CA2165555A1

CA2165555A1 - Thermally-stable photopolymer composition and light transmissive device

Info

Publication number: CA2165555A1
Application number: CA002165555A
Authority: CA
Inventors: Chengjiu Wu; Michael James Mcfarland; Karl Wayne Beeson
Original assignee: Individual
Current assignee: Honeywell International Inc
Priority date: 1993-07-01
Filing date: 1994-06-30
Publication date: 1995-01-12
Also published as: TW262537B; US20010031427A1; DE69425261T2; ATE194715T1; JPH08512146A; EP0706669B1; MX9404970A; EP0706669A1; WO1995001579A3; AU7215894A; US20010025061A1; CN1126518A; DE69425261D1; WO1995001579A2; US6114090A

Abstract

A photopolymerizable composition for use in forming a photopolymer composition for use in forming a light transmissive regions of light transmissive devices, and such devices.

Description

WO 95tO1579 PCT/US94/07368 2165~SS

THERMALLY-STABLE PHOTOPOLYMER COMPOSITION
AND LIGHT TRANSMISSIVE DEVICE

BACKGROUND OF THE INVENTION

15 1. Field of the Invention This invention relates to photo-polymerizable compositions and to thermally stable photopolymer compositions prepared therefrom.
Another aspect of the invention relates to light transmissive optical devices, such as waveguides formed from the photopolymer 20 composition of this invention.

2. Prior Art In optical communication systems, messages are transmitted by carrier waves of optical frequencies that are generated by light 25 sources such as lasers or light-emitting diodes. There is much current interest in such optical communication systems because they offer several advantages over conventional communication systems, such as a greatly increased number of channels of communication and the ability to use other materials besides expensive copper cables for 30 transmitting messages. One such means for conducting or guiding waves of optical frequencies from one point to another is called an "optical waveguide." The operation of an optical waveguide is based on the fact that when a medium which is transparent to light is surrounded or otherwise bounded by another medium having a lower 35 refractive index, then light introduced along the inner medium's axis is highly reflected at the boundary with the surrounding medium, thus producing a guiding effect.

2165~5 The most frequently used material for such a waveguide device is glass, which is formed into a fiber of specified dimension.
However, optically-transparent polymers are increasingly being used as the light transmissive element. Conventional optically-transparent 5 polymers suffer from one or more defects. For example, a common property of optically transparent polymers is that the polymers become discolored when heated for extended periods of time. The visual effect is that the polymers become yellow. The thermally-induced discoloration in polymers results from a number of factors as for 10 example chemical reactions that slowly degrade the polymer Longer heating times usually cause greater discoloration than shorter heating times. What initially might be a light yellow discoloration may eventually turn to brown or even black. If a sample of discolored polymer is examined in an absorption spectrophotometer, an 15 absorption band tail can be observed that extends from the intrinsic ultraviolet absorption bands of the polymer into the visible spectral region (400 nm to 700 nm) and even into the infrared spectral region ( > 700 nm). The absorption tail typically has no discernable fine structure. The absorption of light in the region of transmission 20 reduces the intensity of the optical wave as it passes through the waveguide, a phenonemon which contributes to "optical loss" or "optical power loss".
Multimode optical waveguides are used primarily in the infrared spectral region from 700 nm to 1300 nm. If a polymer optical 25 waveguide is heated for an extended period of time and if a thermally-induced absorption band tail extends into this infrared wavelength region of operation, the transmission of light through the waveguide can be dramatically reduced. For cases of severe discoloration, the waveguide becomes useless.

Photopolymer films and waveguides can crack when heated to elevated temperatures. A crack in a waveguide scatters light and generally reduces the effectiveness of the waveguide. Such cracking is a result of stress. The stress can be internal to the waveguide, 5 resulting from non-uniformities in the photopolymer composition, or stress can result from substrate or overcoat materials in contact with the waveguide which have different coefficients of thermal expansion than the waveguide material. Even the process of forming a photopolymer waveguide on a substrate by UV exposure of monomer 10 precursors generally results in a waveguide that is under tensile stress.
This occurs because the volume occupied by a photopolymer is usually smaller than the volume of the monomer precusors. The amount of shrinkage can be as much as 10%.
A third effect which results from changing the temperature is 15 delamination of the waveguide from the subslrate. Delamination changes the pro,~e. Iies of the waveguide (e.g. the numerical aperture or NA) and weakens the waveguide structure so that it is more susceptible to dz."&ge from vibralion and other environmental factors such as moisture.
SUMMARY OF THE INVENTION
One aspect of this invention relates to a photopolymerizable CG-llpGSiliGn cG-"pr;sing:
one or more ethylenically unsaturated monomers selected from 25 the group consisting of aryl acrylates and aryl methacrylates preferably multi-functional aryl acrylates and aryl methacrylates such as aryl triacrylates, aryl diacrylates and aryl tetra-acrylates; and a photoinitiator that activates polymerization of said unsaturated monomers upon exposure to actinic radiation, said composition can be 30 polymerized to form a photopolymer which on exposure to a 216S5S~

temperature of 190 C in air for 24 hrs. exhibits a coloration on the Gardner Color Scale equal to or less than 8 as determined by ASTM
D1544-80 and which exhibits no cracking or delamination from a glass substrate as defined by ASTM D 4538 -90 A on exposure of same to a temperature of 190 C for 24 hrs. in air Another aspect of this invention relates to a photopolymer formed by exposing the photopolymerizable composition of this invention to actinic radiation.
Yet another aspect of this invention relates to a light transmissive device, such as an optical waveguide, comprising a substrate having a predetermined pattern of light transmissive regions on the surface of the substrate, said device comprising a body comprising a light transmissive region comprising the photopolymer of this invention.
This invention provides for one or more advantages over polymers presently used in the fabrication of light transmissive devices. For example, the photopolymer of this invention exhibits enhanced thermal stability which provides for reduced discoloration after treatment or use at relatively high temperatures (i.e. from about -50C to about 125C), which in turn, results in higher light transmissive properties than those exhibited by less thermally stable polymers. These properties are particularly advantageous when the photopolymer is used in the fabrication of the light transmissive element of a light transmissive device such as a waveguide which is exposed to relatively high temperatures during fabrication. Preferred photopolymers of this invention also are resistant to delamination when bonded to a substrate and cracking, which are also desirable properties for polymers used in the fabrication of the light transmissive elements of light transmissive devices.

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BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 (a) to 1 (c) illustrate in schematic cross-section, several of the major steps in the process of forming a preferred waveguide of 5 this invention.
FIG. 2 illustrates, in sche",a(ic and isometric cross-section, the configuration of a preferred waveguide of this invention.

DF~CRIPTION QF THE P~t~t~ntv EM80DIMENTS
The pl.otopolymerizable composition of this invention comprises two essential ingredients. The first essential ingredient is a photopoly."erizable ethylenically unsaturated monomer selected from the group consisting of aryl acrylates and aryl methacrylates (naryl acrylate monomers~). Illustrative of such aryl acrylate monomers are 15 aryl diacrylates, triacrylates and tetra acrylates as for example di, tri and tet,aacrylates based on benzene, naphthalene, bisphenol-A, biphenylene",-ell,ane biphenylene, trifluoromethane biphenylene, phenoxyphenylene and the like. The preferred aryl acrylate monomers are multifunctional aryl acrylates and methacrylates and more 20 preferred aryl acrylate monomers are di, tri and tetra acrylates and methacrylates based on the bisphenol-A structure. Most preferred aryl acrylate monG,--ers are alkoxylated bisphenol-A diacrylates and d;.--ell.ac,ylates such as ethoxylated bisphenol-A di-acrylate and dimethacrylates, propoxylated bisphenol A diacrylates and 25 di"-~ll)acrylates and ethoxylated hexafluorobisphenol-A diacrylates and dimethacrylates. The aryl acrylate monomers of choice are ethoxylated bisphenol-A diacrylate and dimethacrylates.
The amount of aryl acryiate monomer in the composition may vary widely and amounts normally used in photopolymerizable 30 compositions for use in the preparation of photopolymers for use as ~ 2 1 6 5 ~
-the light transmissive element of light transmissive devices may be used. The amount of aryl acrylate monomer is usually from about 35 to about 99.9 % by weight of the composition, preferably from about 60 to about 98% by weight of the composition and more preferably from about 65 to about 95% by weight of the composition.
As another essential component, the polymerizable composition of this invention includes a photoinitiator system which is activated by actinic radiation to produce activated species which lead to photo polymerization of the aryl acrylate monomer. The photoinitiator system will contain a photoinitiator and preferably a conventional sensitizer which extends the spectral response into regions having spectral utility, e.g. the near U.V. region and the visible spectral regions where lasers excite. Usually the photo-initiator is a free radical-generating addition polymerization initiator activated by actinic light and is preferably thermally inactive at and below room temperature (e.g. about 20C to about 25C.) Illustrative of such initiators are those described in U.S. Patent No. 4,943,112 and references cited therein. Preferred free radical initiators are 1-hydroxy-cyclohexyl-phenyl ketone (Irgacurel 84), benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, benzidimethyl ketal (Irgacure 651 ), o,o-diethyloxy acetophenone, o,o-dimethyloxy-o-hydroxy acetophenone (Darocur 1 173), 1 -14-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1- one (Darocur 2959), 2-methyl-1 -l 4-methylthio)phenyll-2-morpholino-propan-1-one (Irgacure 907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (Irgacure 369), poly{1-[4-(1-methylvinyl)phenyl]-2-hydroxy-2-methyl-propan-1-one~ (Esacure KIP), [4-(4-methylphenylthio)-phenyl]phenylmethanone (Quantacure BMS), di-campherquinone. The more preferred photoinitiators includes benzidimethyl ketal (Irgacure 651 ), a,a-diethyloxy acetophenone, a,a-dimethyloxy-a-hydroxy WO 95/01~79 PCT/US94/07368 ~16555S

acetophenone (Darocur 1173), 1 -hydroxy-cyclohexyl-phenyl ketone (Irgacure 184), 1-14-~2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one (Darocur 2959), 2-methyl--1-4-(methylthio)phenyll-2-morpholino-propan- 1 -one (Irgacure 907), 2-benzyl-2-dimethylamino- 1 -5 (4-morpholinophenyl)butan-1 -one (Irgacure 369) . The most preferred photoinitiators are those which tend not to yellow upon irradiation and , thus, do not increase the coloration of the composition on the Gardner scale to a value of greater than 8 points on exposure to a temperature of 190C for 24 hrs. as determined by ASTM D1544-80.
10 Such photoinitiators include benzidimethyl ketal (Irgacure 651), o,o-dimethyloxy-a-hydroxy acetophenone (Darocur 1173), 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure-184), and 1 -[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one (Darocur 2959).
The amount of photoinitiator may vary widely and conventional amounts may be used. Usually, the amount of photoinitiator is from about 0.1 to about 10 by weight of the composition. The amount of photoinitiator is preferably from about 0.5 to about 10 % by weight, and more preferably from about 0.5 to about 5% by weight based on 20 the total weight of the composition.
In addition to the essential ingredients, the composition of this invention may include various optional ingredients which are typically used in photopolymerizable compositions used to form photopolymers for use as the light transmissive element of light transmissive devices.
25 Such optional ingredients are well known in the art and include stabilizers, inhibitors, plasticizers, optical brightners, release agents, chain transfer agents, other photopolymerizable monomers and the like.
The composition of this invention preferably includes one or 30 more other photopolymerizable monomeric components besides the æl~555~ -essential aryl acrylate monomer. The other monomeric components can be used for many purposes as for example to fine tune the properties of the composition such as to fine tune crosslinking density, viscosity, adhesion, curing rate, refractive index and the like without S unduly endangering the basic properties provided by the aryl acrylate monomer e.g. reduced discoloration, cracking and delamination properties of the photopolymer formed from the composition. Other monomers include photopolymerizable aliphatic ethylenically unsaturated monomers, preferably acrylate or methacrylate monomers 10 and more preferably multifunctional acrylate or methacrylate monomers. Illustrative of useful minor monomeric components are those selected from the group consisting of butyl acrylate (BA), ethylhexyl acrylate (EHA), phenoxyethyl acrylate (PEA), B-carboxylethyl acrylate ( ~-CEA), isobornyl acrylate (IBOA), 15 tetrahydrofurfuryl acrylate (THFEA), cyclohexyl acrylate (CHA), propylene glycol monoacrylate (MPPGA), 2-(2-ethoxyethoxy) ethyl acrylate (EOEOEA), N-vinyl pyrrolidone (NVP),1,6-hexanediol diacrylate (HDDA) or di",elhac,~late (HDDMA), neopentyl glycol diacrylate (NPGDA), diethylene glycol diacrylate (DEGDA) or dimethacrylate 20 (PEGDMA), triethylene glycol diacrylate (TEGDA) or dimethacrylate (TEGDMA), t~ aelh~lene glycol diacrylate (TTEGDA) or dimethacrylate (TTEGDMA), polyethylene glycol diacrylate (PEGDA) or dimethacrylate (PEGDMA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), ethoxylated neopentyl gJycol diacrylate 2S (NP~OGDA), propoxylated neopentyl glycol diacrylate (NPPOGDA), aliphatic diacrylate (ADA), alkoxylated aliphatic diacrylate (AADA), aliphatic carbonate diacrylate (ACDA), trimethylolpropane triacrylate (TMPTA) or trimethacrylate (TMPTMA), pentaerythritol triacrylate (PETA), ethoxylated trimethylolpropane triacrylate (TMPEOTA), 30 propoxylated trimethylolpropane triacrylate (TMPPOTA), glyceryl 2 1 6 ~ ~ 5 5 proxylated triacrylate (GPTA), tris (2-hydroxyethyl) isocyanurate triacrylate (THEICTA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPEPA), ditrimethylolpropane tetraacrylate (DTMPTTA), alkoxylated tetraacrylate (ATTA). The most preferred monomers for minor components includes trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDDA), pentaerythritol triacrylate (PETA), ethoxylated trimethylolpropane triacrylate (TMPEOTA), glyceryl proxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPEPA), 1 0 d i (, i" ,etl)ylolpropane tetraacrylate ( DTM PTTA) .
The total amount of other monomer components in the composition may vary widely and is usually from about O to 65 % by weight of the composition, preferably from about 0 to 40 % by weight of the composition and more preferably from about O to 35 %
by weight of the composition.
The photopolymerizable composition of this invention preferably includes a stabilizer to prevent or reduce degradation which leads to property deterioration such as cracking and delamination after heat aging at 190 C in air for 24 hrs. as defined by ASTM D 4538-9OA
and yellowing ( coloration of greater than 8 on the Gardner Color Scale as determined by ASTM D 1544-80) after such heat aging.
Such stabilizers include UV absorbers, light stabilizers, and antioxidants. UV absorbers include hydroxyphenyl benzotriazoles, such as 2-[2-hydroxy-3, 5-di( 1 ,1 -dimethylbenzyl)phenyl]-2-H-benzotriazole (Tinuvin 900), Poly(oxy-1,2-ethanediyl), o-(3-(3-(2H-benzyotriazol-2-yl)-5-( 1 ,1 -dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)-~-hydroxy(Tinuvin 1130), and 2-[2-hydroxy-3,5-di(1,1-dimethylpropyl)phenyl]-2-H-benzotriazole (Tinuvin 238), and from hydroxybenzophenones, such as 4-methoxy-2-hydroxybenzophenone and 4-n-octoxy-2-hydroxybenzophenone. Light stabilizers include 216ra~

hindered amines such as 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, (Tinuvin 770), bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate (Tinuvin 292), bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-(3,5-di -tert-butyl-4-hydroxybenzyl)malonate (Tinuvin 144), polyester of succinic acid with N-~-hydroxy-ethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine (Tinuvin 622). Antioxidants include substituted phenols such as 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl)-4-hydroxybenzyl)benzene,1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butyl)phenyl)butane, 4,4'-butylidene-bis-(6-tert-butyl-3-methyl)phenol, 4,4'-thiobis-(6-tert-butyl-3-methyl)phenol, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, cetyl-3,5-di-tert-butyl-4-hydroxybenzene (Cyasorb UV2908), 3,5-di-tert-butyl-4-hydroxybenzoic acid, 1,3,5-tris-(tert-butyl-3-hydroxy-2,6-dimethylbenzyl) (Cyasorb 1790), stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)proprionate (Irganox 1076), pentaerythritol tetrabis(3,5-di-tert-butyl-4-hydroxyphenyl) (Irganox 1010), thiodiethylene-bis-(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate (Irganox 1035). The preferred stabilizers used in this invention are antioxidants. rrererred antioxidants are selected from substituted phenols such as 1,3,5-tri"~ell~yl-2,4,6-tris(3,5-di-tert-butyl)-4-hydroxybenzyl)benzene,1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylidene-bis-(6-tert-butyl-3-methylphenol, 4,4'-thiobis-(6-tert-butyl-3-methylphenol, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, cetyl-3,5-di-tert-butyl-4-hydroxybenzene (Cyasorb UV 2908), 3,5-di-tert-butyl-4-hydroxybenzoic acid, 1,3,5-tris-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) (Cyasorb 1790), stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)proprionate(lrganox 1076), pentaerythritol tetrabis(3,5-di-tert-butyl-4-hydroxyphenyl) (Irganox 1010), thiodiethylene-bis-(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate - ~16S5S~

(Irganox 1035). The most preferred stabilizers include pentaerythritol tetrabis(3,5-di-tert-butyl-4-hydroxyphenyl) (Irganox 1010), thiodiethylene-bis-(3,5-di-tert-butyl-4-hYdrOXy)hydrOcinnamate (Irganox 1035), and stearyl-3-(3,5-di-tert-butyl-4-hYdrOXYphenyl)propriOnate 5 (Irganox 1076).
The amount of stabilizers in the composition may vary widely and is usually from about 0.1 to 10 % by weight of the composition.
The amount of stabilizer is preferably from about 0.1 to 5 % by weight of the composition and more preferably from about 0.2 to 3 %
10 by weight of the composition.
The polymerizable composition of this invention is useful as a precursor for forming the photopolyr- ~r of this invention. The photopolymer of the invention is conventionally prepared by exposing the polymerizable composition of this invention to actinic radiation of 15 the required wavelength and intensity for the required duration. As used herein "actinic radiation" is defined as light in the visible, ultraviolet or infrared regions of the spectrum, as well as electron beam, ion or neutron beam or X-ray radiation. Actinic radiation may be in the form of incoherent light or coherent light, as for example 20 light from a laser.
Sources of actinic light, and exposure procedures, times, wavelengths and intensities may vary widely depending on the desired degree of polymerization, the index of refraction of the photopolymer and other factors known to those of ordinary skill in the art. Such 25 conventional photopolymerization processes and their operational parameters are well known in the art. See for example in S.P. Pappas Ed. "Radiation Curing: Science and Technology" Plenum Press, New York, NY; D.R. Randell Ed., "Radiation Curing of Polymers, Il, Royal Society of Chemistry, Cambridge, Mass; and C.E. Hoyle and J.F.
30 Kristle, Ed., "Radiation Curing of Polymeric Materials", American 2165~5~

Chemical Society. Accordingly, they will not be described herein in great detail.
The photopolymer of this invention has one or more advantages over prior art polymers used to form the light transmissive element of 5 light transmissive devices. For example, the photopolymer has less discoloration on exposure to a temperature of about 190C for 24 hrs in air than other photopolymers due to the use of the essential aryl acrylate monomer. The amount of discoloration on a Gardner Color Scale is usually equal to or less than about 8 points, preferably equal 10 to or less than about 6 points, more preferably equal to or less than about 5 points, and most preferably equal to or less than about 3 points after exposure to 190C for 24 hrs as determined by ASTM
D1544-80. The photopolymer of this invention also has no or substantially no cracking or delamination when formed in a layer of thickness 10--200 micron on a glass substrate when exposed to a temperature of 190C in air for 24 hrs as defined by ASTM D4538-90A. Establishment of the absence of cracking and delamination in the photopolymer film is carried out by visual observation of the thermally treated samples under a 50x microscope. This unique 20 feature of the photopolymer is believed to result from use of the essential aryl acrylate monomer.
The photopolymer of this invention can be used in the formation of the light transmissive element of optical devices. Illustrative of such devices are planar optical slab waveguides, channel optical 25 waveguides, optical couplers, micro-optical elements and the like which are described in more detail in U.S. Patent Nos. 4,609,252;

4,877,717 and 5,136,682. In the preferred embodiments of this invention, the polymerizable ccmposition and photopolymer of this invention are used in the fabrication of organic optical waveguides 30 devices such as slab, channel and rib waveguides and waveguide couplers as for example those described in U.S. Patent No. 4,609,252 having a light transmissive element formed from the photopolymer of this invention. In the more preferred embodiments of the invention, the waveguide is of the type comprising a substrate having a 5 waveguide strip or layer on the surface thereof. Such waveguides are formed by applying a thin or thick film of the polymerizable composition of this invention on to the surface of a suitable substrate.
The film may be formed by any of a number of methods known in the art, such as spin coating, dip coating, roller coating, doctor blading, 1 0 evaporation or the like .
The substrate may be any material on which it is desired to establish a waveguide including semiconductor materials such as silicon, silicon oxide, gallium arsenide, silicon nitride, glass, quartz, plastics, ceramics, crystalline materials and the like. The subslrate 15 may or may not contain other devices, either topographical features such as grooves or electrical circuits or electro-optic devices such as laser diodes. On substrates where the light transmissive region is an organic layer of lower refractive index than the substrate material, it is necessary to first form a layer of refractive index lower than the 20 or~qanic waveguide material. Such a layer is known in the art as a buffer layer and may be comprised of a semiconductor oxide, a lower rer.aclive index polymer or a spin-on silicon dioxide glass material.
Once the photopolymerizable composition is formed onto the substrate in a thin or thick film, actinic radiation is directed onto the 25 film in order to delineate the light transmissive region. By delineating, it is meant that the position and dimensions of the light transmissive device is determined by the pattern of the actinic radiation upon the surface of the film on the substrate. The pattern radiation must be chosen so that the photopolymerizable composition is polymerized in ~1$55^~5 the desired pattern and so that other regions of the film remain unreacted.
Sources of actinic radiation and the wavelength of the radiation may vary widely, and any conventional wavelengths and sources can 5 be used. It is preferable that the photochemical excitation be carried out with relatively short wavelength (or high energy) radiation so that exposure to radiation normally encountered before processing (e.g., room lights) will not prematurely polymerize the polymerizable material. Alternatively, the processsing can utilize a multiphoton 10 process initiated by a high intensity source of actinic radiation such as a laser. Thus, exposure to ultraviolet light (300-400 nm wavelength) is convenient. Also, exposure by deep ultraviolet light (190-300 nm wavelength) is useful. Convenient sources are high pressure xenon or mercury-xenon arc lamps fitted with appropriate optical filters to 15 select the desired wavelengths for processing. Also, short wavelength coherent radiation is useful for the practice of this invention. An argon ion laser operatin~ in the "UV" mode at several wavelengths near 350 nm is desireable. Also, a frequency-doubled Argon ion laser with output near 257 nm wavelength is highly desirable. Electron 20 beam or ion beam excitation may also be utilized.
Control of the spatial profile of the actinic radiation, that is, where it falls upon the layer of photo-polymerizable material may be achieved by conventional methods. For example, in one conventional method, a mask bearing the desired light transmissive pattern is 25 interspersed between the source of actinic radiation and the photopolymerizable composition film. The mask has transparent and opaque regions which allow the radiation to fall only on the desired regions of the film surface. Masked exposure of thin films is well known in the art and may include contact, proximity and projection 30 techniques for "printing" the light transmissive pattern onto the film.

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Another conventional method of spatial control is to use a source of actinic radiation which comprises a directed or focussed beam such as a laser or electron beam. Such a beam intersects only a small area of the photo-polymerizable material film surface. The pattern of the 5 desired light transmissive regions is achieved by moving this small intersection point around on the film surface either by scanning the beam in space or by moving the substrate so that the intersection point is changed relative to a stationary beam. These types of exposure using a beam source are known in the art as "direct-write"
1 0 methods.
By choosing the spatial characteristics of irradiation it is possible to create light transmissve regions on the surface of the substrate as for example slab and channel waveguides. A slab waveguide is one in which the optical wave is confined only to the 15 plane of the film. A channel waveguide is one in which the optical wave is also confined laterally within the film. A channel structure is necessary for many nonlinear and electro-optic devices because it allows the light to be directed to certain areas of the substrate as well as providing a mechanism for splitting and combining optical waves.
20 After the photopolymerizable composition has been polymerized to form the predetermined pattern of the photopolymer of this invention on the surface of the substrate, the pattern is then developed to leave behind the predetermined pattern. Any conventional development method can be used, as for example, conventional photolithographic 25 techniques as discussed by William S. DeForest in the book entitled "Photoresist Materials and Process," McGraw-Hill Company, New York, (1975).
The following examples are presented to better illustrate the invention and should not be construed as limitations thereof.

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FIG. 1 shows a substrate 10 such as glass or fused quartz having the photopolymerizable composition of this invention on a surface thereof to form layer 12. The composition of this 5 photopolymerizable material can be varied to produce the desired waveguiding characteristics in the final device but is preferably such that when polymerized forms the photopolymer of this invention which is transmissive to light waves in the range 400-1600 nm and which has an index of refraction in the range of from about 1.40 to 10 about 1.60. In this manner, the device of the present invention can accommodate optical fibers having various refractive indices. The organic layer 12 may be deposited by any suitable conventional procedure, as for example dipping the substrate 10 into a solution of the photoactive composition. The photopolymerizable composition is 15 deposited to a thickness of 5 to 500 micrometers in order to form a device which is compatible with conventional glass and plastic fibers which have light carrying cores of typically 5 to 500 micrometers in diameter. The deposited photopolymerizable composition may be removed from the back (or bottom) side of the substrate 10 as shown 20 in FIG.1 by washing that side with acetone. Optionally, the photopolymerizable composition deposited on the back side of the substrate may be left in place.
Next, using known photolithographic techniques, as discussed, for example, by William S. DeForest in the book entitled "Photoresist 25 Materials and Processes," McGraw-Hill Book Company, New York, 1975, the structure of FIG.1 is exposed to a beam 16 of ultraviolet light, through an off-contact mask 14 which is placed a distance of from 1 to 10 micrometers from the substrate 10 and which defines the desired geometry of the final device as indicated in FIG.1 to cause 30 the photopolymerizable composition to polymerize into a waveguiding WO 95/01~79 PCT/US94/07368 2i6~55~

photopolymer. The deposited and irradiated layer 12 is developed with an appropriate solvent to remove the undesired unpolymerized portion. The pattern 18 of the exposed photopolymerizable composition which remains deposited on the substrate 10 has the 5 configuration which was defined by the mask 14.
FIG.2 shows a preferred embodiment of the present invention in which the predetermined planar geometry transmission path of the device is in the form of the letter "Y". The substrate 10 has deposited thereon the waveguiding pattern 18 which was formed in a manner 10 similar to that described in FIG.1, using a Y-shaped mask for mask 14 of FIG.1. The device shown in FIG.2 finds utility as a waveguide coupler.

A liquid mixture containing 10 parts of Genomer T-1600 (a trifunctional polyester urethane acrylate from Biddle-Sawyer, viscosity 48,000 mPa ), 20 parts of 1,6-hexanediol diacrylate (HDDA, from Scientific Polymer Products), and 0.6 part of a liquid photoinitiator mixture consisting of 0.2 part of Darocur 1173 (a,o-dimethyloxy-o-20 hydroxy acetophenone, EM Industries), 0.2 part of Irgacure 500 ( 1:1 by wei~qht mixture of 1-hydroxy-cyclohexyl-phenyl ketone and benzophenone, Ciba-Geigy) and 0.2 part of Irgacure 651 ~benzidimethyl ketal, Ciba-Geigy) was prepared and filtered through a 0.2 micron Teflon membrane. The liquid mixture was spread on a 25 glass plate to form a layer of 0.2 mm thick, followed by subjecting the layer under nitrogen cover to UV radiation from a medium pressure mercury lamp at an intensity of 25mW/cm2 for a duration of 0.5 minute. The liquid layer turned into a solid coating after irradiation.
The coated substrates were then placed in an air circulated oven and 30 thermal aged at 190-C for 24 hours. The purging rate of air was 5-~6355~

10 I/h. The aged sample was deep brown in color, corresponding to a rate of larger than 18 on the Gardner color scale, as described by ASTM D1544-80. There were no delamination from the substrate, nor was an cracking in the layer; as defined by ASTM D4538-9Oa.
5 The result of inspection was collectively shown in Table 1.

The procedure of Comparative Example 1 was repeated except the HDDA was replaced by IBOA (isobornyl acrylate, Scientific 10 Polymer Products). The aged samples was deep brown in color, corresponding to a larger than 18 rate on a Gardner color scale. There were no delamination from the substrate, nor was an cracking in the layer. The result of inspection was collectively shown in Table 1.

The procedure of Comparative Example 1 was repeated except the HDDA was replaced by TMPTA (trimethylolpropane triacrylate, Scientific Polymer Products). The aged sample was deep brown in color, corresponding to a larger than 18 rate on a Gardner color scale.
There were no delamination from the substrate, nor was an cracking in the layer. The result of inspection was collectively shown in Table 1.

The procedure of Comparative Example 1 was repeated except the Genomer T-1600 was replaced by Genomer T-1200 (a trifunctional polyester urethane acrylate from Biddle-Sawyer, viscosity 75,000 mPa). The aged sam~les was deep brown in color, larger than 18 as rated by Gardner color scale. There were no delamination from 21 6~5S

, g the substrate, nor was an cracking in the layer. The result of inspection was collectively shown in Table 1.

The procedure of Comparative Example 1 was repeated except the Genomer T-1600 was replaced by Genomer T-1030 (a trifunctional polyester urethane acrylate from Biddle-Sawyer). The aged samples was light brown in color, corresponding to a rate of 15 on the Gardner color scale. The polymer layer was delaminated from the glass plate and slightly cracked. The result of inspection was collectively shown in Table 1.

The procedure of Example 1 was repeated except the Genomer T-1600 was replaced by Ebercyl 8800 (oligomeric aliphatic urethane acrylate with a functionality of 2.5, Radcure). The aged sample was brown in color, corresponding to a rate of 18 on the Gardner color scale. The polymer layer was delaminated from the glass plate and slightly cracked. The result of inspection was collectively shown in Table 1.

WO 95/01579 ~ PCT/US94/07368 21~3~

Comparison of Oligomeric Acrylates Containing Polyurethane Segments After Thermal-aged at 190'C for 24 hours 5Exsmplo # Monomor 1 Monomor 2Discolor.~" Dolsm.'~CrNckin~
Cl Gonomor HDDA > 18 No No T~ 00 C2 Gonomor IBOA ~18 No No C3 Gonomor TMPTA > 18 No No T- 1 ~00 C4 Gonomor HDDA ~18 Yos Yos CS Gonomor HDDA 18 Yos Yos C6 Eborc~1 HDDA 15 Yos Yos ,1) Discoloring was rated on a Gardner Color Scale, accorc ing to ASTM D1544 80.
t2) Delamination was defined according to by ASTM D4538-9Oa.
(3) Cracking was defined according to by ASTM D4538-9Oa.

A liquid mixture containing 10 parts of TMPEOTA (Scientific Polymer Products, ethoxylated trimethylolpropane triacrylate) and 0.2 20 part of a liquid photoinitiator mixture consisting of 0.066 part of Darocur 1173, 0.066 part of Irgacure 500, and 0.066 part of Irgacure 651 was prepared. The procedure of photocuring and thermal testing in Example 1 was then repeated. The aged sample was slightly brown in color, corresponding to a rate of 12 on the Gardner color scale. The WO 95/01579 ~ 1 6 5 5 5 S PCT/US94/07368 polymer layer was delaminated from the glass plate and seriously cracked. The result of inspection was collectively shown in Table 2.

COMPARATIVE EXAMPLE ~
The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by TMPTA (Scientific Polymer Products, trimethylolpropane triacrylate). The aged sample was slightly yellow in color, corresponding to a rate of 6 on the Gardner color scale. The polymer layer was delaminated from the glass plate and seriously cracked. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by NPPOGDA (Scientific Polymer Products, propoxylated neopentyl glycol diacrylate). The aged sample was slightly brown in color, corresponding to a rate of 13 on the Gardner color scale. The polymer layer was delaminated from the glass plate and cracked. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by GPTA (Scientific Polymer Products, glyceryl proxylated triacrylate). The procedure of photocuring and thermal testing in Example 1 was then repeated. The aged sample was brown in color, corresponding to a rate of 16 on the Gardner color scale. The polymer layer was delaminated from the glass plate and cracked. The result of inspection was collectively shown in Table 2.

~16SS55 The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by TPGDA (Scientific Polymer Products, tripropylene glycol diacrylate). The aged samples was slightly brown in color, corresponding to a rate of 14 on the Gardner color scale. The 5 polymer layer was delaminated from the glass plate and slightly cracked. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except 10 the TMPEOTA was replaced by PEG200DA (Scientific Polymer Products, polyethylene glycol-200 diacrylate). The aged sample was slightly brown in color, corresponding to a rate of 13 on the Gardner color scale. The polymer layer was delaminated from the glass plate and cracked. The result of inspection was collectively shown in Table 15 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by PEG400DA (Scientific Polymer 20 Products, polyethylene glycol-400 diacrylate). The aged samples was brown in color, corresponding to a rate of 16 on the Gardner color scale. The polymer layer was delaminated from the glass plate and cracked. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by DTMPTTA (Scientific Polymer Products, ditrimethylolpropane tetraacrylate). The aged sample was yellow in color, corresponding to a rate of 8 on the Gardner color WO 95/0157g PCT/US94/07368 scale. The polymer layer was delaminated from the glass plate and cracked. The result of inspection was collectively shown in Table 2.

COMPARATIVE EXAMPLE ~5 The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by HDDA. The aged samples was slightly yellow in color, corresponding to a rate of 6 on the Gardner color scale. The polymer layer was delaminated from the glass plate and cracked. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by a mixture containing 7 parts of CN-11 2C60 (Sartomer, ethoxylated Novolac acrylate) and 3 parts of TMPTA. The procedure of photocuring and thermal testing in Example 1 was then repeated. The aged samples was slightly brown in color, corresponding to a rate of 12 on the Gardner color scale. The polymer layer was delaminated from the glass plate with no crack. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by a mixture containing 7 parts of AS-X95 (Biddle-Sawyer, Oligomeric polyester acrylate) and 3 parts of HDODA. The aged sample was slightly brown in color, corresponding to a rate of 8 on the Gardner color scale. The polymer layer was delaminated from the glass plate and slightly cracked. The result of inspection was collectively shown in Table 2.

WO 95/01579 ~ 16 5 5 5 5 PCT/US94/07368 The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by SR9008 (Sartomer, trifunctional alkoxylated acrylate). The aged sample was yellow in color, 5 corresponding to a rate of 8 on the Gardner color scale. The polymer layer was delaminated from the glass plate with no crack. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by SR9012 (Sartomer, trifunctional oligomeric polyester acrylate). The aged sample was yellow in color, corresponding to a rate of 6 on the Gardner color scale. The polymer layer was delaminated from the glass plate and cracked. The result of 15 inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by a mixture containing 7 parts of TITA
20 (Scientific Polymer Products, tris-(2-hydroxyethyl)isocyanurate triacrylate) and 3 parts of HDDA. The aged sample was slightly brown in color, corresponding to a rate of 12 on the Gardner color scale. The polymer layer was delaminated from the glass plate and cracked. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by EBDA (Scientific Polymer Products, ethoxylated bisphenol 'A' diacrylate). The aged sample was slightly 30 yellow in color, corresponding to a rate of 5 on the Gardner color WO 95/01579 ~15 ~ 5 5 ~ PCT/US94/07368 scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 2.

The procedure of Comparative Example 7 was repeated except the TMPEOTA was replaced by EHFBDA (ethoxylated hexafluoro-bisphenol 'A' diacrylate). The aged sample was slightly yellow in color, corresponding to a rate of 4 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 2.

WO 95/01579 216 5 ~ 5 ~ PCT/US94/07368 Comparison of Various Acrylates After Thermal-aged at 190 C for 24 hours Exomplo #Monomor 1 Monomor 2Discolor.~l~ Dolam.~Crockin C7 TMPEOTA -- 12 Yo9 Yos C8 TMPTA -- 6 Yos Yos C9 NPPOGDA -- 13 Yo9 yo9 C10 GPTA - 16 Yo9 Yo9 C11 TPGDA -- 14 Yo9 Yos C12 PEG200DA - 13 Yo9 Yo8 C13 PCG~lOODA -- 16 Yo9 Yo9 C 14 DTMPTTA - 8 Yo9 Yo9 C15 HDDA -- 6 Yo9 Yo~
1 5 C16 CN-112C60 TMPTA 12 Yo9 No C17 AS-X95 HDDA 8 Yo9 Yo~
C18 SR9008 -- 8 Yos No C19 SR9012 -- 6 Yo9 Yo9 C20 TITA HDDA 12 Yos Yo9 2 E8DA -- 5 No No 3 EHF8DA -- 4 No No (1 ) Discoloring was rated on a Gardner Color Scale, according to (2) Delamination was defined according to by ASTM D4538-9Oa.
(3) Cracking was defined according to by ASTM D4538-9Oa.

The procedure of Example 2 was repeated except the 10 parts of EBDA was replaced by a mixture of 6.6 parts of EBDA and 3.4 parts of HDDA. The aged samples were yellow in color, corresponding to a rate of 8-9 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 3.
The liquid composition prior to photocuring was deposited onto glass or silicon substrates by spin-coating. Depending on the spinning rate, the thickness of the photocured polymer was able to be controlled at 0.5-5 micron.

The procedure of Example 2 was repeated except the 10 parts of EBDA was replaced by a mixture of 6.6 parts of EBDA and 3.4 parts of TMPTA. The aged sample was slightly yellow in color, corresponding to a rate of 5-6 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 3.
The liquid composition prior to photocuring was deposited onto glass or silicon subslrates by spin-coating. Depending on the spinning rate, the thickness of the photocured polymer was able to be controlled at 0.5-5 micron.

The procedure of Example 2 was repeated except the 10 parts of EBDA was replaced by a mixture of 6.6 parts of EBDA and 3.4 parts of ethoxylated trimethylol propane triacrylate (ETMPTA). The aged samples were yellow in color, corresponding to a rate of 8-9 on the Gardner color scale. The polymer layer adhered to the glass plate 2165~

with no delamination and no crack. The result of inspection was collectively shown in Table 3.
The liquid composition prior to photocuring was deposited onto glass or silicon substrates by spin-coating. Depending on the spinning 5 rate, the thickness of the photocured polymer was able to be controlled at 0.5-5 micron.

The procedure of Example 2 was repeated except the 10 parts 10 of EBDA was replaced by a mixture of 6.6 parts of EBDA and 3.4 parts of SR9012 (Sartomer). The aged samples were yellow in color, corresponding to a rate of 8-9 on the Gardner color scale. The polymer layer was delaminated from the glass plate and cracked. The result of inspection was collectively shown in Table 3.

WO 95/0157g PCT/US94/07368 ~1655~3 Comparison of Different Diluents for EBDA After the Photopolymer Aged at 190'C for 24 hours Ex~mpb #Monom~r 1 Monomor 2 Diocolor."'D~lam.'"Crackin~
2 EBDA -- 5 No No 4 E8C~A HDDA 8-9 No No EBDA TMPTA 5-6 No No 6 EBDA E.'rMPTA 8-9 No No 7 EBDA SR9012 8-9 Y~ Y~5 ~ 1) Disroloring was rated on - Gardner ~olor Sca e, accordil g to ASTM D1544-80.
(2) Delamination was defined according to by ASTM D4538-9Oa.
(3) Cracking was defined according to by ASTM D4538-9Oa.

The procedure of Example 5 was repeated except an extra 0.05 part of Tinuvan770 (bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, Ciba-Geigy) was added. Tinuvan 770 is a hindered amine light 20 stabilizer. The aged sample was yellow in color, corresponding to a rate of 9-10 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 5 was repeated except an extra 0.05 part of AM806 (Ferro Corp.) was added. AM806 is also a hindered amine light stabilizer. The aged sample was yellow in color, corresponding to a rate of 9-10 on the Gardner color scale. The WO 9~/01579 216 5 5 ~i 5 PCT/US94/07368 polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 5 was repeated except an extra 0.05 part of Tinuvan238 (2-[2-hydroxy-3,5-di(1,1-dimethylpropyl)phenyl]2-H-benzotriazole, Ciba-Geigy) was added. Tinuvan238 is a benzotriazole UV absorber. The photocuring took 2 minutes to complete. The aged sample was yellow in color, corresponding to a rate of 9-10 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 5 was repeated except an extra 0.05 part of AM340 (Ferro Corp.) was added. AM340 is also a benzotriazole UV absorber. The photocuring took 2 minutes to complete. The aged sample was yellow in color, corresponding to a rate of 9-10 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 5 was repeated except an extra 0.05 part of Irganox1010 (Ciba-Geigy, pentaerythritol tetrakis[3,5-di-tert-butyl-4-hydroxyhydrocinnamate] was added. Irganox1010 is a hindered phenol type antioxidant. The aged samples were only very lightly discolored, corresponding to a rate of 2-3 on the Gardner color scale. The polymer layer adhered to the glass plate with no WO 95/01579 ~ 5 ~i ~ PCT/US94/07368 delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 2 was repeated except the amount of Irganox1010 was reduced to 0.01 part. The aged samples were only very lightly discolored, corresponding to a rate of 2-3 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 5 was repeated except an extra 0.05 part of Irganox 1035 (Ciba-Geigy, thio(diethylene-bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate) was added. Irganox 1035 is a hindered phenol type antioxidant. The aged sample was lightly discolored, corresponding to a rate of 3-4 on the Gardner color scale.
The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 5 was repeated except an extra 0.05 part of Irganox1076 (Ciba-Geigy, stearyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]proprionate) was added. Irganox1076 is a hindered phenol type antioxidant. The aged sample was very lightly discolored, corresponding to a rate of 2-3 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

~16~5~ -The procedure of Example 5 was repeated except an extra 0.05 part of Irganox1520 (Ciba-Geigy, 2,4-bis[octylthiomethyl]-o-cresol) 5 was added. Irganox 1520 is a hindered phenol type antioxidant. The aged sample was lightly discolored, corresponding to a rate of 4-5 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 5 was repeated except an extra 0.05 part of Cyasorb UV2908 (American Cyanamid, cetyl-3,5-di-tert-butyl-4-hydroxybenzene) was added. Cyasorb UV2908 is a hindered phenol 15 type antioxidant. The aged sample was very lightly discolored, corresponding to a rate of 2-3 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

The procedure of Example 5 was repeated except additional 0.02 part of Irganox1010, 0.05 part of Tinuvin 770, and 0.05 part of Tinuvin-238 was added. Irganox1010 is a hindered phenol type antioxidant, Tinuvan770 is a hindered amine light stabilizer and Tinuvan238 is a benzotriazole UV absorber. The photocuring took 2 minutes to complete.The aged sample was yellow, corresponding to a rate of 7-8 on the Gardner color scale. The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

WO 95/01579 '~ PCT/US94/07368 ^3 The procedure of Example 5 was repeated except additional 0.02 part of IrganoxlO10 and 0.05 part of Tinuvin 770 was aaded.
Irganox1010 is a hindered phenol type antioxidant and Tinuvan770 is 5 a hindered amine light stabilizer. The aged sample was very lightly discolored, corresponding to a rate of 3-4 on the Gardner color scale.
The polymer layer adhered to the glass plate with no delamination and no crack. The result of inspection was collectively shown in Table 4.

21~5~

Comparison of Various Additives After Polymer aged at 190'C for 24 hours Examplo # Additivo 1 Additivo 2 Di~color."' Dolom.'''Crackin~

-- 5 No No 8 Tinuvan770 -- 9-10 No No 9 AM806 -- 9-10 No No 10'-~ T;.,.r~t 7 ~8 -- 9-10 No No 1 1~ AM340 9-10 No No 1 2 Ir9anox1 01 0 __ 2-3 No No ~0.05 part~
1 3 Irganox1 01 0 2-3 No No ~0.02 part~
14 Irganox 45 No No Irganox1076 -- 3 4 No No 16 Irganox1520 45 No No 17 C- UV2908 -- 2-3 No No Irganox1010 Tinuvan 7-8 No No 18~ 238 19~-~ Irganox1010 Tinuvan 45 Yo~ Y~

(1 ) Discoloring was rated on a Gardner Co or Scale, according to ASTM D1544-80.
t2) Delamination was defined according to by ASTM D4538-9Oa.

wo 95/0157g 216 ~ 5 S ~ PCT/US94/07368 (3) Cracking was defined according to by ASTM D4538-9Oa.
(4~ The photocuring rate was much slower when using bentriazol UV absorber as additive.
(5) Another additive - Tinuvan770 was added.

A 5 cm long polymer optical waveguide was prepared by photoexposing through a pattern mask a photosensitive monomer mixture consisting of 96 parts ethoxylated bisphenol A diacrylate, 33 parts trimethylol propane triacrylate, 3 parts Irganox 1010, 1 part Darocur 1173, 1 part Irgacure 651 and 1 part Irgacure 500 followed by devolopment with acetone. The waveguide was pigtailed with 100/140 micron glass optical fibers and overcoated with a reactive monomer mixture consisting of 58 weight percent of the above 15 monomer mixture and 42 weight percent of a mixture consisting of 50 parts Genomer T1600 urethane acrylate, 98 parts 1,6-hexanediol diacrylate, 1 part Darocur 1173, 1 part Irgacure 651 and 1 part Irgacure 500. The substrate for the polymer optical waveguide was a polyimide circuit board material with a thin layer of the same 58:42 20 mixture previously listed. Both the substrate coating and the overcoat layer were cured by blanket exposure from a UV xenon lamp under a nitrogen atmosphere. 810 nm laser light was coupled into one end of the polymer optical waveguide via its glass optical fiber pigtail. The power which was transmitted through the waveguide was measured 25 by connecting the glass optical fiber attached to the opposite end of the polymer waveguide to a silicon photodetector coupled to an optical power meter. After obtaining the initial power transmission of the polymer optical waveguide, the substrate bearing the polymer waveguide was placed on top of a hotplate and heated to 190 C, as 30 determined by a thermocouple element attached to the substrate next WO 95/OlS79 ~ PCT/US94/07368 216555~

to the polymer waveguide. The temperature of the polymer optical waveguide was maintained at 190~ C for a total of 45 hours, after which the 810 nm laser light was again passed through the polymer waveguide and its power was remeasured. By subtracting the two 5 power measurements and dividing by the 5 cm length of the waveguide it was determined that the extended exposure to this high temperature treatment had increased the propagation loss of the polymer optical waveguide by only 0.13 dB/cm. Thus the material of the waveguide was demonstrated to be highly resistant to thermal 10 degradation of its optical properties.

Claims

WHAT IS CLAIMED IS:

1. An optical element comprising:
(a) a substrate; and (b) a light transmissive region on the surface of said substrate wherein said light transmissive region is formed from a photopolymer comprising:
one or more ethylenically unsaturated monomers selected from the group consisting of aryl acrylates and aryl methacrylates wherein said photopolymer on exposure to a temperature of 190°C in air for 24 hours exhibits a coloration on the Gardner Color Scale equal to or less than 8 as determined by ASTM D1544-80 and exhibits no cracking or delamination from a glass substrate as defined by ASTM D 4538-90A on exposure of same to a temperature of 190°C for 24 hours in air.

2. The optical element of claim 1 wherein said substrate (a) is glass.

3. The optical element of claim 1 wherein said aryl acrylate and aryl methacrylates are selected from the group consisting of aryl diacrylates, aryl triacrylates, aryl tetra-acrylates, aryl dimethacrylates, aryl trimethacrylates, and aryl tetramethacrylates.

4. The optical element of claim 3 wherein said coloration is equal to or less than about 6 on the Gardner Color Scale.

5. The optical element of claim 4 wherein said coloration is equal to or less than about 5 on the Gardner Color Scale.

6. A planar optical waveguide comprising:
(a) a substrate; and (b) a light transmissive region on the surface of said substrate wherein said light transmissive region is formed from a photopolymer comprising:
one or more ethylenically unsaturated monomers selected from the group consisting of aryl acrylates and aryl methacrylates wherein said photopolymer on exposure to a temperature of 190°C in air for 24 hours exhibits a coloration on the Gardner Color Scale equal to or less than 8 as determined by ASTM D1544-80 and exhibits no cracking or delamination from a glass substrate as defined by ASTM D 4538-90A on exposure of same to a temperature of 190°C for 24 hours in air.

7. The planar optical waveguide of claim 6 wherein said substrate (a) is glass.

8. The planar optical waveguide of claim 7 wherein said aryl acrylate and aryl methacrylates are selected from the group consisting of aryl diacrylates, aryl triacrylates, aryl tetra-acrylates, aryl dimethacrylates, aryl trimethacrylates, and aryl tetramethacrylates.

9. The planar optical waveguide of claim 8 wherein said coloration is equal to or less than about 6 on the Gardner Color Scale.

10. The planar optical waveguide of claim 9 wherein said coloration is equal to or less than about 5 on the Gardner Color Scale.