Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
The response of the applicant has been read and given careful consideration. The election without traverse based upon the lack of any arguments has been received and the application is proceeding to prosecution.
REQUIREMENT FOR UNITY OF INVENTION
As provided in 37 CFR 1.475(a), a national stage application shall relate to one invention only or to a group of inventions so linked as to form a single general inventive concept (“requirement of unity of invention”). Where a group of inventions is claimed in a national stage application, the requirement of unity of invention shall be fulfilled only when there is a technical relationship among those inventions involving one or more of the same or corresponding special technical features. The expression “special technical features” shall mean those technical features that define a contribution which each of the claimed inventions, considered as a whole, makes over the prior art.
The determination whether a group of inventions is so linked as to form a single general inventive concept shall be made without regard to whether the inventions are claimed in separate claims or as alternatives within a single claim. See 37 CFR 1.475(e).
When Claims Are Directed to Multiple Categories of Inventions:
As provided in 37 CFR 1.475 (b), a national stage application containing claims to different categories of invention will be considered to have unity of invention if the claims are drawn only to one of the following combinations of categories:
(1) A product and a process specially adapted for the manufacture of said product; or
(2) A product and a process of use of said product; or
(3) A product, a process specially adapted for the manufacture of the said product, and a use of the said product; or
(4) A process and an apparatus or means specifically designed for carrying out the said process; or
(5) A product, a process specially adapted for the manufacture of the said product, and an apparatus or means specifically designed for carrying out the said process.
Otherwise, unity of invention might not be present. See 37 CFR 1.475 (c).
Restriction is required under 35 U.S.C. 121 and 372.
This application contains the following inventions or groups of inventions which are not so linked as to form a single general inventive concept under PCT Rule 13.1.
In accordance with 37 CFR 1.499, applicant is required, in reply to this action, to elect a single invention to which the claims must be restricted.
Group I, claim(s) 16-24, drawn to a kit containing a dye solution and a monomer/co-photoinitiator solution.
Group II, claim(s) 25-29, drawn to photocured products of the mixture/combination of the dye solution and the monomer/co-photoinitiator solution
The groups of inventions listed above do not relate to a single general inventive concept under PCT Rule 13.1 because, under PCT Rule 13.2, they lack the same or corresponding special technical features for the following reasons:
The groups lack unity of invention because even though the inventions of these groups require the technical feature of the kit containing a dye solution and a monomer/co-photoinitiator solution, this technical feature is not a special technical feature as it does not make a contribution over the prior art in view of Weiser et al. US 9281000 (cited by applicant in IDS of 11/13/2023, Also cited as EP 2372454).
Weiser et al. US 9281000 in example 1 forms a polyol solution of 2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were dissolved in 2.907 g of polyol 1 at 60 ° C. Then, 0.18 g of coinitiator 2 and 0.015 g of 10 μm diameter glass beads were added.
In the dark, a solution of 0.03 g of Coinitiator 1 and 0.015 g of Dye 1 in 1.492 g of N-ethylpyrrolidone (N-ethylpyrilidone in English, BP is 212 degrees C) was mixed so that a clear solution was obtained.
The polyol solution described above was mixed in the dark with the last-described solution at about 35 ° C. It was then cooled to 30 ° C, 0.367 g of isocyanate 1 and 0.006 g of catalyst 1 was added and mixed again. The resulting liquid mass was then placed on a glass plate and covered with a second glass plate which was held by the glass beads at a distance of 10 microns. This specimen was left at room temperature and cured for 16 hours (column 23/lines 5-23)
The holographic media produced as described were subsequently tested by means of a measuring arrangement according to FIG. 1 for their holographic properties as follows:
The beam of a diode-pumped solid-state laser from Newport, Model EXLSR-473-50-CDRH, was converted with the aid of the spatial filter (SF) and together with the collimation lens (CL) into a parallel homogeneous beam. The final cross sections of the signal and reference beam are established by the iris diaphragms (I). The diameter of the iris diaphragm opening is 0.4 cm. The polarization-dependent beam splitters (PBS) split the laser beam into two coherent identically polarized beams. Via the λ/2 plates, the power of the reference beam was adjusted to 1.55 mW and the power of the signal beam to 1.96 mW. The powers were determined using the semiconductor detectors (D) with sample removed. The angle of incidence (α.sub.0) of the reference beam is −22° and the angle of incidence (β.sub.0) of the signal beam is 42°. The angles are measured starting from the sample normal to the beam direction. According to FIG. 1, α.sub.0 therefore has a negative sign and β.sub.0 a positive sign. At the location of the sample (medium), the interference field of the two overlapping beams produced a grating of light and dark strips which are perpendicular to the angle bisectors of the two beams incident in the sample (reflection hologram). The strip spacing Λ, also referred to as grating period, in the medium is ˜164 nm (the refractive index of the medium is assumed to be ˜1.515).
FIG. 1 shows the geometry of a Holographic Media Tester (HMT) at λ=47.3 nm (diode-pumped solid body laser from Newport, model EXLSR-473-50-CDRH): M=mirror, S=shutter, SF=spatial filter, CL=collimator lens, λ/2=λ/2 plate, PBS=polarization-sensitive beam splitter, D=detector, I=iris diaphragm, α.sub.0=−22°, β.sub.0=42° are the angles of incidence of the coherent beams, measured outside the sample (outside the medium). RD=reference direction of the turntable. Holograms were recorded in the medium in the following manner: Bolt shutters (S) are opened for the exposure time t. Thereafter, with the closed shutters (S), the medium was allowed 5 minutes' time for the diffusion of the still unpolymerized writing monomers (column 18/lines 43 to column 19/line 17).
It is clear that the use of separate sensitizer and monomer/coinitiator solutions are known in the photopolymer and holographic arts as is the use of a polyol as the solvent for the monomer solution. It is also clear that the beads are spacers for keeping the substrates separated by a uniform distance which keeps the thickness of the hologram constant even when during might induce shrinkage.
A telephone call was made to Brian Jackson (68157) on 03/11/2026 to request an oral election to the above restriction requirement, but did not result in an election being made.
Applicant is advised that the reply to this requirement to be complete must include (i) an election of a species or invention to be examined even though the requirement may be traversed (37 CFR 1.143) and (ii) identification of the claims encompassing the elected invention.
The election of an invention or species may be made with or without traverse. To preserve a right to petition, the election must be made with traverse. If the reply does not distinctly and specifically point out supposed errors in the restriction requirement, the election shall be treated as an election without traverse. Traversal must be presented at the time of election in order to be considered timely. Failure to timely traverse the requirement will result in the loss of right to petition under 37 CFR 1.144. If claims are added after the election, applicant must indicate which of these claims are readable on the elected invention or species.
Should applicant traverse on the ground that the inventions have unity of invention (37 CFR 1.475(a)), applicant must provide reasons in support thereof. Applicant may submit evidence or identify such evidence now of record showing the inventions to be obvious variants or clearly admit on the record that this is the case. Where such evidence or admission is provided by applicant, if the examiner finds one of the inventions unpatentable over the prior art, the evidence or admission may be used in a rejection under 35 U.S.C. 103 or pre-AIA 35 U.S.C. 103(a) of the other invention.
Applicant is reminded that upon the cancelation of claims to a non-elected invention, the inventorship must be corrected in compliance with 37 CFR 1.48(a) if one or more of the currently named inventors is no longer an inventor of at least one claim remaining in the application. A request to correct inventorship under 37 CFR 1.48(a) must be accompanied by an application data sheet in accordance with 37 CFR 1.76 that identifies each inventor by his or her legal name and by the processing fee required under 37 CFR 1.17(i).
The examiner has required restriction between product or apparatus claims and process claims. Where applicant elects claims directed to the product/apparatus, and all product/apparatus claims are subsequently found allowable, withdrawn process claims that include all the limitations of the allowable product/apparatus claims should be considered for rejoinder. All claims directed to a nonelected process invention must include all the limitations of an allowable product/apparatus claim for that process invention to be rejoined.
In the event of rejoinder, the requirement for restriction between the product/apparatus claims and the rejoined process claims will be withdrawn, and the rejoined process claims will be fully examined for patentability in accordance with 37 CFR 1.104. Thus, to be allowable, the rejoined claims must meet all criteria for patentability including the requirements of 35 U.S.C. 101, 102, 103 and 112. Until all claims to the elected product/apparatus are found allowable, an otherwise proper restriction requirement between product/apparatus claims and process claims may be maintained. Withdrawn process claims that are not commensurate in scope with an allowable product/apparatus claim will not be rejoined. See MPEP § 821.04. Additionally, in order for rejoinder to occur, applicant is advised that the process claims should be amended during prosecution to require the limitations of the product/apparatus claims. Failure to do so may result in no rejoinder. Further, note that the prohibition against double patenting rejections of 35 U.S.C. 121 does not apply where the restriction requirement is withdrawn by the examiner before the patent issues. See MPEP § 804.01.
Applicant’s election of group I in the reply filed on 5/18/2026 is acknowledged. Because applicant did not distinctly and specifically point out the supposed errors in the restriction requirement, the election has been treated as an election without traverse (MPEP § 818.01(a)).
Claims 25-29 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention , there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 5/18/2026.
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 24 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 24 seems to be directed to a specific mixture of the two. The claims are to the composition as separate solutions. This is not a meaningful limitation until they are being combined.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claims 16,17,19 and 22-24 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Weiser et al. US 9281000.
Weiser et al. US 9281000 in example 1 forms a polyol solution of 2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were dissolved in 2.907 g of polyol 1 at 60 ° C. Then, 0.18 g of coinitiator 2 and 0.015 g of 10 μm diameter glass beads were added.
In the dark, a solution of 0.03 g of Coinitiator 1 and 0.015 g of Dye 1 in 1.492 g of N-ethylpyrrolidone ( BP is 212 degrees C) was mixed so that a clear solution was obtained. A polyisocyanate solution was then added..
The polyol solution described above was mixed in the dark with the last-described solution at about 35 ° C. It was then cooled to 30 ° C, 0.367 g of isocyanate 1 and 0.006 g of catalyst 1 was added and mixed again. The resulting liquid mass was then placed on a glass plate and covered with a second glass plate which was held by the glass beads at a distance of 10 microns. This specimen was left at room temperature and cured for 16 hours (column 23/lines 5-23) Coinitiator 1 is 1H-imidazole-2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-2H-imidazol-2-yl]-4,5-biphenyl and was obtained from ABCR GmbH & Co. KG, Karlsruhe, Germany, (CAS: 7189-82-4). Coinitiator 2 is 2-mercaptobenzoxazole and was obtained from Sigma-Aldrich Chemie GmbH, Steinheim, Germany, (CAS: 2382-96-9). Dye 1 is ketocoumarin and was obtained from Acros Organics, New Jersey, USA, (CAS: 63226-13-1) (18/15-26). Suitable dyes shall be selected from the classes of the aminotriarylmethanes, triarylmethanes, hydroquinone ethers, acridines, phenazines, phenothiazines, pyrenes, polymethines, diphenylmethanes, coumarins, subject to the proviso that the absorption maximum is positioned in the range of 400-800 nm (16/4-22)
While the process of use in the example cures isocyanate/polyol before exposure, when mixed the composition includes a sensitizing dye, photoinitiator and polymerizable monomer, so it is immediately photosensitive. Please note the relative weights of the polyol/acrylate/coinitiator solution and the dye solution. The process uses three compositions: the polyol/acrylate/co-initiator solution, the dye/photoinitiator solution and the isocyanate/catalysts mixture. The dye/coinitiator/N-ethylpyrrolidone is 1.537 g and the composition including the polyol/acrylate/coinitiator/beads weighed 8.602 g
Claims 16,17,19 and 22-24 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Weiser et al. US 9281000, as evidenced by Dhar et al. 20020142227.
Dhar et al. 20020142227 (cited by applicant) establishes in the table at [0029], that the (meth)acrylate and urethane formation are independent reaction, which means that the photopolymerization of the acrylate monomer is not inhibited by the reactants/reactants for the urethane (isocyanate/hydroxyl) reaction.
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To preemptively address any arguments by the applicant the examiner cites the teachings of Dhar et al. 20020142227 to support the position that the composition of Weiser et al. US 9281000 is immediately photosensitive and that the isocyanate and polyol reacted to form the urethane matrix do not affect the polymerization of the composition.
Claims 16-24 are rejected under 35 U.S.C. 103 as being unpatentable over Rolle et al. 20150261938, in view of Berneth et al. 20180223100 and Weiser et al. US 9281000
Rolle et al. 20150261938 in example medium 1 where 3.38 g of polyol component 1 were mixed with 2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1, 0.10 g of CGI 909 (product from BASF SE, Basle, Switzerland), 0.010 g of New Methylene Blue (=F7) and 0.35 g of N-ethylpyrrolidone at 60.degree. C. so that a clear solution was obtained. The dye and solvent weighed 0.36 g. the polyol/acrylate/additive/initiator weighed 8/98 g. This was followed by cooling to 30.degree. C., addition of 0.65 g of Desmodur.RTM. N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, DE, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) and renewed mixing. Finally, 0.01 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added before renewed brief mixing. The liquid mass obtained was then poured onto a glass plate and covered there with a second glass plate. This sample specimen was left to lie at room temperature for 12 hours for curing [0113]. In example medium 2, 3.38 g of polyol component 1 were mixed with 2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1, 0.10 g of Irgacure.RTM. 250 (product from BASF SE, Basle, Switzerland), 0.10 g of EDB, 0.010 g of dye F1 and 0.35 g of N-ethylpyrrolidone at 60.degree (the dye/solvent/IRG250 weighed 0.46 g, while the polyol, acrylate/additive/EDB weighed 8.98 g. C. so that a clear solution was obtained. This was followed by cooling to 30.degree. C., addition of 0.65 g of Desmodur.RTM. N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, DE, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) and renewed mixing. Finally, 0.01 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added before renewed brief mixing. The liquid mass obtained was then poured onto a glass plate and covered there with a second glass plate. This sample specimen was left to lie at room temperature for 12 hours for curing [0114].
The operating assumption is that, for a given task, the photopolymer formulation is to be exposed with an HeNe laser having a wavelength of 630 nm. The method of the present invention will now be used to verify the suitability of the two-component initiator system New Methylene Blue (NMB F7)/CGI909 for the application described. The reaction mechanism of the New Methylene Blue (NMB/F7)/CGI909 two-component initiator system consists of the following steps: [0123] 1. Light absorption by the dye. With transition from the electronic ground state (S.sub.0) into the first excited singlet state (S.sub.1). 2. Intersystem crossing into a triplet state of the dye and fast relaxation to the lowest triplet state (T.sub.1). 3. Reaction of the dye molecule in the T.sub.1 state with CGI909 to form a neutral NMB free-radical NMB.sub.rad, a borane BAr.sub.3 and also a hexyl free-radical Hex.sub.rad in accordance with the following reaction equation:
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The three-dimensional structures of New Methylene Blue and CGI909 and also of the descendant products of CGI909 were subjected to a conformer analysis by means of the conformer module in the Materials Studio software package from Accelrys. The result of this analysis was that, in the present case, only the stablest conformer had to be considered in each case, since the molecules are very rigid apart from the hexyl free-radical. Therefore, the stablest conformer according to the force field computation performed in the conformer analysis was used in each case as starting point for the quantum-chemical computations [0121-0125].
Berneth et al. 20180223100 teaches that to produce the photopolymer composition, a mixture of 30.0 g of urethane acrylate 1 and 30.0 g of urethane acrylate 2, 22.5 g of additive 1, 0.15 g of triazine 1 or 2, 1.5 g of the borate, 0.075 g of Fomrez UL 28 and 1.35 g of the surface-active additive BYK® 310 and 50 g of ethyl acetate was added stepwise to 53.7 g of polyol 1 (OH number 59.7), and mixed. Subsequently, 0.3 g of a dye according to the invention was added to the mixture in the dark and mixed, so as to obtain a clear solution. If necessary, the composition was heated at 60° C. for a short period in order to bring the starting materials into solution more quickly. This mixture was introduced into one of the two reservoir vessels 1 of the coating rig. The second reservoir vessel 1′ was charged with the polyisocyanate component (Desmodur® N 3900, commercial product from Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%). The two components were then each conveyed by means of the metering units 2 in a ratio of 18.2 (component mixture) to 1.0 (isocyanate) to the vacuum devolatilization unit 3 and devolatilized. From here, they were then each passed through the filters 4 into the static mixer 5, in which the components were mixed to give the photopolymer composition. The liquid material obtained was then sent in the dark to the coating unit 6. In example 5, the dye is a concentrated solution with butyl acetate as the solvent [0301]. Suitable coinitiators are ammonium alkylarylborates which, together with the dyes according to the invention, form a type II photoinitiator (Norrish type II) are described in principle in EP 0 223 587. Suitable ammonium alkylarylborates of this kind are, for example (Cunningham et al., RadTech'98 North America UV/EB Conference Proceedings, Chicago, Apr. 19-22, 1998): tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinaphthylhexylborate, tetrabutylammonium tris(4-tert-butyl)phenylbutylborate, tetrabutylammonium tris(3-fluorophenyl)hexylborate hexylborate ([191726-69-9], CGI 7460, product from BASF SE, Basle, Switzerland), 1-methyl-3-octylimidazolium dipentyldiphenylborate and tetrabutylammonium tris(3-chloro-4-methylphenyl)hexylborate ([1147315-11-4], CGI 909, product from BASF SE, Basle, Switzerland). Other suitable borates are known from WO 2015/055576 A1 and may find use as coinitiators in the context of the invention. Further suitable coinitiators are electron acceptors, for example tris(trihalomethyl)triazine and/or derivatives thereof, especially substituted bis(trihalomethyl)triazines, as described, for example, in JP 2008201912, EP 1 457 190 A1, EP 0 332 042, U.S. Pat. No. 3,987,037 or U.S. Pat. No. 5,489,499. In the context of the invention, the photoinitiator system may thus consist of at least one ammonium alkylarylborate as described above and/or at least one electron acceptor, for example a tris(trihalomethyl)triazine and/or derivatives thereof, especially a substituted bis(trihalomethyl)triazine. It is also possible for further electron acceptors known from the prior art (US000005500453A1, WO2006138637A1), for example iodonium or sulphonium salts, to be part of the photoinitiator system. It is also possible to use any desired mixtures of the coinitiators mentioned [0119-0121]
With respect to claims 16 and 19-24, it would have been obvious to one skilled in the art to modify the production of formation example 1 of Rolle et al. 20150261938 by combining the acrylate monomers, polyol and borate (CGI-909) to form a solution and then adding the dye as taught in Berneth et al. 20180223100 and Weiser et al. US 9281000 as a solution of New Methylene Blue (F7) in N-ethylpyrrolidone based upon the disclosed addition of a solution of the sensitizing dye 5 in Berneth et al. 20180223100 and in Weiser et al. US 9281000 and the solubility of New Methylene Blue (F7) in N-ethylpyrrolidone in Rolle et al. 20150261938 then adding the isocyanate and urethane catalyst with a reasonable expectation of forming useful sensitized composition.
With respect to claims 16 and 19-24, it would have been obvious to one skilled in the art to modify the production of formation example 1 of Rolle et al. 20150261938 by combining the acrylate monomers, polyol and borate (CGI-909) to form a solution as taught in Berneth et al. 20180223100 and then adding the other disclosed sensitizing dyes as a solution of in N-ethylpyrrolidone based upon the disclosed addition of a solution of sensitizing dyes in Berneth et al. 20180223100 and the solubility of sensitizing dyes in N-ethylpyrrolidone in Rolle et al. 20150261938 then adding the isocyanate and urethane catalyst with a reasonable expectation of forming useful sensitized composition.
With respect to claims 16 and 19-24, it would have been obvious to one skilled in the art to modify the production of formation example 1 of Rolle et al. 20150261938 by combining the acrylate monomers, polyol and borate (CGI-909) to form a solution as taught in Berneth et al. 20180223100 and then adding the dye as a solution of New Methylene Blue (F7) and irgacure 250 in N-ethylpyrrolidone based upon the disclosed addition of a solution of the sensitizing dye 5 in Berneth et al. 20180223100 and the solubility of and New Methylene Blue (F7) and irgacure 250 in N-ethylpyrrolidone in Rolle et al. 20150261938 based upon the disclosure of the use of the dye with irgacure 250 and the addition of the dye and photoinitiator in Weiser et al. US 9281000 then adding the isocyanate and urethane catalyst with a reasonable expectation of forming useful sensitized composition.
With respect to claims 16 and 19-24, it would have been obvious to one skilled in the art to modify the production of formation example 1 of Rolle et al. 20150261938 by combining the acrylate monomers, polyol and borate such as those disclosed in Berneth et al. 20180223100
to form a solution similar to that taught in Berneth et al. 20180223100 and then adding the dye as a solution of New Methylene Blue (F7) and photoinitiators such as those taught in Rolle et al. 20150261938, in view of Berneth et al. 20180223100 and Weiser et al. US 9281000 in N-ethylpyrrolidone based upon the disclosed addition of a solution of the sensitizing dye 5 in Berneth et al. 20180223100 and the solubility of and New Methylene Blue (F7) and irgacure 250 in N-ethylpyrrolidone in Rolle et al. 20150261938 based upon the disclosure of the use of the dye with irgacure 250 and the addition of the dye and photoinitiator in Weiser et al. US 9281000 then adding the isocyanate and urethane catalyst with a reasonable expectation of forming useful sensitized composition.
Claims 16-24 are rejected under 35 U.S.C. 103 as being unpatentable over Rolle et al. 20150261938, in view of Berneth et al. 20180223100 and Weiser et al. US 9281000, further in view of Nishimae et al. KR 201100252111.
Nishimae et al. KR 201100252111 (machine translation attached) teaches composition which can be used in holography [0452]. Examples of further photoinitiators (d) include radical photoinitiators such as camphor quinone; Benzophenone, benzophenone derivatives; Ketal compounds such as benzyldimethylketal (IRGACURE .sup.(R) 651); Acetophenones, acetophenone derivatives, for example α-hydroxycycloalkyl phenyl ketones or α-hydroxyalkylphenylketones, such as 2-hydroxy-2-methyl-1-phenyl-propanone (DAROCURE .sup.(R) 1173) , 1-hydroxycyclohexyl-phenylketone (IRGACURE .sup.(R) 184), 1- (4-dodecylbenzoyl) -1-hydroxy-1-methyl-ethane, 1- (4-isopropylbenzoyl)- 1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE .sup.(R) 2959) ; 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methyl-propane-1-one (IRGACURE .sup.(R) 127); 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -phenoxy] -phenyl} -2-methyl-propan-1-one; Dialkoxyacetophenone, α-hydroxy- or α-aminoacetophenone, for example (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane (IRGACURE .sup.(R) 907), (4-mor Polynobenzoyl) -1-benzyl-1-dimethylaminopropane (IRGACURE .sup.(R) 369), (4-morpholinobenzoyl) -1- (4-methylbenzyl) -1-dimethylaminopropane (IRGACURE .sup.(R) 379), (4- (2-hydroxyethyl) aminobenzoyl) -1-benzyl-1-dimethylaminopropane), (3,4-dimethoxybenzoyl) -1-benzyl-1-dimethylaminopropane; 4-aroyl-1,3-dioxolane, benzoin alkyl esters and benzyl ketals such as dimethyl benzyl ketal, phenylglyoxal esters and derivatives thereof such as oxo-phenyl-acetic acid 2- (2-hydroxy -Ethoxy) -ethyl ester, dimer phenylglyoxal esters such as oxo-phenyl-acetic acid 1-methyl-2- [2- (2-oxo-2-phenyl-acetoxy) -propoxy] -ethyl Esters (IRGACURE .sup.(R) 754); Oxime esters such as 1,2-octane-dione 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (IRGACURE .sup.(R) OXE01), ethanone 1- [9-ethyl- 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (IRGACURE .sup.(R) OXE02), 9H-thioxanthene-2-carboxaldehyde 9-oxo- 2- (O-acetyloxime), perester, for example benzophenone tetracarboxylic perester as described in EP 126541, monoacyl phosphine oxide, for example (2,4,6-trimethylbenzoyl) di Phenylphosphine oxide (DAROCUR .sup.(R) TPO), ethyl (2,4,6-trimethylbenzoyl phenyl) phosphine acid ester; Bisacylphosphine oxides, for example bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosph Pin oxide (IRGACURE .sup.(R) 819), bis (2,4,6-trimethylbenzoyl) -2,4-dipentoxy-phenylphosphine oxide, triacylphosphine oxide, halomethyltriazine, for example 2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- (4-methoxy-phenyl) -4,6- Bis-trichloromethyl- [1,3,5] triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trichloromethyl- [1,3,5] triazine, 2 -Methyl-4,6-bis-trichloromethyl- [1,3,5] triazine, hexaarylbisimidazole / initiator system, for example ortho-chloro in combination with 2-mercaptobenzthiazole Hexaphenyl-bisimidazole, ferrocenium compound or titanocene, for example bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium (I RGACURE .sup.(R) 784). Borate compounds are also described, for example, in US Pat. No. 4,772,530, EP 775706, GB 2307474, GB 2307473 and GB 2304472. The borate compound is preferably used in combination with an electron acceptor compound, for example a dye cation or thioxanthone derivative. DAROCUR .sup.(R) and IRGACURE .sup.(R) compounds are available from Ciba Incorporated [0473]
With respect to claims 16 and 19-24, it would have been obvious to one skilled in the art to modify the production of formation example 1 of Rolle et al. 20150261938 by combining the acrylate monomers, polyol and borate such as those disclosed in Berneth et al. 20180223100
to form a solution similar to that taught in Berneth et al. 20180223100 and then adding the dye as a solution of a sensitizing dye disclosed in Rolle et al. 20150261938, Berneth et al. 20180223100, Weiser et al. US 9281000 and photoinitiators such as those taught in Nishimae et al. KR 20110025211 in N-ethylpyrrolidone based upon the disclosed addition of a solution of the sensitizing dye 5 in Berneth et al. 20180223100 and the solubility of and New Methylene Blue (F7) and irgacure 250 in N-ethylpyrrolidone in Rolle et al. 20150261938 based upon the disclosure of the use of the sensitizing dye with irgacure 250 and the addition of the dye and photoinitiator in Weiser et al. US 9281000 and the these photoinitiators being known in the holographic art and commercially available as evidenced in Nishimae et al. KR 20110025211 then adding the isocyanate and urethane catalyst with a reasonable expectation of forming useful sensitized composition.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure..
Choi et al. 20140127611 1 mg of methylene blue and 10 mg of sodium bis(2-ethylhexyl) sulfosuccinate were dissolved in 1 ml of chloroform and 200 .mu.l of acetone to prepare a dye solution. To prepare a photosensitive composition, 12 mg of 1,4-bis(acryloyl)piperazine, 2.5 mg of 5-methyl-1,3,4-thiadiazole-2-thiol and 2.5 mg of 1-(4-hydroxyphenyl)-1H-tetrazole-5-thiol were dissolved in 250 .mu.l of chloroform and 200 .mu.l of acetone. Then, 10 .mu.l of the dye solution, 120 .mu.l of a monomer solution (N-acryloylthiomorpholine in chloroform by 1:1, by volume ratio), and 600 .mu.l of a polymer binder solution (12 wt % of polyvinyl acetate in chloroform) were added into the thus obtained solution. All the components were thoroughly stirred by using a mechanical stirrer and an ultrasonic bath [0085].
Weiser et al. 20160282719 teaches Component E: C.I. Basic Blue 3 (converted to bis(2-ethylhexyl)sulphosuccinate salt) 0.26%, Safranin O (converted to bis(2-ethylhexyl)sulphosuccinate salt) 0.13% and Astrazone Orange G (converted to bis(2-ethylhexyl)sulphosuccinate salt) 0.13% with CGI 909, experimental product of BASF SE, Basel, Switzerland, 1.5%, as solution in 5.8% ethyl acetate. Percentages are based on the overall formulation of the medium [0120]. Component F is ethyl acetate
[0121]. In example 1, a photopolymer formulation, 304.3 g of Component A in a stirring vessel were admixed in steps with a writing monomer mixture of 138 g of Component B1 and 138 g of Component B2, with 191 g of Additive C, 0.60 g of Component D, 2.55 g of BYK® 310 and 101 g of Component F, and these components were mixed. Then 66.5 g of Component E were added to the mixture in the dark and the composition was mixed so as to give a clear solution. If necessary, the formulation was heated at 60° C. for a short time in order to bring the ingredients into solution more rapidly [0148]. Photoinitiators of component d) are customarily compounds which can be activated by actinic radiation and which are able to initiate polymerization of the writing monomers. Among the photoinitiators, a distinction may be made between unimolecular (type I) and bimolecular (type II) initiators. In addition, they are distinguished according to their chemical nature into photoinitiators for radical, anionic, cationic or mixed mode of polymerization. Type I photoinitiators (Norrish type I) for radical photopolymerization form free radicals on irradiation, as a result of a unimolecular bond scission. Examples of type I photoinitiators are triazines, oximes, benzoin ethers, benzyl ketals, bisimidazoles, aroylphosphine oxides, sulphonium salts and iodonium salts. Type II photoinitiators (Norrish type II) for radical polymerization consist of a dye as sensitizer and of a coinitiator, and undergo a bimolecular reaction on irradiation with light adapted to the dye. First of all, the dye absorbs a photon and, from an excited state, transfers energy to the coinitiator. This coinitiator releases the polymerization-initiating radicals as a result of electron transfer or proton transfer or of direct hydrogen abstraction. For the purposes of this invention, type II photoinitiators are used with preference. Such photoinitiator systems are described in principle in EP 0 223 587 A and consist preferably of a mixture of one or more dyes with ammonium alkylarylborate(s). Suitable dyes which together with an ammonium alkylarylborate form a type II photoinitiator are the cationic dyes described in WO 2012062655, in combination with the anions also described therein. Cationic dyes are preferably those of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri(het)arylmethane dyes—especially diamino and triamino(het)arylmethane dyes, mono-, di-, tri- and pentamethinecyanine dyes, hemicyanine dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine dyes, nullmethine dyes—especially naphtholactam dyes, streptocyanine dyes. Such dyes are described for example in H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008, H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008, T. Gessner, U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethane and Diarylmethane Dyes, Wiley-VCH Verlag, 2000, Particularly preferred are phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri(het)arylmethane dyes—especially diamino and triamino(het)arylmethane dyes, mono-, di-, tri- and pentamethinecyanine dyes, hemicyanine dyes, nullmethine dyes—especially naphtholactam dyes, streptocyanine dyes. Examples of cationic dyes are Astrazone Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violet 7, Methylene Blue, New Methylene Blue, Azure A, 2,4-diphenyl-6-(4-methoxyphenyl)pyrylium, Safranin O, Astraphloxin, Brilliant Green, Crystal Violet, Ethyl Violet and Thionine. Preferred anions are, in particular, C.sub.8 to C.sub.25 alkanesulphonate, preferably C.sub.13 to C.sub.25 alkanesulphonate, C.sub.3 to C.sub.18 perfluoroalkanesulphonate, C.sub.4 to C.sub.18 perfluoroalkanesulphonate carrying at least 3 hydrogen atoms in the alkyl chain, C.sub.9 to C.sub.25 alkanoate, C.sub.9 to C.sub.25 alkenoate, C.sub.8 to C.sub.25 alkylsulphate, preferably C.sub.13 to C.sub.25 alkylsulphate, C.sub.8 to C.sub.25 alkenylsulphate, preferably C.sub.13 to C.sub.25 alkenylsulphate, C.sub.3 to C.sub.18 perfluoroalkylsulphate, C.sub.4 to C.sub.18 perfluoroalkylsulphate carrying at least 3 hydrogen atoms in the alkyl chain, polyethersulphates based on at least 4 equivalents of ethylene oxide and/or equivalents 4 of propylene oxide, bis-C.sub.4 to C.sub.25 alkyl, C.sub.5 to C.sub.7 cycloalkyl, C.sub.3 to C.sub.8 alkenyl or C.sub.7 to C.sub.11 aralkyl sulphosuccinate, bis-C.sub.2 to C.sub.10 alkyl-sulphosuccinate substituted by at least 8 fluorine atoms, C.sub.8 to C.sub.25 alkyl-sulphoacetates, benzenesulphonate substituted by at least one radical from the group of halogen, C.sub.4 to C.sub.25 alkyl, perfluoro-C.sub.1 to C.sub.8 alkyl and/or C.sub.1 to C.sub.12 alkoxycarbonyl, naphthalenesulphonate or biphenylsulphonate optionally substituted by nitro, cyano, hydroxyl, C.sub.1 to C.sub.25 alkyl, C.sub.1 to C.sub.12 alkoxy, amino, C.sub.1 to C.sub.12 alkoxycarbonyl or chloro, benzene-, naphthalene- or biphenyldisulophonate optionally substituted by nitro, cyano, hydroxyl, C.sub.1 to C.sub.25 alkyl, C.sub.1 to C.sub.12 alkoxy, C.sub.1 to C.sub.12 alkoxycarbonyl or chloro, benzoate substituted by dinitro, C.sub.6 to C.sub.25 alkyl, C.sub.4 to C.sub.12 alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl, the anion of naphthalenedicarboxylic acid, diphenyl ether disulphonate, sulphonated or sulphated, optionally at least monounsaturated C.sub.8 to C.sub.25 fatty acid esters of aliphatic C.sub.1 to C.sub.8 alcohols or glycerol, bis(sulpho-C.sub.2 to C.sub.5 alkyl)-C.sub.3 to C.sub.12 alkanedicarboxylic esters, bis-(sulpho-C.sub.2 to C.sub.6 alkyl)itaconic esters, (sulpho-C.sub.2 to C.sub.6 alkyl)-C.sub.6 to C.sub.18 alkanecarboxylic esters, (sulpho-C.sub.2 to C.sub.6 alkyl)-acrylic or methacrylic esters, triscatechol phosphate optionally substituted by up to 12 halogen radicals, an anion of the group tetraphenylborate, cyanotriphenylborate, tetraphenoxyborate, C.sub.4 to C.sub.12 alkyl-triphenylborate, whose phenyl or phenoxy radicals may be substituted by halogen, by C.sub.1 to C.sub.4 alkyl and/or by C.sub.1 to C.sub.4 alkoxy, C.sub.4 to C.sub.12 alkyl-trinaphthylborate, tetra-C.sub.1 to C.sub.20 alkoxyborate, 7,8- or 7,9-dicarba-nido-undecaborate(1-) or (2-), optionally substituted on the B and/or C atoms by one or two C.sub.1 to C.sub.12 alkyl or phenyl groups, dodecahydro-dicarbadodecaborate(2-) or B-C.sub.1 to C.sub.12 alkyl-C-phenyl-dodecahydro-dicarbadodecaborate(1-), where A.sup.− in the case of polyvalent anions such as naphthalenedisulphonate stands for one equivalent of this anion, and where the alkane and alkyl groups may he branched and/or may be substituted by halogen, cyano, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl. It is also preferable for the anion A.sup.− of the dye to have an AClogP in the range from 1 to 30, more preferably in the range from 1 to 12 and especially preferably in the range from 1 to 6.5. The AClogP is computed as described in J. Comput. Aid. Mol. Des, 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org. Examples of suitable ammonium alkylarylborates are (Cunningham et al., RadTech'98 North America UV/EB Conference Proceedings, Chicago, Apr. 19-22, 1998): tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinaphthylhexylborate, tetrabutylammonium tris(4-tert-butyl)phenylbutylborate, tetrabutylammonium tris(3-fluorophenyl)hexylborate hexylborate ([191726-69-9], CGI 7460, product of BASF SE, Basel, Switzerland), 1-methyl-3-octylimidazolium dipentyldiphenylborate and tetrabutylammonium tris(3-chloro-4-methylphenyl)hexylborate ([1147315-11-4], CGI 909, product of BASF SE, Basel, Switzerland). It may be advantageous to use mixtures of these photoinitiators. Depending on the radiation source employed, it is necessary to adapt the type and concentration of photoinitiator, in the manner known to the skilled person. Further details are described in, for example, P. K. T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3,1991, SITA Technology, London, pp. 61-328 [0061-0073].
Knocke 20250277122, 20240142873 and 20240317904 are similar, but do not claim the composition divided into two solutions.
Takeda et al. WO 2009113490 (machine translation attached) teaches the radiation sensitive resin composition of the present invention is dissolved in a solvent (D) and used in a solution state. For example, the novolak resin (A) is dissolved in the solvent (D), and the heat-reactive compound (B) and the radiation-sensitive compound (C), and, if necessary, the surfactant (E) or the dye, A radiation-sensitive resin composition in a solution state can be prepared by mixing a dye (F) such as a pigment at a predetermined ratio immediately before use [0051]
Heeschen 20070187947 teaches in example 1, the photopolymerizable composition of the example had the following composition. TABLE-US-00001 Component Amount [wt.-%] Sartomer SR349 91.93 Safranin O solution (3% in ethanol) 0.03 CGI 7460 0.34 Castor oil 3.75 Palm kernel oil 3.75 Schwego-Fluor 8038 0.2. The two oils were mixed, followed by the addition of Sartomer SR349. Subsequently CGI 7460, then Safranin O and finally the surfactant Schwego-Fluor 8038 were added while stirring was continued. If the mixture is not homogeneous, it can be optionally heated, e.g., for 5 minutes at 50 to 80.degree. C [0074-0075].
Organic solvents can be used in minor amounts, e.g., to dissolve the photoinitiator [0064]. Typically the photoinitiator system will include a photoinitiator and optionally a co-initiator. The photoinitiator is usually a UV or a VIS photoinitiator, preferably a UV photoinitiator. Typically the absorbance of the photoinitiator will be in the range of 266 to 700 nm, preferably 350 to 680 nm, with the peak absorbances more preferably being in the range of 450 to 650 nm. Suitable photoinitiators include the substituted or unsubstituted polynuclear quinones which are compounds having two intracyclic carbon atoms in a conjugated carbocyclic ring system, e.g., 9,10-anthraquinone 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2-3-diphenylanthraquinone, sodium salts of anthraquinone alpha-sulfonic acid, 3-chloro-2-methylanthraquinone, retenequinone, 7,8,9,10-tetrahydronaphthacenequinone, and 1,2,3,4-tetrahydrobenz(a)anthracene-7,12-dione. Other photoinitiators which are also useful are described in U.S. Pat. No. 2,760,863 and include vicinal ketaldonyl alcohols, such as benzoin, pivaloin, acyloin ethers, e.g., benzoin methyl and ethyl ethers; .alpha.-hydrocarbon-substituted aromatic acyloins, including .alpha.-methylbenzoin, .alpha.-allylbenzoin and .alpha.-phenylbenzoin. Photoreducible dyes and reducing agents, such as those disclosed in U.S. Pat. Nos. 2,850,445; 2,875,047; 3,097,096; 3,074,974; 3,097,097; 3,145,104 and 3,579,339; as well as dyes of the phenazine, oxazine, and quinone classes; Michler's ketone; benzophenone; 2,4,5-triphenylimidazolyl dimers with hydrogen donors, and mixtures thereof as described in U.S. Pat. Nos. 3,427,161; 3,479,185; 3,549,367; 4,311,783; 4,622,286; and 3,784,557 can be used as initiators. A useful discussion of dye sensitized photopolymerization can be found in "Dye Sensitized Photopolymerization" by D. F. Eaton in Adv. in Photochemistry, Vol. 13, D. H. Volman, G. S. Hammond, and K. Gollinick eds., Wiley-Interscience, New York, 1986, pp. 427-487. Similarly the cyclohexadienone compounds of U.S. Pat. No. 4,341,860 are useful as initiators. Co-initiators (sensitizers) useful with the photoinitiators include methylene blue and those disclosed in U.S. Pat. Nos. 3,554,753; 3,563,750; 3,563,751; 3,647,467; 3,652,275; 4,162,162; 4,268,667; 4,351,893: 4,454,218; 4,535,052; and 4,565,769; each of which is incorporated herein by reference. The co-initiator is preferably active in the UV-region, e.g. from 266 to 480 nm. A particularly preferred photoinitiator system includes a phenazine dye as a co-initiator. An example of a suitable phenazine dye is 3,7-diamino-2,8-dimethyl-5-phenyl-phenazinium chloride (Safranin O). With phenazine dye-based co-initiators the photoinitiator will typically be a borate compound such as member of the CGI series, which are available from Ciba Specialty Chemicals. Preferred examples are CGI 909 and CGI 7460. In an alternative embodiment the photoinitiator system comprises a co-initiator based on fluorone or pyronin Y derivatives, such as those described in U.S. Pat. No. 5,451,343 and U.S. Pat. No. 5,395,862. Photoinitiators for this type of photoinitiator system are preferably amines, borates, nitrohalomethanes, diazosulfones, onium salts, ferrocenium salts and thiapyrylium salts. Particularly preferred photoinitiators are amines and borates, even more preferred are borates such as tetra-C.sub.1-4-alkylammonium triphenyl-C.sub.1-4-alkyl borate, e.g., tetramethylammonium triphenylbutyl borate. Such photoinitiator systems are available, e.g., from Spectra Group Ltd. under the trade designations H-Nu 470, H-Nu 535 und H-Nu 635. The co-initiator is typically present in an amount of 0.15 to 0.5 weight-%, preferably about 0.3 weight-%, based on the total weight of the photopolymerizable composition. If present, the photoinitiator is typically included in an amount of 0.015 to 0.1 weight-%, preferably about 0.05 weight-%, based on the total weight of the photopolymerizable composition [0051-0057].
Adair et al. 4801392 in example 1 teaches a solution A which includes UV initiator isopropylthioxanthone in trimethylolpropanetriacrylate and solution B which includes a cyanine borate dye and trimethylolpropanetriacrylate (col 16).
In solution B, the trimethylolpropanetriacrylate is considered the solvent. The claims rejected under this heading do not preclude the dye solution also including a monomer.
Knocke 20100112458 in example 1 teaches a photosensitive composition inkling SR-349 (monomer), a mixture of Ricinus, or castor oil and palm oil, tetrabutylammonium tris(fluorophenyl)hexylborate (photoinitiator), Safrinin-O (in ethanol) and a surfactant/wetting agent). The oil mixture was combined with the monomer to form a clear solution, the photoinitiator was then added and finally, the photosensitizing agent and wetting agent [0072-0078]. Preferably, photoinitiators are used which are activated by visible light, i.e., by light having a wavelength of >300 nm, preferably light with a wavelength in the range of 400-800 nm. Such initiators preferably have an absorption coefficient of 1000 or more for light having wavelength of more than 300 nm. Such photoinitiators can initiate the polymerisation reaction of the ethylenically unsaturated monomer upon irradiation with visible light (i.e., light having a wavelength of >300 nm, preferably light with a wavelength of 400-800 nm). Radical-forming polymerisation initiators are known, see, for example, Timpe, H. J. and S. Neuenfeld, "Dyes in photoinitiator systems", Kontakte (1990), pp. 28-35 and Jakubiak, J. and J. F. Rabek, "Photoinitiators for visible light polymerisation", Polimery (Warsaw) (1999), 44, pp. 447-461 Amongst the suitable radical-forming polymerisation initiators which are activated by UV radiation and that are generally inactive at temperatures up to 185.degree. C., there are the substituted or unsubstituted multi-nuclear quinones; these are compounds with two intracyclic carbon atoms in a conjugated carbocyclic ring system, for example 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, sodium salt of anthraquinone-.alpha.-sulfonic acid, 3-chloro-2-methylanthraquinone, retenquinone, 7,8,9,10-tetrahydronaphthacenequinone and 1,2,3,4-tetrahydrobenz[a]anthracene-7,12-dione. Further photoinitiators which are also useful, although some of them may be thermally active at temperatures as low as 85.degree. C., are described in U.S. Pat. No. 2,760,663 and these comprise vicinal ketaldonyl alcohols, such as benzoin, pivaloin, acyloinethers, for example, benzoinmethyl and ethylether, .alpha.-hydrocarbon substituted aromatic acyloins, including .alpha.-methylbenzoin, .alpha.-allylbenzoin and .alpha.-phenylbenzoin. Useful as initiators are photoreducible dyes and reducing agents, such as those described in U.S. Pat. Nos. 2,850,445, 2,875,047, 3,097,096, 3,074,974, 3,097,097, 3,145,104 and 3,579,339, as well as dyes of the class of phenazines, oxazines and quinones; Michler's ketone, benzophenone, 2,4,5-triphenylimidazolyl dimers with hydrogen donors and their mixtures, as described in U.S. Pat. Nos. 3,427,161, 3,479,185, 3,549,367, 4,311,783, 4,622,286 and 3,784,557. A useful discussion of dye-sensitized photopolymerization may be found in "Dye Sensitized Photopolymerization" by D. F. Eaton in Adv. in Photochemistry, Vol. 13, D. H. Volman, G. S. Hammond and K. Gollnick, Eds., Wiley-Interscience, New York, 1986, pp. 427-487. In the same way, the cyclohexadienone compounds of U.S. Pat. No. 4,341,860 are also useful as initiators. The useful photoinitiators comprise CDM-HABI, i.e., 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazole-dimer; o-Cl-HABI, i.e., 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole; and TCTM-HABI, i.e., 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-1H-imidazole-dimer, each of which is typically used with a hydrogen donor, for example, 2-mercaptobenzoxazole. A particularly preferred photoinitiator is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, which is available from Ciba under the designation "irgacure 369" and which is preferably used in an amount of 0.1 to 10% by weight. As useful photoinitiators there may also be used photopolymerization initiators of the formula S-L-A, as described in US patent application 2005/0026081, wherein, in the aforementioned formula, S represents a light-absorbing moiety having a chromophoric group, resulting in absorption coefficients of 1000 or more for wavelength of more than 300 nm; A represents an active moiety which interacts with the light-absorbing moiety S in order to form a free radical; and L represents a linking group which joins the light-absorbing moiety S and the active moiety A together. Suitable examples for photopolymerization initiators of the aforementioned formula are described in the aforementioned US patent application. The aforementioned photoinitiators can be used alone or in combination. Together with the aforementioned photoinitiators there may be employed sensitizing agents, such as, for example, methylene blue and the sensitizing agents described in U.S. Pat. Nos. 3,554,753, 3,563,750, 3,563,751, 3,647,467, 3,652,275, 4,162,162, 4,268,667, 3,351,893, 4,454,218, 4,535,052 and 4,565,769 which are expressly referred to herein. The particular preferred sensitizing agents comprise the following: DBC, i.e., 2,5-bis[(4-diethylamino-2-methylphenyl)methylene]cyclopentanone; DEAW, i.e., 2,5-bis[(4-diethylaminophenyl)methylene]cyclopentanone; dimethoxy-JDI, i.e., 2,3-dihydro-5,6-dimethoxy-2-[(2,3,6,7-tetrahydro-1H,5H-benzo[i,j]quinoliz- ine-9-yl)methylene]-1H-indene-1-one; and Safranin O, i.e., 3,7-diamino-2,8-dimethyl-5-phenyl-phenaziniumchloride [0035-0042]. The photopolymerizable composition of the present invention is essentially free of organic solvents. Preferably, the composition contains at most 5% by weight, more preferably at most 1% by weight of organic solvents [0058].
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 June 2, 2026
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