JP2016031816A - Infrared ray processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an infrared ray processing method for applying infrared ray energy while two materials contained in a target are provided with priority levels.SOLUTION: Infrared ray to be applied to a coating film 82 containing first and second materials is made different between a step (a) when the coating film 82 is passed through a first processing space 12a and then a step (b) when the coating film is passed through a second processing space 12a. In the step (a), infrared ray energy is preferentially applied to the first material of the first and second materials in the coating film 82. In the step (b), infrared ray energy is applied to the second material in the coating film 82. Accordingly, the second material can be evaporated in the step (b) after the first material is evaporated to increase the concentration of the second material in the coating film 82 in the step (a).SELECTED DRAWING: Figure 1

Description

  The present invention relates to an infrared processing method.

  Conventionally, it is known to perform treatment such as drying by emitting infrared rays to an object such as a coating film. Various infrared heaters that emit infrared rays have been developed. For example, Patent Document 1 describes an infrared heater including a heating element, and an inner tube and an outer tube surrounding the heating element. In this infrared heater, the inner tube and the outer tube function as a filter that transmits infrared light having a wavelength of 3.5 μm or less and absorbs infrared light having a wavelength exceeding 3.5 μm. Infrared rays having a wavelength of 3.5 μm or less are said to be excellent in ability to break hydrogen bonds, and it is said that the object can be efficiently dried by emitting infrared rays having this wavelength.

Japanese Patent No. 4790092

  However, in the drying process using the infrared heater described in Patent Document 1 described above, no consideration has been given to the case where processes other than hydrogen bond breaking are performed. For example, in the case where both of two types of substances contained in an object are evaporated, the wavelength range of infrared rays suitable for evaporation may differ depending on the substance, but this is not considered. Further, when two kinds of substances are evaporated, there is a demand for setting a priority order for the evaporation, for example, one of the substances is evaporated first.

  The present invention has been made in order to solve such a problem, and has as its main object to give priority to two substances included in the object and input infrared energy.

  The present invention employs the following means in order to achieve the main object described above.

The infrared processing method of the present invention comprises:
An infrared processing method of radiating infrared rays to an object including at least a first substance and a second substance, and infrared-treating at least the first and second substances in the object,
(A) a first absorption region that is a wavelength region from the rising to the falling of an absorption spectrum including a wavelength of a first absorption peak that is an infrared absorption peak of the first material in an infrared absorption spectrum; and the second material. In the second absorption region, which is a wavelength region from the rise to the fall of the absorption spectrum including the wavelength of the second absorption peak, which is an infrared absorption peak of the second absorption peak having a wavelength different from the first absorption peak, Selectively emitting infrared radiation having a wavelength in the first absorption region;
(B) after the step (a), selectively emitting infrared rays having a wavelength in the second absorption region out of the first absorption region and the second absorption region;
Is included.

  In the infrared processing method of the present invention, in step (a), infrared light having a wavelength within the first absorption region is selectively emitted from the first absorption region and the second absorption region to the object. Here, the first absorption region is a wavelength region in which the infrared absorption rate of the first material is relatively high, and the second absorption region is a wavelength region in which the infrared absorption rate of the second material is relatively high. Therefore, by selectively radiating infrared rays having wavelengths within the first absorption region of the first and second absorption regions, infrared rays are preferentially given to the first material among the first and second materials in the object. Of energy. And after supplying infrared energy preferentially to the first substance, in the step (b), the object within the second absorption region among the first absorption region and the second absorption region is applied to the object. Selectively emits infrared rays of a wavelength. Thereby, infrared energy can be efficiently injected into the second substance. As described above, by changing the infrared rays radiated to the object in step (a) and step (b), priority is given in the order of the first substance and the second substance to the two substances contained in the object. Infrared energy can be input. Thereby, the first substance is preferentially infrared-treated (treatment using infrared rays) over the second substance in the object in the step (a), and then the second substance is infrared-treated in the step (b). Can do. Here, the “infrared treatment” includes a process that causes a physical change such as evaporation, drying, and dehydration, a process that causes a chemical reaction such as imidization, and a process that causes a temperature change such as a temperature rise.

  In the infrared processing method of the present invention, in the step (a), at least a part of the emission half-value width region that is a half-value width region of a wavelength with reference to the radiation intensity of the infrared radiation peak emitted to the object is Irradiating the object with infrared rays so as to overlap at least a part of the first absorption half-width region, which is a half-value width region of the wavelength based on the absorption rate of the first absorption peak of the first substance, In the step (b), at least a part of the emission half-width region is at least a second absorption half-width region that is a half-width region of a wavelength based on the absorption rate of the second absorption peak of the second substance. Infrared rays may be emitted to the object so as to overlap a part. In this way, by making at least a part of the half-width region of the radiating infrared ray overlap with the half-width region of the infrared absorption of the substance to be infrared-treated, it is more efficient for the substance to be infrared-treated in each step. Infrared energy can be input well and infrared processing can be performed efficiently.

  In the infrared treatment method of the present invention, the first substance is a liquid other than water, the second substance is water, and in the step (a), at least the first substance among the substances contained in the object. One substance may be evaporated, and in the step (b), at least the second substance may be evaporated among substances contained in the object. If it carries out like this, after reducing the density | concentration of the 1st substance in a target object in a process (a), water can be evaporated in a process (b). Thereby, for example, problems due to an increase in the concentration of the first substance during processing can be further suppressed.

  In the infrared treatment method of the present invention, the first substance may be water, and in the step (a), at least the first substance may be evaporated among substances contained in the object. If it carries out like this, after raising the density | concentration of the 2nd substance in a target object by a process (a), a 2nd substance can be infrared-processed at a process (b). In this case, the second substance may be a liquid or a water-soluble substance.

1 is a longitudinal sectional view of an infrared processing device 10. FIG. AA sectional drawing of the near-infrared heater 30 of FIG. The conceptual diagram of the radiation intensity distribution of the near-infrared heater 30 and the far-infrared heater 60, and the infrared absorption spectrum of acetone and water. Sectional drawing of the infrared processing apparatus 110 of a modification. Sectional drawing of the infrared processing apparatus 210 of a modification.

  Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a longitudinal sectional view of an infrared processing apparatus 10 for executing the infrared processing method of the present invention. FIG. 2 is a cross-sectional view of the near infrared heater 30 of the infrared processing apparatus 10 of FIG. The infrared processing apparatus 10 radiates infrared rays to the coating film 82 as an object applied on the sheet 80 to perform infrared treatment (heat treatment in the present embodiment) of the coating film 82. A near infrared heater 30, a far infrared heater 60, and a controller 90 are provided. Further, the infrared processing apparatus 10 includes a roll 21 provided in front of the furnace body 11 (left side in FIG. 1) and a roll 25 provided in the rear of the furnace body 11 (right side in FIG. 1). . The infrared processing apparatus 10 is configured as a roll-to-roll heat treatment furnace that continuously heats a sheet 80 having a coating film 82 formed on its upper surface by rolls 21 and 25. In this embodiment, the left-right direction, the front-back direction, and the up-down direction are as shown in FIGS.

  The furnace body 11 forms the processing space 12 in which the coating film 82 is heat-treated. The furnace body 11 is a heat insulating structure formed in a substantially rectangular parallelepiped, and includes a processing space 12 that is an internal space, and an entrance to the processing space 12 from the outside formed in the front end face 13 and the rear end face 14 of the furnace body, respectively. Openings 17 and 18 are formed. The furnace body 11 has a length from the front end face 13 to the rear end face 14 of, for example, 2 to 10 m. The sheet 80 having the coating 82 applied on one side passes through the processing space 12 from the opening 17 to the opening 18 substantially horizontally. The processing space 12 is divided into a front first processing space 12a and a rear second processing space 12b with a center line 11a in the front-rear direction of the furnace body 11 shown in FIG. 1 as a boundary. A plurality of near infrared heaters 30 are arranged in the first processing space 12a, and a plurality of far infrared heaters 60 are arranged in the second processing space 12b. The furnace body 11 may include a partition wall that partitions the first processing space 12a and the second processing space 12b and has an opening through which the sheet 80 and the coating film 82 can pass back and forth. Although not shown, the furnace body 11 is connected to an air supply line that supplies an inert gas (for example, nitrogen gas) to the inside of the processing space 12 and an exhaust line that exhausts the atmosphere of the processing space 12. Yes.

  The near-infrared heater 30 is a device that mainly emits near-infrared rays (infrared rays having a wavelength of 0.7 μm to 3.5 μm) to the coating film 82 that passes through the first processing space 12 a in the furnace body 11. A plurality (five in this embodiment) of near infrared heaters 30 are arranged at equal intervals in the front-rear direction in the first processing space 12a. Each of the near infrared heaters 30 is attached so that the longitudinal direction is along the left-right direction. Since the plurality of near infrared heaters 30 have the same configuration, the configuration of one near infrared heater 30 will be described below.

  The near-infrared heater 30 includes a heater main body 38 formed so that the inner tube 36 surrounds the filament 32 as a heating element, as shown in the enlarged view shown in the broken line frame of FIG. 1 and FIG. 38 formed between the heater body 38 and the outer tube 40, and the outer tube 40 formed so as to surround the outer tube 40, the bottomed cylindrical cap 42 that is airtightly fitted to both ends of the outer tube 40, and the heater main body 38 and the outer tube 40. A refrigerant flow path 47. A reflective layer 41 is disposed on the upper surface of the outer tube 40. A temperature sensor 56 for detecting the surface temperature of the outer tube 40 is attached to the lower surface of the outer tube 40 (see FIG. 2).

  The filament 32 is a heating element that emits infrared rays when heated, and in this embodiment, a W (tungsten) electric wire is spirally wound. In addition, examples of the material of the filament 32 include nichrome alloys, Mo, Ta, and iron chromium alloys. When the filament 32 is supplied with power from the power supply source 50 and is heated to 700 to 1700 ° C. for example, the filament 32 emits infrared light having a peak in an infrared region having a wavelength of 3.5 μm or less (for example, around 2 to 3 μm). Radiate. The electrical wiring 34 connected to the filament 32 is drawn out to the outside airtightly through a wiring lead-out portion 44 provided in the cap 42 and penetrating through the upper portion (ceiling) of the furnace body 11, and is connected to the power supply source 50. . The inner tube 36 and the outer tube 40 are formed of an infrared absorbing material that functions as a filter that passes infrared rays having a wavelength of 3.5 μm or less among the electromagnetic waves radiated from the filament 32 and absorbs infrared rays having a wavelength exceeding 3.5 μm. ing. Examples of such infrared transmitting material used for the inner tube 36 and the outer tube 40 include quartz glass. The inner tube 36 has an atmosphere in which a halogen gas is added to an argon gas.

  The heater body 38 is supported at both ends by holders 49 disposed inside the cap 42. Each cap 42 has a refrigerant inlet / outlet port 48. A refrigerant is supplied from a refrigerant supply source 52 to one of the refrigerant ports 48. The refrigerant that has flowed into the outer tube 40 from one refrigerant inlet / outlet 48 flows through the refrigerant passage 47 and flows out from the other refrigerant inlet / outlet 48. The refrigerant flowing through the refrigerant flow path 47 is, for example, a gas such as air or an inert gas, and cools these by contacting the inner tube 36 and the outer tube 40 to remove heat.

  The reflection layer 41 is formed in a region on the outer peripheral surface of the outer tube 40 including the side (upper side) opposite to the coating film 82 when viewed from the filament 32, and is provided so as to cover only a part of the periphery of the filament 32. Yes. In the present embodiment, the reflective layer 41 covers the entire upper half of the outer tube 40. The reflective layer 41 is arranged so that the filament 32 is positioned at the center of a circle including the arc of the cross section. The reflection layer 41 is formed of an infrared reflecting material that reflects at least a part of infrared rays of electromagnetic waves emitted from the filament 32. Examples of the infrared reflecting material include gold, platinum, and aluminum. In particular, the reflective layer 41 preferably has a high reflectance of infrared rays with a wavelength of 3.5 μm or less emitted from the filament 32. The reflective layer 41 is formed by depositing an infrared reflective material on the surface of the outer tube 40 using a film deposition method such as coating and drying, sputtering, CVD, or thermal spraying.

  In the near infrared heater 30 configured in this way, when infrared rays having a wavelength of 3.5 μm or less are emitted from the filament 32, infrared rays having a wavelength of 3.5 μm or less (wavelengths of 0.7 μm to 3.5 μm). Of the near infrared rays) passes through the inner tube 36 and the outer tube 40 and is radiated to the coating film 82 inside the first processing space 12a of the furnace body 11. The inner tube 36 and the outer tube 40 absorb infrared light having a wavelength exceeding 3.5 μm. However, the inner tube 36 and the outer tube 40 are cooled by the refrigerant flowing through the refrigerant flow path 47 (for example, 200 ° C. or less), so that the inner tube 36 and the outer tube 40 are secondary to infrared. It can suppress becoming a radiator.

  The far-infrared heater 60 is a device that mainly emits far-infrared rays (infrared rays having a wavelength of 3.5 μm to 1000 μm) to the coating film 82 that passes through the second processing space 12 b in the furnace body 11. A plurality of far infrared heaters 60 (five in this embodiment) are arranged at equal intervals in the front-rear direction in the second processing space 12b. The far-infrared heater 60 has a substantially flat plate shape, and is attached so that the longitudinal direction is along the left-right direction. Although the detailed illustration of the far infrared heater 60 is omitted, a metal heating element is embedded in ceramics. The far-infrared heater 60 radiates far-infrared rays to the coating film 82 due to the radiation characteristics of the ceramics by heating the surrounding ceramics with a heating element.

  The coating film 82 becomes a p-type organic semiconductor layer of the organic thin film solar cell by heat treatment in the infrared processing apparatus 10. The coating film 82 includes, for example, a soluble porphyrin precursor that becomes a porphyrin compound by heat treatment, water, and an organic solvent. In this embodiment, the coating film 82 is a liquid containing a tetrabenzoporphyrin precursor, water, and acetone as an organic solvent. The sheet 80 becomes a substrate and an electrode of the organic thin film solar cell. In the present embodiment, the sheet 80 is a glass sheet having an ITO electrode pattern formed on the surface. The film thickness of the sheet 80 may be in a range that can be wound around the roller 21 or the roller 25 and is, for example, several tens of μm.

  The controller 90 is configured as a microprocessor centered on a CPU. The controller 90 outputs a control signal for adjusting the magnitude of the power supplied from the power supply source 50 to the filament 32 to the power supply source 50, and calculates the heat generation amount of each filament 32 of the near infrared heater 30. Control individually. Similarly, the controller 90 outputs a control signal for adjusting the power supplied to the heating element of the far infrared heater 60 to a power supply source for the far infrared heater 60 (not shown) to individually control the temperature of the far infrared heater 60. To do. Further, the controller 90 inputs the temperature of the near-infrared heater 30 detected by the temperature sensor 56 that is a thermocouple, or outputs a control signal to an on-off valve or a flow rate adjustment valve (not shown) of the refrigerant supply source 52, The flow rate of the refrigerant flowing through the refrigerant flow path 47 of the near infrared heater 30 is individually controlled. Further, the controller 90 transmits a control signal to the rolls 21 and 25 to switch between rotation and stop of the rolls 21 and 25. The controller 90 also adjusts the rotation speed of the rolls 21 and 25 to adjust the passage time of the sheet 80 and the coating film 82 in the furnace body 12 and the tension applied to the sheet 80 and the coating film 82.

  Next, a state in which infrared processing is performed using the infrared processing apparatus 10 configured in this manner will be described. First, the user passes the sheet 80 wound around the roller 21 through the processing space 12 and connects the sheet 80 to the roller 25. Next, the controller 90 adjusts the electric power supplied to the near-infrared heater 30 and the far-infrared heater 60 so that the near-infrared heater 30 and the far-infrared heater 60 emit infrared rays having a predetermined emission peak wavelength. The radiation peak wavelengths of the near infrared heater 30 and the far infrared heater 60 will be described later. Further, the controller 90 is configured so that the inside of the processing space 12 is constantly filled with nitrogen gas, and the temperature inside the processing space 12 becomes a temperature suitable for heat treatment of the coating film 82 (for example, 40 ° C. to 60 ° C.). Then, exhausting is performed through the exhaust line while supplying nitrogen gas through the air supply line. Then, the controller 90 rotates the rolls 21 and 25 and starts conveying the sheet 80 at a predetermined speed. As a result, the sheet 80 is unwound from the roll 21. The sheet 80 is coated with a coating film 82 on the upper surface by a coater (not shown) immediately before being brought into the furnace body 11 from the opening 17. After passing through the inside of the processing space 12 of the furnace body 11, the sheet 80 to which the coating film 82 has been applied is unloaded from the heating furnace main body 10 through the opening 18 and wound around the roller 25. At this time, in the first treatment space 12a, the step (a) described later is performed on the coating film 82 by infrared rays from the near infrared heater 30, and water in the coating layer 82 is mainly evaporated. Further, in the second processing space 12b, the step (b) described later is performed on the coating film 82 by infrared rays from the far infrared heater 60, and acetone in the coating layer 82 is mainly evaporated. Further, during the steps (a) and (b), the ethylene group as a substituent is desorbed from the tetrabenzoporphyrin precursor in the coating film 82 and crystallized by heat of the processing space 12 or the like. Thus, the heat-treated coating film 82 becomes a p-type organic semiconductor layer made of tetrabenzoporphyrin crystals. Then, for the sheet 80 and the p-type organic semiconductor layer (the coating film 82 after the heat treatment) wound around the roller 25, an n-type organic semiconductor layer made of, for example, a fullerene compound, and an electrode layer on the p-type organic semiconductor layer Are formed in this order to obtain an element for an organic thin film solar cell. In addition, you may convey the sheet | seat 80 carried out from the furnace body 11 as it is to the apparatus which performs the next process (formation process of an n-type organic-semiconductor layer etc.) as it is, without winding up to the roller 25. FIG. In addition, after the post-treatment such as heat treatment is further performed on the heat-treated coating film 82 carried out of the furnace body 11, the next step (such as an n-type organic semiconductor layer forming step) may be performed. It is also known to obtain a p-type organic semiconductor layer composed of a porphyrin compound crystal having low solubility by using a structure of an organic thin film solar cell using a porphyrin compound and a fullerene compound or a soluble porphyrin precursor. For example, it describes in Unexamined-Japanese-Patent No. 2010-16212.

  Here, the above-described steps (a) and (b) performed in the first and second processing spaces 12a and 12b will be described in detail. First, about the 1st absorption peak of the 1st substance (water), the 1st absorption field, the 1st absorption half width area, and the 2nd absorption peak of the 2nd substance (acetone), the 2nd absorption area, and the 2nd half width area explain. FIG. 3 is a conceptual diagram of the infrared absorption spectra of water and acetone and the radiation intensity distribution of the near infrared heater 30 and the far infrared heater 60. 3 shows the infrared absorption spectrum of water, the middle shows the infrared absorption spectrum of acetone, and the lower shows the radiation intensity distribution of the near infrared heater 30 and the far infrared heater 60. Infrared absorption spectra as shown in the upper and middle stages of FIG. 3 are obtained by changing the water and acetone to the same state as the coating film 82 (for example, the same thickness as the coating film 82). It shall be obtained by measurement using an external analyzer (FT / IR-6100). Further, the radiation intensity distribution as shown in the lower part of FIG. 3 shows that the infrared radiation intensity emitted from the near infrared heater 30 and the far infrared heater 60 to the same position as the coating film 82 is Fourier transformed by JASCO Corporation. It shall be obtained by measurement using an infrared analyzer (FT / IR-6100). As shown in the upper part of FIG. 3, the infrared absorption spectrum of water has an absorption peak PA near a wavelength of 3 μm and an absorption peak PB near a wavelength of 6 μm. As described above, when a plurality of absorption peaks exist in the first substance, any one of them is defined as the first absorption peak. In the present embodiment, the absorption peak PA, which is the peak having the highest absorption rate, is defined as the first absorption peak. The first absorption region is a wavelength region from the rise to the fall of the absorption spectrum including the wavelength of the first absorption peak (absorption peak PA) (from the left end to the right end of the mountain-shaped waveform). Therefore, the wavelength region AA shown in the upper part of FIG. 3 is the first absorption region. Further, the first absorption half width region is a half width region of a wavelength based on the absorption rate of the first absorption peak (absorption peak PA). Therefore, the full width at half maximum HA shown in the upper part of FIG. 3 (the region where the absorption rate at the absorption peak PA is X%, where the absorption rate is X / 2% or more) is the first absorption half width region.

  In the present embodiment, the second absorption peak of the second substance (acetone) is also determined as the peak having the highest absorption rate among the plurality of absorption peaks, similarly to the first absorption peak. That is, as shown in the middle of FIG. 3, there are absorption peaks Pa to Pd and the like in the infrared absorption spectrum of acetone, and among these, the absorption peak Pa in the vicinity of the wavelength of 6 μm having the highest absorption rate was taken as the second absorption peak. When the second absorption peak is determined, the second absorption region and the second absorption half width region are determined in the same manner as the first absorption region and the first absorption half width region, based on the second absorption peak. That is, the wavelength region Aa from the rise to the fall of the absorption spectrum including the wavelength of the absorption peak Pa shown in the middle stage of FIG. 3 is the second absorption region. Further, the half width region Ha shown in the middle of FIG. 3 (a region where the absorption rate at the absorption peak Pa is Y%, where the absorption rate is Y / 2% or more) is the second absorption half width region. The second absorption peak (absorption peak Pa) has a wavelength different from that of the first absorption peak (absorption peak PA).

  And the process (a) performed in the 1st process space 12a carries out the infrared rays of the wavelength in a 1st absorption area among 1st absorption area (wavelength area AA) and 2nd absorption area (wavelength area Aa). This is a step of selectively irradiating and evaporating water in the coating film 82. Here, “selectively radiate infrared rays having a wavelength in the first absorption region out of the first absorption region and the second absorption region” means that the wavelength in the first absorption region emitted to the coating film 82 is This means that the infrared radiation intensity is higher than the infrared radiation intensity of the wavelength within the second absorption region radiated to the coating film 82. In the present embodiment, the infrared radiation intensity distribution of the near-infrared heater 30 that radiates infrared rays to the coating film 82 in the first processing space 12a is supplied to the near-infrared heater 30 so as to have a waveform shown on the left side of the lower part of FIG. It is assumed that the controller 90 adjusts the power to be used. In the lower part of FIG. 3, the radiation peak of the radiation intensity distribution of the near infrared heater 30 is shown as the radiation peak P1. Further, the half-value width region of the wavelength based on the radiation intensity of the radiation peak P1 is shown as the radiation half-value width region H1. That is, the radiation intensity at the radiation peak P1 is represented by S, and a region where the radiation intensity is S / 2 or more is represented as a radiation half-width region H1. In addition, in order to make it easy to understand the positional relationship with the infrared absorption spectrum of water or acetone, the position (wavelength) of the radiation peak P1 and the radiation half-width region H1 are also illustrated in the upper and middle stages of FIG. As shown in FIG. 3, the radiation intensity distribution of the near-infrared heater 30 is relatively high in the first absorption region (wavelength region AA) and relatively low in the second absorption region (wavelength region Aa). By doing in this way, among the water and acetone in the coating film 82, the infrared energy is preferentially given to water having a relatively high infrared absorption rate in the first absorption region (wavelength region AA). Can be thrown in. Therefore, water evaporates preferentially over acetone in the first processing space 12a where the step (a) is performed. As shown in the lower part of FIG. 3, the infrared radiation intensity from the near-infrared heater 30 is drastically reduced in a wavelength region exceeding 3.5 μm. This is because the inner tube 36 and the outer tube 40 absorb infrared rays in a region exceeding the wavelength of 3.5 μm. In the lower part of FIG. 3, the infrared radiation intensity distribution from the filament 32 before being absorbed by the inner tube 36 and the outer tube 40 in a region exceeding the wavelength of 3.5 μm is indicated by a one-dot chain line. The first absorption region (wavelength region AA) is in the range of about 2.5 μm to about 3.6 μm, and the inner tube 36 and the outer tube 40 reduce the infrared radiation intensity in the long wavelength region outside this range. Yes. Therefore, the near-infrared heater 30 can more selectively emit infrared rays having a wavelength in the first absorption region out of the first absorption region and the second absorption region.

  In the step (a), it is preferable that at least a part of the emission half width region H1 overlaps at least a part of the first absorption region (wavelength region AA), and the first absorption half width region (half width). More preferably, it overlaps at least part of the area HA). Moreover, it is preferable that the wavelength of the radiation peak P1 exists in the 1st absorption area | region (wavelength area AA), and it is more preferable to exist in the 1st absorption half width area (half width area HA). Furthermore, it is preferable that the wavelength of the first absorption peak (absorption peak PA) exists in the emission half-width region H1. In this embodiment, the power (temperature of the filament 32) supplied to the near-infrared heater 30 is determined in advance so that the wavelength of the radiation peak P1 matches the wavelength of the first absorption peak (absorption peak PA), and the controller 90 To be remembered. Therefore, in the step (a) of the present embodiment, all the above preferable conditions are satisfied. Moreover, water can be more efficiently evaporated by making the wavelength of the radiation peak P1 coincide with the wavelength of the first absorption peak (absorption peak PA).

  In the step (a), the number of main absorption peaks of the second substance (acetone) present in the emission half-width region H1 is preferably small, and more preferably zero. For example, when an absorption peak having an absorption rate of 1/2 or more of the absorption rate Y% of the absorption peak Pa, which is the maximum peak, is a main absorption peak, the absorption peaks Pa to Pd correspond to the main peaks in the middle stage of FIG. To do. In this embodiment, since these absorption peaks Pa to Pd do not exist in the emission half-width region H1, the number of main absorption peaks of acetone existing in the emission half-width region H1 is zero. Further, it is preferable that the emission half-width region H1 and the half-width region of the main absorption peak of the second substance (acetone) do not overlap as much as possible. In the present embodiment, the emission half-width region H1 and the half-width region of the main absorption peak of acetone do not overlap at all. In the present embodiment, an absorption peak Pd of acetone or the like exists in the emission half-width region H1, but this absorption peak Pd or the like is not a main peak but has a relatively low absorption rate, and therefore acetone is used in step (a). Water can preferentially evaporate over. However, the number of absorption peaks of the second substance (acetone) existing in the emission half-width region H1 is preferably small, and more preferably zero, in addition to the main absorption peak of the second substance. The smaller the number of absorption peaks of the second substance (acetone) present in the emission half-width region H1, the more the first substance is preferentially controlled by suppressing the evaporation of the second substance (acetone) in the step (a). (Water) can be evaporated.

  In the step (b) performed in the second processing space 12b, infrared rays having wavelengths within the second absorption region are selectively selected from the first absorption region (wavelength region AA) and the second absorption region (wavelength region Aa). Is a step of evaporating acetone in the coating film 82. Here, “selectively radiate infrared rays having a wavelength in the second absorption region out of the first absorption region and the second absorption region” means that the wavelength in the second absorption region emitted to the coating film 82 is This means that the infrared radiation intensity is higher than the infrared radiation intensity of the wavelength within the first absorption region radiated to the coating film 82. In the present embodiment, the infrared radiation intensity distribution of the far-infrared heater 60 that radiates infrared rays to the coating film 82 in the second processing space 12b is supplied to the far-infrared heater 60 so as to have a waveform shown on the right side of the lower part of FIG. It is assumed that the controller 90 adjusts the power to be used. In the lower part of FIG. 3, the radiation peak of the radiation intensity distribution of the far infrared heater 60 is shown as a radiation peak P2. Further, the half width region of the wavelength with reference to the radiation intensity of the radiation peak P2 is shown as a radiation half width region H2. That is, the radiation intensity at the radiation peak P2 is represented by T, and a region where the radiation intensity is T / 2 or more is represented as a radiation half-width region H2. In addition, in order to make it easy to understand the positional relationship with the infrared absorption spectrum of water or acetone, the position (wavelength) of the radiation peak P2 and the radiation half-value width region H2 are also illustrated in the upper and middle stages of FIG. As shown in FIG. 3, the radiation intensity distribution of the far-infrared heater 60 is relatively high in the second absorption region (wavelength region Aa) and relatively low in the first absorption region (wavelength region AA). By doing in this way, energy can be efficiently injected | thrown-in and evaporated to acetone with the comparatively high infrared absorption factor in the 2nd absorption area | region (wavelength area | region Aa).

  In the step (b), it is preferable that at least a part of the emission half width region H2 overlaps at least a part of the second absorption region (wavelength region Aa), and the second absorption half width region (half width). More preferably, it overlaps at least part of the region Ha). The wavelength of the radiation peak P2 is preferably present in the second absorption region (wavelength region Aa), and more preferably present in the second absorption half width region (half width region Ha). Furthermore, it is preferable that the wavelength of the second absorption peak (absorption peak Pa) exists in the emission half width region H2. In the present embodiment, the power (temperature of the heating element and surrounding ceramics) supplied to the far infrared heater 60 is determined in advance so that the wavelength of the radiation peak P2 matches the wavelength of the second absorption peak (absorption peak Pa). And stored in the controller 90. Therefore, in the step (b) of the present embodiment, all the above preferable conditions are satisfied. Moreover, acetone can be more efficiently evaporated by making the wavelength of the radiation peak P2 coincide with the wavelength of the second absorption peak (absorption peak Pa).

  In this embodiment, all the water is evaporated in the step (a). Therefore, unlike the step (a), in the step (b), even if the absorption peak of the first substance (water) exists in the emission half width region H2, the first substance itself does not exist in the coating film 82. So there is no problem. Further, in the step (b), the emission half width region H2 may be determined so that the wavelength of the main absorption peak of the first substance (water) is positively included in the emission half width region H2. By so doing, the slight amount of the first substance (water) remaining without being evaporated in step (a) can be reliably evaporated in step (b).

  Thus, in this embodiment, the water in the coating film 82 is preferentially evaporated in the first treatment space 12a by making the infrared rays radiated to the coating film 82 different in the step (a) and the step (b). Then, acetone is evaporated in the second processing space 12b. In addition, by evaporating water first and increasing the concentration of acetone in the coating film 82, elimination of substituents from the tetrabenzoporphyrin precursor in the coating film 82 and crystallization into tetrabenzoporphyrin can be achieved. It is thought to be promoted. As a result, it is considered that a p-type organic semiconductor layer can be efficiently produced from the coating film 82.

  Here, the correspondence between the components of the present embodiment and the components of the present invention will be clarified. The water of this embodiment corresponds to the first substance of the present invention, acetone corresponds to the second substance, the coating film 82 corresponds to the object, the absorption peak PA corresponds to the first absorption peak, and the wavelength region AA. Corresponds to the first absorption region, the absorption peak Pa corresponds to the second absorption peak, and the wavelength region Aa corresponds to the second absorption region. Further, the radiation peak P1 corresponds to the radiation peak in the step (a), the radiation half width region H1 corresponds to the radiation half width region in the step (a), and the half width region HA corresponds to the first absorption half width region. . Furthermore, the radiation peak P2 corresponds to the radiation peak in the step (b), the radiation half-width region H2 corresponds to the radiation half-width region in the step (b), and the half-width region Ha becomes the second absorption half-width region. Equivalent to.

  In the infrared processing apparatus 10 of the present embodiment described above, in the step (a) when the coating film 82 passes through the first processing space 12a, the first absorption region (wavelength region AA) and the coating film 82 are separated. Infrared rays having a wavelength in the first absorption region out of the second absorption region (wavelength region Aa) are selectively emitted from the near-infrared heater 30. Here, the first absorption region is a wavelength region in which the infrared absorption rate of the first substance (water) is relatively high, and the second absorption region is a wavelength region in which the infrared absorption rate of the second material (acetone) is relatively high. It is. Therefore, by selectively emitting infrared rays having a wavelength within the first absorption region of the first and second absorption regions, the infrared energy is preferentially input to the water of the coating film 82 and acetone. can do. And after supplying infrared energy preferentially to water, in the step (b) when the coating film 82 passes through the second treatment space 12b, the first absorption region ( Infrared light having a wavelength in the second absorption region out of the wavelength region AA) and the second absorption region (wavelength region Aa) is selectively emitted from the far-infrared heater 60. Thereby, infrared energy can be efficiently put into acetone. As described above, by changing the infrared rays radiated to the coating film 82 in the steps (a) and (b), the order of water and acetone with respect to the two substances (water and acetone) contained in the coating film 82 is changed. The infrared energy can be input with priority. Thus, in the step (a), water is preferentially treated with infrared (evaporation) over acetone in the coating film 82, and then the second substance is subjected to infrared treatment (evaporation) in the step (b). Can do.

  In step (a), at least a part of the emission half-value width region H1, which is a half-value width region of the wavelength based on the radiation intensity of the radiation peak P1 of the near infrared heater 30, is the first absorption peak (absorption peak of water). Infrared rays are radiated to the coating film 82 so as to overlap with at least a part of the first absorption half-value width region (half-value width region HA) which is a half-value width region of the wavelength based on the absorption rate of (PA). Further, in the step (b), at least a part of the emission half width region H2, which is a half width region of the wavelength based on the radiation intensity of the radiation peak P2 of the far infrared heater 60, is a second absorption peak (absorption peak) of acetone. Infrared rays are emitted to the coating film 82 so as to overlap at least part of the second absorption half width region (half width region Ha), which is the half width region of the wavelength based on the absorption rate of Pa). Thus, by making at least a part of the half-width region of the infrared ray to be emitted and the half-width region of the infrared absorption of the substance to be evaporated overlap, it is more efficient for the substance to be evaporated in each step. Infrared energy can be input well and can be evaporated efficiently.

  Further, the first substance is water, and in the step (a), at least the first substance out of the substances contained in the coating film 82 is evaporated. Therefore, after increasing the concentration of acetone in the coating film 82 by the step (a), the acetone can be evaporated in the step (b).

  It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.

  For example, in the above-described embodiment, the object is the coating film 82, the first substance contained in the object is water, and the second substance is acetone, but the object, the first substance, and the second substance are the same. Not limited. For example, the first substance is a liquid other than water, the second substance is water, the first substance (liquid other than water) is preferentially evaporated in step (a), and the water is evaporated in step (b). Good. If it carries out like this, after reducing the density | concentration of the 1st substance (liquid other than water) in a target object in a process (a), water can be evaporated in a process (b). For example, in the case where the first substance and the second substance are to be evaporated together without performing the two steps (a) and (b), the second substance (water) is first evaporated and the target. The concentration of the first substance in the object may increase. And depending on the kind of 1st substance, the malfunction may arise, such as a target being damaged, when a density | concentration increases. Such a problem can be further suppressed by preferentially evaporating the first substance in the step (a). Moreover, only the 1st substance and the 2nd substance may be contained in the target object. The object may further include one or more substances other than the first substance and the second substance. That is, the target object may contain three or more substances.

  In the embodiment described above, the first and second substances are evaporated in the steps (a) and (b). However, the present invention is not limited to this, and energy is input to the first substance and the second substance by infrared rays. Anything can be processed. The “infrared treatment” includes a process for causing a physical change such as evaporation, drying, and dehydration, a process for causing a chemical reaction such as imidization, and a process for causing a temperature change such as a temperature increase. Further, the infrared treatment of the first substance and the infrared treatment of the second substance may be different, for example, the first substance is evaporated and the second substance is chemically reacted. The target object, the first substance, and the second substance are not limited to liquids, and at least one of them may be a solid.

  In the embodiment described above, when there are a plurality of absorption peaks in the infrared absorption spectrum of the first substance, the peak having the highest absorption rate is determined as the first absorption peak, but the present invention is not limited thereto. . In step (a), it is possible to selectively emit infrared rays having a wavelength in the first absorption region out of the first absorption region and the second absorption region, so that infrared energy can be preferentially input to the first substance. In addition, an appropriate one of the plurality of absorption peaks may be determined as the first absorption peak. For example, consider the case where the absorption peak PB has a higher absorption rate than the absorption peak PA in the upper part of FIG. In such a case, when an infrared ray having a wavelength in the wavelength region from the rise to the fall of the absorption spectrum including the absorption peak PB having the highest absorption rate in step (a) is to be emitted, the absorption peak Pa in the middle of FIG. Infrared rays are also radiated into the wavelength region Aa including the same. Therefore, it is easy to inject infrared energy into the first substance and the second substance in the same manner. In such a case, instead of the absorption peak PB having the highest absorption rate, it is more preferable that the absorption peak PA is set as the first absorption peak and infrared rays having a wavelength in the wavelength region AA are emitted in the step (a). It is easy to input infrared energy preferentially.

  In the above-described embodiment, when a plurality of absorption peaks exist in the infrared absorption spectrum of the second substance, the peak having the highest absorption rate is determined as the second absorption peak, but the present invention is not limited to this. .

  If there is only one absorption peak in the infrared absorption spectrum of the first substance, the absorption peak may be determined as the first absorption peak. The same applies to the second absorption peak.

  In the embodiment described above, the step (a) is performed using the near-infrared heater 30 and the step (b) is performed using the far-infrared heater 60. However, the present invention is not limited to this, and any infrared heater is used. Also good. For example, you may use the infrared heater of the same structure from which the material of a heat generating body differs in a process (a) and a process (b). If the emission peak or the like is changed between step (a) and step (b), the same infrared heater may be used in step (a) and step (b). In this case, the radiation peak may be changed by changing the temperature of the heating element of the infrared heater. Moreover, the radiation peak is changed between the step (a) and the step (b) by disposing an infrared absorption filter between the infrared heater and the coating film 82 at least one of the step (a) and the step (b). May be. Or you may vary the absorption characteristic of the infrared rays absorption filter arrange | positioned between an infrared heater and the coating film 82 by a process (a) and a process (b). Moreover, you may use what formed the layer which consists of thermochromic materials in the surface of the pipe | tube etc. which cover the heat generating body of an infrared heater. In this case, the infrared heater used in the step (a) and the infrared heater used in the step (b) are radiated to the coating film 82 by changing the degree of cooling of the tube and changing the infrared transmittance of the thermochromic material. The infrared radiation peak can be changed. In addition, various infrared heaters can be used in appropriate combination. For example, a microcavity may be formed on the surface of the heating element or on the surface of a member disposed between the heating element and the coating film 82 so as to increase the emissivity of infrared rays in a specific wavelength region. By so doing, the radiation intensity of infrared rays in a specific wavelength range increases, so that energy can be efficiently input into the specific wavelength range.

  In the above-described embodiment, the same number of near-infrared heaters 30 and far-infrared heaters 60 are arranged in the furnace body 11 at equal intervals. However, the present invention is not limited to this. For example, gradations may be added to the arrangement intervals of the infrared heaters, or the number of arrangement of the infrared heaters may be changed between the first processing space 12a and the second processing space 12b.

  In the embodiment described above, the steps (a) and (b) are performed in one furnace body 11, but each of the steps (a) and (b) is performed in two adjacent furnace bodies. Also good. Moreover, you may perform another process between a process (a) and a process (b). Moreover, although the infrared processing apparatus 10 is a roll-to-roll type continuous furnace, the infrared processing apparatus 10 may be a roller hearth kiln. Further, the infrared processing apparatus 10 is not limited to a continuous furnace but may be a batch furnace. FIG. 4 is a cross-sectional view of a modified infrared processing apparatus 110 configured as a batch furnace. The furnace body 111 of the infrared processing apparatus 110 has a furnace body entrance / exit 117 on the front end face 113. The furnace body entrance / exit 117 serves as an entrance / exit for the sheet 80 and the coating film 82 placed on the pedestal 184. A furnace door 119 which is an airtight door is attached in front of the furnace body entrance 117. A plurality of near-infrared heaters 30 and far-infrared heaters 60 are alternately arranged in a processing space 112 that is a space inside the furnace body 111. In the infrared processing apparatus 110, when the coating film 82 placed on the pedestal 184 is heat-treated, the near infrared heater 30 and the far infrared heater 60 are switched on and off to use the process (a) described above. , (B) can be performed. That is, first, the infrared rays from the near infrared heater 30 are emitted to the coating film 82 to perform the step (a), and then the infrared rays from the far infrared heater 60 are emitted to perform the step (b). Note that only one type of infrared heater may be disposed in the processing space 112, and the radiation peak may be varied by changing the temperature of the heating element of the infrared heater in the step (a) and the step (b). In this case, the pedestal 184 may be movable up and down by providing an elevating mechanism 270 shown in FIG. By carrying out like this, the distance of an infrared heater and the coating film 82 can be changed, and the infrared radiation intensity radiated | emitted from the infrared heater to the coating film 82 can be adjusted. When the radiation peak is made different by one type of infrared heater, for example, when the power supplied to the infrared heater is increased, the radiation peak is shifted to the short wavelength side and the radiation intensity to be radiated is increased. That is, when the radiation peak is changed, the radiation intensity is also changed. By making the pedestal 184 movable up and down, the infrared radiation intensity to the coating film 82 can be adjusted independently of the adjustment of the radiation peak. Therefore, it becomes easy to adjust both the radiation peak and the radiation intensity to appropriate states in each of the steps (a) and (b). In addition to or in place of the vertical movement of the base 184, the infrared radiation intensity to the coating film 82 may be adjusted by changing the number of infrared heaters to be energized.

  Moreover, you may perform process (a), (b) using the infrared processing apparatus 210 of FIG. In the infrared processing apparatus 210 of FIG. 5, a plurality of near infrared heaters 30 are arranged near the ceiling of the furnace body 111, and a plurality of far infrared heaters 60 are arranged near the bottom of the furnace body 111. In addition, the infrared processing device 210 includes an elevating mechanism 270 that moves the base 184 up and down in the processing space 112. Also in this infrared processing apparatus 210, the steps (a) and (b) described above can be performed by switching on and off the near infrared heater 30 and the far infrared heater 60 in the same manner as the infrared processing apparatus 110 in FIG. Further, the distance between the near infrared heater 30 and the far infrared heater 60 and the coating film 82 can be changed by the lifting mechanism 270. Therefore, the infrared radiation intensity to the coating film 82 can be adjusted without changing the peak wavelength of the infrared radiation radiated from the near infrared heater 30 or the far infrared heater 60 to the coating film 82. The pedestal 184 may be formed of a material having a high infrared transmittance from the far-infrared heater 60 or a mesh shape so as not to prevent infrared radiation from the far-infrared heater 60 to the coating film 82. .

  In the above-described embodiment, the coating film 82 becomes a p-type organic semiconductor layer of an organic thin film solar cell by heat treatment, but is not limited thereto. The infrared treatment method of the present invention may be used in any technical field as long as the first substance and the second substance are treated with infrared rays.

  DESCRIPTION OF SYMBOLS 10 Infrared processing measures, 11 Furnace body, 11a Center line, 12 Processing space, 12a, 12b 1st, 2nd processing space, 13 Front end surface, 14 Rear end surface, 17, 18 Opening, 21, 25 Roller, 30 Near infrared heater , 32 Filament, 34 Electrical wiring, 36 Inner pipe, 38 Heater body, 40 Outer pipe, 41 Reflective layer, 42 Cap, 44 Wiring lead-out part, 47 Refrigerant flow path, 48 Refrigerant inlet / outlet, 49 Holder, 50 Power supply source, 52 Refrigerant supply source, 56 temperature sensor, 60 far infrared heater, 80 sheet, 82 coating film, 90 controller, 110, 210 infrared processing device, 111 furnace body, 112 processing space, 113 front end face, 117 furnace body inlet / outlet, 119 furnace body Door, 184 base, 270 lifting mechanism.

Claims (4)

An infrared processing method of radiating infrared rays to an object including at least a first substance and a second substance, and infrared-treating at least the first and second substances in the object,
(A) a first absorption region that is a wavelength region from the rising to the falling of an absorption spectrum including a wavelength of a first absorption peak that is an infrared absorption peak of the first material in an infrared absorption spectrum; and the second material. In the second absorption region, which is a wavelength region from the rise to the fall of the absorption spectrum including the wavelength of the second absorption peak, which is an infrared absorption peak of the second absorption peak having a wavelength different from the first absorption peak, Selectively emitting infrared radiation having a wavelength in the first absorption region;
(B) after the step (a), selectively emitting infrared rays having a wavelength in the second absorption region out of the first absorption region and the second absorption region;
Infrared processing method. In the step (a), at least a part of the emission half-width region, which is a half-width region of a wavelength based on the radiation intensity of the infrared radiation peak radiated to the object, is the first substance of the first substance. Radiating infrared rays to the object so as to overlap with at least a part of the first absorption half width region which is a half width region of the wavelength based on the absorption rate of one absorption peak,
In the step (b), at least a part of the emission half-width region is at least a second absorption half-width region that is a half-width region of a wavelength based on the absorption rate of the second absorption peak of the second substance. Radiate infrared rays on the object so as to overlap with a part,
The infrared processing method according to claim 1. The first substance is a liquid other than water,
The second substance is water;
In the step (a), at least the first substance of the substance contained in the object is evaporated,
In the step (b), at least the second substance of the substance contained in the object is evaporated.
The infrared processing method according to claim 1 or 2. The first substance is water;
In the step (a), at least the first substance of the substance contained in the object is evaporated.
The infrared processing method according to claim 1 or 2.

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