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 .
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 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 1-10 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Nozawa WO 2020110854.
Nozawa WO 2020110854 (US 2021040631 is English equivalent) in example 1 describes the preparation of Block Copolymer Composition Using a 2 liter pressure resistant reactor, 400 g of a mixed solvent having a ratio of n-butane/cyclohexane=30/70, tetramethylethylenediamine 0.07 mmol, initiator n-butyllithium 1.75. In the presence of millimoles, 22 g of styrene was added, and polymerization was carried out at 30° C. for 1 hour. Subsequently, 0.75 mmol of n-butyllithium and 78 g of isoprene were added, and polymerization was carried out for about 1 hour and a half while controlling the temperature by reflux cooling so that the reaction temperature was between 50°C and 60°C. Then, divinylbenzene (DVB) as a coupling agent was added in an amount of 4 times equivalent to all n-butyllithium, and a coupling reaction was carried out for 2 hours. Then, 1 ml of methanol as a polymerization terminator and 0.05 g of 2,6-di-tert-butyl-p-cresol as an antioxidant were added to the reaction mixture and mixed well, and the resulting mixed solution was added little by little to 85 ml. The solvent was volatilized by dropping into warm water heated to ˜95° C. The obtained polymer was pulverized and dried with hot air at 85° C. to obtain a block copolymer composition. The styrene content of the entire block copolymer composition was 22%, the polystyrene-converted weight average molecular weight (Mw) was 433,000, the vinyl bond content was 7%, and the melt index (G condition) was 10 g. /10 minutes. The molecular weight distribution (Mw/Mn) of the block copolymer A in the block copolymer composition was 1.10, and the content of the block copolymer A in the block copolymer composition was 95%.The molecular weight distribution (Mw/Mn) of the diblock copolymer B in the block copolymer composition was 1.01, and the content of the diblock copolymer B in the block copolymer composition was 4%. there were [0126-0127. The block copolymers if examples 2-7, and comparative examples 1 and 3 are similarly produced. The characteristics appear in table 1.
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100 parts of the block copolymers were charged into a stirring blade type kneader, and tackifying resin (Quintone R100; aliphatic hydrocarbon resin, manufactured by Nippon Zeon Co., Ltd.). ) 110 parts, naphthene-based process oil (shelflex 371, manufactured by Shell Kagaku Co.) as a plasticizer, 10 parts, photocurable monomer (trimethylolpropane triacrylate) 0.5 part, crosslinkg agent (2,2-dimethoxy) -1,2-diphenylethan-1-one, Irgacure 651 (photoinitiator), manufactured by BASF) 2.5 parts, antioxidant (Irganox 1010, manufactured by BASF) 1.5 parts, and antioxidant (Irgafos 168, manufactured by BASF) 1 part) was added to replace the inside of the system with nitrogen gas, and then the mixture was kneaded at 160° C. for 1.5 hours to prepare a hot melt adhesive composition. The obtained hot-melt adhesive composition was evaluated by the following methods. The results are shown in Table 1[0128]. These were coated to a thickness of 25 microns on a PET film.
The coated film is considered to meet the limitation of claim 10.
Claims 1-8 and 10 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Nozawa et al. JP 2018021112.
Nozawa et al. JP 2018021112 (machine translation attached) Preparation of Block Copolymer Composition Using a 50-liter pressure-resistant reactor, 18.75 kg of a mixed solvent having a ratio of n-butane / cyclohexane = 30/70, N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as “the block copolymer composition”) In the presence of 20 mmol, initiator n-butyllithium 110 mmol, polymerized by adding 1.0 kg of styrene for 1 hour at 30 ° C., followed by 7.0 kg of isoprene. The polymerization was carried out for about an hour and a half while controlling the temperature by reflux cooling so that the reaction temperature was between 50 ° C and 60 ° C. Subsequently, divinylbenzene (DVB) was added as a coupling agent in an amount of 6 times the initiator, and a coupling reaction was performed for 2 hours. Thereafter, 50 ml of methanol as a polymerization terminator and 40 g of 2,6-di-tert-butyl-p-cresol as an antioxidant were added to the reaction mixture and mixed well, and the resulting mixed solution was added in small portions by 85 to 95. The solvent was volatilized by dropwise addition to warm water heated to ° C. The obtained polymer was pulverized and dried with hot air at 85 ° C. to obtain a block copolymer composition. The block copolymer composition had a styrene content of 12.5% by mass and a polystyrene-equivalent weight average molecular weight (Mw) of 540,000. The vinyl bond content in the conjugated diene monomer was 10%. The melt index (G condition) was 19 g / 10 min. The molecular weight distribution (Mw / Mn) of the block copolymer A was 1.11, and the content of the block copolymer A in the block copolymer composition was 96% by mass. The molecular weight distribution (Mw / Mn) of the block copolymer B was 1.01, and the content of the block copolymer B in the block copolymer composition was 2% by mass [0116-0117]. The other block copolymers are similar (see table 1). 100 parts of the above block copolymer composition was put into a stirring blade type kneader, and a tackifier resin (Alcon M-100; alicyclic hydrocarbon resin, Arakawa) was added thereto. 100 parts by Chemical Industry Co., Ltd., 20 parts naphthenic process oil as plasticizer (Shelf Rex 371, manufactured by Shell Chemical), cross-linking agent (2,2-dimethoxy-1,2-diphenylethane-1-one, 1 part of Irgacure 651, manufactured by BASF) and 1.5 parts of antioxidant (Irganox 1010, manufactured by Ciba Geigy Co., Ltd.) were added, and the system was replaced with nitrogen gas. A hot melt adhesive composition was prepared by kneading [0118]. This was then coated upon a substrate.
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Claims 1-6 and 9-10 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Tsibaki et al. 20060263715.
Tsibaki et al. 20060263715 in comparative example 2, forms a styrene/isoprene block copolymer with a MW of 327,300 using tetramethoxysilane as the coupling agent (see table 1 on page 9). The block copolymer was combined with liquid polybutadiene, 2,6-di-t-butyl-cresol, 1,4-butandiol diacrylate, hexanediol diacrylate, hydroxyquinone and benzoin isopropyl ether (photoinitiator) and coated onto a substrate to form a flexographic printing plate [0110-0112,0120]. Examples 1 is formed similarly (table and [0107-0112]. The weight-average molecular weight of the whole of the block copolymer composition for photosensitive flexographic plates of the present invention is preferably 100,000 to 500,000, more preferably 150,000 to 400,000. When this weight-average molecular weight is in the above range, a sheet-shaped composition for photosensitive flexographic plates more excellent in balance among antiflowing properties, smoothness and stickiness can be obtained [0053].
The coated film is considered to meet the limitation of claim 10.
Claims 1-10 are rejected under 35 U.S.C. 103 as being unpatentable over Ikeda et al. JP 2006284615.
Ikeda et al. JP 2006284615 (machine translation attached) teaches in reference example 1, the formation of a block copolymer by reacting 112 parts of cyclohexane, 0.0012 parts of N, N, N ′, N′-tetramethylethylenediamine (TMEDA) and 7.2 parts of styrene were added and stirred at 40 ° C. 0.0441 parts of butyl lithium was added, and polymerization was carried out for 1 hour while raising the polymerization temperature to 50 ° C. At this time, the polymerization conversion of styrene was 100%. A part of the reaction solution was collected, and the weight average molecular weight of the polystyrene block was measured. Subsequently, 40.8 parts of isoprene were continuously added over 1 hour. After completing the addition of isoprene, polymerization was continued for an additional hour. The polymerization temperature was controlled to maintain 50-60 ° C. The polymerization conversion rate at this point was 100%. A part of the reaction solution was sampled, and the weight average molecular weight of a styrene-isoprene diblock copolymer (corresponding to the block copolymer (b)) was measured. The results are shown in Table 1. Next, 0.0254 parts of tetramethoxysilane was added as a coupling agent, and a coupling reaction was performed for 2 hours. A coupling body in which a styrene-isoprene diblock copolymer was bonded via a coupling agent [block copolymer Corresponding to (a)]. Thereafter, 0.0661 part of methanol was added as a polymerization terminator and mixed well to stop the reaction.
Thus, a reaction solution containing a styrene-isoprene block copolymer composition (block copolymer composition) was obtained. A part of the reaction solution is collected to measure the weight average molecular weight of the entire block copolymer composition, the styrene unit content and the vinyl content in the composition, and the content and calculation of each block copolymer. The value of formula (I) was determined. The results are shown in Table 1.
After adding 0.3 part of 2,6-di-t-butyl-p-cresol as an antioxidant to 100 parts of the solid content to the obtained reaction liquid, the solution is heated to 85 to 95 ° C. little by little. The solvent was volatilized by dropping into the warm water. The precipitate was pulverized and dried with hot air at 85 ° C. The obtained pulverized product was supplied to a single screw extruder equipped with an underwater hot cut device at the tip of the extruder to obtain pellets having an average diameter of 5 mm. The MW was 231.700 (see table 1.) [0096-0100]
In references example 2, pellets were obtained in the same manner as in Reference Example 1 except that the types of styrene, n-butyllithium, TMEDA, isoprene, coupling agent (dimethyldichlorosilane) and amount, and the amount of methanol were changed as shown in Table 1. The results are shown in Table 1 [0101].
Example 1- 100 parts of pellets of Reference Example 1 (styrene-isoprene block copolymer composition) as a thermoplastic elastomer, 10 parts of liquid polyisoprene of Reference Example 3 as a plasticizer, and 2,6-di-t-butyl-p-cresol 2 parts are dissolved in cyclohexane and mixed in a solution state, and then the mixed solution is dropped little by little into warm water heated to 85 to 90 ° C. to volatilize the solvent, and the resulting precipitate is pulverized to 85 ° C. The solvent was removed by drying with hot air (premixing). To the obtained mixture, 5 parts of 1,4-butanediol diacrylate, 4 parts of hexanediol dimethacrylate, 0.01 part of methylhydroquinone and 0.8 part of benzoin isopropyl ether were added and kneaded at 130 ° C. An elastomer composition was obtained. Table 2 shows the evaluation results for the sheet surface smoothness, flow resistance under load, and sheet adhesiveness of the photosensitive elastomer composition [0104-0105].
Example 2 -100 parts of the pellets of Reference Example 1, 10 parts of the liquid polyisoprene of Reference Example 3 as a plasticizer, and 2 parts of 2,6-di-t-butyl-p-cresol at 200 ° C. using a kneader-kneader. Kneaded (preliminary mixing). Subsequently, the kneading temperature is lowered to 130 ° C., 5 parts of 1,4-butanediol diacrylate, 4 parts of hexanediol dimethacrylate, 0.01 part of methylhydroquinone and 0.8 part of benzoin isopropyl ether are added and kneaded. A photosensitive elastomer composition was obtained. Table 2 shows the evaluation results for the sheet surface smoothness, flow resistance under load, and sheet adhesiveness of the photosensitive elastomer composition [0106-0107].
Place the photosensitive elastomer composition in a sheet-shaped mold with a spacer thickness of 3 mm, sandwich the top and bottom with a polyester film (protective film) with a thickness of 0.1 mm, and heat-press at 110-130 ° C. for 10 minutes with a press machine The sheet was cooled to form a sheet having a thickness of 3 mm. Thereafter, the polyester film on the upper surface of the sheet was peeled off, and the surface state of the sheet after being allowed to stand at room temperature for 24 hours was observed with the naked eye, and the smoothness of the sheet surface was evaluated according to the following evaluation criteria. The number of samples in each composition was 10 [0093].
As the coupling agent, a coupling agent containing halogen or a coupling agent not containing halogen can be used. From the viewpoint of improving the transparency of the thermoplastic elastomer and enhancing the sensitivity to light and the resolution of fine lines after photocuring, a coupling agent containing no halogen is preferable. Moreover, as a functional group of a coupling agent, Preferably it is an alkoxyl group, More preferably, they are a methoxy group and an ethoxy group. When a coupling agent having such a functional group is used, the transparency of the thermoplastic elastomer is improved, and the sensitivity to light and the resolution of fine lines after photocuring are increased.
Specific examples of the coupling agent containing halogen include bifunctional halogenated silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; bifunctional halogenations such as dichloroethane, dibromoethane, methylene chloride, and dibromomethane. Alkane: Bifunctional tin halide such as dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin, dibutyldichlorotin; Trifunctional halogenated alkane such as trichloroethane and trichloropropane A tetrafunctional halogenated silane such as tetrachlorosilane or tetrabromosilane; a tetrafunctional tin compound such as tetrachlorotin or tetrabromotin;
Specific examples of the halogen-free coupling agent include organotin compounds such as tetramethoxytin, tetraethoxytin, and tetrabutoxytin; dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, alkyltriphenoxysilane, Organic silicon compounds such as methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, bis (trimethoxysilyl) ethane; unsaturated nitriles such as ethylacrylonitrile; methyl formate, ethyl formate, Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl trimethyl acetate, methyl caproate, capron Carboxylic acid esters such as ethyl, methyl benzoate, ethyl benzoate, phenyl benzoate, dimethyl adipate, diethyl adipate, dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate, dimethyl isophthalate; trisnonylphenyl phosphite, Organophosphorus compounds such as trimethyl phosphite and triethyl phosphite; and divinylbenzene. Among these, organic silicon compounds are preferable, and tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane are more preferable [0028-0031]. The weight average molecular weight of the entire block copolymer composition of the present invention is preferably 100,000 to 500,000, more preferably 150,000 to 400,000. If the weight average molecular weight is 100,000 or more, the hardness of the sheet is appropriate, and if it is 500,000 or less, the heat resistance of the sheet is good [0016]. There is no limitation in particular as a photosensitive ethylenically unsaturated compound used at a process (2), What is necessary is just to use a well-known thing. Examples of the compound include diacrylates or dimethacrylates of dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, 1,4-butanediol, and 1,6-hexanediol. Triacrylate or trimethacrylate of trimethylolpropane; tetraacrylate or tetramethacrylate of pentaerythritol; N, N′-hexamethylenebisacrylamide, N, N′-hexamethylenebismethacrylamide, diacetone acrylamide, diacetone methacrylamide, Styrene, vinyl toluene, divinyl benzene, diallyl phthalate, triallyl cyanurate and the like can be mentioned. There is no limitation in particular as a photoinitiator used at a process (2), What is necessary is just to use a well-known thing. Examples of the initiator include benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α-methylbenzoin, α-methylbenzoin methyl ether, α-methoxybenzoin methyl ether, benzoin phenyl. Ether, α-t-butylbenzoin, anthraquinone, benzanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-2'-dimethoxyphenylacetophenone, 2,2-diethoxyphenylacetophenone, 2 , 2-diethoxyacetophenone, piperoin and the like [0069-0070]. The formation of an image on the flexographic including exposure using a negative and development with solvent is disclosed [0079-0083]
Ikeda et al. JP 2006284615 does not exemplify a photosensitive composition containing a block copolymer with a weight average MW of 300,000-800,000 and the coupling agent bonds to 3 or more blocks.
With respect to claims 1-7 and 10, It would have been obvious to one skilled in the art to modify example 1 by using a block-copolymer similar to that of reference example 1, but where the processing conditions are modified so that the resultant block copolymer has a MW or 300,000-500,000 based upon the range taught at [0016] with a reasonable expectation of forming a useful composition which is then placed in the mold to form a sheet with a thickness of 3 mm as taught at [0093] with a reasonable expectation of forming a useful photosensitive layer suitable for flexographic printing.
With respect to claims 1-10, It would have been obvious to one skilled in the art to modify example 1 by using a block-copolymer similar to that of reference example 1, but where the tetramethoxysilane coupling agent is replaced with divinylbenzene based upon the functional equivalence at [0028-0031] and the processing conditions are modified so that the resultant block copolymer has a MW or 300,000-500,000 based upon the range taught at [0016] with a reasonable expectation of forming a useful composition which is then placed in the mold to form a sheet with a thickness of 3 mm as taught at [0093] with a reasonable expectation of forming a useful photosensitive layer suitable for flexographic printing.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Ishii et al. JP 2019056062 (machine translation attached) in production example 1formed a block copolymer by combining 23.0 kg of cyclohexane, 3 mmol of N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) and 1.6 kg of styrene are added to a pressure-resistant reactor and stirred at 40 ° C. Then, 92 mmol of n-butyllithium was added, and polymerization was performed for 1 hour while raising the temperature to 50 ° C. The polymerization conversion of styrene was 100%. Subsequently, 4.9 kg of isoprene was continuously added to the reactor over 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After completing the addition of isoprene, polymerization was continued for an additional hour. The polymerization conversion rate of isoprene was 100%. Next, 15 mmol of dimethyldichlorosilane is added as a coupling agent, and a coupling reaction is performed for 2 hours to form a block copolymer b, which is a symmetrical styrene-isoprene-styrene represented by (Ar-D) .sub.n -X. A block copolymer was formed. Thereafter, 110 mmol of methanol was added as a polymerization terminator and mixed well to stop the reaction, and the active end of the styrene-isoprene block copolymer having an active end that did not react with the coupling agent was deactivated. Then, a styrene-isoprene block copolymer represented by Ar-D to be a block copolymer c was formed. The amount of each reagent used in the reaction is summarized in Table 1. A part of the obtained reaction solution is taken out, and the weight average molecular weight of each block copolymer and block copolymer mixture, the weight average molecular weight of each styrene polymer block, the weight average molecular weight of each isoprene polymer block, and each block copolymer. The styrene unit content of the polymer, the styrene unit content of the block copolymer mixture, the vinyl bond content of the isoprene polymer block, and the weight ratio of each block copolymer were determined. Further, the melt index of the block copolymer mixture was measured. These values are shown in Table 2, including the weight average MW of the polymer which is 132,000. This has utility as an adhesive and in the formation of flexographic printing plates [0006]. The weight average molecular weight of the block copolymer (I) is not particularly limited, but is usually 30,000 to 500,000, preferably 35,000 to 400,000, more preferably 40,000 to 250,000 [0037]. Molecular weight represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of each block constituting the block copolymer (I) and the block copolymer (I) The distribution is not particularly limited, but is usually 1.1 or less, preferably 1.05 or less. When the molecular weight distribution of the block copolymer (I) and each polymer block constituting the block copolymer (I) is in such a range, the adhesive property can be excellent [0038]
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 July 26, 2026
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