1. A production process of a poly(arylene sulfide), comprising the following steps (a), (b) and (d) or (a) to (d):
(a) a polymerization step of subjecting at least one sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides and a dihalo-aromatic compound to a polymerization reaction in an organic amide solvent to form a polymer;
(b) a separation step of separating and collecting the polymer from a liquid reaction mixture containing the polymer formed after the polymerization step;
(c) a washing step of washing the polymer collected with at least one washing liquid selected from the group consisting of water, an organic solvent and a mixed solution of water and an organic solvent and then separating and collecting the polymer; and
(d) an aqueous oxidizing solution treatment step of treating the polymer collected by bringing the polymer into contact with an aqueous oxidizing solution.
2. The production process according to claim 1, which further comprises
(e) a separated liquid-treating step of treating at least one separated liquid selected from the group consisting of a liquid after the polymer is separated from the liquid reaction mixture in the separation step and a washing waste liquid after the polymer is separated in the washing step by bringing the liquid into contact with an aqueous oxidizing solution.
3. The production process according to claim 1, wherein the aqueous oxidizing solution is aqueous hydrogen peroxide.
4. The production process according to claim 3, wherein the amount of hydrogen peroxide is 0.005 to 50 parts by mass per 100 parts by mass of the poly(arylene sulfide).
5. The production process according to claim 1, wherein the organic solvent includes acetone.
6. The production process according to claim 1, wherein the polymerization step is at least two-stage polymerization steps comprising:
a first-stage polymerization step of subjecting at least one sulfur source selected from the group consisting of the alkali metal sulfides and the alkali metal hydrosulfides and the dihalo-aromatic compound to a polymerization reaction in the organic amide solvent to form a polymer in which a conversion of the dihalo-aromatic compound is 80 to 99%; and
a second-stage polymerization step of continuing the polymerization reaction in the presence of the phase separation agent in a phase-separated state that a concentrated formed polymer phase and a dilute formed polymer phase are present in a mixed state within the polymerization reaction system.
7. The production process of the poly(arylene sulfide) according to claim 1, wherein the polymerization step is at least two-stage polymerization steps comprising:
a first-stage polymerization step of subjecting at least one sulfur source selected from the group consisting of the alkali metal sulfides and the alkali metal hydrosulfides and the dihalo-aromatic compound to a polymerization reaction at a temperature of 170 to 270\xb0 C. in the organic amide solvent in a state that water is present in a proportion of 0.02 to 2.0 mol per mol of a charged sulfur source, thereby forming a polymer in which a conversion of the dihalo-aromatic compound is 80 to 99%; and
a second-stage polymerization step of controlling the amount of water in the polymerization reaction system so as to bring about a state that water exists in a proportion of from higher than 2.0 mol to not higher than 10 mol per mol of the charged sulfur source, and heating the polymerization reaction system to a temperature of 245 to 290\xb0 C., thereby continuing the polymerization reaction in a phase-separated state that a concentrated formed polymer phase and a dilute formed polymer phase are present in a mixed state within the polymerization reaction system.
8. The production process of the poly(arylene sulfide) according to claim 7, wherein in the second-stage polymerization step, the amount of water in the polymerization reaction system is controlled so as to bring about a state that water exists in a proportion of from higher than 2.0 mol to not higher than 10 mol per mol of the charged sulfur source, and at least one phase separation agent selected from the group consisting of organic carboxylic acid metal salts, organic sulfonic acid metal salts, alkali metal halides, alkaline earth metal halides, aromatic carboxylic acid alkaline earth metal salts, phosphoric acid alkali metal salts, alcohols and paraffinic hydrocarbons is caused to exist within a range of 0.01 to 3 mol per mol of the charged sulfur source.
9. The production process of the poly(arylene sulfide) according to claim 1, wherein prior to the polymerization step, are arranged a dehydration step of heating and reacting a mixture containing the organic amide solvent, the sulfur source containing the alkali metal hydrosulfide and an alkali metal hydroxide in a proportion of 0.95 to 1.05 mol per mol of the alkali metal hydrosulfide to discharge at least a part of a distillate containing water from the interior of the system containing the mixture to the exterior of the system; and
a charging step of adding an alkali metal hydroxide and water to the mixture remaining in the system after the dehydration step, as needed, to adjust the mixture in such a manner that the total number of moles of the number of moles of an alkali metal hydroxide formed with hydrogen sulfide formed upon the dehydration, the number of moles of the alkali metal hydroxide added prior to the dehydration and the number of moles of the alkali metal hydroxide added after the dehydration becomes 1.00 to 1.09 mol per mol of the sulfur source existing in the system after the dehydration step, and the number of moles of water becomes 0.02 to 2.0 mol per mol of the charged sulfur source.
10. A poly(arylene sulfide) produced by the production process of the poly(arylene sulfide) according to claim 1, in which the content of mesityl oxide is 65 ppm or less.
11. A poly(arylene sulfide) produced by the production process of the poly(arylene sulfide) according to claim 1, in which the content of diacetone alcohol is 35 ppm or less.
12. A poly(arylene sulfide) produced by the production process of the poly(arylene sulfide) according to claim 1, in which the content of a dihalo-aromatic compound is 110 ppm or less
13. A poly(arylene sulfide) produced by the production process of the poly(arylene sulfide) according to claim 1, in which the total content of mesityl oxide and diacetone alcohol is 100 ppm or less.
14. The production process according to claim 2, wherein the aqueous oxidizing solution is aqueous hydrogen peroxide.
15. The production process according to claim 14, wherein the amount of hydrogen peroxide is 0.005 to 50 parts by mass per 100 parts by mass of the poly(arylene sulfide).
16. The production process according to claim 2, wherein the organic solvent includes acetone.
17. The production process according to claim 2, wherein the polymerization step is at least two-stage polymerization steps comprising:
a first-stage polymerization step of subjecting at least one sulfur source selected from the group consisting of the alkali metal sulfides and the alkali metal hydrosulfides and the dihalo-aromatic compound to a polymerization reaction in the organic amide solvent to form a polymer in which a conversion of the dihalo-aromatic compound is 80 to 99%; and
a second-stage polymerization step of continuing the polymerization reaction in the presence of the phase separation agent in a phase-separated state that a concentrated formed polymer phase and a dilute formed polymer phase are present in a mixed state within the polymerization reaction system.
18. The production process of the poly(arylene sulfide) according to claim 2, wherein the polymerization step is at least two-stage polymerization steps comprising:
a first-stage polymerization step of subjecting at least one sulfur source selected from the group consisting of the alkali metal sulfides and the alkali metal hydrosulfides and the dihalo-aromatic compound to a polymerization reaction at a temperature of 170 to 270\xb0 C. in the organic amide solvent in a state that water is present in a proportion of 0.02 to 2.0 mol per mol of a charged sulfur source, thereby forming a polymer in which a conversion of the dihalo-aromatic compound is 80 to 99%; and
a second-stage polymerization step of controlling the amount of water in the polymerization reaction system so as to bring about a state that water exists in a proportion of from higher than 2.0 mol to not higher than 10 mol per mol of the charged sulfur source, and heating the polymerization reaction system to a temperature of 245 to 290\xb0 C., thereby continuing the polymerization reaction in a phase-separated state that a concentrated formed polymer phase and a dilute formed polymer phase are present in a mixed state within the polymerization reaction system.
19. The production process of the poly(arylene sulfide) according to claim 18, wherein in the second-stage polymerization step, the amount of water in the polymerization reaction system is controlled so as to bring about a state that water exists in a proportion of from higher than 2.0 mol to not higher than 10 mol per mol of the charged sulfur source, and at least one phase separation agent selected from the group consisting of organic carboxylic acid metal salts, organic sulfonic acid metal salts, alkali metal halides, alkaline earth metal halides, aromatic carboxylic acid alkaline earth metal salts, phosphoric acid alkali metal salts, alcohols and paraffinic hydrocarbons is caused to exist within a range of 0.01 to 3 mol per mol of the charged sulfur source.
20. The production process of the poly(arylene sulfide) according to claim 2, wherein prior to the polymerization step, are arranged a dehydration step of heating and reacting a mixture containing the organic amide solvent, the sulfur source containing the alkali metal hydrosulfide and an alkali metal hydroxide in a proportion of 0.95 to 1.05 mol per mol of the alkali metal hydrosulfide to discharge at least a part of a distillate containing water from the interior of the system containing the mixture to the exterior of the system; and
a charging step of adding an alkali metal hydroxide and water to the mixture remaining in the system after the dehydration step, as needed, to adjust the mixture in such a manner that the total number of moles of the number of moles of an alkali metal hydroxide formed with hydrogen sulfide formed upon the dehydration, the number of moles of the alkali metal hydroxide added prior to the dehydration and the number of moles of the alkali metal hydroxide added after the dehydration becomes 1.00 to 1.09 mol per mol of the sulfur source existing in the system after the dehydration step, and the number of moles of water becomes 0.02 to 2.0 mol per mol of the charged sulfur source.
21. A poly(arylene sulfide) produced by the production process of the poly(arylene sulfide) according to claim 2, in which the content of mesityl oxide is 65 ppm or less.
22. A poly(arylene sulfide) produced by the production process of the poly(arylene sulfide) according to claim 2, in which the content of diacetone alcohol is 35 ppm or less.
23. A poly(arylene sulfide) produced by the production process of the poly(arylene sulfide) according to claim 2, in which the content of a dihalo-aromatic compound is 110 ppm or less
24. A poly(arylene sulfide) produced by the production process of the poly(arylene sulfide) according to claim 2, in which the total content of mesityl oxide and diacetone alcohol is 100 ppm or less.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A pumped pixel including:
a first photo-diode accumulating charge in response to impinging photons, a second photo-diode and a floating diffusion positioned on a substrate of the pixel;
a charge barrier positioned on the substrate between the first photo-diode and the second photo-diode, the charge barrier temporarily blocking charge transfer between the first photo-diode and the second photo-diode;
a pump gate positioned on the substrate adjacent to the charge barrier, the pump gate pumping the accumulated charge from the first photo-diode to the second photo-diode through the charge barrier in response to a pump voltage applied by a controller; and
a transfer gate positioned on the substrate between the second photo-diode and the floating diffusion, the transfer gate transferring the pumped charge from the second photo-diode to the floating diffusion in response to a transfer voltage applied by a controller.
2. The pumped pixel of claim 1,
wherein the second photo-diode has a greater well depth than the first photo-diode for storing the charge, and the substrate below the pump gate has a clock well for storing charge and a clock barrier to block the charge in the clock well from transferring back into the first photo-diode, and
wherein during an integration period or a storage period, the controller is configured to repeatedly:
a) apply a positive pump voltage to the pump gate to lower the clock barrier and the clock well to transfer accumulated charge from the first photo-diode into the clock well, and
b) apply a negative pump voltage to the pump gate to raise the clock barrier and the clock well, to transfer the charge from the clock well over a top portion of the charge barrier and into the second photo-diode for storage.
3. The pumped pixel of claim 1,
wherein the first photo-diode and second photo-diode have equal well depths for storing the charge, and the substrate below the pump gate has a clock well for storing charge and a clock barrier to block the charge in the clock well from transferring back into the first photo-diode, and
wherein during an integration period or a storage period, the controller is configured to:
a) apply a positive pump voltage to the pump gate to lower the clock barrier and the clock well to transfer accumulated charge from the first photo-diode into the clock well, and
b) apply a negative pump voltage to the pump gate to raise the clock barrier and the clock well to transfer the charge from the clock well over a top portion of the charge barrier and into the second photo-diode for storage.
4. The pumped pixel of claim 1,
wherein the pump gate has a clock well for storing charge and a clock barrier to block the charge in the clock well from transferring back into the first photo-diode, the clock well is doped to be deeper than the clock barrier, and the charge barrier is an n-doped region of the substrate below a p-doped surface that blocks the flow of electrons.
5. The pumped pixel of claim 1,
wherein the substrate below the transfer gate has a transfer well for transferring charge from the second photo-diode to the floating diffusion, and
wherein during an integration period and a storage period, the controller is configured to apply a negative transfer voltage to the transfer gate to raise the transfer well and block charge from entering the floating diffusion.
wherein during a readout period, the controller is configured to apply a positive transfer voltage to the transfer gate to lower the transfer well and transfer the pumped charge stored in the second photo-diode to the floating diffusion for pixel readout.
6. The pumped pixel of claim 1,
wherein a CMOS imager includes an array of the pumped pixels, and
during a rolling shutter mode of the imager, for each of the pumped pixels in a selected row of the array, the controller is configured to successively:
a) apply a reset voltage during a reset period to the floating diffusion, the first photo-diode and the second photo-diode to clear stored charge,
b) apply a positive and then negative voltage during a storage period after the integration period to the pump gate to transfer the accumulated charge from the first photo-diode over the charge barrier into the second photo-diode for storage, and
c) apply a positive voltage during a readout period to the transfer gate to transfer the charge stored in the second photo-diode to the floating diffusion for pixel readout.
7. The pumped pixel of claim 1,
wherein a CMOS imager includes an array of the pumped pixels, and
during a global shutter mode of the imager, the controller is configured to successively:
a) apply a reset voltage during a reset period to the floating diffusion, the first photo-diode and the second photo-diode of every pumped pixel in the array to simultaneously clear stored charge,
b) apply a positive and then negative voltage during a storage period after the integration period to the pump gate of every pumped pixel to simultaneously transfer the accumulated charge from the first photo-diode over the charge barrier into the second photo-diode, and
c) apply a positive voltage during a readout period to the transfer gate of each pumped pixel in a selected row to transfer the charge stored in the second photo-diode to the floating diffusion for each pixel row.
8. A pumped pixel including:
a first photo-diode accumulating charge in response to impinging photons, a second photo-diode and a floating diffusion positioned on a substrate of the pixel;
a charge barrier positioned on the substrate between the second photo-diode and the floating diffusion, the charge barrier temporarily blocking charge transfer between the second photo-diode and the floating diffusion;
a transfer gate positioned on the substrate between the first photo-diode and the second photo-diode, the transfer gate transferring the accumulated charge from the first photo-diode to the second photo-diode for storage in response to a transfer voltage applied by a controller; and
a pump gate positioned on the substrate adjacent to the charge barrier, the pump gate pumping the transferred charge stored in the second photo-diode to the floating diffusion over the charge barrier in response to a pump voltage applied by a controller.
9. The pumped pixel of claim 8,
wherein the floating diffusion has a deeper well depth than the second photo-diode for storing the charge, and the substrate below the pump gate has a clock well for storing charge and a clock barrier to block the charge in the clock well from transferring back into the second photo-diode, and
wherein during a readout period, the controller is configured to repeatedly:
a) apply a positive pump voltage to the pump gate to lower the clock barrier and the clock well to transfer the charge stored in the second photo-diode into the clock well, and
b) apply a negative pump voltage to the pump gate to raise the clock barrier and the clock well, to transfer the charge from the clock well over a top portion of the charge barrier and into the floating diffusion.
10. The pumped pixel of claim 8,
wherein the second photo-diode and floating diffusion have equal well depths for storing the charge, and the substrate below the pump gate has a clock well for storing charge and a clock barrier to block the charge in the clock well from transferring back into the second photo-diode, and
wherein during a readout period, the controller is configured to:
a) apply a positive pump voltage to the pump gate to lower the clock barrier and the clock well to transfer the accumulated charge from the second photo-diode into the clock well, and
b) apply a negative pump voltage to the pump gate to raise the clock barrier and the clock well, to transfer the charge from the clock well over a top portion of the charge barrier and into the floating diffusion.
11. The pumped pixel of claim 8,
wherein the pump gate has a clock well for storing charge and a clock barrier to block the charge in the clock well from transferring back into the second photo-diode, the clock well is doped to be deeper than the clock barrier, and the charge barrier is an n-doped region of the substrate below a p-doped surface that blocks the flow of electrons.
12. The pumped pixel of claim 8,
wherein the substrate below the transfer gate has a transfer well for transferring charge from the first photo-diode to the second photo-diode, and
wherein during an integration period, the controller is configured to apply a negative transfer voltage to the transfer gate to raise the transfer well and block charge from entering the second photo-diode.
wherein during a storage period, the controller is configured to apply a positive transfer voltage to the transfer gate to lower the transfer well and transfer the accumulated charge from the first photo-diode to the second photo-diode for pixel storage.
13. The pumped pixel of claim 8,
wherein a CMOS imager includes an array of the pumped pixels, and
during a rolling shutter mode of the imager, for each of the pumped pixels in a selected row of the array, the controller is configured to successively:
a) apply a reset voltage during a reset period to the floating diffusion, first photo-diode and second photo-diode to clear stored charge,
b) apply a positive voltage during a storage period to the transfer gate to transfer the charge accumulated in the first photo-diode to the second photo-diode for pixel storage, and
c) repeatedly apply a positive and then a negative voltage during a readout period to the pump gate to transfer the stored charge from the second photo-diode over the charge barrier into the floating diffusion.
14. The pumped pixel of claim 8,
wherein a CMOS imager includes an array of the pumped pixels, and
during a global shutter mode of the imager, the controller is configured to successively:
a) apply a reset voltage during a reset period to the floating diffusion, first photo-diode and second photo-diode of every pumped pixel to simultaneously clear stored charge,
b) apply a positive voltage during a storage period to the transfer gate of each pumped pixel to simultaneously transfer the charge accumulated in the first photo-diode to the second photo-diode, and
c) apply a positive and then a negative voltage during a readout period to the pump gate of pumped pixels in a selected row to transfer the stored charge from the second photo-diode through the charge barrier into the floating diffusion.
15. A pumped pixel including:
a first photo-diode accumulating charge in response to impinging photons, a second photo-diode and a floating diffusion positioned on substrate of the pixel;
a first charge barrier positioned on the substrate between the first photo-diode and the second photo-diode, the first charge barrier temporarily blocking charge transfer between the first photo-diode and the second photo-diode;
a second charge barrier positioned on the substrate between the second photo-diode and the floating diffusion, the second charge barrier temporarily blocking charge transfer between the second photo-diode and the floating diffusion;
a first pump gate positioned on the substrate adjacent to the first charge barrier, the first pump gate pumping the accumulated charge from the first photo-diode to the second photo-diode over the first charge barrier in response to a first pump voltage applied by a controller; and
a second pump gate positioned on the substrate adjacent to the second charge barrier, the second pump gate pumping the pumped charge from the second photo-diode to the floating diffusion over the second charge barrier in response to a second pump voltage applied by a controller.
16. The pumped pixel of claim 15,
wherein the first photo-diode and second photo-diode have wells for storing the charge, and the substrate below the first pump gate has a first clock well for storing charge and a first clock barrier to block the charge in the first clock well from transferring back into the first photo-diode, and
wherein during a storage period, the controller is configured to:
a) apply a positive pump voltage to the first pump gate to lower the first clock barrier and the first clock well to transfer accumulated charge from the first photo-diode into the first clock well, and
b) apply a negative pump voltage to the first pump gate to raise the first clock barrier and the first clock well, to transfer the charge from the first clock well over a top portion of the first charge barrier and into the second photo-diode for storage.
17. The pumped pixel of claim 15,
wherein the substrate below the second pump gate has a second clock well for storing charge and a second clock barrier to block the charge in the second clock well from transferring back into the second photo-diode, and
wherein during a storage period, the controller is configured to apply a negative voltage to the second pump gate to raise the second clock barrier and well and block charge from entering the floating diffusion.
wherein during a readout period, the controller is configured to apply a positive voltage and then a negative voltage to the second pump gate to transfer the charge stored in the second photo-diode over a top portion of the second charge barrier and into the floating diffusion for pixel readout.
18. The pumped pixel of claim 15,
wherein the first pump gate has a first clock well for storing charge and a first clock barrier to block the charge in the first clock well from transferring back into the first photo-diode, the first clock well is doped to be deeper than the first clock barrier, the second pump gate has a second clock well for storing charge and a second clock barrier to block the charge in the second clock well from transferring back into the second photo-diode, the second clock well is doped to be deeper than the second clock barrier, and
wherein the first charge barrier and the second charge barrier are n-doped regions of the substrate below a p-doped surface that block the flow of electrons.
19. The pumped pixel of claim 15,
wherein a CMOS imager includes an array of the pumped pixels, and
during a rolling shutter mode of the imager, for each of the pumped pixels in a selected row of the array, the controller is configured to successively:
a) apply a reset voltage during a reset period to the floating diffusion, first photo-diode and second photo-diode to clear stored charge,
b) repeatedly apply a positive and then a negative voltage during a storage period to the first pump gate to transfer the accumulated charge from the first photo-diode over the first charge barrier into the second photo-diode for storage, and
c) repeatedly apply a positive and then a negative voltage during a readout period to the second pump gate to transfer the stored charge from the second photo-diode over the second charge barrier into the floating diffusion for readout.
20. The pumped pixel of claim 15,
wherein a CMOS imager includes an array of the pumped pixels, and
during a global shutter mode of the imager, the controller is configured to successively:
a) apply a reset voltage during a reset period to the floating diffusion, first photo-diode and second photo-diode of every pumped pixel to simultaneously clear stored charge,
b) apply a negative and positive voltage during a storage period to the first pump gate of each pumped pixel to simultaneously transfer the charge accumulated in the first photo-diode through the first charge barrier and into the second photo-diode, and
c) apply a positive and negative voltage during a readout period to the second pump gate of every pumped pixel in a selected row to transfer the stored charge from the second photo-diode through the charge barrier into the floating diffusion for readout of each pixel row.