CN101365990B - Intermediate transfer belt and manufacturing method thereof - Google Patents
Intermediate transfer belt and manufacturing method thereof Download PDFInfo
- Publication number
- CN101365990B CN101365990B CN2007800018639A CN200780001863A CN101365990B CN 101365990 B CN101365990 B CN 101365990B CN 2007800018639 A CN2007800018639 A CN 2007800018639A CN 200780001863 A CN200780001863 A CN 200780001863A CN 101365990 B CN101365990 B CN 101365990B
- Authority
- CN
- China
- Prior art keywords
- transfer belt
- intermediate transfer
- belt according
- polysiloxane
- heat conduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
- E06B9/26—Lamellar or like blinds, e.g. venetian blinds
- E06B9/262—Lamellar or like blinds, e.g. venetian blinds with flexibly-interconnected horizontal or vertical strips; Concertina blinds, i.e. upwardly folding flexible screens
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
- E06B9/26—Lamellar or like blinds, e.g. venetian blinds
- E06B9/28—Lamellar or like blinds, e.g. venetian blinds with horizontal lamellae, e.g. non-liftable
- E06B9/30—Lamellar or like blinds, e.g. venetian blinds with horizontal lamellae, e.g. non-liftable liftable
- E06B9/32—Operating, guiding, or securing devices therefor
- E06B9/322—Details of operating devices, e.g. pulleys, brakes, spring drums, drives
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
- E06B9/26—Lamellar or like blinds, e.g. venetian blinds
- E06B9/262—Lamellar or like blinds, e.g. venetian blinds with flexibly-interconnected horizontal or vertical strips; Concertina blinds, i.e. upwardly folding flexible screens
- E06B2009/2622—Gathered vertically; Roman, Austrian or festoon blinds
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/56—Operating, guiding or securing devices or arrangements for roll-type closures; Spring drums; Tape drums; Counterweighting arrangements therefor
- E06B9/58—Guiding devices
- E06B2009/583—Cords or cables
Landscapes
- Engineering & Computer Science (AREA)
- Structural Engineering (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
Abstract
Disclosed are an intermediate transfer belt for use in a laser printer, a fax machine and a copier, and a production method thereof. Specifically, an intermediate transfer belt including silicone modified polyimide resin and a production method thereof are provided, thereby realizing a monolayer intermediate transfer belt having excellent electrical properties, water repellency and heat dissipation properties and good mechanical strength. Further, even without the additional use of an adhesive layer for adhesion to a fluorine resin layer and fluorine resin, the intermediate transfer belt can exhibit satisfactory properties, and process efficiency can be maximized.
Description
[technical field]
In general, the present invention relates to a kind of intermediate transfer belt and manufacture method thereof that is used for laser printer, facsimile recorder and duplicating machine, more specifically, relate to a kind of by polysiloxane-modified polyimide resin manufacturing intermediate transfer belt and make the method for this intermediate transfer belt.
[background technology]
Usually, the intermediate transfer belt that can be used for laser printer, facsimile recorder and duplicating machine should possess excellent thermal diffusivity, water proofing property, grease proofness, stain resistance, thermotolerance, elastic modulus, the performance of the release property, antistatic behaviour and the permanance that discharge from paper.
In addition, when the long-time operation said apparatus, in printing process, because the heat of friction that is caused between the paper of intermediate transfer belt and supply, the big calorimetric of generation at the interface betwixt, so need the heat dispersion of efficiently radiates heat, this is considered to important.Yet under the situation of such heat dispersion deficiency, transfer belt is out of shape because of the heat of friction that long-time operation produced, thereby causes insecure product.And, do not dispersed and remain in the small space high temperature afterheat device is on every side had adverse effect, thus life-span of device and cause its fault around having reduced unfavourably.
In addition, intermediate transfer belt should have the specific insulation that is suitable for realizing toner transfer printing function.If transfer belt has when being below or above required specific insulation, then antistatic behaviour, transfer printing, imaging performance, release property, stain resistance etc. may produce the critical defect as the image of difference thus with deterioration.
The polyimide film that is mainly used in traditional intermediate transfer belt has high thermal stability and excellent machinery and electrical property, but very sensitive to moisture, thereby has reduced the reliability of electrical insulating property gradually along with the time.And, because polyimide film has high glass transition temperature, its processability is restricted, and it become charged easily.In addition, its specific insulation is higher than the requirement to middle transfer belt, therefore is difficult to use in intermediate transfer belt.
This aspect on, a kind of method of making transfer belt is disclosed among Japanese unexamined patent publication 2003-270967,2002-218339 and the 2004-255828, wherein will be as the polyamic acid solution polymerization of polyimide precursor, place mould, thermal treatment, further be coated with release property, water proofing property and the grease proofness that discharges from paper to increase, thermal treatment then with the fluoropolymer compound.
Yet, preceding method has many economic and physicochemical problems relevant with the time when practical application, this mainly owing to: in addition the complex process of the polyamic acid solution that solidifies with fluoropolymer compound coated portion, can be used for as the polyimide layer of intermediate transfer belt substrate and the selection of the bonding subbing (primer) between the fluoroplymer layer, and based on the poor therebetween bonding problem of peeling off.In addition, because the three-decker of being made up of polyimide layer, subbing layer and fluoropolymer compound layer is provided, thereby this method efficient is low, and complicated.That is, the thickness of the subbing of spraying and fluoropolymer compound may be according to processing conditions and other factors and inhomogeneous, same because must repeat processing for several times, and working (machining) efficiency reduces.
Simultaneously, because the intermediate transfer belt of laser printer, facsimile recorder and duplicating machine works in the transfer printing toner, therefore it must be manufactured seamless.When making seamless intermediate transfer belt, utilized employing centrifugal forming (centrifugal molding) to realize atwirl washing bath method (wash tub process) with classic method.Yet, make seamless intermediate transfer belt because be difficult to use in, so this kind technology is not good.
[summary of the invention]
[technical matters]
Cause of the present inventionly being, the inventor is for fear of being used as laser printer, the problem that is run in the correlation technique of the conventional polyimide of the intermediate transfer belt of facsimile recorder and duplicating machine-parent tube shape band, low as working (machining) efficiency, to making a kind of excellent thermal diffusivity that has, antistatic behaviour, water proofing property, grease proofness, the intermediate transfer belt of the individual layer solid drawn tube form of economic benefit and transfer printing has carried out deeply and extensive studies, this has caused a kind of exploitation of intermediate transfer belt of solid drawn tube form, described intermediate transfer belt can disperse the heat that produces effectively when the medium-term and long-term use of small space, and can show good water proofing property, grease proofness, antistatic behaviour and the release property that discharges from paper.
Therefore, an object of the present invention is to provide a kind of intermediate transfer belt, described intermediate transfer belt is by the polyimide resin manufacturing, and has the water proofing property of improvement.
Another object of the present invention provides a kind of individual layer intermediate transfer belt, and described individual layer intermediate transfer belt is by the polyimide resin manufacturing, and shows excellent thermal diffusivity.
Another purpose of the present invention provides a kind of method of making intermediate transfer belt, and described intermediate transfer belt has the water proofing property of improvement.
A further object of the present invention provides a kind of method of using polyimide resin to make intermediate transfer belt, and described intermediate transfer belt has excellent thermal diffusivity, is in the form of individual layer solid drawn tube.
[technical scheme]
For achieving the above object, the invention provides a kind of intermediate transfer belt that comprises polysiloxane-modified polyimide resin.
It is more than the 20W/mk that this intermediate transfer belt can also comprise thermal conductivity, and resistivity is 10
1The heat conduction filling agent that Ω cm is above.
This heat conduction filling agent can be that particle diameter is the sphere-packing agent of 0.2～20 μ m, and this sphere-packing agent comprises with 6～7: 4～3 ratio mixes, and has first particle of large-size of 5～20 μ m and second particle with reduced size of 0.2～5 μ m.
The amount that can be 0.01～30 weight % with the total amount based on solute comprises described heat conduction filling agent.
The heat conduction filling agent can comprise and is selected from a kind of in following or two or more potpourris: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, silicon dioxide, aluminium oxide, aluminium borate, silit, titanium carbide, boron carbide, silicon nitride, boron nitride, aluminium nitride, titanium nitride, mica, potassium titanate, metatitanic acid beryllium, lime carbonate, magnesium oxide, zirconia, tin oxide, beryllia, aluminium oxide and aluminium hydroxide.
This intermediate transfer belt can have the thermal conductivity of 5.1～7.4W/mK.
This intermediate transfer belt can also comprise conductive filler.
This intermediate transfer belt can have 10
8～10
13The specific insulation of Ω cm, 105 °～113 ° contact angle and the elastic modulus of 0.8～4.5Gpa.
Polysiloxane-modified polyimide resin can be for comprising the multipolymer of dianhydride, diamines and polyorganosiloxane resin.
This polyorganosiloxane resin can have 600 to 2,000 number-average molecular weight, and can be to be that the amount of 10～30 weight % comprises with the amount based on diamines.
Polyorganosiloxane resin can comprise and is selected from a kind of in following or two or more potpourris: dimethyl silicone polymer, poly-diphenyl siloxane and as their PSI of multipolymer.
In addition, the invention provides a kind of manufacture method of intermediate transfer belt, described method comprises: dianhydride, diamines and polyorganosiloxane resin are dissolved in the aprotic solvent of high polarity, thereby prepare polysiloxane-modified polyamic acid solution; And this polysiloxane-modified polyamic acid solution is loaded in the mould, then with its thermal treatment to induce imidizate (imidation).
When this polysiloxane-modified polyamic acid solution of preparation, can also comprise thermal conductivity is more than the 20W/mk and resistivity is 10
1The heat conduction filling agent that Ω cm is above.
This mould can be the cylindrical die that has by out cylinder and the dual structure that inner cylinder constituted.
When this polysiloxane-modified polyamic acid solution of preparation, can also comprise conductive filler.
Induce the thermal treatment of imidizate to carry out at 60～400 ℃.
[embodiment]
Below, will provide detailed description of the present invention.
The polyimide resin that is used for intermediate transfer belt of the present invention comprises the polysiloxane-modified polyimide resin of using the polyorganosiloxane resin copolymerization.
Polysiloxane-modified polyimide resin obtains by the following method: dianhydride, diamines and polyorganosiloxane resin are dissolved in the aprotic solvent of high polarity, preparing polysiloxane-modified polyamic acid solution, this polysiloxane-modified polyamic acid solution again through thermal treatment to induce imidizate.
The dianhydride and the diamines that are used to prepare polysiloxane-modified polyimide resin are not particularly limited, as long as they are commonly used to prepare polyimide resin.The example of diamines comprises 1, and the 4-phenylenediamine (1,4-PDA), 1, the 3-phenylenediamine (1,3-PDA), 4,4 '-methylene dianiline (MDA) (MDA), 4,4 '-benzidine ether (4,4 ' oxydianiline, ODA), 4,4 '-oxygen phenylenediamine (OPDA) etc.; And the example of dianhydride comprises 1,2,4,5 benzenetetracarboxylic acid dianhydride (PMDA), 3,3 ', 4, and 4 '-bibenzene tetracarboxylic dianhydride (BTDA), 4, the two phthalic anhydrides (ODPA) and 4 of 4 '-oxygen, the two phthalic anhydrides of 4 '-hexafluoro isopropylidene etc.So, diamines and dianhydride with etc. mol ratio use.
The polyorganosiloxane resin that has organic performance and inorganic performance simultaneously is used to the release property giving stain resistance, water proofing property, grease proofness and discharge from paper, and comprises and be selected from dimethyl silicone polymer, poly-diphenyl siloxane and as in their PSI of multipolymer one or more.This resin has the number-average molecular weight in 600 to 2,000 scope, so that the micron-scale phase separation when the polyimide polymerization minimizes.This polyorganosiloxane resin is to be that the amount of 10～30 weight % is used with the amount based on diamines preferably.
Repetition Si-O key with Si and O atom as the polyorganosiloxane resin of the present invention of its main chain preferably by the following compounds example: dimethyl silicone polymer, wherein two methyl as the main body organic substituent are connected on the Si atom; And poly-diphenyl siloxane, wherein two phenyl are connected on the Si atom.In the polysiloxane industrial circle, useful especially is that glass transition temperature is-123 ℃ a dimethyl silicone polymer, and this glass transition temperature is minimum in hitherto known elastic body.In addition, known poly-diphenyl siloxane has the glass transition temperature higher than dimethyl silicone polymer, and shows good thermal stability and mechanical property.Because its nonpolar performance and low surface energy, in polysiloxane-modified polymer compound, this polysiloxane component is separated from this polymkeric substance, therefore the interface movement between air and polymkeric substance.By this way, owing to silicone components comes out from this polymer surfaces, so polymer surfaces can show excellent water proofing property, grease proofness and release property.Mix together at two copolymer phases under the situation of thing and also observe these performances.Yet in the present invention, polyorganosiloxane resin is not limited to dimethyl silicone polymer and poly-diphenyl siloxane.
In the preparation of polysiloxane-modified polyamic acid solution, using under the situation of this polyorganosiloxane resin less than the amount of 10 weight % with amount based on diamines, water proofing property and grease proofness are not greatly improved, thereby do not significantly improve the low moisture resistance as the shortcoming of polyimide.On the other hand, if should amount surpass 30 weight %, be attributable to respect to polyimide have flexible polyorganosiloxane resin influence be that physical strength sharply descends.
When polymerization, can use the solvent among the aprotic solvent that is selected from high polarity, such as N, dinethylformamide (DMF), dimethyl acetamide (DMAc) and N-N-methyl-2-2-pyrrolidone N-(NMP).
Consider thermal diffusivity, resulting intermediate transfer belt preferably has the thermal conductivity of 5.1～7.4W/mk.Therefore, when preparing polysiloxane-modified polyamic acid solution, also comprise the heat conduction filling agent, and make it 0～30 ℃ of reaction, the time is in 30 minutes to 12 hours scope.
In order to prepare compound substance, should carry out the heat conduction filling agent method of filling in the matrix of compound substance effectively with excellent thermal diffusivity.So, the pack density of heat conduction filling agent can change according to its shape, size and amount.In addition, conducting heat, promptly by the caused thermal energy transfer of the temperature difference, is with three types, i.e. conduction, convection current and radiation realize.In these types, thermal conductivity increases with the area that transport phenomenon wherein takes place with being directly proportional.
Under the situation with thermal diffusivity compound substance, heat is transmitted by conducting, and the calorific value that transmits increases with the sectional area of compound substance with being directly proportional, and is inversely proportional to thickness, and is directly proportional with the temperature difference.
This kind phenomenon can be represented compactly by following Fourier heat-conduction equation:
Wherein, A is the area of compound substance; T is a temperature; X is the thickness of compound substance; The calorific value of q for being transmitted by conduction; And k is the thermal conductivity of compound substance.
Therefore, preferably this heat conduction filling agent has the above thermal conductivity of 20W/mk.
In addition, this heat conduction filling agent preferably has 10
1The resistivity that Ω cm is above.If resistivity is less than above-mentioned value, then transfer belt has low-down specific insulation, thereby is unaccommodated.
As the heat conduction filling agent, what use is a kind of inorganic filler that is selected from following, or two or more potpourris: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, silicon dioxide, aluminium oxide, aluminium borate, silit, titanium carbide, boron carbide, silicon nitride, boron nitride, aluminium nitride, titanium nitride, mica, potassium titanate, metatitanic acid beryllium, lime carbonate, magnesium oxide, zirconia, tin oxide, beryllia, aluminium oxide and aluminium hydroxide.
The shape of heat conduction filling agent is not particularly limited, but can be spherical, needle-like or sheet.Under the situation of needle-like filling agent, it can not get effective filling, therefore has low pack density.In addition, under the situation of sheet filling agent,, therefore be difficult to realize high pack density because its thermal conductivity changes according to axial orientation.Therefore, useful especially is the sphere-packing agent.
The particle diameter of this sphere-packing agent is 0.2～20 μ m, and the particle diameter of needle-like filling agent is 0.5～5 μ m, and the particle diameter of sheet is 0.5～10 μ m.Especially, the sphere-packing agent preferably comprises with 6～7: 4～3 ratio mixes, and has first particle of large-size of 5～20 μ m and second particle with reduced size of 0.2～5 μ m.This is because the filling agent that has than small particle diameter is filled in the pore space of the filling agent with greater particle size effectively, thereby can be formed uniformly the heat conduction network that is used to dispel the heat.
In intermediate transfer belt, when the heat conduction filling agent with the state that keeps the intrinsic heat conductance and when being evenly dispersed in the described band with suitable amount, can form the heat-transfer path that can dispel the heat.
For conduction heat effectively, be that the amount of 0.01～30 weight % is used this heat conduction filling agent preferably with the total amount of solute.
Except that the heat conduction filling agent, can also comprise the specific insulation of conductive filler with the control polyimide resin.As conductive filler, can be being that the amount of 2～35 weight % is used and to be selected from cut late black (ketjen black), acetylene black and the furnace black one or more based on the solute total amount.And, can also comprise aluminium wherein, nickel, silver or mica mix (dipping) metal filler of antimony is arranged, Dentall TM-200 for example, and can be the amount use of 0.1～5 weight % with total amount with it based on solute.
The polysiloxane-modified polyamic acid solution of so preparation is loaded in the mould, and thermal treatment is to induce imidizate.
Though mould is not particularly limited, use cylindrical die to make seamless intermediate transfer belt.Useful especially is the cylindrical teflon mould that has by out cylinder and the dual structure that inner cylinder constituted.Therefore, can utilize the diameter difference of out cylinder and inner cylinder to control the thickness of transfer belt, preferably, described band has the thickness of 30～300 μ m.About the manufacturing of intermediate transfer belt, in order to improve thermal diffusivity, if described band forms too thinly, then described band has the rigidity of rapid decline, therefore may split or warpage under the repetition rotation stress in printing process.In order to disperse the heat that certainly leads to when the long-time operation intermediate transfer belt effectively, the heat conduction filling agent should be added in the resin that is used for described band.
Thermal treatment is carried out in 50～400 ℃ temperature range step by step.That is, carried out prebake 10～120 minutes,, then, under 350～400 ℃, carry out the back and solidify, to remove solvent and moisture fully from its surface with the rate of heat addition of 2～10 ℃/min with preliminary solvent and the moisture removed from the surface of described band at 50～100 ℃.Thus, when imidizate carries out, when finishing subsequently, obtained the transfer belt of the film that solidifies.
Intermediate transfer belt has the thermal conductivity of 5.1～7.4W/mK usually, and 10
8～10
13Therefore the resistivity of media of Ω cm has realized that a kind of semiconduction intermediate transfer belt that is used for laser printer, facsimile recorder and duplicating machine, described intermediate transfer belt have excellent antistatic behaviour and impressionability.
Transfer belt preferably has 105 °～113 ° contact angle.This contact angle is meant the thermodynamic equilibrium angle that liquid contacts on solid surface, and is to estimate by the section of the set drop on the solid surface.Equally, little contact angle is meant the water wettability sample, and big contact angle is meant the hydrophobicity sample.Be that water proofing property and grease proofness are low, thereby cause low-down moisture resistance under 20～70 ° the situation of polyimide-based polymer compound at contact angle.Therefore, should increase contact angle to improve moisture resistance.
In addition, transfer belt of the present invention preferably has the elastic modulus of 0.8～4.5GPa.If elastic modulus is lower than lower limit, then when using intermediate transfer belt for a long time, cause mechanically deform.On the other hand, if elastic modulus is higher than the upper limit, then physical strength reduces.
By following embodiment, can obtain better understanding of the present invention, described embodiment sets forth for explanation, and should not be construed as restriction the present invention.
＜embodiment 1 〉
When nitrogen is being guided into be equipped with mechanical stirrer, reflux condenser and nitrogen to be filled in the four neck flasks of inlet in, with the PMDA of 47g with and 43g 4,4 '-benzidine ether is dissolved among the aprotic solvent DMF of high polarity of 380g, afterwards, with based on 4, the weight of 4 '-benzidine ether is that number-average molecular weight that the amount of 10 weight % adds 10 weight % is 600 and has the dimethyl silicone polymer that contains the amine aminopropyl at its two end, prepares complete solution thus.Then, general assembly (TW) based on solute, to be scattered in the above-mentioned solution with ultrasonic divider late deceiving as 2 weight % cuts of conductive filler with 0.5 weight %Dentall TM-200, it was at room temperature reacted 1 hour, prepare the polyamic acid solution of the polydimethylsiloxane--modified that contains conductive filler thus.
The polyamic acid solution of polydimethylsiloxane--modified of preparation thus is loaded in the cylindrical teflon mould with the dual structure that is made of out cylinder and inner cylinder, afterwards 70 ℃ of following prebake 1 hour, tentatively to remove solvent and moisture, afterwards inner cylinder is separated with out cylinder from belt surface.Afterwards, with 5 ℃/minute the rate of heat addition, carry out the back at 350 ℃ and solidify processing, thereby remove solvent and moisture fully from belt surface and inside.
The polyimide-based intermediate transfer belt of resulting polydimethylsiloxane--modified has the thickness of 65 μ m.
＜embodiment 2 〉
With with embodiment 1 in identical mode make the polyimide-based intermediate transfer belt of polydimethylsiloxane--modified, difference is not use Dentall TM-200 as conductive filler.
＜embodiment 3 〉
With with embodiment 1 in identical mode make the polyimide-based intermediate transfer belt of polydimethylsiloxane--modified, difference is that with based on 4, the weight of 4 '-benzidine ether is that the amount of 30 weight % is used dimethyl silicone polymer.
＜embodiment 4 〉
With with embodiment 1 in identical mode make the polyimide-based intermediate transfer belt of polydimethylsiloxane--modified, it is 620 that difference is to use number-average molecular weight, and contain the dimethyl silicone polymer of aminopropyl at its two end, being that to use thermal conductivity be 10 as 105W/mK and resistivity for the amount of 3 weight % based on the solute general assembly (TW)
2Spherical alumina (the Al of Ω cm
2O
3) as the heat conduction filling agent, described aluminium oxide is made up of the particle of the 6 μ m sizes of mixing with 7: 3 ratio and the particle of 0.5 μ m size, and being that the amount of 1.5 weight % uses that cut is late deceives as conductive filler based on the solute general assembly (TW).
＜embodiment 5 〉
With with embodiment 4 in identical mode make the polyimide-based intermediate transfer belt of polydimethylsiloxane--modified, difference is not use aluminium oxide as the heat conduction filling agent.
＜embodiment 6 〉
With with embodiment 4 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is to use number-average molecular weight to be 750 and to contain the poly-diphenyl siloxane of aminopropyl at its two end.
＜embodiment 7 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is to use the aluminium oxide of particle of the particle that comprises the 6 μ m sizes of mixing with 6: 4 ratio and 0.5 μ m size as the heat conduction filling agent.
＜embodiment 8 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is to use the aluminium oxide of particle of the particle that comprises the 6 μ m sizes of mixing with 3: 7 ratio and 0.5 μ m size as the heat conduction filling agent.
＜embodiment 9 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is as the heat conduction filling agent, amount with 3 weight % is used the needle-like aluminium oxide separately, and this aluminium oxide has the length of 5 μ m, the thermal conductivity of 100W/mK and 10
2The resistivity of Ω cm.
＜embodiment 10 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is as the heat conduction filling agent, amount with 3 weight % is used the sheet boron nitride separately, and this boron nitride has the length of 5 μ m, the thermal conductivity of 156W/mK and 10
2The resistivity of Ω cm.
＜embodiment 11 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is as the heat conduction filling agent, with the general assembly (TW) based on solute is the amount use aluminium oxide of 1.5 weight %, and this aluminium oxide comprises the particle of the 6 μ m sizes of mixing with 7: 3 ratio and the particle of 0.5 μ m size.
＜embodiment 12 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is as the heat conduction filling agent, with the general assembly (TW) based on solute is the amount use aluminium oxide of 0.01 weight %, and this aluminium oxide comprises the particle of the 6 μ m sizes of mixing with 7: 3 ratio and the particle of 0.5 μ m size.
＜embodiment 13 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is not use cut late black in conductive filler.
＜embodiment 14 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, it is that 5 μ m, thermal conductivity are 10 as 20W/mK and resistivity that difference is to use length
1The needle-like mica of Ω cm replaces aluminium oxide.
＜embodiment 15 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is that with based on 4, the weight of 4 '-benzidine ether is that the amount of 5 weight % is used poly-diphenyl siloxane.
＜embodiment 16 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is that with based on 4, the weight of 4 '-benzidine ether is that the amount of 35 weight % is used poly-diphenyl siloxane.
＜embodiment 17 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, difference is to use heat conduction filling agent aluminium oxide with the amount of 36 weight %.
＜embodiment 18 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, it is 10 as 75W/mK and resistivity that difference is to use thermal conductivity
0The late black aluminium oxide that replaces of the cut of Ω cm.
＜embodiment 19 〉
With with embodiment 6 in identical mode make the polyimide-based intermediate transfer belt of poly-diphenyl siloxane modification, be that 12W/mK and resistivity are 10 but be to use thermal conductivity
1The molybdenum powder of Ω cm replaces aluminium oxide.
＜comparative example 1 〉
With with embodiment 1 in identical mode make polyimide-based intermediate transfer belt, difference is not use dimethyl silicone polymer.
＜comparative example 2 〉
With with comparative example 1 in identical mode make polyimide-based intermediate transfer belt, use spraying process polyimide-based intermediate transfer belt coating to go up subbing, this subbing is the polysiloxane component, sprays 3 times with containing the late dimethyl silicone polymer black and 0.5 weight %Dentall TM-200 of 2 weight % cuts afterwards.At last, the sample that sprays was being solidified below 350 ℃ 10～60 minutes, producing polysiloxane-modified polyimide-based intermediate transfer belt thus, this intermediate transfer belt has the three-decker that is made of polyimide, subbing and dimethyl silicone polymer.
＜comparative example 3 〉
With with embodiment 6 in identical mode make polyimide-based intermediate transfer belt, difference is not use poly-diphenyl siloxane.
＜comparative example 4 〉
With with comparative example 3 in identical mode make polyimide-based intermediate transfer belt, use spraying process, should polyimide-based intermediate transfer belt coating go up subbing, this subbing is the polysiloxane component, sprays three times with containing the late dimethyl silicone polymer black and 0.5 weight %DentallTM-200 of 2 weight % cuts afterwards.At last, the sample that sprays was being solidified below 350 ℃ 10～60 minutes, producing polysiloxane-modified polyimide-based intermediate transfer belt thus, this intermediate transfer belt has the three-decker that is made of polyimide, subbing and dimethyl silicone polymer.
Measure the performance of the intermediate transfer belt of manufacturing in embodiment and comparative example according to following method.In table 1, provided the result.
(1) thermal conductivity
According to ASTM E1461, use FL5000 analysis of thermal conductivity device, measure thermal conductivity based on polyethylene, polysiloxane rubber, quartz glass, zirconia.
(2) specific insulation
Utilization applies voltage available from the resistivity tester of Mitsubishi Chemical Ind (Mitsubishi Chemical) continuously to sample and measures.So, the number change of the voltage on being applied to sample is measured during to 10V, 100V, 250V, 500V and 1000V.In addition, measurement volumes resistance by this way: sample is installed on the metal substrate, then with 10～30 seconds time interval measurement resistivity.At this moment, use cycling probe.
(3) contact angle
Measure the contact angle of polysiloxane-modified polyimide-based intermediate transfer belt, to determine its water proofing property and grease proofness.For this reason, at the dynamic contact angle meter DCA3115 of 25 ℃ of uses available from CAHN.The solution of deionized water and 6 μ L ethylene glycol is dropped on the sample surfaces with set drop form, then by being used to amplify the monitor estimation contact angle at the interface between sample surfaces and the solution droplets.Carry out ten times continuously and measure, and its value is average.
(4) elastic modulus
According to JIS K 6301, use the elastic modulus of measuring polysiloxane-modified polyimide-based intermediate transfer belt available from the universal testing machine Model 1000 of Instron.
Table 1
| ? | Thermal conductivity (W/mK) | Specific insulation (Ω cm) | Contact angle (°) | Elastic modulus (GPa) |
| Embodiment 1 | 3.25 | 1.53×10 8 | 107 | 1.29 |
| Embodiment 2 | 2.92 | 3.57×10 10 | 105 | 1.27 |
| Embodiment 3 | 3.22 | 8.19×10 13 | 113 | 0.97 |
| Embodiment 4 | 6.95 | 3.24×10 10 | 108 | 2.60 |
| Embodiment 5 | 3.01 | 8.07×10 11 | 106 | 3.00 |
| Embodiment 6 | 7.33 | 3.53×10 10 | 109 | 3.30 |
| Embodiment 7 | 6.92 | 3.07×10 10 | 111 | 3.15 |
| Embodiment 8 | 6.27 | 1.11×10 10 | 105 | 3.07 |
| Embodiment 9 | 5.10 | 2.32×10 10 | 105 | 3.03 |
| Embodiment 10 | 6.31 | 1.21×10 10 | 112 | 3.05 |
| Embodiment 11 | 5.95 | 3.23×10 10 | 107 | 3.02 |
| Embodiment 12 | 5.27 | 1.22×10 10 | 108 | 3.02 |
| Embodiment 13 | 7.01 | 7.08×10 16 | 110 | 3.13 |
| Embodiment 14 | 5.33 | 5.22×10 10 | 107 | 3.01 |
| Embodiment 15 | 7.00 | 4.11×10 10 | 103 | 3.31 |
| Embodiment 16 | 7.35 | 3.46×10 10 | 114 | 2.10 |
| Embodiment 17 | 8.33 | 7.53×10 5 | 112 | 3.50 |
| Embodiment 18 | 6.75 | 2.56×10 4 | 107 | 2.95 |
| Embodiment 19 | 4.53 | 5.75×10 10 | 106 | 3.00 |
| Comparative example 1 | 2.86 | 2.3×10 10 | 46 | 1.28 |
| Comparative example 2 | 3.39 | 5.7×10 10 | 105 | 0.86 |
| Comparative example 3 | 7.09 | 1.58×10 10 | 67 | 2.80 |
| Comparative example 4 | 4.31 | 6.13×10 10 | 103 | 0.95 |
Measurement result as described performance, when the amount that polysiloxane is no less than 10 weight % with the amount based on diamines adds in the main chain of polyimide, the contact angle of the polysiloxane-modified polyimide-based intermediate transfer belt of copolymerization is increased to about 105 ° or bigger.That is, but therefore the modification hydrophobic property by polysiloxane has improved the low moisture resistance as the shortcoming of polyimide, in addition the release property height that discharges from the paper of supplying with.Yet, do not use in polysiloxane-modified comparative example 1 and the comparative example 3, though specific insulation is suitable for intermediate transfer belt, contact angle is respectively 46 ° and 67 °.Hence one can see that, and low moisture resistance does not improve.Be added with therein among the embodiment 15 of lesser amounts of polysiloxane resins, contact angle is 103 °, and hence one can see that reveals improvement in the required expectation for the low not indicator gauge of low moisture resistance.In comparative example 2 and 4, contact angle slightly improves, but compares with the embodiment that wherein the polysiloxane compound chemistry is incorporated in the polyimide main chain, and working (machining) efficiency reduces, and reason is owing to three-decker repeats repeatedly to process.Equally, elastic modulus reduces, thus intermediate transfer belt when appearing at long-term the use about the problem of its mechanically deform.
Introduce therein in the embodiment of the invention of polyorganosiloxane resin, it is needed that electrical property, moisture resistance and physical strength all show as.Under the situation that comprises the heat conduction filling agent in addition, thermal conductivity is further promoted.Add therein among the embodiment 17 of excessive heat conduction filling agent, the too high and volume resistance of thermal conductivity sharply descends, and therefore makes the image that is difficult to realize toner on color laser printer.
As the heat conduction filling agent, when use comprised the spherical alumina of particle of the particle of the 6 μ m sizes that the ratio with 7: 3 or 6: 4 mixes and 0.5 μ m size, thermal conductivity was the highest.
Add among the embodiment 6 and 7 of aluminium oxide with the amount bigger relatively therein with big particle diameter than aluminium oxide with small particle diameter, to add the embodiment 8 of the aluminium oxide with small particle diameter and compare than having the relative bigger amount of large-sized aluminium oxide, thermal conductivity is good with wherein.Therefore, under the situation of embodiment 6 and 7, the aluminium oxide pack density is higher than the aluminium oxide pack density in embodiment 8.
The embodiment 6 and the embodiment 9 that uses the needle-like aluminium oxide of spherical alumina will be used, compare with the embodiment 10 that uses the sheet boron nitride, even filling agent uses with the same amount of 3 weight %, and have similar thermal conductivity, the thermal diffusivity of resulting conductive membranes is also than better when using spherical alumina.According to the shape of the aluminium oxide that uses, the needle-like aluminium oxide does not obtain effective filling, thereby has low pack density, thereby causes uneven heat conduction network.Sheet boron nitride with the intrinsic heat conductance that is better than spherical alumina shows and be the high-cooling property of 156W/mK on a direction of principal axis, and is the low heat emission of 2W/mK on the c direction of principal axis, and reason is that its particle configuration has schistose texture.Therefore, this kind filling agent is not to be filled in to heavens in the basal body structure of intermediate transfer belt.Draw by these results, use therein among the embodiment of spherical alumina, and under the situation of using needle-like or tabular alumina, compare, obtained higher thermal diffusivity relatively.
Using thermal conductivity to be 75W/mK, and resistivity is 10
0Under the situation of the embodiment 18 of the filling agent of Ω cm, specific insulation sharply drops to about 2.56 * 10
4Ω cm.In addition, be 10 using resistivity
1Ω cm, and thermal conductivity is that thermal conductivity significantly drops to about 4.53W/mK under the situation of embodiment 19 of filling agent of 12W/mK.These situations all are considered to not be suitable for intermediate transfer belt.
Under the situation of adding conductive filler, specific insulation shows 10
8～10
13In the scope of Ω cm, thereby be regarded as being suitable for the intermediate transfer belt of laser printer, facsimile recorder and duplicating machine.Yet, not adding therein under the situation of embodiment 13 of conductive filler, specific insulation significantly increases, so variation such as antistatic behaviour, transfer printing, imaging performance, release property and stain resistance, thereby causes image deflects.
[industrial usability]
As mentioned above, the invention provides a kind of intermediate transfer belt and manufacture method thereof.According to the present invention, a kind of individual layer intermediate transfer belt that uses polysiloxane-modified polyimide resin can be provided, thereby make it possible to achieve a kind of thermal diffusivity, electrical property and water proofing property with excellence, and the intermediate transfer belt of excellent mechanical intensity.
In addition, even be not formed for being adhered to the adhesive phase of fluororesin layer and fluororesin in addition, this intermediate transfer belt also can show satisfactory performance.In addition, can provide a kind of and have the method for the intermediate transfer belt of excellent thermal diffusivity, electrical property and water proofing property, therefore make the working (machining) efficiency maximization with efficient mode manufacturing.
Although for the illustrative purpose discloses the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that under the situation that does not depart from disclosed scope and spirit of the present invention in appended claim, various changes, interpolation and replacement are fine.
Claims (19)
1. intermediate transfer belt, it comprises polysiloxane-modified polyimide resin, and wherein said polysiloxane-modified polyimide resin is to comprise dianhydride, the multipolymer of diamines and silicone resin.
2. intermediate transfer belt according to claim 1, it also comprises thermal conductivity is more than the 20W/mK and resistivity is 10
1The heat conduction filling agent that Ω cm is above.
3. intermediate transfer belt according to claim 2, wherein said heat conduction filling agent are that particle diameter is the sphere-packing agent of 0.2～20 μ m.
4. intermediate transfer belt according to claim 3, wherein said sphere-packing agent comprises with 6～7: 4～3 ratio mixes, and is of a size of first particle and second particle that is of a size of 0.2～5 μ m of 5～20 μ m.
5. intermediate transfer belt according to claim 2 is wherein being that the amount of 0.01～30 weight % comprises described heat conduction filling agent based on the solute total amount.
6. intermediate transfer belt according to claim 2, wherein said heat conduction filling agent comprises and is selected from a kind of in following or two or more potpourris: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, silicon dioxide, aluminium oxide, aluminium borate, silit, titanium carbide, boron carbide, silicon nitride, boron nitride, aluminium nitride, titanium nitride, mica, potassium titanate, metatitanic acid beryllium, lime carbonate, magnesium oxide, zirconia, tin oxide, beryllia, aluminium oxide and aluminium hydroxide.
7. intermediate transfer belt according to claim 2, it has the thermal conductivity of 5.1～7.4W/mK.
8. intermediate transfer belt according to claim 1 and 2, it also comprises conductive filler.
9. intermediate transfer belt according to claim 1, it has 10
8～10
13The specific insulation of Ω cm.
10. intermediate transfer belt according to claim 1, it has 105 °～113 ° contact angle, and described contact angle refers to the thermodynamic equilibrium angle that liquid contacts on solid surface, and is to estimate by the section of the set drop on the solid surface.
11. intermediate transfer belt according to claim 1, it has the elastic modulus of 0.8～4.5GPa.
12. intermediate transfer belt according to claim 1, wherein said polyorganosiloxane resin has 600 to 2,000 number-average molecular weight.
13. intermediate transfer belt according to claim 1 is that the amount of 10～30 weight % comprises described polyorganosiloxane resin with the amount based on described diamines wherein.
14. intermediate transfer belt according to claim 1, wherein said polyorganosiloxane resin comprise and are selected from dimethyl silicone polymer, poly-diphenyl siloxane and as a kind of, the perhaps two or more potpourri in their PSI of multipolymer.
15. a method of making intermediate transfer belt, described method comprises:
Dianhydride, diamines and polyorganosiloxane resin are dissolved in the aprotic solvent of high polarity, thereby prepare polysiloxane-modified polyamic acid solution; And
Described polysiloxane-modified polyamic acid solution is loaded in the mould, afterwards with its thermal treatment to induce imidizate.
16. method according to claim 15, wherein when the described polysiloxane-modified polyamic acid solution of preparation, also comprising thermal conductivity and be the above and resistivity of 20W/mK is 10
1The heat conduction filling agent that Ω cm is above.
17. method according to claim 15, wherein said mould are the cylindrical dies with the dual structure that is made of out cylinder and inner cylinder.
18. method according to claim 15 wherein when the described polysiloxane-modified polyamic acid solution of preparation, also comprises conductive filler.
19. method according to claim 15 wherein induces the described thermal treatment of described imidizate to carry out at 60～400 ℃.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060000320A KR100739403B1 (en) | 2006-01-03 | 2006-01-03 | Intermediate transfer belt and manufacturing method thereof |
| KR1020060000320 | 2006-01-03 | ||
| KR10-2006-0000320 | 2006-01-03 | ||
| KR10-2006-0100286 | 2006-10-16 | ||
| KR1020060100286A KR101213908B1 (en) | 2006-10-16 | 2006-10-16 | Intermediate transfer belt and manufacturing method thereof |
| KR1020060100286 | 2006-10-16 | ||
| PCT/KR2007/000018 WO2007078140A1 (en) | 2006-01-03 | 2007-01-03 | Intermediate transfer belt and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101365990A CN101365990A (en) | 2009-02-11 |
| CN101365990B true CN101365990B (en) | 2011-09-21 |
Family
ID=38507623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800018639A Expired - Fee Related CN101365990B (en) | 2006-01-03 | 2007-01-03 | Intermediate transfer belt and manufacturing method thereof |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100739403B1 (en) |
| CN (1) | CN101365990B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101453085B1 (en) * | 2007-11-23 | 2014-10-28 | 코오롱인더스트리 주식회사 | Polyimide resin and film |
| KR101157321B1 (en) * | 2008-03-06 | 2012-06-15 | 코오롱인더스트리 주식회사 | Intermediate transfer belt and manufacturing method thereof |
| CN102004421B (en) * | 2009-08-26 | 2013-05-15 | 株式会社理光 | Intermediate transfer method for electronic camera, intermediate transfer system, image forming method and its device |
| KR101376438B1 (en) * | 2009-09-24 | 2014-03-20 | 코오롱인더스트리 주식회사 | Seamless belt and preparation method thereof |
| US8543031B2 (en) * | 2010-12-02 | 2013-09-24 | Xerox Corporation | Intermediate transfer member reconditioning |
| CN106566462A (en) * | 2015-10-09 | 2017-04-19 | 北京化工大学 | Preparation method for high temperature resistant polyimide adhesive |
| CN107189436B (en) * | 2017-07-20 | 2019-12-27 | 中国科学院长春应用化学研究所 | Polyimide nano foam and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042168A (en) * | 1988-09-26 | 1990-05-16 | M&T化学有限公司 | Polyimide film die attach adhesives |
| CN1363860A (en) * | 2001-01-05 | 2002-08-14 | 佳能株式会社 | Procedure for producing trip transferrer, trip transferrer and imaging apparatus |
| CN1388419A (en) * | 2001-05-28 | 2003-01-01 | 佳能株式会社 | Processing box, electric photographic apparatus and imaging method |
| CN1530761A (en) * | 2002-10-31 | 2004-09-22 | ���ǵ�����ʽ���� | Image transferring belt on polymer film with polymer coating on electric conductive substrate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940009420B1 (en) * | 1990-12-31 | 1994-10-13 | 고려화학주식회사 | Process for preparation of modified silicone polyimide resin and composition with thereof |
| US5732310A (en) | 1995-04-21 | 1998-03-24 | Canon Kabushiki Kaisha | Image forming apparatus having cleaning device for cleaning intermediate transfer member |
-
2006
- 2006-01-03 KR KR1020060000320A patent/KR100739403B1/en active IP Right Grant
-
2007
- 2007-01-03 CN CN2007800018639A patent/CN101365990B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042168A (en) * | 1988-09-26 | 1990-05-16 | M&T化学有限公司 | Polyimide film die attach adhesives |
| CN1363860A (en) * | 2001-01-05 | 2002-08-14 | 佳能株式会社 | Procedure for producing trip transferrer, trip transferrer and imaging apparatus |
| CN1388419A (en) * | 2001-05-28 | 2003-01-01 | 佳能株式会社 | Processing box, electric photographic apparatus and imaging method |
| CN1530761A (en) * | 2002-10-31 | 2004-09-22 | ���ǵ�����ʽ���� | Image transferring belt on polymer film with polymer coating on electric conductive substrate |
Non-Patent Citations (1)
| Title |
|---|
| CN 1388419 A,说明书第9也第5-25行。. |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070072943A (en) | 2007-07-10 |
| KR100739403B1 (en) | 2007-07-16 |
| CN101365990A (en) | 2009-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101365990B (en) | Intermediate transfer belt and manufacturing method thereof | |
| JP4571218B2 (en) | Intermediate transfer belt and manufacturing method thereof | |
| EP2072581B1 (en) | Polyimide tube, method for production thereof, method for production of polyimide varnish, and fixing belt | |
| TW200307000A (en) | Thermally conductive formed article and method of manufacturing the same | |
| JP6253328B2 (en) | Thermally conductive resin composition and thermal conductive sheet using the same | |
| EP2754683A1 (en) | Composition of aqueous polyimide precursor solution and method for producing composition of aqueous polyimide precursor solution | |
| CN107433757B (en) | Endless belt comprising boron nitride nanotubes | |
| US6760214B2 (en) | Electrostatic chuck for ion injector | |
| KR20200084806A (en) | Method for manufacturing heat dissipation sheet | |
| Haruki et al. | Controlling thermal conductivities and electrical insulation properties of carbon nanofiber/polyimide composites using surface coating techniques | |
| WO2022153931A1 (en) | Method for producing liquid composition and composition | |
| EP3467328A1 (en) | Sliding structure and method for producing same | |
| WO2022045237A1 (en) | Liquid composition and base material with protrusions | |
| US20220404751A1 (en) | Electrophotographic belt, electrophotographic image forming apparatus, fixing device, and varnish | |
| CN116063676A (en) | Polyimide film | |
| KR101213908B1 (en) | Intermediate transfer belt and manufacturing method thereof | |
| KR20030026352A (en) | Polyimide resin composition and polyimide product formed into film and intermediate transfer belt comprising the same | |
| JP5209685B2 (en) | Seamless belt and manufacturing method thereof | |
| JP2022100950A (en) | Thermally conductive sheet and method for producing the same | |
| JP7354577B2 (en) | Thermoelectric conversion members, thermoelectric conversion elements, and thermoelectric conversion devices | |
| JP2001040102A (en) | Tubular article | |
| JP2001215821A (en) | Fixing belt and method of producing the same | |
| JP2006301196A (en) | Seamless belt | |
| WO2023189699A1 (en) | Thermally conductive silicone composition | |
| KR101210030B1 (en) | Intermediate transfer belt and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110921 Termination date: 20200103 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |