WO2003010607A2 - Electrooptical photosensitive material and method of fabrication - Google Patents
Electrooptical photosensitive material and method of fabrication Download PDFInfo
- Publication number
- WO2003010607A2 WO2003010607A2 PCT/IB2002/004218 IB0204218W WO03010607A2 WO 2003010607 A2 WO2003010607 A2 WO 2003010607A2 IB 0204218 W IB0204218 W IB 0204218W WO 03010607 A2 WO03010607 A2 WO 03010607A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrooptical
- prepolymerization
- chromophore
- mixture
- photoinitiator
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- the present invention relates to high-molecular compounds, more particularly, to polymer materials that possess both electrooptical and photosensitive properties and can be used for fabrication of various optical devices.
- optical materials to be used in the devices designed for multiplexing and demultiplexing of optical signals, in particular, optical spectral filters, is that they should exhibit photosensitive and electrooptical properties. Photosensitivity of the material enables recording of holograms, which are typically diffraction gratings, while its electrooptical properties are used for fabrication of electrically controlled optical devices.
- Polymers with photorefractive properties are known and used for recording of holograms, in particular, holographic diffraction gratings, to be a component of optical filters and devices designed for multiplexing of optical signals.
- a typical composition of such a polymer and includes 42 % of poly-N-vinylcarbozole as the so-called polymer matrix, 7 % of N-ethylcarbozole as a plasticizer, 25 % of 2,5-dimethyl-4,4'- nitrophenylazoanisole as a nonlinear chromophore, 25 % of 3-methoxy-4,4'- nitrophenylazoanisole as as a nonlinear chromophore, and 1 % of 2,4,7- trinitrolfuorenone as a TNF sensitizer.
- the polymer sample is prepared in the form of a thin layer sandwiched between two transparent electrodes deposited on glass plates.
- the sample thickness ranges from several tens to one-two hundred of microns. For instance, in [1] the sample thickness was 125 ⁇ m.
- Photosensitivity of such polymers is provided by a sensitizer. For instance, some polymers had sensitivity in the red region of the spectrum (in the vicinity of 633 nm).
- Photoconductivity of the polymer was provided by poly-N-vinylcarbozole, and the electrooptical properties resulted from nonlinear chromophore.
- An external electric field with a strength of the order of 6.2- 10 7 V/m was applied to the sample to ensure transfer of photoinduced charges du ⁇ ng hologram recording.
- photorefractive polymers are high light absorption and scattering. Because of this, they can be used only as thin samples with the thickness of not more than 0.2 mm. Taking into account that 1 cm sample thickness is required for achieving spectral selectivity of the order of 10 "5 with a filter based on Bragg diffraction, it becomes evident that photorefractive polymers are unsuitable for the applications where high spectral selectivity is needed.
- photorefractive polymers Another shortcoming of photorefractive polymers is the necessity for application of a very high external electric field both during hologram recording and readout.
- the hologram exists in the photorefractive polymer only when it is illuminated with recording radiation and when an external electric field with the strength of about
- a polymer including polymethylmethacrylate (PMMA) as a matrix and titanocene dichloride as a photoinitiator is prepared as follows.
- a high-purity monomer of methylmethacrylate (MMA) in a liquid form is mixed with a photoinitiator and thermoinitiator (2,2'-azobis-2-methylpropionite in the ratio 98: 1 :1).
- the obtained mixture is placed into a cuvette in the form of two parallel glass plates with an elastic polychlorvinyl ring between them.
- the mixture fills the cavity formed by the inner space of the ring confined by the plates.
- the cuvette with the mixture is placed into a heating chamber and kept there for 48 hours at 50°C.
- the samples becomes solid after this period of time; about 90 % of the monomer becomes a polymer - polymethylmethacrylate, and the remaining 10 % of the monomer remain in the sample in the form of a free monomer - methylmethacrylate.
- a specific feature of the reaction is that a part of the initial monomer of methylmethacrylate remains unpolymerized. For this reason this process is called prepolymerization.
- the free methylmethacrylate monomer and the photoinitiator contained into the composition of the obtained polymer provide its photosensitive properties, which manifest themselves as follows.
- a diffraction grating When a diffraction grating is recorded by, for example, two intersecting coherent light beams, an interference pattern is formed in the sample.
- the wavelength of recording light has to match the absorption spectrum of the photoinitiator.
- titanocene dichloride mentioned above is used as a photoinitiator, the recording light wavelength has to be chosen in the green region of the spectrum.
- the photosensitive polymers considered above have low absorption and scattering coefficients, and therefore samples of sufficient thickness can be made. However, this material does not exhibit any electrooptical properties, which hinders their applications in electrically controlled optical devices.
- a diffraction grating When a diffraction grating is recorded by, for example, two intersecting coherent light beams, an interference pattern is formed in the sample.
- the recording radiation wavelength has to be matched with the absorption spectrum of the photoinitiator.
- titanocene dichloride mentioned above is used as a photoinitiator, the sample is sensitive in the green region of the spectrum.
- the photochemical reaction starts.
- a molecule of the photoinitiator decays into two radicals, which initiate polymerization of free molecules of the methylmethacrylate monomer thus forming macroradicals, i.e., very long molecules.
- macroradicals i.e., very long molecules.
- the photosensitive polymers considered above have low absorption and scattering coefficients, and therefore samples of sufficient thickness can be made. However, this material does not exhibit electrooptical properties, which makes them inapplicable for electrically controlled optical devices.
- electrooptical polymers exhibiting electrooptical properties - electrooptical polymers, used, for example, for electrooptical modulation of the light wave phase.
- the electrooptical polymers typically contain 50-70 % of polymethylmethacrylate as a matrix, and the remaining 50-30 % are electrooptical chromophores, or nonlinear chromophores.
- the electrooptical chromophore can be, for instance, 2,5-dimethyl-4,4'- nitrophenylazoanisole and 3-methoxy-4,4'-nitrophenylazoanisole or ring-locked phenyltertaene bridged chromophore (CLD).
- CLD ring-locked phenyltertaene bridged chromophore
- Other molecules can also be used as an electrooptical chromophore provided that they are oblong and bipolar.
- Electrooptical properties of such a polymer are achieved by heating it up to the poling temperature and application of an external electric field.
- the heating provides required mobility of the chromophore molecules, and the applied electric field orients them in a given direction.
- the polymer sample acquires a preffered polar axis and gains electrooptical properties.
- the electrooptical polymers are analogs of electrooptical ferroelectric crystals.
- the object of the present invention is to create a new class of polymer materials - electrooptical photosensitive polymers (EPP) possessing simultaneously both electrooptical and photosensitive properties.
- the electrooptical photosensitive polymer material consists of electrooptical chromophore, photoinitiator, and the product of methylmethacrylate prepolymerization, that contains polymethylmethacrylate and unreacted methacrylate monomer.
- the above ingredients are represented in the following proportion (in wt %): electrooptical chromophore - 10-30; photoinitiator - up to 1 ; methylmethacrylate prepolymerization product - the rest; the chromophore molecules having preferentially the same polar orientation.
- the particular type of the photoinitiator and chromophore is chosen depending on the wavelength range in which the proposed polymer material will be used.
- the substance, used as the initiator has to absorb light in the desired spectral region, decay into radicals, and thus provides the required photochemical reaction.
- titanocene dichloride is used as a photoinitiator
- the obtained polymer has its photosensitivity in the green region.
- the photoinitiator is 2,2-dimetoxy-2- phenylacetophenone (DMPA), C 16 H 10 O 3
- DMPA 2,2-dimetoxy-2- phenylacetophenone
- chromophore The major requirement to the chromophore is that it has to have oblong bipolar molecules.
- chromophores There a number of references that give examples of such chromophores; all of them can be used to obtain the polymer of the present invention [1, 2, 10, 11].
- 2,5-dimethyl-4,4'-nitrophenylazoanizole and 3-methoxy-4,4- nitrophenylazoanisole are described as chromophores.
- the polymer with the electrooptical properties in the red and near-infrared spectral regions can be obtained.
- the proportion between the ingredients of the polymer material of the present invention is determined by contradictory requirements for photosensitive and electrooptical properties of the material on the one hand and high optical quality on the other hand.
- the proposed polymer material has to meet the above requirements simultaneously.
- the concentrations of the ingredients given above in the electrooptical photosensitive polymer of the present invention were experimentally found to be optimal with respect to the compromise between the acceptable light absorption and photosensitivity and electrooptical properties.
- the optimal ingredient proportion indicated above provides the following characteristics of the polymer material: optical absorption of a 1 cm thick sample - not more than 5 %; photosensitivity - approximately 20 mJ/cm 2 ; electrooptic coefficient - approximately (2 ⁇ 3)- 10 "12 m/V.
- the concentration of the photoinitiator is greater than its optimal value indicated above, the obtained material still has photosensitivity.
- the obtained material still has photosensitivity.
- such polymer is practically unusable as an optical material because of high light absorption induced by higher photoinitiator concentration.
- the concentration of the chromophore that provides electrooptical properties of the invented material.
- the chromophore concentration is less than 10 %, the obtained material has extremely low electrooptic coefficient, which prevents from using the material for electrically control of refractive index in optical devices.
- the chromophore concentration is higher than 30 %, the obtained material has good electrooptical properties, but strongly absorbs and scatters light, which also makes the material unusable as an optical material.
- the photoinitiator determines the spectral range where the invented polymer material exhibits its photosensitive properties.
- one or more photoinitiators that have their photosensitivity in different spectral ranges, can be added to the material composition at amount less than 1 % for each additional photoinitiator.
- the present invention enables a new class of polymer materials which are electrooptical photosensitive polymers. If the material contains several photoinitiators, it has photosensitivity in multiple spectral ranges, which substantially extends its applications in fabrication of various optical devices
- the electrooptical photosensitive polymer of the present invention can be fabricated as follows.
- the ingredients indicated above, i.e., the photoinitiator and nonlinear chromophore, are added to a high-purity monomer of methylmethacrylate, and the monomer with the added ingredients is stirred to obtain a homogeneous mixture.
- the obtained mixture is then placed into a special cuvette, which is constructed so that access of air to the mixture is prevented both at the stage of mixture loading into the cuvette and during prepolymerization, and kept at a temperature of about 50°C until the prepolymerization is finished.
- the process is carried out in the dark and under mechanical pressure applied to the mixture.
- the mixture is stirred by, for example, periodically turning the cuvette, which prevents separation of the components of the mixture under their own weight.
- the electric field of the range (4 ⁇ 10)- 10 5 V/m is applied.
- the field is kept applied until the prepolymerization is completed.
- the electric field provides alignment of polar molecules in one direction. As a result, the material becomes solid and acquires both the photosensitive and electrooptical properties.
- the cuvette with the polymer sample is cooled, the cooling rate being not more than 0.25°C/min. If cooling is more rapid, the glass or polymer can crack because of different thermal expansion coefficients of these materials.
- thermoinitiator In order to accelerate prepolymerization, a thermoinitiator is added to the mixture during its preparation.
- the thermoinitiator may be, for instance, 2,2'-Azobis(2- methylpropionite).
- the thermoinitiator determines the time of reaction. In particular, if the amount of the thermoinitiator is approximately 1 % of the mixture, the total time of reaction is of the order of 48 hours. If the thermoinitiator is not used, the time of reaction is of the order of 4-5 days, i.e., 2-2.5 times as long as the time of reaction in the case the amount of the thermoinitiator indicated above is used.
- the optical characteristics (light absorption and scattering coefficients) of the polymer sample prepared from the initial mixture without thermoinitiator are better.
- the concentration of the thermoinitiator is kept under a constant external mechanical pressure of the order of 3-5 kg/cm during the entire prepolymerization process.
- Fig. 1 shows the cuvette used for preparation of the polymer sample in accordance with the present invention
- Fig. 2 shows the cuvette of Fig.1 placed into a holder to provide application of the external electric field and mechanical pressure to the sample during its preparation;
- Fig. 3 shows the prepared sample of the electrooptical photosensitive polymer of the present invention
- Fig. 4 shows the optical scheme for recording a holographic diffraction grating in the prepared sample
- Fig. 5 shows the optical scheme for readout of the holographic grating recorded in the sample to measure the grating and sample characteristics.
- the monomer of methylmethacrylate is a readily evaporating liquid substance with extremely high chemical activity
- the mixture of methylmethacrylate with the components indicated above has to be placed in a sealed reservoir to prevent it from evaporation and the mixture surface has to be in vacuum or inert atmosphere to avoid its chemical reaction with air;
- the final volume of the polymer in the solid state is about 10 % smaller than the volume of the initial monomer in the liquid state
- the cuvette (see Fig. 1) consists of two glass plates 1 and 2 separated by a tubular elastic ring 3 made from polyvinylchloride. Since methylmethacrylate is very aggressive chemically, the ring 3 is made from the material resistant to chemical action of methylmethacrylate.
- Two glass plates 4 and 5 of parallelepiped shape are rigidly mounted between the plates 1 and 2 inside the ring 3. To prepare the sample with two pairs of facets of a high optical quality, the surfaces of the plates 1 and 2 facing each other, and also the surfaces of the plates 4 and 5 facing each other, have to have high optical quality.
- Access to the clearance can be provided by means of two needles 6 and 7 that pierce the ring 3.
- the height h of the plates 4 and 5 is chosen to be slightly less than the gap H between the plates 1 and 2 determined by the elastic ring 3 in the unloaded state. This allows shift the plates 1 and 2 closer during prepolymerization process. This shift is necessary since during prepolymerization the volume of the mixture decreases by about 10 % compared with the initial volume and the mixture has to be under a constant mechanical pressure from the side of the plates 1 and 2.
- Example of fabrication of the polymer of the present invention Into 100 ml of a high-purity monomer of methylmethacrylate (C 5 H 8 O 2 ), the following components are added:
- the filled cuvette is placed into a special holder (see Fig.2) between plates 8 and 9 pulled together by springs 10.
- a special holder see Fig.2
- the electrodes 11 and 12 could be placed on the outer surfaces of the plates 1 and 2 and connected to the voltage source 13.
- the springs 10 provide compression of the plates 1 and 2 of the cuvette with a force of approximately 3-5 kg/cm .
- the holder with the cuvette is placed into a heating chamber and kept there for 48 hours at the temperature of the order of 50°C. The thermoinitiator accelerating prepolymerization is initiated at this temperature.
- the holder with the cuvette is rotated by 90° in different directions every 15-20 minutes. This is necessary to ensure a uniform distribution of the initial components of the mixture throughout the cuvette volume because the mixture at this stage is in the liquid state, and the mixture components may subside under their own weight.
- the methylmethacrylate monomer begins to turn into the polymethylmethacrylate polymer, and the reaction mixture starts to solidify.
- the electric field with a strength of about 10 6 V/m is applied to the cuvette with the help of the voltage source 13 and the electrodes 11 and 12.
- the constant action of the electric field results in alignment of long chromophore molecules along the direction of the applied field.
- the electric field is kept applied until the prepolymerization process is completed.
- the cuvette with the sample is naturally cooled to room temperature during 2-3 hours.
- the required cooling rate of not more than 0.25°C/min is provided by a large mass of the holder.
- the sample is removed from the cuvette.
- the prepared polymer sample 14 typically has the shape shown in Fig. 3.
- the surfaces 15 and 16 which contact with the plates 1 and 2, respectively, during prepolymerization, and also the surfaces 17 and 18 which contact with the plates 4 and 5, respectively, during prepolymerization have an optical quality.
- the polymer sample 21 is finally shaped in the form of a parallelepiped by cutting unneeded parts along lines 19 and 20.
- the initial mixture shall include:
- thermoinitiator 100 ml of a high-purity monomer of methylmethacrylate (C 5 H 8 O 2 ), 1 g of 2,2'-Azobis(2-methylpropionitril) (C 8 H 12 N ) as a thermoinitiator;
- the photosensitive and electrooptical properties of the polymer sample prepared in accordance of the present invention were tested by recording a holographic diffraction grating in the sample and its subsequent readout through the Bragg diffraction of optical radiation from this grating depending on external electrical field applied to the sample.
- an interference pattern was formed in the sample 21 by two coherent light beams 22 and 23 directed onto the surface 15 at the angle ⁇ .
- the sample 21 was illuminated with light during 5 s.
- the light initiated the photochemical reaction of the remaining 10 % of the methylmethacrylate monomer with the photoinitiator, during which a diffraction grating 24 was formed in the volume of the sample 21.
- the sample 21 After being illuminated with the recording light, the sample 21 was kept in the dark for about 24 hours. After this period, the photochemical reaction was completed in the previously illuminated portion of the sample and the photoinitiator and methylmethacrylate monomer molecules were removed from the nonilluminated sites in a natural way - by diffusing into the environment. During the reaction, local variations of the material density arose in the illuminated portion of the sample, which, in turn, resulted in local variations of the refractive index, i.e., recording of the diffraction grating 24 in the sample 21 was performed. The period ⁇ of the grating 24 is given by a well-known expression:
- the sample loses photosensitive properties after a hologram is recorded and the photochemical reaction is completed because all the photoinitiator has reacted with methylmethacrylate in the illuminated portion of the sample and diffused out of the nonilluminated portion. This means that the photosensitive properties of the obtained polymer can be used only once.
- the holographic sensitivity of the prepared polymer sample is defined as the energy needed to record a holographic diffraction grating with a diffraction efficiency of 1 %.
- the holographic photosensitivity of the fabricated material was determined by a conventional procedure. The procedure is as follows. Holograms are recorded at in the material under test with different recording energies (the recording energy is the product of the recording light intensity, in W/cm 2 , and recording time, in seconds). Typically the recording time is set constant, while the light intensity is varied. Then the dependence of the grating diffraction efficiency on the recording energy is measured. The recording energy that provides 1 % diffraction efficiency is taken as the holographic sensitivity.
- the recording energy of about 20 mJ/cm was needed. Note that it is comparable with the holographic sensitivity of a heavily doped lithium niobate sample.
- the above measurements were done for the diffraction grating with a length of 1 cm.
- a diffraction grating recorded in an electrooptical material When it is illuminated with a light beam in the direction parallel to the diffraction grating vector, the light with the wavelength satisfying the Bragg condition is backreflected from the grating.
- T the grating length
- the polymer sample 21 with the recorded diffraction grating 24 was illuminated from the sample side 17 with a laser beam 25, and the light beam 26 reflected from the grating 24 was detected. Readout was performed at the wavelength of the order of 1500 nm, and the period of the grating 24 satisfied the Bragg condition in the absence of the external electric field.
- the external field was applied to the sample with the help of electrodes 27 and 28. When the electric field was applied, the average refractive index of the sample changed and, hence, the Bragg condition was violated and the readout beam intensity changed.
- the effective electrooptic coefficient r e ⁇ - was determined. It was found to be equal to
- the present invention provides fabrication of electrooptical photosensitive polymers based on polymethylmethacrylate in wide range of electrooptical and photosensitive parameters suitable for use as an optical material.
- Electro-optic polymer modulators for 1.55 ⁇ m wavelength using phenyltetraene bridged chromophore in polycarbonate Appl. Phys. Letters, Vol.76, N.24, 3525-3527 (2000).
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002355198A AU2002355198A1 (en) | 2001-05-01 | 2002-05-01 | Electrooptical photosensitive material and method of fabrication |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28810001P | 2001-05-01 | 2001-05-01 | |
US60/288,100 | 2001-05-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2003010607A2 true WO2003010607A2 (en) | 2003-02-06 |
WO2003010607A3 WO2003010607A3 (en) | 2007-11-08 |
Family
ID=23105738
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2002/004218 WO2003010607A2 (en) | 2001-05-01 | 2002-05-01 | Electrooptical photosensitive material and method of fabrication |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU2002355198A1 (en) |
WO (1) | WO2003010607A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1526709A2 (en) * | 2003-10-22 | 2005-04-27 | Alps Electric Co., Ltd. | Optical image reader |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB486660A (en) * | 1935-11-06 | 1938-06-07 | Chem Ind Basel | Manufacture of dyestuffs |
GB679837A (en) * | 1949-07-05 | 1952-09-24 | Jack Ernest Duddington | Improvements in and relating to the production of translucent material |
US4329384A (en) * | 1980-02-14 | 1982-05-11 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive tape produced from photoactive mixture of acrylic monomers and polynuclear-chromophore-substituted halomethyl-2-triazine |
US4330590A (en) * | 1980-02-14 | 1982-05-18 | Minnesota Mining And Manufacturing Company | Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-2-triazine |
US4362895A (en) * | 1980-03-03 | 1982-12-07 | California Institute Of Technology | Ultraviolet absorbing copolymers |
US4391687A (en) * | 1980-02-14 | 1983-07-05 | Minnesota Mining And Manufacturing Company | Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-1-triazine |
DE4007576A1 (en) * | 1989-03-09 | 1990-09-13 | Fuji Photo Film Co Ltd | Presensitised plate for prodn. of lithographic printing plates - has substrate, primer, light-sensitive layer contg. unsatd. monomer or oligomer, photo-initiator and di:azo-resin etc. |
US5244994A (en) * | 1992-03-20 | 1993-09-14 | Eastman Kodak Company | Bleachable polymeric filter dyes |
US5879591A (en) * | 1995-05-24 | 1999-03-09 | Tokuyama Corporation | Process for production of photochromic cured product |
US5891931A (en) * | 1997-08-07 | 1999-04-06 | Alcon Laboratories, Inc. | Method of preparing foldable high refractive index acrylic ophthalmic device materials |
EP0942019A2 (en) * | 1998-03-09 | 1999-09-15 | Siemens Aktiengesellschaft | Non-linear optically active copolymers, polyadducts formed from it and their use in non-linear optical media |
-
2002
- 2002-05-01 AU AU2002355198A patent/AU2002355198A1/en not_active Abandoned
- 2002-05-01 WO PCT/IB2002/004218 patent/WO2003010607A2/en not_active Application Discontinuation
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB486660A (en) * | 1935-11-06 | 1938-06-07 | Chem Ind Basel | Manufacture of dyestuffs |
GB679837A (en) * | 1949-07-05 | 1952-09-24 | Jack Ernest Duddington | Improvements in and relating to the production of translucent material |
US4329384A (en) * | 1980-02-14 | 1982-05-11 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive tape produced from photoactive mixture of acrylic monomers and polynuclear-chromophore-substituted halomethyl-2-triazine |
US4330590A (en) * | 1980-02-14 | 1982-05-18 | Minnesota Mining And Manufacturing Company | Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-2-triazine |
US4391687A (en) * | 1980-02-14 | 1983-07-05 | Minnesota Mining And Manufacturing Company | Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-1-triazine |
US4362895A (en) * | 1980-03-03 | 1982-12-07 | California Institute Of Technology | Ultraviolet absorbing copolymers |
DE4007576A1 (en) * | 1989-03-09 | 1990-09-13 | Fuji Photo Film Co Ltd | Presensitised plate for prodn. of lithographic printing plates - has substrate, primer, light-sensitive layer contg. unsatd. monomer or oligomer, photo-initiator and di:azo-resin etc. |
US5244994A (en) * | 1992-03-20 | 1993-09-14 | Eastman Kodak Company | Bleachable polymeric filter dyes |
US5879591A (en) * | 1995-05-24 | 1999-03-09 | Tokuyama Corporation | Process for production of photochromic cured product |
US5891931A (en) * | 1997-08-07 | 1999-04-06 | Alcon Laboratories, Inc. | Method of preparing foldable high refractive index acrylic ophthalmic device materials |
EP0942019A2 (en) * | 1998-03-09 | 1999-09-15 | Siemens Aktiengesellschaft | Non-linear optically active copolymers, polyadducts formed from it and their use in non-linear optical media |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1526709A2 (en) * | 2003-10-22 | 2005-04-27 | Alps Electric Co., Ltd. | Optical image reader |
EP1526709A3 (en) * | 2003-10-22 | 2005-12-21 | Alps Electric Co., Ltd. | Optical image reader |
US7193755B2 (en) | 2003-10-22 | 2007-03-20 | Alps Electric Co., Ltd. | Optical image reader |
Also Published As
Publication number | Publication date |
---|---|
WO2003010607A3 (en) | 2007-11-08 |
AU2002355198A1 (en) | 2003-02-17 |
AU2002355198A8 (en) | 2008-01-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3707371A (en) | Photosensitive element comprising a polymer matrix including styrene,auramine o,and a proxide and the use thereof in volume recording | |
Guo et al. | A review of the optimisation of photopolymer materials for holographic data storage | |
US5569565A (en) | Hologram recording material | |
US6624915B1 (en) | Holographic recording and micro/nanofabrication via ultrafast holographic two-photon induced photopolymerization (H-TPIP) | |
Gleeson et al. | Comparison of a new self developing photopolymer with AA/PVA based photopolymer utilizing the NPDD model | |
Ryabchun et al. | Novel effective approach for the fabrication of PDMS‐based elastic volume gratings | |
US20040137204A1 (en) | Switchable volume hologram materials and devices | |
KR19980018701A (en) | Optical recording media | |
Royal et al. | Photochromic and fluorescent probe studies in glassy polymer matrices. 4. Effects of physical aging on poly (methyl methacrylate) as sensed by a size distribution of photochromic probes | |
Close et al. | Monomer diffusion rates in photopolymer material. Part II. High-frequency gratings and bulk diffusion | |
US20020042004A1 (en) | Phase contrast variation of a photo-induced refractive material | |
Mikulchyk et al. | N-isopropylacrylamide-based photopolymer for holographic recording of thermosensitive transmission and reflection gratings | |
Veniaminov et al. | Diffusional enhancement of holograms: phenanthrenequinone in polycarbonate | |
CA1317059C (en) | Poly-yne nonlinear optical materials | |
Marotz | Holographic storage in sensitized polymethyl methacrylate blocks | |
US4783136A (en) | Optical waveguides and methods for making same | |
Lougnot et al. | Photopolymers for holographic recording. II. Self-developing materials for real-time interferometry | |
Zager et al. | Display holograms in Du Pont's OmniDex films | |
WO2003010607A2 (en) | Electrooptical photosensitive material and method of fabrication | |
Spagnoli et al. | γ-Ray polymerization of urethane-substituted diacetylenes: Reactivity and chain lengths | |
Pavani et al. | Photoinduced surface relief studies in an acrylamide-based photopolymer | |
Kojima et al. | Characterization of index and surface-relief gratings formed in methacrylate photopolymers | |
Pi et al. | Effect of monomers on the holographic properties of poly (vinyl alcohol)-based photopolymers | |
Bartolini et al. | Volume holographic recording characteristics of an organic medium | |
US5213915A (en) | Holographic recording material and method for holographic recording |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EE ES FI GB GD GE GH GM HU ID IL IN IS JP KE KG KP KR KZ LK LR LS LT LU LV MA MD MG MK MW MX MZ NO NZ PL PT RO RU SD SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE CH CY DE DK FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ ML MR NE SN TD TG Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
122 | Ep: pct application non-entry in european phase | ||
NENP | Non-entry into the national phase in: |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |