealing composition comprising at least a photoinitiator responsive to the wavelength of light emitted by the LED array. Curing times for such an LED array and seam sealing composition can be about 0.5 second to about two minutes; about 1 second to about 5 seconds; about 1 second to about 10 seconds; about 5 seconds to about 30 seconds; about 30 seconds to about two minutes; or about 45 seconds to about 1.5 minutes.

[0084] In example wand configurations, such as that of FIG. 2, emitter 26 can include an elongate array of 240 LEDs. As discussed below with reference to FIG. 4, diodes of the array can be arranged in a staggered pattern. The staggering pattern can be configured such that a uniform, efficient, radiometrically intense, short wavelength photonic system can result, which can be useful for initiating curing reactions. The 240 LEDs can be driven by controller 22 at up to 2W (~2 J/sec) per LED, which can result in a 480W (-480 J/sec) electrical load. Various means can be used to dissipate thermal heat generated by the 240 LEDs. For example, if the 240 LEDs are approximately 40% efficient, the estimated thermal load can be approximately 480 W x 0.6, which equals approximately 300 W (300 J/sec). Thus, fans 30A and 30B can be configured to remove a corresponding amount of heat.

[0085] In some embodiments, light beams 60 can pass through lens 32. Lens 32 can comprise a transparent plate, a Fresnel lens or an optical filter. Lens 32 can have edges that can be shaped or treated with filtering or reflective material to minimize photonic leakage. That is, the sides of lens 32 can be configured to recycle some of light beams 60 that would escape the sides of lens 32 and direct it through the planar faces of lens 32. In examples, a polyimide tape or a reflective film can be applied to the edges of lens 32. Lens 32 can comprise a hard material so as to be configured to protect emitter 26. Lens 32 can, by partially closing off opening 54, can cause turbulence within air flowing through housing 50 adjacent emitter 26 to promote heat transfer.

[0086] Most of the heat from the LEDs can be conducted from the backside of emitter 26 by heat sink banks 28A - 28C. Lens 32 can be used to aid in conducting air past emitter 26. Fans 30 A and 30B can be configured to flow air from a first side of housing 50 to a second side of housing 50. As shown in FIG. 2, air can enter gap 54 near fan 30A, can be pushed through channel 56, and can be pulled through channel 56 by fan 30B. Lens 32 can be positioned relative to emitter 26 to increase turbulence. Fans 30 A and 30B can also be positioned to push and pull air through heat sink banks 28A - 28C. Cross slots 52A and 52B can assist in reducing resistance, or drag, of airflow through heat sink 28. Furthermore, a gap can be included between the upper surfaces of heat sink banks 28A - 28C and upper housing component 5 OA to permit additional air mixing.

[0087] Sensors 24A and 24B can be operated by controller 22 to monitor the temperature in curing head 12. Controller 22 can thus adjust operation of fans 30A and 30B to adjust the temperature of emitter 26. Other types of sensors, such as power sensors and radiometric energy sensors, can be included in curing head 12. Output of sensors used with curing head 12 can be communicated to controller 22 or another control module using various wired or wireless connections.

[0088] FIG. 3 is a schematic cross-sectional view of an embodiment of curing head 12 of

FIG. 1 configured as a "wand" wherein emitter 26 comprises an elongate bank of light emitting diodes and curing head 12 additionally includes LED spotlight 56. Features of the embodiments of curing head 12 shown in FIGS. 2 and 3 can be combined in any desirable permutation.

[0089] In some embodiments, curing head 12 of FIG. 3 can include the same components as curing head 12 of FIG. 2 with the addition of LED spotlight 56, handle 58 and insulation 60. LED spotlight 56 can comprise an additional array of LEDs to provide an additional light beam for curing or illuminating purposes. LED spotlight 56 can be positioned to emit light at an angle to the primary direction that emitter 26 emits light beams 60. LED spotlight 56 can be used to provide spot curing of a sealing composition, such as to provide touch-up work, with emitter 26 powered off.

[0090] Handle 58 can be connected to upper housing component 50 A to facilitate manual operation of curing head 12. For example, handle 58 can comprise an elongate bar that an operator of curing head 12 can grasp to manipulate curing head 12. Insulation 60 can be positioned in upper housing component 50A between heat sink banks 28A - 28C and handle 58 in order to insulate, or thermally separate, handle 58 from heat dissipated by heat sink banks 28A - 28C. [0091] FIG. 4 is a close-up view of light emitting diode array 70 having staggered LEDs

72 and 74. LEDs 72 and 74 can be arranged in alternating columns (with respect to the orientation of FIG. 4) where rows of LEDs 72 and 74 in each column are offset from each other. Thus, LEDs 72 are offset by a particular pitch defined as the gap, in millimeters, between each individual LED 72. In addition, LEDs 72 are displaced higher than LEDs 74 in a vertical direction (with respect to the orientation of FIG. 4) and the distance between each of LEDs 72 and/or each of LEDs 74 is from about 1.5 mm to about 12 mm (e.g., 1.5 mm to about 3 mm; 2 mm to about 6 mm; 1.5 mm to about 4 mm; or about 3 mm to about 5 mm). Staggering of LEDs 72 and 74 can optimize light coverage provided by array 70 for curing purposes, such as by providing an overall light emission that has consistent intensity throughout. This can be useful in curing sealing compositions in a uniform and expedient manner. Staggering can also permit cooling air to uniformly pass between each LED, thereby improving cooling efficiency. Staggering of LEDs 72 and 74 can permit the quantity of LEDs to be scaled up or down while maintaining uniformity as well as spacing that is conducive to cooling.

[0092] In some embodiments, the LEDs 72 are arranged in a plurality of columns, each column comprising a plurality of light emitting diodes having a pitch within each column of from about 1.5 mm to about 12 mm (e.g., 1.5 mm to about 3 mm; 2 mm to about 6 mm; 1.5 mm to about 4 mm; or about 3 mm to about 5 mm).

[0093] Although the LEDs shown in FIG. 4 do not comprise lenses or optics, in some embodiments, the LEDs can have lenses or other optics.

[0094] FIG. 5 is a perspective view of an example heat sink 80 that can be used in curing heads 14 of FIGS. 2 and 3. Heat sink 80 can include base 82 and fins 84. Base 82 can comprise a plate or other structure that can permit fins 84 to be mounted to a structure, such as emitter 26 or chassis 48 (FIG. 2). Fins 84 can comprise rectilinear plates having first ends connected to base 82 and second ends cantilevered away from base 82. Fins 84 can thus be configured to draw heat away from base 82, which can be positioned to be in thermal communication with array 26. In an example, fins 84 can be fabricated from aluminum.

[0095] FIG. 6 is a perspective view of curing head 90 of the present disclosure having housing 92 in which an array 94 of light emitting diodes 94 is located. Housing 92 can include upper housing component 92 A and lower housing component 92B. Upper and lower housing components 92A and 92B can have an elongate, wand-like form factor in order to provide a wide emission of light that can be waved or moved across narrower strips of sealing composition, such as along the edge of a windshield.

[0096] FIG. 7 is a perspective view of curing head 90 of FIG. 6 showing housing 92 partially exploded to expose fans 94A and 94B positioned on opposite sides of heat sink 96. Upper and lower housing components 92A and 92B can be connected by any suitable means, such as threaded fasteners or snap couplings. Upper housing component 92A and lower housing component 92B can come together to form opening 97 to permit light from light emitting diodes 94 to escape. Opening 97 can be covered with a lens or plate.

[0097] Upper and lower housing components 92A and 92B can include various features to promote airflow through housing 92. For example, upper housing component 92A can include vents 98, which can comprise openings through upper housing component 92A that permit heat and air to escape from housing 92. Also, upper housing component 92A and lower housing component 92B can include side vents, such as vents 99A and 99B, respectively, that come together to form vent 99. A corresponding vent can be positioned on the opposite side of housing 92 so that fans 94A and 94B can push air through housing 92 from one side to the other, as illustrated with arrows in FIG. 2.

[0098] FIG. 8 is a block diagram of system circuit architecture 100 for an exemplary curing head of the present disclosure, such as curing head 12. Architecture 100 can include LED array 102, power switch 104, heat sink 106, fans 108A and 108B, bridge 110, LED drivers 112, isolation resistors 114, selector switches 116, AC/DC converter 118, power supply 120, power supply fan 120 and power supply 122.

[0099] Power switch 104 can be used to control transmission of power from power supply

122, which can be a battery, to LED array 102. Selector switches 116 can also be configured as switches to individually control power to different banks of LED array 102. For example, as shown in FIG. 8, LED array 102 can include 240 LEDs distributed on twenty four circuit groups. Four circuits can be grouped together and connected to bridge 110 to form six groups. Each group can be connected to one of LED drivers 112, which are each connected to isolation resistors 114. Two groups can be connected to one selector switch 116 to form an LED bank. Thus, selector switches 116 can be used to control one-third of the 240 LEDs. As mentioned, selector switches 116 can be configured as switches in order to allow an operator of architecture 100 to power on less than all of the 240 LEDs.

[00100] In another embodiment, the sealing compositions of the various embodiments described herein can be polymerized/cured using a light-emitting curing device, several non-limiting examples of which are depicted in FIGS. 9-15. In some embodiments, the light-emitting curing device(s) shown in FIGS. 9-15 can be compact and/or flexible, such that it (they) can be placed in areas that might be difficult to reach or in curved areas, such as behind the fritted portion behind a windshield.

[00101] The light-emitting curing device 310 shown in FIG. 14, for example, includes a light injection assembly 312 optically coupled with an optical fiber 314. Light injection assembly 312 includes a light source (not shown), which can, in some examples be LEDs emitting light at a wavelength of from about 260 nm to about 550 nm (e.g., from about 400 nm to about 500 nm; about 425 nm to about 475 nm; or about 440 nm to about 460 nm) and having a radiometric energy of about at least about 0.5 W/cm ² (e.g., about 0.5 W/cm ² to about 5 W/cm ² ; about 1 W/cm ² to about 3 W/cm ² ; about 1 W/cm ² to about 2 W/cm ² ; or about 0.5 W/cm ² to about 2 W/cm ² ). Light injection assembly 312 can also include a collimating assembly (not shown) for collimating light into a divergence cone which may be accepted by optical fiber 314. Optical fiber 314 includes a light emitting region 316 extending along a portion of its length. Light emitting region 316 includes at least one optical element 318 disposed about a first longitudinal axis and a second optical element 320 disposed about a second longitudinal axis, as depicted in FIGS. 9 and 10. In use, light from the light source is injected into optical fiber 314 such that the light propagates through optical fiber 314 according to Snell's law. A portion of the light propagating through optical fiber 314 becomes incident on the reflective surfaces of optical elements 318, 320 and is reflected from the fiber.

[00102] FIG. 9 illustrates that light injected into an optical fiber 210 propagates through fiber 210 along an axis of propagation 212 substantially coincident with the longitudinal axis of fiber 210. The light propagates through the fiber with a maximum cone angle, β, measured from the axis of propagation 212 that is determined by the critical angle necessary for total internal reflection. The angle β may be derived by first calculating the critical angle (Oc) required for total internal reflection from Snell's law as follows:

sin O _c = (n2 / T|l)

where ηΐ is the refractive index of the optical fiber core material and η2 is the refractive index of the surrounding medium, typically a cladding material or air. The cone angle β is the complement of the critical angle 0 _C . Thus, light propagates through optical fiber 210 in a cone angle β that is proportional to the ratio of the refractive index of the core material to the refractive index of the medium surrounding the core.

[00103] In one example, an optical fiber is provided with reflective elements for extracting light from the fiber in a manner that broadens the lateral (e.g. cross-fiber) distribution of light energy extracted from the fiber without substantially affecting the longitudinal (e.g. down-fiber) distribution of light energy extracted from the fiber. In the examples depicted in FIGS. 9-15, there is provided an optical fiber including an optical fiber core having an optically smooth surface for propagating light through the fiber and a light emitting region along at least a portion of its length, the light emitting region preferably includes a plurality of optical elements centered about a first longitudinal axis extending along the optically smooth surface of the optical fiber core and a plurality of optical elements centered about a second longitudinal axis along the optically smooth surface of the optical fiber core. Each optical element includes at least one optically reflective surface extending into the optical fiber core such that a portion of the light striking the optical element is reflected out of the optical fiber.

[00104] FIG. 10 is a perspective view of a portion of an optical fiber 220 and FIG. 11 is a plan view of a portion thereof. In the examples shown in FIGS. 10-11, optical fiber 220 includes an optical fiber core 222 having a first end surface 224, a second end surface 226, and an optically smooth surface 228 extending longitudinally along the length of fiber 220. In some examples, optically smooth surface 228 corresponds to the circumferential surface of optical fiber core 222. As used herein, the term "optically smooth surface" can refer to a surface that is capable of reflecting light incident on the surface with minimal scattering or diffusion such as is possible when the surface roughness is small in comparison to the wavelength of light. Although the fiber depicted in FIG. 10 is a 'naked' fiber, it will be appreciated by one of ordinary skill in the optical arts that the fiber may include a cladding layer(s) and/or additional jacketing layers.

[00105] Optical fiber 220 is provided with a plurality of optical elements 230 centered about a first longitudinal axis 238 extending along the optically reflective surface 228 of optical fiber 220 and a plurality of optical elements 240 centered about a second longitudinal axis 248 of optical fiber 220. First longitudinal axis 238 is displaced from second longitudinal axis 248. For most optical fibers, it is convenient to measure the angular displacement δ (FIG. 13) between first longitudinal axis 238 and second longitudinal axis 248. However, the displacement between the two longitudinal axes may also be measured as a distance along the reflective surface 228 of optical fiber 220. A distance measurement may be appropriate for optical fibers having polygonal cross-sectional shapes.

[00106] Referring to FIGS. 11 and 12, optical fiber 220 is provided with a plurality of optical elements 230 centered about a first longitudinal axis 238 along optically reflective surface 228 of fiber 220. In the examples shown in FIGS. 11-12, each optical element 230 includes a first optically reflective surface 232 that extends into the core 222 of optical fiber 220. Optically reflective surface 232 is preferably a substantially optically smooth surface, meaning that it is capable of reflecting light with minimal losses due to scattering or diffusion. Surface 232 may be disposed at any useful angle between 0° and 90° from an axis perpendicular to the axis of propagation. Each optical element 230 also includes a second surface 234 which may or may not be optically reflective. Surfaces 232 and 234 intersect to define the base 236 of optical element 230. Optical fiber 220 is further provided with a plurality of optical elements 240 centered about a second longitudinal axis 248 along the optically reflective surface of fiber 220. Preferably, each optical element 240 includes a first optically reflective surface 242 that extends into the core 222 of optical fiber 220. Optically reflective surface 242 is also preferably a substantially optically smooth surface, meaning that it is capable of reflecting light with minimal losses due to scattering or diffusion. Surface 242 may be disposed at any useful angle between 0° and 90° from an axis perpendicular to the axis of propagation. Each optical element 240 also includes a second surface 244 which may or may not be optically reflective. Surfaces 242 and 244 intersect to define the base 246 of optical element 240.

[00107] Referring to FIGS. 12 and 13, in use, a first portion of the light propagating through optical fiber core 222, represented by light ray 250 becomes incident on an optically reflective surface 232 of optical element 230 and is reflected through optical fiber 220 such that it strikes the optically smooth surface 228 of optical fiber 220 at an angle greater than the critical angle required for continued propagation through the fiber and thus is at least partially refracted from optical fiber 220. A second portion of the light propagating through optical fiber 210, represented by light ray 258, strikes the optically reflective surface 228 of optical fiber 210 and continues to propagate through optical fiber 210. And a third portion of the light propagating through optical fiber core 222, represented by light ray 260 becomes incident on an optically reflective surface 242 of optical element 240 and is reflected through optical fiber 220 such that it strikes the optically smooth surface 228 of optical fiber 220 at an angle less than the critical angle required for continued propagation and thus is at least partially refracted from optical fiber 220.

[00108] FIG. 13 is a schematic, cross-sectional view, taken perpendicular to a longitudinal axis of optical fiber 220. Dashed line 236 represents the bottom edge of an optical element 230, disposed about first longitudinal axis 238, while solid line 246 represents the bottom edge of an optical element 240, disposed about second longitudinal axis 248. Axes 238 and 248 are angularly displaced by an angle δ. Light rays 252 and 254 represent the limiting light rays reflected from optical fiber 220 by an optical element 230 disposed about first axis 238. Accordingly light reflected from optical element 230 emerges in a profile that extends through the included angle defined by light rays 252 and 254. Similarly, light rays 262 and 264 represent the limiting light rays reflected from optical fiber 220 by an optical element 240 disposed about second axis 248. Accordingly light reflected from optical element 240 emerges in a profile that extends through the included angle defined by light rays 262 and 264.

[00109] Reflective surfaces 232, 242 of optical elements 230, 240 respectively may be coated with a specularly reflective substance (e.g. silver, aluminum) such that light striking these surfaces is specularly reflected. However, if reflective surfaces 232, 242 are not coated with a specularly reflective substance, light incident on the reflective surface at an angle less than the critical angle defined by Snell's law will be transmitted (and refracted) through the optical element. By contrast, light incident on the reflective surface at an angle greater than the critical angle defined by Snell's law will be totally internally reflected, much like the light depicted by rays 258.

[00110] Optical fiber 220 is, in some examples, formed from a substantially optically transmissive material exhibiting high optical transmission and relatively high refractive indices. Common materials include polymethylmethacrylate (refractive index 1.49) and polycarbonate (refractive index 1.58). Optionally, optical fiber 220 may include a cladding material (not shown) surrounding the core of the fiber. A cladding layer may comprise any suitable material known in the art having a refractive index appropriate for the chosen core material. Common optical fiber cladding materials include polyvinylidene fluoride (refractive index 1.42), perfluoroacrylate (refractive index 1.35) and polytetrafuloroethylene (refractive index 1.40), and tetrafluoroethylene- hexafluoropropylene-vinylidene fluoride, the refractive index of which varies with the relative concentration of its constituents, but may generally considered as approximately 1.36.

[00111] It will be appreciated that the morphology of each optical element 230, 240, for example: the angle of inclination of the first optically reflective surfaces 232, 242 and, to a lesser extent, the second surfaces 234, 244; whether the optically reflective surfaces 232, 242 is planar or curved; the cross-sectional area of each optically reflective surface 232, 242 etc., will influence the amount and direction of light emitted from the fiber 220 at that particular point. Consequently, the amount and direction of the light reflected from the fiber can be controlled by selecting the appropriate notch type, as well as the pattern and spacing of the notches along the fiber. Although each notch on a given fiber would ordinarily be of similar morphology, any useful combination of optical elements may be employed.

[00112] In the embodiment shown, the first optically reflective surface 234 of the optical element 218 is inclined at an angle of approximately 45° to an axis perpendicular to the axis of propagation, though angles of from 10° to 80°, preferably from 20° to 70° and more preferably from 30° to 60°, are also useful. Depending on the desired amount and direction of travel of the light exiting from the fiber, any useful angle from 0° to 90° may be used. Particularly preferred angular ranges for particular embodiments of an optical waveguide are set forth below.

[00113] The second optically reflective surfaces 234, 244 of the optical elements 230, 240 may be normal to the longitudinal axis of the fiber 220, or inclined to or away from a plane normal to the longitudinal axis of the fiber 220, to define 'V shaped or undercut optical elements. Additionally, one or both optically reflective surfaces 234, 244 of the optical element 230, 240 may for certain uses be curved, but ordinarily they are substantially planar. The surfaces of the notch are normally fabricated so as to be of optical quality, meaning that the surfaces reflect incident light with minimal scattering or diffusion.

[00114] FIG. 14 is a schematic depiction of light-emitting curing device 310. Light-emitting curing device 310 includes a light injection assembly 312 optically coupled with an optical fiber 314. Light injection assembly 312 includes a light source (not shown), which can, in some examples be LEDs emitting light at a wavelength of from about 260 nm to about 550 nm (e.g., from about 350 nm to about 550 nm, about 400 nm to about 500 nm; about 425 nm to about 475 nm; or about 440 nm to about 460 nm) and having a radiometric energy of about at least about 0.1 W/cm ² (e.g., about 0.5 W/cm ² to about 5 W/cm ² ; about 1 W/cm ² to about 3 W/cm ² ; about 1 W/cm ² to about 2 W/cm ² ; or about 0.5 W/cm ² to about 2 W/cm ² ). Light injection assembly 312 can also include a collimating assembly (not shown) for collimating light into a divergence cone which may be accepted by optical fiber 314. Suitable commercially available light injection assemblies include the Light Pump 350, commercially available from Remote Source Lighting International, Inc. of San Juan Capistrano, Calif, USA; and the Powerhouse™ Metal Halide Illuminator commercially available from Lumenyte International Corporation of Costa Mesa, Calif, USA. Optical fiber 314 includes a light emitting region 316 extending along a portion of its length. Light emitting region 316 includes at least one optical element 318 disposed about a first longitudinal axis and a second optical element 320 disposed about a second longitudinal axis, as depicted in FIGS. 9 and 10. In use, light from the light source is injected into optical fiber 314 such that the light propagates through optical fiber 314 according to Snell's law. A portion of the light propagating through optical fiber 314 becomes incident on the reflective surfaces of optical elements 318, 320 and is reflected from the fiber. [00115] In some embodiments, the optical fiber of the present disclosure relates to controlling the impact of shadowing effects on the angular distribution of light energy reflected from an optical fiber. Shadowing effects introduce variability into the angular distribution of light energy reflected from an optical fiber. Controlling shadowing effects can be useful for optical fibers having closely spaced optical elements. The angle the reflective surfaces form in the optical fiber may be modified to control shadowing effects in the fiber.

[00116] Although the light-emitting curing device shown in FIG. 14 relies on injection of light from the light injection assembly and emitting light from the light emitting region, another type of light-emitting curing device is also contemplated herein (not shown), one where LEDs are arranged in a row substantially along the length of what would correspond to the optical fiber 314 in FIG. 14. Multiple rows of LEDs are also contemplated. Such a light-emitting device can be compact and/or flexible, such that it can be placed in areas that might be difficult to reach or in curved areas, such as behind the fritted portion behind a windshield.

[00117] Referring to FIG. 15, an optical fiber 270 includes a core 272 having a first surface

274 adapted to receive light from a light source (not shown) and an optically reflective surface 278 that reflects light propagating through optical fiber 270. Optically reflective surface 278 preferably corresponds to the circumferential surface of optical fiber core 272. A first optical element 280 is disposed at a first distance, dl, from first surface 274 and a second optical element 290 is disposed at a second distance d2, greater than dl, from first surface 274. First optical element 280 includes a first optically reflective surface 282 disposed at an angle Θ from an axis perpendicular to the longitudinal axis 273 of optical fiber 270 and a second surface 284. Second optical element 290 also includes a first optically reflective surface 292 disposed at an angle Θ from an axis perpendicular to the longitudinal axis 273 of optical fiber 270 and a second surface 294.

[00118] As previously discussed in connection with FIG. 9, light injected into optical fiber

270 propagates through optical fiber 270 along an axis of propagation generally coincident with the longitudinal axis 273 of fiber 270 in a cone having a cone angle β determined by the relative refractive indices of the optical fiber core and the surrounding medium. For the present disclosure, it will be assumed that light propagates through optical fiber 270 from left to right. As a matter of convention, angular measurements taken above an axis parallel to the longitudinal axis 273 of optical fiber 270 will be considered positive, while angular measurements taken below an axis parallel to the axis of propagation will be considered negative.

[00119] When adjacent optical elements 280, 290 are spaced relatively closely (e.g. from

0.05 millimeters to 5.0 millimeters), first optical element 280 shadows a portion of the light that would otherwise be incident on reflective surface 292 of second optical element 290. The shadowing effect of first optical element 280 on second optical element 290 may be illustrated by comparing the angular distribution of light rays incident on reflective surface 282 of first optical element 280, which is not shadowed by an adjacent optical element, with the angular distribution of light rays incident on reflective surface 292 of second optical element 290, which is shadowed by first optical element.

[00120] Each point on reflective surface 282 of first optical element 280 receives light rays from the entire angular distribution (e.g. from -β to β) of light propagating through optical fiber 270. By contrast, the presence of first optical element 280 blocks a portion of the angular distribution of light incident propagating through optical fiber 270 from becoming incident on reflective surface 292 of second optical element 290.

[00121] FfG. 15 illustrates the shadowing effect of first optical element 280 at a point at the bottom edge 296 of reflective surface 292 of second optical element 290. Light propagates through optical fiber 270 with a cone angle of β. The shadowing angle a may be defined as the angle between a first optical path 300 extending from the bottom edge 296 of second optical element 290 to the top of first optical element 280 and a second optical path 302 extending from the same point on second optical element 290 to the bottom edge 286 of first optical element 280. All light rays within the angular range defined by shadowing angle a are blocked from becoming incident on the reflective surface 292 of second optical element 290 by first optical element 280. Additionally, optical path 304 represents the angle of the limiting light ray that passes the bottom edge 286 of first optical element 280, reflects from the surface 278 of optical fiber 270 and is incident on the bottom edge 296 of second optical element 290. Accordingly, all light rays within the angular range between optical path 304 and 300 are also blocked by first optical element 280. Applying principles of geometric optics, it can be shown that the angle circumscribed by optical path 304 and optical path 300 is equal to the shadowing angle a. Thus, from the angular range of -β to β, light rays in the angular range extending from 0° (e.g. parallel to the axis of propagation) to 2a degrees are blocked, or shadowed, by optical element 280.

[00122] The term "alkyl" as used herein refers to straight chain and branched alkyl groups having from 1 to 40 carbon atoms (C1-C40), 1 to about 20 carbon atoms (C1-C20), 1 to 12 carbons (C1-C12), 1 to 8 carbon atoms (Ci-Cg), 1 to 6 carbon atoms (Ci-Cg) or, in some embodiments, from 3 to 6 carbon atoms (C3-C6) . Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec- butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.

[00123] The term "alkoxy" as used herein refers to the group -O-alkyl, wherein "alkyl" is defined herein.

[00124] The term "aryl" as used herein refers to cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring. Thus aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, aryl groups contain about 6 to about 14 carbons (Ce-C ) or from 6 to 10 carbon atoms (Ce-Cio) in the ring portions of the groups.

[00125] The term "about" as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range.

[00126] Unless specified otherwise herein, the term "substantially" as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

[00127] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range were explicitly recited. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement "about X to Y" has the same meaning as "about X to about Y," unless indicated otherwise. Likewise, the statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z," unless indicated otherwise.

[00128] In this document, the terms "a," "an," or "the" are used to include one or more than one unless the context clearly dictates otherwise. The term "or" is used to refer to a nonexclusive "or" unless otherwise indicated. In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting. Further, information that is relevant to a section heading may occur within or outside of that particular section. Furthermore, all publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[00129] In the methods described herein, the steps can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified steps can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed step of doing X and a claimed step of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

EXAMPLES [00130] The examples described herein are intended solely to be illustrative, rather than predictive, and variations in the manufacturing and testing procedures can yield different results. All quantitative values in the Examples section are understood to be approximate in view of the commonly known tolerances involved in the procedures used. The foregoing detailed description and examples have been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom.

[00131] The following abbreviations are used to describe the examples:

°C: degrees Centigrade cm: centimeter cm/min: centimeters per minute in/min: inches per minute

Kg: kilogram lb: pound min: minute μ-inch: 10- ⁶ inch mm: millimeter urn: micrometer m/min: meters per minute mW/cm ² : milliwatt per square centimeter

N: Newton

N-mm: Newton millimeter pbw: parts by weight rpm: revolutions per minute

T _g : glass transition temperature

UV: ultraviolet

W/cm ² : Watts per square centimeter wt.%: weight percent [00132] Unless stated otherwise, all chemical components were obtained or are available from chemical vendors such as Sigma- Aldrich Company, St. Louis, Missouri, or may be synthesized by known methods. Unless otherwise reported, all chemical components (e.g., those listed in Table 1 herein) are parts by weight.

[00133] Abbreviations for materials used in the examples are as follows:

PSU1612 aliphatic polyurethane diacrylate from Solmer Soltech Ltd.

EB8411: an aliphatic urethane diacrylate diluted 20% by weight with the reactive diluent isobornyl aery late (IBOA) from Allnex, Frankfurt am Main, Germany.

IRGACURE® 819: bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide.

TPO-L: 2,4,6-trimethylbenzoylphenyl phosphinate available from BASF Corporation, Wyandotte, Mi.

HEM A Phosphate: 2-hydroxy ethyl methacry late (HEMA) phosphate.

Silopren 2060: Polydimethylsiloxane containing vinyl groups from Momentive,

Waterford, Ny.

Triethoxysilane: adhesion promoter, Sigma Aldrich, St. Louis, Mo.

Methacry loy loxy ethy 1

maleate: adhesion promoter, Esstech, Essington,

8682: single step primer, 3M, St. Paul, Mn.

AP-111: primer, 3M, St. Paul, Mn.

Example 1-14: Compositions

[00134] Examples of sealing compositions of the various embodiments described herein were prepared by combining the components listed herein in Table 1, where the amounts of each component is given in weight percent:

Table 1

PSU 1612; B = EB8411; C = Silopren 2060; HP = HEMA Phosphate; TES = triethoxysilane; MEM = methacryloyloxy ethyl maleate.

[00135] Example sealing compositions were made by charging an amber glass jar with the components listed in Table 1. The amber glass jar was heated on a hot roller at 80°C until the components were substantially dissolved. The warm mixture was transferred to a plastic syringe.

[00136] A 0.3 inch gap between a piece of aluminum metal and a glass is created by two rubber shims. The windshield sealant was dispensed into the gap by syringe. A "rope shape light," of which the light-emitting curing device 310 shown in FIG. 14 is one example, was set at the edge of the dispensed sealant. One minute blue light exposure from the rope shape light was applied.

[00137] It will be apparent to those skilled in the art that the specific structures, features, details, configurations, etc., that are disclosed herein are simply examples that can be modified and/or combined in numerous embodiments. All such variations and combinations are contemplated by the inventor as being within the bounds of this disclosure. Thus, the scope of the disclosure should not be limited to the specific illustrative structures described herein, but rather extends at least to the structures described by the language of the claims, and the equivalents of those structures. To the extent that there is a conflict or discrepancy between this specification as written and the disclosure in any document incorporated by reference herein, this specification as written will control. Furthermore, all publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though they were fully set forth herein.