WO2018165333A1 - Adhésif à la demande pour pare-brise, durcissant sous l'effet d'une lumière led bleue - Google Patents

Adhésif à la demande pour pare-brise, durcissant sous l'effet d'une lumière led bleue Download PDF

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Publication number
WO2018165333A1
WO2018165333A1 PCT/US2018/021395 US2018021395W WO2018165333A1 WO 2018165333 A1 WO2018165333 A1 WO 2018165333A1 US 2018021395 W US2018021395 W US 2018021395W WO 2018165333 A1 WO2018165333 A1 WO 2018165333A1
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WIPO (PCT)
Prior art keywords
light
sealing composition
curing
optical fiber
urethane acrylate
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PCT/US2018/021395
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English (en)
Inventor
Sheng Ye
Michael E. Griffin
Mark G. MATHEWS
Margaux B. Mitera
Jay S. Schlechte
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3M Innovative Properties Company
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Publication of WO2018165333A1 publication Critical patent/WO2018165333A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/04—Joining glass to metal by means of an interlayer
    • C03C27/048—Joining glass to metal by means of an interlayer consisting of an adhesive specially adapted for that purpose

Definitions

  • 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.
  • Embodiment 2 is directed to the method of Embodiment 1, further comprising applying a primer and subsequently applying the sealing composition on the primer.
  • Embodiment 3 is directed to the method of Embodiments 1 -2, wherein the substrate is at least a portion of an automotive windshield assembly.
  • 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.
  • Embodiment 5 is directed to the method of Embodiments 1-4, wherein the light- emitting curing device is flexible.
  • 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.
  • 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.
  • Embodiment 8 is directed to the method of Embodiments 1-7, wherein the photoinitiator comprises a quinone, a phosphine oxide or a phosphinate.
  • Embodiment 9 is directed to the method of Embodiments 1-8, wherein the photoinitiator comprises camphor quinone.
  • Embodiment 10 is directed to the method of Embodiments 1-8, wherein the photoinitiator comprises:
  • 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.
  • 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.
  • 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-ter
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 4 is a close-up view of a light emitting diode array having staggered LEDs.
  • Linear or other geometric LED arrangements are also contemplated.
  • FIG. 5 is a perspective view of an example heat sink that can be used in the curing heads of FIGS. 2 and 3.
  • 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.
  • 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.
  • FIG. 8 is a block diagram of a system circuit architecture for an exemplary curing head of the present disclosure.
  • FIG. 9 is a cross-sectional view of an optical fiber illustrating the propagation of light through the fiber.
  • FIG. 10 is a perspective view of a segment of an optical fiber.
  • FIG. 11 is a plan view of the optical surface of the optical fiber depicted in FIG. 10.
  • FIG. 12 is a cross-sectional view, taken along a longitudinal axis, of a portion of an optical fiber depicted in FIG. 10.
  • FIG. 13 is a cross-sectional view, taken perpendicular to a longitudinal axis, of a portion of the optical fiber depicted in FIG. 10.
  • FIG. 14 is a schematic view of an optical fiber illumination system in accordance with aspects of the present disclosure.
  • FIG. 15 is a cross-sectional view of an optical fiber illustrating shadowing effects in the fiber.
  • the sealing compositions of the various embodiments described herein employ a light-emitting curing device that balances the depth of cure and cure speed.
  • longer wavelength light such as visible light
  • short wavelength light such as UV.
  • short wavelength light has higher energy and more efficiently trigger the initiator, compared with longer wavelength light.
  • there is a fine balance between depth of cure and cure speed by designing the right wavelength lamp and sealing composition.
  • 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.
  • 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.
  • a sealing composition comprising: a urethane aery late component; and a photoinitiator.
  • 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.%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.%).
  • an opaque filler component e.g. 70 wt.%
  • 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.%).
  • 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.
  • 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
  • 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.
  • Suitable urethane acrylate components for use in the sealing compositions include aliphatic urethane acrylates and aromatic urethane acrylates.
  • the urethane acrylates can be mono-acrylates, di-acrylates, tri-acrylates or mixtures of mono-, di-, and/or tri- acrylates.
  • 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,
  • 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.
  • 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
  • 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 (de
  • 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).
  • 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).
  • 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.
  • 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.
  • 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-mo ⁇ holinophenyl)-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
  • the photoinitiator is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the photoinitiator is present in an amount of about 0.1, about
  • 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.%.
  • 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.
  • alumina e.g., alpha alumina
  • silica e.g., fumed, such as CAB-O-SIL TS-720 and TS- 710 or fused
  • 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.
  • 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.
  • 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 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.
  • Suitable one or more polythiols include, but are not limited to dithiols, trithiols, and tetrathiols.
  • 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
  • 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.
  • 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.
  • dithiols wherein X is -O- and -S- and pendant alkyl groups.
  • 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.
  • treatrathiols include, but are not limited to, 1, 4,9,12-tetramercapto-
  • Aromatic polythiols are also contemplated.
  • 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
  • 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.
  • 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.
  • 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.).
  • dialkyl phthalates such as dibutyl phthalate, diisoctyl phthalate, dibutyl adipate, dioct
  • 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.
  • 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.
  • 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.
  • (meth)acrylate functional silanes including (3-acryloxypropyl)trimethoxysilane, methacryloxypropyltrimethoxysilane, N-(3-acryloxy-2-hydropropyl)-3- aminopropyltriethoxysilane
  • 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.
  • 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-iso
  • Suitable one or more diluents for use in the sealing compositions include, but are not limited to reactive and non-reactive diluents.
  • 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.
  • Tackifiers can also act as non-reactive diluents, including hydrogenated rosins and synthetic hydrocarbon resins.
  • the sealing compositions of the various embodiments described herein can further comprise any number of additives as desired.
  • 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 Y
  • the additives 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.%).
  • 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.
  • a suitable primer such as 8682 (a single step primer) or AP-111, both available from 3M, St. Paul, Mn.
  • the sealing composition is, in turn, applied as a layer on the primer, in some embodiments a layer that substantially covers the primer.
  • the sealing compositions of the various embodiments described herein can be polymerized/cured by any suitable method, including photochemically.
  • 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 ).
  • a light-emitting curing device emitting light at a wavelength of from about 260 nm
  • 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.
  • 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.
  • LEDs light emitting diodes
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • dispensing device 18 and curing device 14 can be manually positioned and operated devices.
  • the light-emitting curing device 14 can be held at any suitable distance from object
  • 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).
  • 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.
  • system 10 can be used to apply any of the compositions of the various embodiments described herein to any object.
  • 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.
  • components of the sealing composition can be individually loaded into containers 40A and 40B and dispensed from nozzles 42 A and 42B, respectively.
  • the components can become mixed and entrained while in transit from nozzles 42A and 42B to object 46.
  • the components of the sealing composition can be pre-mixed and dispensed using only a single storage container and nozzle.
  • 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.
  • dispensing device 18 can comprise a hand-held, manually operated device, such as something akin to a caulking gun or a syringe-type device.
  • Curing device 14 can be used to treat material dispensed by dispensing device 18.
  • 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.
  • emitter 26 can comprise one or more light emitting diodes (LEDs).
  • LEDs light emitting diodes
  • 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.
  • heat sink 28 can be positioned adjacent emitter 26.
  • heat sink 28 can be positioned behind emitter 26, e.g., away from the direction of object 46.
  • 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.
  • fans 30A and 30B can be used to push air past fins of heat sink 28.
  • Curing head 12 can include sensor system 24 that can be used to control operation of curing device 14.
  • 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.
  • 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.
  • 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.
  • Heat sink banks 28 A, 28B and 28C can be mounted to chassis 48 opposite emitter
  • 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.
  • 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.
  • fans 30A and 30B can be mounted on chassis 48.
  • Cross slots 30A and 30B can be mounted on chassis 48.
  • FIG. 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.
  • 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.
  • 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.
  • emitter 26 can include an elongate array of 240 LEDs.
  • 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).
  • fans 30A and 30B can be configured to remove a corresponding amount of heat.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • emitter 26 comprises an elongate bank of light emitting diodes
  • curing head 12 additionally includes LED spotlight 56.
  • 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.
  • Handle 58 can be connected to upper housing component 50 A to facilitate manual operation of curing head 12.
  • 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.
  • FIG. 4 is a close-up view of light emitting diode array 70 having staggered LEDs
  • 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.
  • 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).
  • the LEDs shown in FIG. 4 do not comprise lenses or optics, in some embodiments, the LEDs can have lenses or other optics.
  • 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.
  • fins 84 can be fabricated from aluminum.
  • 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.
  • 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.
  • Upper and lower housing components 92A and 92B can include various features to promote airflow through housing 92.
  • 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.
  • 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.
  • 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.
  • Power switch 104 can be used to control transmission of power from power supply
  • 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.
  • 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.
  • 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.
  • 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 ).
  • a light source not shown
  • LEDs emitting light at a wavelength of from about 260 nm to
  • 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.
  • 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.
  • 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, ⁇ , measured from the axis of propagation 212 that is determined by the critical angle necessary for total internal reflection.
  • the angle ⁇ may be derived by first calculating the critical angle (Oc) required for total internal reflection from Snell's law as follows:
  • ⁇ is the refractive index of the optical fiber core material and ⁇ 2 is the refractive index of the surrounding medium, typically a cladding material or air.
  • the cone angle ⁇ is the complement of the critical angle 0 C .
  • 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.
  • lateral e.g. cross-fiber
  • longitudinal e.g. down-fiber
  • 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.
  • 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.
  • 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.
  • optically smooth surface 228 corresponds to the circumferential surface of optical fiber core 222.
  • 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.
  • 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.
  • 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.
  • ⁇ angular displacement
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ .
  • 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.
  • 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.
  • 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.
  • a specularly reflective substance e.g. silver, aluminum
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 PowerhouseTM 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.
  • 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.
  • 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.
  • an optical fiber 270 includes a core 272 having a first surface
  • 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 ⁇ 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 ⁇ from an axis perpendicular to the longitudinal axis 273 of optical fiber 270 and a second surface 294.
  • 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 ⁇ determined by the relative refractive indices of the optical fiber core and the surrounding medium.
  • ⁇ cone angle
  • light propagates through optical fiber 270 from left to right.
  • 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.
  • 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.
  • Each point on reflective surface 282 of first optical element 280 receives light rays from the entire angular distribution (e.g. from - ⁇ to ⁇ ) of light propagating through optical fiber 270.
  • 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.
  • 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 ⁇ .
  • 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.
  • 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.
  • the angle circumscribed by optical path 304 and optical path 300 is equal to the shadowing angle a.
  • alkyl 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) .
  • 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.
  • branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec- butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
  • alkoxy refers to the group -O-alkyl, wherein “alkyl” is defined herein.
  • aryl refers to cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.
  • 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.
  • 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.
  • Kg kilogram lb: pound min: minute ⁇ -inch: 10- 6 inch mm: millimeter urn: micrometer m/min: meters per minute mW/cm 2 : milliwatt per square centimeter
  • N-mm Newton millimeter pbw: parts by weight rpm: revolutions per minute
  • UV ultraviolet
  • W/cm 2 Watts per square centimeter wt.%: weight percent
  • EB8411 an aliphatic urethane diacrylate diluted 20% by weight with the reactive diluent isobornyl aery late (IBOA) from Allnex, Frankfurt am Main, Germany.
  • IBOA isobornyl aery late
  • IRGACURE® 819 bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide.
  • TPO-L 2,4,6-trimethylbenzoylphenyl phosphinate available from BASF Corporation, Wyandotte, Mi.
  • HEM 2-hydroxy ethyl methacry late
  • Silopren 2060 Polydimethylsiloxane containing vinyl groups from Momentive,
  • Triethoxysilane adhesion promoter, Sigma Aldrich, St. Louis, Mo.
  • AP-111 primer, 3M, St. Paul, Mn.
  • 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:
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne un procédé comprenant : l'application d'une composition adhésive sur un substrat, la composition adhésive comprenant un constituant acrylate d'uréthane ; et un photoamorceur présentant un coefficient d'extinction d'environ 10 à environ 2000 L/mol.cm à une longueur d'onde d'environ 400 nm à environ 500 nm, en une quantité d'environ 0,1 % en poids à environ 5 % en poids ; et le durcissement de la composition adhésive par utilisation d'un dispositif de durcissement électroluminescent émettant une lumière à une longueur d'onde d'environ 260 à environ 550 nm ; la composition adhésive durcissant à une profondeur de durcissement allant jusqu'à environ 10 mm en 0,5 seconde à 2 minutes par unité d'aire d'exposition à la lumière.
PCT/US2018/021395 2017-03-08 2018-03-07 Adhésif à la demande pour pare-brise, durcissant sous l'effet d'une lumière led bleue WO2018165333A1 (fr)

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WO2021007658A1 (fr) * 2019-07-12 2021-01-21 Mondofix Inc. Formulations adhésives à base de thiol pour la réparation de pares-brise

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US7781493B2 (en) 2005-06-20 2010-08-24 Dow Global Technologies Inc. Protective coating for window glass
EP2551136A1 (fr) * 2010-03-25 2013-01-30 Asahi Glass Company, Limited Procédé de fabrication d'un élément de vitre de véhicule
WO2016096652A1 (fr) * 2014-12-18 2016-06-23 Agfa Graphics Nv Articles en verre stratifié

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US7781493B2 (en) 2005-06-20 2010-08-24 Dow Global Technologies Inc. Protective coating for window glass
EP2551136A1 (fr) * 2010-03-25 2013-01-30 Asahi Glass Company, Limited Procédé de fabrication d'un élément de vitre de véhicule
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021007658A1 (fr) * 2019-07-12 2021-01-21 Mondofix Inc. Formulations adhésives à base de thiol pour la réparation de pares-brise
EP3997172A4 (fr) * 2019-07-12 2023-01-18 Mondofix Inc. Formulations adhésives à base de thiol pour la réparation de pares-brise

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