Patent Application
20130052450
The present invention relates to a polymer porous film, which is used for a heat insulating material, a lightweight structural material, an adsorbing material, a sound absorbing material, a catalyst carrier, or the like and a method of producing the same.
A polymer porous film is produced in a combination of various polymer raw materials and porosification technologies. The polymer porous film exhibits a characteristic function depending on its porosity size, porosity ratio, surface properties, and the like. For example, foamed bodies such as foamed polystyrene and foamed polyurethane are used as a lightweight structural material, a heat insulating material, a buffer material, and the like in a wide range of fields such as houses, automobiles, and household appliances. Further, porous films having a finer porosity size from nanometer to micrometer are also used as separation membranes, permeable membranes, the separators for secondary cells, hemodialysis membranes, or the like. Technological fields to which such porous film is applied are expanding year by year. For example, Japanese Patent Application Laid-Open No. 2008-071579 proposes a gas-selective permeable film characterized in that its porosity size shows a gradient change.
Recently, porous films are also developed particularly with respect to the so-called engineering plastics such as polymeric materials having heat resistance exceeding 200° C. Making use of properties such as high mechanical properties and chemical resistance, instances of application of such material are increasing even under a chemically or physically high load environment such as the aerospace industry or transportation vehicles. A porous film using such highly heat-resistant resin can be used with increased heat insulating property by increasing its porosity ratio to some extent, and hence evolution into various applications is under consideration, such as highly durability, heat-resistant filters, low-k films (low dielectric films) for electronic component substrates, and heat insulating materials of aerospace rockets.
In the printing field as well, such as electrophotography and printers, there are many environments having exposed to a large amount of a solvent under high temperature and high pressure, for example, a transfer and fixation portion for toner and discharge portions of dye in image forming apparatuses. In order to achieve a new printing system by enhancing functions of materials (such as an intermediate transfer belt, an organic photosensitive member, a roller, and an ink head) for forming those portions, it is required to use materials capable of withstanding the above-mentioned environments. Even at present, polyimides are usually used in an intermediate transfer belt of an electrophotographic apparatus.
As described above, in order to enhance the functions of materials, porosification of a resin is a very effective method. In order to develop a new printing mode that achieves, for example, energy saving, high speed, or high image quality by applying a porosified material to the printing field, it is very important to use an optimal material for the system by appropriately designing, for example, a porosity size, a foam structure, a porosity ratio, and uniformity of porosity sizes in a film thickness direction depending on a function desired to be exhibited. The term “foam structure” means, for example, an independent foam structure or a continuous foam structure.
For example, Japanese Patent Application Laid-Open No. 2006-133704 proposes inhibiting an increase in the surface temperature of a photosensitive member by providing a porous layer in a belt material serving as both an intermediate transfer member and a fixing member.
However, a porous film has an airspace in the film, and hence its mechanical strength is liable to deteriorate. Accordingly, even though a porous film has excellent functions such as high heat insulating property, a low dielectric constant, and high adsorptive property, mechanical durability, impact resistance, and the like can hardly be compatible therewith. Therefore, members and applications to which the porous film is applicable are generally limited. For example, in the porous film in which porosity sizes show a gradient change proposed in Japanese Patent Application Laid-Open No. 2008-071579, mechanical strength is inhibited from deteriorating because the film is selectively permeable to gas and its porosity sizes are each close to the mean free path of gas. However, when the film is used as a heat insulating material, the film can exhibit heat insulating property that is only comparable to that of a nonporous film because of its extremely small porosity sizes. Further, the disclosed production method for the porous film is based on drying of a solvent, and hence the porous film is difficult to produce with its porosity sizes controlled so as to be gradient particularly when a high-boiling solvent is used. In addition, with the production method, there is a problem in that production of a structure of gradient porosity sizes from both surfaces as starting points is extremely difficult.
Further, there has also been proposed a film obtained by attaching films different in porosity size together so that porosity sizes show a gradient change. However, such film generates, with the origins at the attached portions, deterioration of the mechanical strength of the film and discontinuity in the porosity function of the film. Further, in the porous film produced by the method for porosification described in Japanese Patent Application Laid-Open No. 2006-133704, porosity morphology is not controlled, and hence the film has a macrovoid or a continuous porosity. Accordingly, the porous film is poor in mechanical strength and has no resistance against deformation or compression. As a result, the material deteriorates during printing. Therefore, it is difficult to use the porous film as a belt material for mass printing or high-speed printing.
PTL 1]Japanese Patent Application Laid-Open No. 2008-071579
PTL 2]Japanese Patent Application Laid-Open No. 2006-133704
In view of the foregoing, the present invention aims to solve the above-mentioned problems. That is, an object of the present invention is to provide a porous material excellent in heat insulating property, mechanical properties, and surface properties (such as adhesiveness and abrasion property) through the control of the functions of a porous film by setting the porosity sizes and porosity size distribution, and porosity ratio of the porous film within predetermined ranges. Another object of the present invention is to provide a method of producing the porous film, which can be used for a wide range of applications, including the case of using a high-boiling solvent, through efficient removal of a solvent via a solid-liquid interface in the production of the porous film. The use of the porous material for an electrophotographic material, in particular, an electrophotographic belt member allows the inhibition of thermal diffusion from toner to provide an electricity-saving and/or high-speed-printing image fixing apparatus.
Provided is a polymer porous film of a single layer, including a first porosity size changing portion formed of independent porosities each showing a gradual increase in porosity size across a region accounting for 10% or more of a film thickness from a first surface side toward a second surface side.
The present invention can provide the polymer porous film excellent in heat insulating property, mechanical properties, and surface properties, and the like through the control of the porosity sizes of porosities each formed of an independent foam structure so as to show a gradient change from the film surface in the porous structure of a resin composition formed of an engineering plastic, and the method of producing the polymer porous film. In particular, when the porous film has a porosity having the minimal porosity size in at least one film surface, there can be provided a material having excellent mechanical durability against external pressure, impact, and the like while maintaining heat insulating property and the like. Further, when the material of the present invention is used as an electrophotographic functional member, such an effect that heat insulating property, mechanical properties, and the like are asymmetric between both surfaces of the film can be exhibited. As a result, the image fixing apparatus capable of electricity saving, high-speed printing or mass printing can be provided.
Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings.
In order to describe the present invention in detail, modes for carrying out the invention are hereinafter illustrated with reference to the drawings. It should be noted that separately disclosed embodiments are each an example in which a resin composition as the present invention, a laminated film including the resin composition, or an image forming apparatus using the laminated film as a component is actually used, and the technical scope of the present invention is not limited thereto.
The structure of a porous film of the present invention is described based on
As illustrated in
As illustrated in
The term “porosity size changing portion” means a portion where porosity sizes show a gradual increase or decrease along the film thickness direction. As described later, the phrase “show a gradual increase or decrease” is not limited to the case where porosity sizes change as a linear function along the film thickness direction.
The resin composition in this embodiment is formed of a single polymer layer and is formed of a porous structure in which porosity sizes show a gradient change across a region accounting for 10% or more of a film thickness from one or both surfaces toward the inner side of the film. Alternatively, the resin composition in this embodiment is formed of a single polymer layer and is formed of a porous structure which has a nonporous portion made of a polymeric material across a region accounting for 10% or more of the film thickness from one or both surfaces toward the inner side of the film and in which porosity sizes show a gradient change from one nonporous portion toward the other nonporous portion or toward the opposite surface. The structure in which porosity sizes show a gradient change in this embodiment means a structure which has a minimal porosity size or a nonporous portion in at least one film surface portion and in which porosity sizes show a gradient increase toward the inner side of the film, in porosity arrangement in the film thickness direction. In view of the foregoing, at least the following five modes are included in this embodiment:
1) a mode in which porosity sizes show an increase from one surface to the other surface (see
2) a mode in which porosity sizes show a gradient increase from one surface toward the film thickness direction to a certain depth and show a gradient decrease from a certain depth to the other surface (see
3) a mode in which porosity sizes show a continuous increase (meaning the same as “show a gradient increase”) from one surface toward the film thickness direction to a certain depth and a nonporous portion of a polymeric material is formed from a certain depth to the other surface (see
4) a mode in which nonporous portions of a polymeric material are formed from both surfaces to a certain depth and porosity sizes show a gradient increase from one nonporous portion toward the other nonporous portion (see
5) a mode in which nonporous portions of a polymeric material are formed from both surfaces to a certain depth and porosity sizes show a gradient increase from one nonporous portion toward the other nonporous portion to a certain depth and show a gradient decrease from a certain depth (see
Here, the phrase “show a gradient change” or “show a gradual increase” in porosity size mainly means that the porosity sizes show a linear and continuous increase or decrease. However, the porosity sizes may show a hyperbolic change, an exponential change, or the like. Further, the term “single layer” refers to a single film produced by one process without, for example, attaching two or more kinds of films. Further, the term “nonporous portion” refers to a portion formed of a homogeneous polymeric material having no porosity.
The gradient porosity sizes allow different functions related to porosity, such as heat insulating property, specific gravity, and dielectric constant, between the surface and the inside of a film, or between both surfaces. Further, it is possible to provide, for example, a film having improved mechanical properties while having an equivalent function related to porosity, such as heat insulating property, to a porous film formed of a uniform porosity size.
Any one of the portion in which porosity sizes show a linear increase from the surface portion and the nonporous portion is preferably formed across a region accounting for 10% or more of the film thickness. When the ratio is less than 10%, the mechanical strength of the surface portion is insufficient, resulting in a lack of resistance against external pressure, physical stimulation, and the like.
Further, the porous structure in this embodiment is formed of independent porosities in which airspaces are separated by curved resin walls. In the independent porosities, individual porosities are each independent and a resin wall is provided between porosities. Accordingly, as compared to continuous porosities, not only the elastic modulus of the resin, but also the resin composition as a whole is expected to exhibit a high elastic modulus because of the effect of air pressure in the porosities. Further, the independent porosities can reduce migration of impurities generated in an image forming process or the like from a first porosity to an adjacent second porosity. As a result, the appearance of material deterioration and a change in physical property can be inhibited. In addition, even when a bonding material is laminated, a laminated material can be inhibited from entering the inside of the film. Further, in the porous structure of this embodiment, independent porosities account for 80% or more of all porosities. Here, the term “independent porosity” refers to one in which a resin wall existing between adjacent first and second porosities has no holes therein.
The porosity sizes of the resin composition in this embodiment are each appropriately selected from the range of 0.1 μm or more and 10 μm or less. From the view point of heat insulating property, when a porosity size is equal to or less than a mean free path (65 nm for air), air contained in the porosity is reduced in thermal conductivity, and the inside can be regarded as a vacuum. On the other hand, however, when a porosity size is less than 0.1 μm, the configuration of the resin composition is similar to that of a nonporous film, and hence heat propagation by heat conduction via resin walls of porous portion increases. Accordingly, the resin composition as a whole is caused to increase in thermal conductivity. As a result, it is difficult to use the resin composition as a heat insulating material. Further, the porous structure of the resin composition of the present invention is a structure free of a macrovoid having a porosity size of more than 10 μm. When a macrovoid exists, the material is liable to deteriorate upon an external physical change such as compression or tension. Here, the term “macrovoid” refers to a nonuniform porosity having a porosity size of more than 10 μm and an unspecified structure. A method of measuring a porosity size in this embodiment is not particularly limited, and a conventional measuring method such as a mercury intrusion method or image analysis after an SEM observation may be used. A minimal porosity size and a maximal porosity size can each be calculated from the vicinity of a starting or terminal portion of a gradient change in porosity size by subjecting an SEM observation photograph of a film cross-section to image analysis. The porosity ratio of the resin composition of the present invention preferably falls within the range of 5% or more and 90% or less, particularly 20% or more and 60% or less. Here, the term “porosity ratio” is defined as a ratio of the volume of the porosities to the volume of the film. When the porosity ratio is excessively low, a reduction in thermal conductivity is inhibited, and hence heat insulating property cannot be exhibited. Further, when the porosity ratio is excessively high, the film is poor in mechanical strength, and hence it is difficult to use the film as an electrophotographic functional member or the like. A method of measuring the porosity ratio in this embodiment is not particularly limited. For example, the porosity ratio may be calculated by a density measuring method.
A highly heat-resistant polymer to be used for the present invention is a functional resin having an upper temperature limit of 110° C. or more, i.e., the so-called engineering plastic kind. Here, the term “upper temperature limit” refers to a temperature up to which a resin can be used continuously without causing deformation, deterioration, or the like, and, for example, refers to a glass transition temperature.
The engineering plastic to be used for the present invention is formed of a resin composition formed of a resin selected from the group consisting of polycarbonate, polyimide, polyamide-imide, polyamide, polyetherimide, polysulfone, and polyethersulfone or a resin combined thereof. Those resin compositions are each a material excellent in heat resistance, mechanical properties, solvent resistance, and the like.
The inventors of the present invention have studied the optimal configuration for the case of using such material as a transfer member or a fixing belt member of an electrophotographic image forming apparatus. As a result, the inventors have found that the porous structure of the present invention can inhibit material deterioration and a change in physical property even when exposed to a heating or chemical environment, and moreover, the use of a porous film in which porosity sizes show a gradient change provides high mechanical strength even when the porosity ratio is set to a high value in order to improve heat insulating property.
Hereinafter, a method of producing the resin composition in the present invention is described in detail.
The resin composition is preferably produced using a phase separation method. A solution (resin solution) of a resin such as polycarbonate serving as a raw material is molded, and then the resultant is immersed in a coagulating solvent, thereby performing porosification. The shape into which the resin solution is molded may appropriately be selected. The molding is preferably performed by a method involving cast molding into a film shape. In addition, the cast film is immersed in the coagulating solvent in a state in which the solvent in the cast film is positively provided with a concentration gradient by covering the cast film with a predetermined covering sheet before the immersion in the coagulating solvent as described later. The immersion causes a change (phase transition) in the state of the film. The method is called the phase separation method. Here, the term “phase transition” refers to a phenomenon in which a resin precipitates as a solid through the immersion of a solution system in a coagulating solvent (poor solvent).
During the production of a porous film by the above-mentioned method, the resin solution preferably has a viscosity of 10,000 cP or less, more preferably 5,000 cP or less. As described later, when the resin has a high viscosity, the solvent in the resin solution cannot migrate to the covering sheet promptly, and hence a gradient in solvent concentration is not formed in the cast film of the resin solution. As a result, a structure of gradient porosity sizes cannot be produced.
In order that the porous film in which porosity sizes show a gradient change in the film thickness direction in the present invention may be produced, solvent concentration in the cast film is required to be made gradient along the thickness direction of the cast film before the cast film is immersed in the coagulating solvent. This is because the phase separation due to the gradient solvent concentration is believed to result in a gradient change in porosity size.
In the present invention, in order to achieve the above-mentioned phase separation state, the porous film is produced by a method involving immersing the cast film in a coagulating solvent while covered with a predetermined sheet.
Here, the predetermined sheet is one having an affinity to the solvent in the cast film and having such property that the solvent is efficiently removed from the cast film by saturating or dissolving the sheet in the solvent. Specific examples of such material include cellulose, nitrocellulose, and cellulose acetate, but are not limited thereto. The sheet has only to have an affinity to the resin solvent. Such a sheet that an SP value difference between the sheet and the resin solvent falls within the range of ±3 is particularly suitably used. Absorption via a solid-liquid interface through contact with the sheet unlike the evaporation of the solvent, which is via a gas-liquid interface, is carried out, and hence a concentration change of the solvent can be effectively formed. Further, a gradient structure can be produced generally even for a high-boiling solvent such as NMP.
A linear change in porosity size can be controlled by changing the film thickness or a covering time of the sheet. A portion having a low solvent concentration results in having small porosity sizes, which is close to a nonporous film. On the other hand, a portion having a high solvent concentration results in having large porosity sizes. Accordingly, porosity sizes can be appropriately changed by changing the film thickness and the covering time of the sheet, thereby controlling the capability of removing the solvent. On the other hand, as described above, when the resin solution has a high viscosity, migration of the solvent to the sheet is remarkably inhibited, and hence a porous film having porosity sizes showing a gradient change cannot be produced.
Here, a sheet having a film thickness of 5 μm to 500 μm, suitably 100 μm to 300 μm is used. When the film thickness is excessively small, effective removal of a solvent cannot be achieved. On the other hand, when the film thickness is excessively large, the surface of the cast film is roughened upon covering. The covering time may be appropriately adjusted between 10 seconds to 60 minutes.
In the present invention, the cast film is produced on the above-mentioned sheet having an ability to remove a solvent, and then a sheet may be further covered on a surface of the cast film to produce a porous film. In this case, a porous film in which porosity sizes show a gradient change from both surfaces toward the inner side of the film can be produced. The case allows the production of various gradient structures through the provision of differences in, for example, covering time and film thickness of the sheet between both surfaces.
Examples of the coagulating solvent include water, alcohols (such as methanol, ethanol, and propanol), hydrocarbons (such as hexane, cyclohexane, and heptane), ketones (such as acetone, butanone, and 2-butanone), and esters (such as ethyl acetate). Water is suitably used in terms of ease of handling and cost.
After having been immersed in the coagulating solvent for a given time, a precipitated film is taken out and the sheet is peeled off. After that, the film is fixed with a pin, a chuck, a pinch roll, a pin tenter, or the like so as to prevent heat shrinkage. The film is then subjected to heat treatment to remove the remaining solvent. Thus, a polymer porous film can be obtained.
In the porous film thus obtained, porosity sizes show a linear change from a film surface toward the inner side of the film. A surface that has been covered with a sheet has a large removal ratio of the solvent and a low solvent concentration. Accordingly, the resultant porosity sizes are the smallest ones, and in some cases, a uniform film of a polymeric material is obtained. On the other hand, a portion at a certain depth from the film surface has a small removal ratio of the solvent compared to the surface, and hence, has a high solvent concentration, resulting in increased porosity sizes. When the sheet is covered on only one surface, the other surface, which is not covered with the sheet, eventually has the largest porosity sizes. Meanwhile, when the sheet is covered on both surfaces, an inner portion positioned at a certain depth from each of the surfaces eventually has the largest porosity sizes.
The application and shape of the resin composition of the present invention may be appropriately selected depending on its function. For example, a polyimide resin composition has high heat resistance, low dielectric constant, chemical resistance, and high mechanical strength, and hence may be used as an electrolyte film of a fuel battery or a support substrate for an electronic material as well as for a heat resistant filter, a lightweight member for an automobile, or the like. Particularly when the resin composition is used for an electrophotographic fixing member or the like as a heat insulating member, a belt shape is preferred. It should be noted that the resin composition may also be formed into a cylindrical shape or a cylinder shape to be used as it is as a fixing roller.
For example, the resin composition may be used in an image fixing apparatus having a simultaneous transfer and fixing system (hereinafter, also simply referred to as “fixing system”) as illustrated in
The apparatus illustrated in
Other than the above-mentioned application, the porous film in the present invention is applicable not only to a belt material but also to resin members in general, such as an organic photosensitive member and a frame in the electrophotographic field.
Further, outside the electrophotographic field, the porous film can also be used as a low dielectric material having high mechanical strength in a covering material for an electronic component or an electric wire, or the like, as well as a lightweight material or a heat insulating material in a structural member for a transport vehicle or the aerospace industry or in a construction material. The porous film is potentially applicable to processing components in general each of which uses a heat resistant resin.
Further, the porous film has a region where independent porosities account for 80% or more of all porosities, and hence permeation of fluid (gas or liquid) in the film can substantially be blocked. That is, from a first surface side toward a second surface side of the film, suitable heat insulating property can be provided while blocking off gas or liquid. This creates an expectation of new applications different from those of conventional permeable films, such as a sheath material capable of holding fluid without a leakage while insulating heat.
Hereinafter, the present invention is described in detail by way of examples. However, the present invention is not limited to these examples.
Porosity size distribution (size distribution and number distribution of fine porosity sizes) and a ratio of independent porosities were calculated with an image processing system (LUZEX AP, manufactured by Nireco Corporation) from an image obtained by observing a cross-section of a polymer porous film with a scanning electron microscope (SEM). A minimal porosity size and a maximal porosity size were each able to be analytically calculated from the vicinity or the like of the starting or terminal portion of a gradient change in porosity size by subjecting an SEM observation photograph of the film cross-section to image analysis.
A porosity ratio was calculated according to the following equation after measuring the film thickness and weight of a porous film cut into a 3 cm square. S represents the area of the porous film, d represents the film thickness, w represents the weight of the porous film, and D represents the density of a nonporous resin.
Porosity ratio (%)=100-100×w/(D×S×d)
A thermal conductivity was calculated by multiplying a thermal diffusivity measured with a thermal diffusivity measuring system (FTC-1, manufactured by ULVAC-RIKO, Inc.) by a separately determined density and specific heat.
As for each of a polyimide resin and a polyamide-imide resin, compression resistance was calculated from a film thickness change rate before and after compression performed with a high precision hot press (manufactured by TESTER SANGYO CO., LTD.) under conditions of a pressure of 7 kgf/cm2, a compression temperature of 170° C., and a compression time of 4 hours. Further, as for a polycarbonate resin, compression resistance was calculated from a film thickness change rate before and after compression performed with a high precision hot press (TESTER SANGYO CO., LTD.) under conditions of a pressure of 7 kgf/cm2, a treatment temperature of 70° C., and a compression time of 4 hours.
Measurement of a viscosity was performed with a cone-plate rheometer Physica MCR-300 (manufactured by Anton Paar GmbH).
Polycarbonate (Z200, manufactured by Mitsubishi Gas Chemical Company, Inc) was dissolved in N-methylpyrrolidone (NMP) to prepare an 18 wt % solution. The solution had a viscosity of 300 cP. A polyester material (manufactured by Teijin Limited) was prepared as a substrate, and an application bar was used to make a cast film of the above-mentioned polycarbonate solution. The cast film was covered with a sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate and left to stand still for 200 seconds. After that, the cast film was immersed in distilled water while covered with the sheet and left to stand for 10 minutes. The substrate was taken out of water, the sheet was peeled off, and the resultant film was washed with distilled water.
Water remaining on the film was wiped off, the film was placed in a drying oven, and dried at a temperature of 80° C. for 1 hour. The resultant film had a film thickness of 60 μm.
An N-methylpyrrolidone (NMP) solution of polyamic acid serving as a polyimide precursor (trade name: U-varnish A, manufactured by Ube Industries, Ltd.) having a resin concentration of 10 wt % was prepared. In this case, the solution had a viscosity of 950 cP. A polyimide material (trade name: Kapton, manufactured by Du Pont-Toray Co., Ltd.) having a thickness of 120 μm was prepared as a substrate, and an application bar was used to cast the above-mentioned polyamic acid varnish on the substrate. After that, the cast film was covered with a sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate and left to stand still for 300 seconds. After that, the cast film was immersed in distilled water while covered with the sheet and left to stand for 10 minutes. The substrate was taken out of water, the sheet was peeled off, and the resultant film was washed with distilled water.
Water remaining on the film was wiped off, and the film was placed in a drying oven. The film was dried at a temperature of 80° C. for 1 hour. After that, the temperature was raised to 150° C. at a rate of 10° C./minute. The film was heated at the temperature of 150° C. for 30 minutes. After that, the temperature was raised to 250° C. at a rate of 10° C./minute. The film was heated at the temperature of 250° C. for 10 minutes. After that, the temperature was raised to 350° C. at a rate of 10° C./minute. The film was heated at the temperature of 350° C. for 10 minutes. Thus a polyimide resin composition was produced.
Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 0.28 μm and 3.4 μm, respectively. Further, the porosity ratio was 52%, and the resultant film had a film thickness of 60 μm. 84% of all porosities were independent porosities. From one surface toward the other surface, porosity sizes showed a linear, gradient change across the entire layer of the film.
An N-methylpyrrolidone solution of polyamide-imide (HL-1210, manufactured by Hitachi Chemical Co., Ltd.) was prepared. The resin concentration was set to 10 wt %. In this case, the resin viscosity was 880 cP. A polyimide material (trade name: Kapton, manufactured by Du Pont-Toray Co., Ltd.) was prepared as a substrate, and an application bar was used to make a cast film of the above-mentioned polyamide-imide solution. After that, the cast film was covered with a sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate and left to stand still for 300 seconds. After that, the cast film was immersed in distilled water while covered with the sheet and left to stand for 10 minutes. The substrate was taken out of water, the sheet was peeled off, and the resultant film was washed with distilled water.
Water remaining on the film was wiped off, and the film was placed in a drying oven. The film was dried at a temperature of 80° C. for 1 hour. After that, the temperature was raised to 150° C. at a rate of 10° C./minute. The film was heated at the temperature of 150° C. for 30 minutes. After that, the temperature was raised to 250° C. at a rate of 10° C./minute. The film was heated at the temperature of 250° C. for 10 minutes. Thus a polyamide-imide resin composition was produced.
Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 0.22 μm and 3.2 μm, respectively. Further, the porosity ratio was 53%, and the resultant film had a film thickness of 50 μm. 83% of all porosities were independent porosities. From one surface toward the other surface, porosity sizes showed a linear, gradient change across the entire layer of the film.
A polycarbonate porous film was produced in the same way as in Example 1 except that the cast film was covered with the sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate and then left to stand still for 600 seconds.
Examination of the porosity morphology of the resultant film revealed that a uniform layer of a polymeric material having a thickness of 8 μm was contained in the layer and the maximal porosity size was 6.1 μm. Further, the porosity ratio was 38%, and the resultant film had a film thickness of 35 μm.
A polyimide porous film was produced in the same way as in Example 2 except that the cast film was covered with the sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate and then left to stand still for 700 seconds.
Examination of the porosity morphology of the resultant film revealed that a uniform layer of a polymeric material having a thickness of 7 μm was contained in the layer and the maximal porosity size was 7.7 μm. Further, the porosity ratio was 41%, and the resultant film had a film thickness of 35 μm. 86% of all porosities were independent porosities. From a nonporous portion toward the other surface, porosity sizes showed a linear, gradient change.
Polycarbonate (Z200, manufactured by Mitsubishi Gas Chemical Company, Inc.) was dissolved in N-methylpyrrolidone (NMP) to prepare a 20 wt % solution. The solution had a viscosity of 320 cP. A sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate was used as a substrate, and an application bar was used to make a cast film of the above-mentioned polycarbonate solution. 20 seconds later, the cast film was covered with a sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate and left to stand still for 200 seconds. After that, the cast film was immersed in distilled water while covered on both sides with the sheets and left to stand for 10 minutes. The substrate was taken out of water, the sheets were peeled off, and the resultant film was washed with distilled water.
Water remaining on the film was wiped off, the film was placed in a drying oven, and dried at a temperature of 80° C. for 1 hour. Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 0.23 μm and 3.5 μm, respectively. Further, the porosity ratio was 49%, and the resultant film had a film thickness of 90 μm.
An N-methylpyrrolidone (NMP) solution of polyamic acid serving as a polyimide precursor (trade name: U-varnish A, manufactured by Ube Industries, Ltd.) having a resin concentration of 10 wt % was prepared. In this case, the solution had a viscosity of 900 cP. A sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate was used as a substrate, and an application bar was used to cast the above-mentioned polyamic acid varnish on the substrate. 20 seconds later, the cast film was covered with a sheet (GSWP14250, Nihon Millipore K. K., 150 μm thick) made of cellulose nitrate and left to stand still for 300 seconds. After that, the cast film was immersed in distilled water while covered with the sheets and left to stand for 10 minutes. The substrate was taken out of water, the sheets were peeled off, and the resultant film was washed with distilled water.
Water remaining on the film was wiped off, and the film was placed in a drying oven. The film was dried at a temperature of 80° C. for 1 hour. After that, the temperature was raised to 150° C. at a rate of 10°0 C./minute. The film was heated at the temperature of 150° C. for 30 minutes. After that, the temperature was raised to 250° C. at a rate of 10°0 C./minute. The film was heated at the temperature of 250° C. for 10 minutes. After that, the temperature was raised to 350° C. at a rate of 10°0 C./minute. The film was heated at the temperature of 350° C. for 10 minutes. Thus a polyimide resin composition was produced.
Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 0.26 μm and 3.8 μm, respectively. In addition, from both surfaces toward the inner side of the film, porosity sizes showed an increase by a linear, gradient change across a distance of 35 μm. Further, the porosity ratio was 47%, and the resultant film had a film thickness of 70 μm. 82% of all porosities were independent porosities.
A polycarbonate porous film was produced in the same way as in Example 6 except that the cast film was covered with the sheet made of cellulose nitrate on the opposite surface of the substrate surface and left to stand still for 380 seconds.
Examination of the porosity morphology of the resultant film revealed that a uniform layer of a polymeric material having a thickness of 10 μm was contained in the layer and the maximal porosity size was 7.4 μm. Further, the porosity ratio was 43%, and the resultant film had a film thickness of 70 μm.
A polyimide porous film was produced in the same way as in Example 7 except that the cast film was covered with the sheet made of cellulose nitrate on the opposite surface of the substrate surface and left to stand still for 480 seconds.
Examination of the porosity morphology of the resultant film revealed that a uniform layer of a polymeric material having a thickness of 15 μm was contained in the layer and the maximal porosity size was 7.3 μm. Further, the porosity ratio was 43%, and the resultant film had a film thickness of 90 μm. From both surfaces toward the inner side of the film, porosity sizes showed an increase by a linear, gradient change. 81% of all porosities were independent porosities.
A polycarbonate porous film was produced in the same way as in Example 1 except that a solution in which a resin concentration was set to 23 wt % so as to achieve a viscosity of 1,230 cP was used. Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 0.81 μm and 4.7 μm, respectively. In addition, from one surface of the film toward the other surface of the film, porosity sizes showed an increase by a linear, gradient change. Further, the porosity ratio was 47%, and the resultant film had a film thickness of 70 μm. 84% of all porosities were independent porosities.
A polycarbonate porous film was produced in the same way as in Example 1 except that a solution in which a resin concentration was set to 28 wt % so as to achieve a viscosity of 3,800 cP was used.
Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 1.5 μm and 7.2 μm, respectively. In addition, from one surface of the film toward the other surface of the film, porosity sizes showed an increase by a linear, gradient change. Further, the porosity ratio was 45%, and the resultant film had a film thickness of 80 μm. 84% of all porosities were independent porosities.
A polycarbonate porous film was produced in the same way as in Example 1 except that a solution in which a resin concentration was set to 32 wt % so as to achieve a viscosity of 5,700 cP was used.
Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 2.2 μm and 8.5 μm, respectively. In addition, from one surface of the film toward the other surface of the film, porosity sizes showed an increase by a linear, gradient change. Further, the porosity ratio was 45%, and the resultant film had a film thickness of 95 μm. 82% of all porosities were independent porosities.
A polycarbonate porous film was produced in the same way as in Example 1 except that a sheet (microfiltration (MF) membrane filter) formed by cellulose acetate and cellulose nitrate was used as the sheet for covering the cast film.
Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 0.24 μm and 2.5 μm, respectively. In addition, from one surface of the film toward the other surface of the film, porosity sizes showed an increase by a linear, gradient change. Further, the porosity ratio was 52%, and the resultant film had a film thickness of 40 μm. 82% of all porosities were independent porosities.
Polycarbonate (Z200, manufactured by Mitsubishi Gas Chemical Company, Inc.) was dissolved in methanol to prepare an 18 wt % solution. The solution had a viscosity of 420 cP. A polyester material (manufactured by Teijin Limited) was prepared as a substrate, and an application bar was used to make a cast film of the above-mentioned polycarbonate solution. The cast film was left to stand for several minutes to evaporate methanol from the cast film. The cast film in this state was immersed in distilled water and left to stand for 10 minutes. After that, the substrate was taken out of water, and the resultant film was washed with distilled water.
Water remaining on the film was wiped off, the film was placed in a drying oven, and dried at a temperature of 80° C. for 1 hour. Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 0.010 μm and 0.055 μm, respectively. From one surface toward the other surface, porosity sizes showed an erratic, gradient change across the entire layer of the film, and the porosities were formed of continuous porosities. Further, the porosity ratio was 32%, and the resultant film had a film thickness of 60 μm.
An N-methylpyrrolidone (NMP) solution of polyamic acid serving as a polyimide precursor (trade name: U-varnish A, manufactured by Ube Industries, Ltd.) having a resin concentration of 14 wt % was prepared. In this case, the solution had a viscosity of 1,800 cP. A polyimide material (trade name: Kapton, manufactured by Du Pont-Toray Co., Ltd.) having a thickness of 120 μm was prepared as a substrate, and an application bar was used to cast the above-mentioned polyamic acid varnish on the substrate. The cast film was left stand at 150° C. for several minutes to evaporate NMP from the cast film. After that, the cast film was immersed in distilled water and left to stand for 10 minutes. The substrate was taken out of water, the sheet was peeled off, and the resultant film was washed with distilled water.
Water remaining on the film was wiped off, and the film was placed in a drying oven. The film was dried at a temperature of 80° C. for 1 hour. After that, the temperature was raised to 150° C. at a rate of 10°0 C./minute. The film was heated at the temperature of 150° C. for 30 minutes. After that, the temperature was raised to 250° C. at a rate of 10°0 C./minute. The film was heated at the temperature of 250° C. for 10 minutes. After that, the temperature was raised to 350° C. at a rate of 10°0 C./minute. The film was heated at the temperature of 350° C. for 10 minutes. Thus a polyimide resin composition was produced.
Examination of the porosity morphology of the resultant film revealed that the minimal porosity size and the maximal porosity size were 0.003 μm and 0.045 μm, respectively. From one surface toward the other surface, porosity sizes showed an erratic, gradient change across the entire layer of the film, and the porosities were formed of continuous porosities.
Further, the porosity ratio was 38%, and the resultant film had a film thickness of 60 μm.
An N-methylpyrrolidone (NMP) solution of polyamic acid serving as a polyimide precursor (trade name: U-varnish A, manufactured by Ube Industries, Ltd.) having a resin concentration of 18 wt % was prepared. The solution had a viscosity of 7,800 cP. A polyimide material (trade name: Kapton, manufactured by Du Pont-Toray Co., Ltd.) having a thickness of 120 μm was prepared as a substrate, and an application bar was used to cast the above-mentioned polyamic acid varnish on the substrate. The cast film was immersed in distilled water while covered with a solvent displacement adjuster (polyolefin, Gurley value: 210 seconds/100 cc, manufactured by Ube Industries, Ltd.) for 10 minutes. The film was taken out of water, the solvent displacement adjuster was peeled off, and the resultant film was washed in distilled water.
Examination of the porosity morphology of the resultant film revealed that the porosities were formed of uniform, continuous porosities and the average porosity size was 0.50 μm. The film thickness was 45 μm and the porosity ratio was 47%.
A polyimide porous film was produced in the same way as in Comparative Example 3 except that a solvent displacement adjuster made of polyolefin having a Gurley value of 500 seconds/100 cc was used.
Examination of the porosity morphology of the resultant film revealed that the porosities were formed of uniform, continuous porosities and the average porosity size was 3.3 μm. The film thickness was 40 μm and the porosity ratio was 44%.
The two films obtained in Comparative Example 3 and
Comparative Example 4 were attached together by means of a polyamide-imide primer, thereby affording a polyimide porous film having gradient porosity sizes.
The resin compositions (3 cm×3 cm) obtained in Examples 1 to 13 and Comparative Examples 1 to 5 were each used to evaluate thermal conductivity, compression resistance, and thermal conductivity after compression. The compression resistance was evaluated after compression with a press machine under conditions of a pressure of 7 kgf/cm2, a compression temperature of 170° C., and a compression time of 4 hours. Tables 1-1 and 1-2 show the results.
In the column “covering time”, a) represents “covering time for the surface opposite to the substrate” and b) represents “covering time for the surface on the side of the substrate”.
For each of those examples, thermal conductivity and compression resistance (change rate of the film thickness before and after compression) were evaluated according to the criteria as described below.
Thermal conductivity λ [W/mK]:
A: λ<0.05, B: 0.05≦λ<0.075,
C: 0.075≦λ<0.1, D: λ≧0.1
Compression resistance (change rate of the film thickness before and after compression):
A=less than 1%,
B=1% or more and less than 5%,
C=5% or more and less than 10%,
D=10% or more
Tables 1-1 and 1-2 revealed that a composition having gradient porosity sizes from both surfaces and small porosity sizes near both surfaces had excellent properties against compression while maintaining heat resistance. On the other hand, it was revealed that a composition having excessively small porosity sizes was poor in heat insulating property, and inversely, a composition having excessively large porosity sizes was poor in compression resistance.
Lamination of PFA was carried out on the surface side having the smaller porosity sizes on the resin composition obtained in Example 2. A PFA dispersion (510 CL, manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.) was applied onto the resin composition with a spraying apparatus and was heated at 350° C. for 10 minutes to carry out the lamination. The thickness of the PFA film was measured and found to be 5 μm and the film had a surface roughness Rz of 0.5 μm. PFA is a copolymer of ethylene tetrafluoride (C2F4) and perfluoroalkoxyethylene. The surface roughness Rz is a ten point height of roughness profile.
Lamination of PFA was carried out in the same way as in Example 14 except that the lamination was carried out on the surface side having the larger porosity sizes on the resin composition obtained in Example 2. The thickness of the PFA film was measured and found to be 5.2 μm and the film had a surface roughness Rz of 0.5 μm.
Lamination of PFA was carried out in the same way as in Example 14 except that the lamination was carried out on the surface side having the smaller porosity sizes in the resin composition obtained in Example 5. The thickness of the PFA film was measured and found to be 5.5 μm and the film had a surface roughness Rz of 0.5 μm.
Lamination of PFA was carried out in the same way as in Example 14 except that the lamination was carried out on the surface side having the smaller porosity sizes in the resin composition obtained in Example 7. The thickness of the PFA film was measured and found to be 5.3 μm and the film had a surface roughness Rz of 0.5 μm.
Lamination of PFA was carried out in the same way as in Example 14 except that the lamination was carried out on the surface side having the smaller porosity sizes in the resin composition obtained in Example 9. The thickness of the PFA film was measured and found to be 5.5 μm and the film had a surface roughness Rz of 0.5 μm.
Lamination of PFA was carried out in the same way as in Example 14 except that the resin composition obtained in Comparative Example 2 was used. The thickness of the PFA film was measured and found to be 5.5 μm and the film had a surface roughness Rz of 0.5 μm.
Lamination of PFA was carried out in the same way as in Example 14 except that the lamination was carried out on the surface side having the smaller porosity sizes in the resin composition obtained in Comparative Example 5. The thickness of the PFA film was measured and found to be 5.5 μm and the film had a surface roughness Rz of 0.5 μm.
The resin compositions of Examples 14 to 18, and Comparative Examples 6 and 7 were each used to perform a fixing test. First, an image press C1 (manufactured by Canon Inc.) was used to transfer toner onto the resin composition. In the fixing test, the film onto which toner had been transferred was immobilized on an aluminum stage, heated with an 800 W halogen lamp for 100 milliseconds, and then the stage was moved at a speed of 360 mm/second, thereby examining the fixation on a medium after 100 milliseconds. The medium has such a configuration as to be fixed on an aluminum roller wrapped by an elastic rubber to form a nip portion with the aluminum stage. The fixation was performed with a pressure at the nip portion of 10 kgf/cm2 and a pressurizing time of 10 milliseconds. Table 2 shows the results.
For those examples, evaluations were performed according to the criteria as described below.
Cover ratio: evaluated in terms of the residual ratio of toner on the medium when the fixed matter at the thousandth fixation was cross-folded and the printed matter was rubbed with brass wrapped by lens-cleaning paper.
A=toner residual ratio after test of 90% or more,
B=toner residual ratio after test of 75% or more and less than 90%,
C=toner residual ratio of 50% or more and less than 75%,
D=toner residual ratio of less than 50%
Change rate of the film thickness: change rate of the film thickness of the resin composition laminated at the thousandth fixation with respect to at the initial.
A=less than 1%,
B=1% or more and less than 5%,
C=5% or more and less than 10%,
D-10% or more
Table 2 revealed that a composition having small porosity sizes in the surface is excellent in cover ratio (toner residual ratio) and change rate of the film thickness. The composition was revealed to serve as a belt material excellent in heat insulating property by its high toner residual ratio. The composition was revealed to serve as a belt material excellent in compression resistance by its low change rate of the film thickness. It was also revealed that lowering the heat conductivity of the surface on which toner was placed improved fixing property.
On the other hand, a composition which was obtained by merely attaching films was poor in mechanical properties and the film was broken during the fixation test.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
This application claims the benefit of Japanese Patent Application No. 2010-117844, filed May 21, 2010, which is hereby incorporated by reference herein in its entirety.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010-117844 | May 2010 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2011/060689 | 4/27/2011 | WO | 00 | 11/6/2012 |
