JP2020076041A - Polypropylene carbonate containing layer, manufacturing method thereof and substrate equipped with polypropylene carbonate containing layer - Google Patents

Abstract

To provide a polypropylene carbonate containing layer with different liquid repellant properties.SOLUTION: A polypropylene carbonate containing layer 22 is a layer that contains a polypropylene carbonate. According to a change of exposure time and/or applied electric power when at least a surface of the layer 22 is exposed to oxygen plasma 70, a contact angle of the surface after the exposure to the oxygen plasma 70 can be changed within a range of 0.70-0.99, based on a contact angle of the surface before the exposure to the oxygen plasma 70 being 1.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a polypropylene carbonate-containing layer, a method for producing the same, and a substrate including the polypropylene carbonate-containing layer.

  With the demand for various types of information terminals and information appliances from the industrial world and consumers, the method of forming wiring for various devices in various fields, represented by miniaturized electronic devices, is evolving day by day. Is continuing.

  As a method of forming wiring or the like for various electronic devices, a manufacturing method requiring a relatively long time and / or expensive equipment such as a process using a vacuum process or a photolithography method has been adopted for many years. ..

  To date, the applicant of the present invention utilizes a precursor of an oxide semiconductor in which a compound of a metal that becomes an oxide semiconductor when oxidized is dispersed in a solution containing a binder made of an aliphatic polycarbonate. Disclosed is a technique for providing an oxide semiconductor layer that is reduced in generation and is excellent in electrical characteristics and stability, and a semiconductor element and an electronic device including the oxide semiconductor layer (Patent Document 1).

  Further, the applicant of the present application has found that when at least the surfaces of the plurality of island-shaped aliphatic polycarbonate-containing layers arranged on the substrate are exposed to ultraviolet light having a wavelength of 180 nm or more and 370 nm or less for 15 minutes, Disclosed is a composite member in which the contact angle between water and its surface is 50 ° or more, and the metal ink on the above-mentioned substrate is provided in at least a part of the region sandwiched between the precursor layers ( Patent Document 2).

International Publication No. WO2015 / 019771 International Publication No. WO2017 / 047227

  As described above, a manufacturing method typified by a vacuum process or a process using a photolithography method requires a lot of processing and a long time for manufacturing various devices, and thus lowers the use efficiency of raw materials and manufacturing energy. Leads to deterioration. Therefore, it is not preferable to adopt such a manufacturing method from the viewpoint of industrial property or mass productivity, and it becomes relatively difficult to increase the area.

  On the other hand, a low-energy manufacturing process represented by a printing method has been particularly attracting attention in the industrial world from the viewpoint of flexibility of electronic devices and the above-mentioned industrial property or mass productivity. By using the printing method or the coating method, it is possible to directly pattern a desired layer on the substrate, and therefore, it is possible to obtain an advantage that a vacuum process for patterning can be omitted. Therefore, realizing fine patterning using a layer containing an aliphatic polycarbonate (in particular, a layer containing polypropylene carbonate (hereinafter, also referred to as “polypropylene carbonate-containing layer”) is disclosed in Patent Document 1). Utilizing the rare features of the layers present can lead to the provision of technologies that are very attractive for various devices.

  However, the present inventor has learned that the polypropylene carbonate-containing layer can be a so-called obstacle because of its highly stable liquid repellency. Specifically, for example, when forming a metal wiring pattern formed by using a metal ink as a starting material, in order to selectively dispose the metal ink, in the same plane of the polypropylene carbonate-containing layer, depending on a region, A high degree of ingenuity, that is, high liquid repellency (as a representative index, the contact angle of pure water on the surface of the layer) and relatively low liquid repellency, can be required. Therefore, in order to widely utilize the polypropylene carbonate-containing layer for various devices, it is required to appropriately adjust between high liquid repellency and relatively low liquid repellency. However, it was difficult to realize this.

  Therefore, research and development toward the realization of a polypropylene carbonate-containing layer having different liquid repellency, which may be used in various devices in various fields typified by miniaturized electronic devices, is still in the midway. is there.

  The present invention can greatly contribute to the realization of polypropylene carbonate-containing layers having different liquid repellency.

  The present inventors consider that it is difficult to change the high liquid repellency, which is a feature of the surface of the polypropylene carbonate-containing layer, to a relatively low liquid repellency, depending on the technical information that has already been disclosed. We have conducted intensive research and analysis to realize liquid repellency that can be adjusted to As a result, they have found that it is possible to appropriately adjust the liquid repellency while maintaining a certain degree of liquid repellency by applying a special treatment to the surface of the polypropylene carbonate-containing layer. The present invention was created by the above-mentioned device.

  One polypropylene carbonate-containing layer of the present invention is a layer containing polypropylene carbonate, wherein the oxygen content of the above-mentioned oxygen is changed according to the change of exposure time and / or applied power when at least the surface of the layer is exposed to oxygen plasma. The contact angle of the surface after being exposed to the oxygen plasma, where the contact angle of the surface before being exposed to plasma is 1, can be changed within a range of 0.70 to 0.99. is there.

  According to this polypropylene carbonate-containing layer, at least the surface of the polypropylene carbonate-containing layer is exposed to oxygen plasma, and by changing the exposure time and / or the applied electric power, the contact angle of the surface of the layer is increased. It is possible to realize the layer that can be changed within a certain range while maintaining the liquidity.

  Further, another polypropylene carbonate-containing layer of the present invention is a layer containing polypropylene carbonate, wherein at least the surface of the layer is irradiated with ultraviolet rays, and / or at least the surface of the layer is irradiated with ultraviolet rays. When the contact angle of the surface before irradiation of the above-mentioned ultraviolet rays is set to 1 in accordance with the change in the distance between the surface and the ultraviolet irradiation source, the contact of the surface after irradiation of the ultraviolet rays The angle can be changed within the range of 0.70 or more and 0.99 or less.

  According to this polypropylene carbonate-containing layer, the irradiation time of irradiating at least the surface of the polypropylene carbonate-containing layer with ultraviolet rays, and / or the layer and the ultraviolet irradiation source when irradiating at least the surface of the layer with ultraviolet rays By changing the distance, it is possible to realize the layer in which the contact angle of the surface of the layer can be changed within a certain range while maintaining high liquid repellency.

In each of the above-mentioned inventions, among all the above-mentioned polypropylene carbonates, the polypropylene carbonate having a molecular weight of 1 × 10 ⁴ or more is 99.0 mass% or more, and the number average molecular weight is 1 × 10 ⁴ or more. Is a preferred embodiment because, when forming irregularities on the polypropylene carbonate using, for example, a nano-imprint method, a polypropylene carbonate-containing layer having irregularities with high dimensional accuracy can be realized with high accuracy. is there.

  In addition, one method for producing a polypropylene carbonate-containing layer of the present invention is to change the exposure time and / or the applied power when exposing at least the surface of the polypropylene carbonate-containing layer to oxygen plasma to obtain the aforementioned oxygen plasma. The contact angle of the surface after being exposed to the oxygen plasma, where the contact angle of the surface before being exposed to 1 is 1, is varied in the range of 0.70 to 0.99. Including a corner changing step.

  According to this method for producing a polypropylene carbonate-containing layer, at least the surface of the polypropylene carbonate-containing layer is exposed to oxygen plasma, and the exposure time and / or the applied power is changed to change the contact angle of the surface of the layer. It is possible to produce a polypropylene carbonate-containing layer adjusted in a certain range while maintaining high liquid repellency.

  In addition, another method for producing a polypropylene carbonate-containing layer of the present invention is to irradiate at least the surface of the layer containing polypropylene carbonate with an ultraviolet ray, and / or when at least the surface of the layer is irradiated with the ultraviolet ray. By changing the distance between the surface and the ultraviolet ray irradiation source, the contact angle of the surface after the ultraviolet ray is irradiated, when the contact angle of the surface before the ultraviolet ray is set to 1, The step of changing the contact angle is made different in the range of 0.70 or more and 0.99 or less.

  According to this polypropylene carbonate-containing layer, the irradiation time of irradiating at least the surface of the polypropylene carbonate-containing layer with ultraviolet rays, and / or the layer and the ultraviolet irradiation source when irradiating at least the surface of the layer with ultraviolet rays By changing the distance, it is possible to produce a polypropylene carbonate-containing layer in which the contact angle of the surface of the layer is adjusted within a certain range while maintaining high liquid repellency.

  Further, the substrate of the present invention comprises a first polypropylene carbonate-containing layer and a second polypropylene carbonate-containing layer, and comprises the above-mentioned first polypropylene carbonate-containing layer having a surface having a high contact angle and the surface having a low contact angle. The above-mentioned second polypropylene carbonate-containing layer.

  The substrate has a plurality of regions of polypropylene carbonate-containing layers (that is, at least a first polypropylene carbonate-containing layer and a second polypropylene carbonate-containing layer) each having a surface with a different contact angle. Therefore, for example, when the liquid metal ink is arranged on the polypropylene carbonate-containing layer described above, a gradient of “wettability” is formed, so to speak, as compared with the polypropylene carbonate-containing layer having high liquid repellency, The metal ink is more likely to be placed on the polypropylene carbonate-containing layer having low liquid repellency. More generalized, the substrate comprising the above-mentioned polypropylene carbonate-containing layer can realize the selective arrangement of the liquid substance on the polypropylene carbonate-containing layer.

  By the way, in the present application, the “gel state” is, as a typical example, a certain amount of solvent by heat treatment from a liquid state (typically, 80% or more by mass ratio to the whole solvent However, polypropylene carbonate is in a state of being removed, but polypropylene carbonate is not substantially decomposed or removed.

  In addition, the “layer” in the present application is a concept including not only a layer but also a film. On the contrary, the “film” in the present application is a concept including not only a film but also a layer. The "contact angle" in the present application means the contact angle of pure water on the surface of the polypropylene carbonate-containing layer.

  In addition, the “base material” in the present application is not limited to the base of the plate-shaped body, but includes a base or a base material of other forms (for example, a curved surface). In addition, in each of the embodiments described later in the present application, “coating” means a low energy manufacturing process, typically a printing method, a spin coating method, a bar coating method, a slit coating method, or a nano imprint method. Forming a layer on a substrate.

In addition, the phrase “substantially free of polypropylene carbonate having a molecular weight of less than 10,000 (that is, less than 1 × 10 ⁴ )” in the present application means that a commercially available analyzer (manufactured by Tosoh Corporation, model: HLC) at the time of filing of the present application -8020) is below the detection limit value.

  According to one polypropylene carbonate-containing layer of the present invention, it is possible to realize the layer capable of changing the contact angle of the surface of the layer within a certain range while maintaining high liquid repellency.

  Further, according to one method for producing a polypropylene carbonate-containing layer of the present invention, a polypropylene carbonate-containing layer in which the contact angle of the surface of the layer is adjusted within a certain range while maintaining high liquid repellency is produced. be able to.

  Further, one substrate of the present invention has a plurality of regions of polypropylene carbonate-containing layers (that is, at least a first polypropylene carbonate-containing layer and a second polypropylene carbonate-containing layer) each having a surface with a different contact angle. Therefore, this substrate can realize the selective arrangement of the liquid substance on the polypropylene carbonate-containing layer.

It is a graph which shows an example of the TG-DTA characteristic of the polypropylene carbonate containing solution of a 1st embodiment. It is a cross-sectional schematic diagram which shows 1 process of the manufacturing method of the composite member in 1st Embodiment. It is a cross-sectional schematic diagram which shows 1 process of the manufacturing method of the composite member in 1st Embodiment. It is a cross-sectional schematic diagram which shows 1 process of the manufacturing method of the composite member in 1st Embodiment. It is a cross-sectional schematic diagram which shows 1 process of the manufacturing method of the composite member in 2nd Embodiment. It is a cross-sectional schematic diagram which shows 1 process of the manufacturing method of the composite member in 2nd Embodiment. It is a cross-sectional schematic diagram which shows 1 process of the manufacturing method of the composite member in 2nd Embodiment. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the composite member in the modification of 2nd Embodiment. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the composite member in the modification of 2nd Embodiment. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the composite member in the modification of 2nd Embodiment. It is a cross-sectional schematic diagram which shows 1 process of the manufacturing method of the composite member in other embodiment. It is a side view which shows the whole structure of the composite member in other embodiments. It is an example of a graph showing a step measurement result showing one step of a method for manufacturing a composite member in another embodiment. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the composite member in a comparative example.

  A composite member, a polypropylene carbonate-containing layer, and a method for producing the composite member, which are embodiments of the present invention, will be described in detail with reference to the accompanying drawings. In this description, common parts are denoted by common reference symbols throughout the drawings unless otherwise specified. In addition, in the drawings, the elements of the respective embodiments are not necessarily described in a mutually reduced scale. Further, some symbols may be omitted to make the drawings easier to see.

<First Embodiment>
1. Polypropylene carbonate-containing solution and polypropylene carbonate-containing layer, and methods for producing them The polypropylene carbonate-containing solution (which may contain unavoidable impurities; hereinafter the same) of the present embodiment has the polypropylene carbonate-containing layer (which may contain unavoidable impurities). Hereinafter, the same) is a raw material for manufacturing.

  In the present embodiment, it is possible to realize a layer in which the contact angle of the surface of the polypropylene carbonate-containing layer can be changed within a certain range while maintaining high liquid repellency. In other words, by adopting the polypropylene carbonate-containing layer of the present embodiment, the contact angle of the surface of the layer can be adjusted within a certain range while maintaining high liquid repellency. The polypropylene carbonate-containing solution of the present embodiment and the polypropylene carbonate-containing layer of the present embodiment will be described below.

(About polypropylene carbonate-containing solution and polypropylene carbonate-containing layer)
In the present embodiment, a state in which polypropylene carbonate having a number average molecular weight of 1 × 10 ³ or more and 2 × 10 ⁶ or less is dissolved in a solvent (typically, an organic solvent) is the “polypropylene of the present embodiment”. A carbonate-containing solution ".

  In addition, by heating the polypropylene carbonate-containing solution, the solvent is removed to the extent that it can be used in the nano-imprinting method or various printing methods (for example, screen printing method) (typically, " The layer in the "gel state") is the "polypropylene carbonate-containing layer" of the present embodiment.

  The polypropylene carbonate-containing solution of the present embodiment mainly contains polypropylene carbonate, but may contain compounds, compositions, or materials other than polypropylene carbonate. The lower limit of the polypropylene carbonate content in the polypropylene carbonate-containing solution is not particularly limited, but typically, the mass ratio of the polypropylene carbonate to the total amount of solutes is 80% or more. The upper limit of the polypropylene carbonate content in the polypropylene carbonate-containing solution is not particularly limited, but typically, the mass ratio of the polypropylene carbonate to the total amount of solutes is 100% or less.

  In addition, the polypropylene carbonate-containing layer becomes the polypropylene carbonate-containing layer having irregularities formed by, for example, the embossing step described later.

(Example of polypropylene carbonate-containing solution and polypropylene carbonate-containing layer)
In this embodiment, polypropylene carbonate having a good thermal decomposability is used. Such polypropylene carbonate has a high oxygen content and is capable of decomposing into a low molecular compound at a relatively low temperature.

  Further, in the present embodiment, the organic solvent that can be adopted in the “polypropylene carbonate-containing solution” that is a solution containing polypropylene carbonate is not particularly limited as long as it is an organic solvent that can dissolve polypropylene carbonate. As a specific example of the organic solvent, the organic solvent disclosed in International Publication No. WO2016 / 098423 is preferably used.

  If desired, the polypropylene carbonate-containing solution, which is a solution containing polypropylene carbonate, may further contain a dispersant and / or a plasticizer, which are disclosed in International Publication No. WO2016 / 098423.

  Moreover, the method of forming the polypropylene carbonate-containing layer of the present embodiment is not particularly limited. The formation of the layer by a low energy manufacturing process represented by the formation of the layer by a coating method or the like is one preferable mode. When forming a polypropylene carbonate-containing layer having irregularities formed on a base material, for example, a simple method such as nano-imprint method may be adopted.

<TG-DTA (thermogravimetric and differential heat) characteristics>
Here, with regard to polypropylene carbonate, which can be decomposed into a low-molecular compound at a relatively low temperature, the present inventors have more specifically investigated the process of decomposition and disappearance thereof.

  FIG. 1 is a graph showing an example of TG-DTA characteristics of a solution containing polypropylene carbonate as a solute, which is a typical example of polypropylene carbonate (that is, the polypropylene carbonate-containing solution of the present embodiment). The graph shows the results of a DEGMEA solution containing 6.25% by mass of polypropylene carbonate under normal pressure. Further, as shown in FIG. 1, the solid line in the figure is the thermogravimetric (TG) measurement result, and the dotted line in the figure is the differential thermal (DTA) measurement result.

  From the results of thermogravimetric measurement shown in FIG. 1, from 140 ° C. to around 190 ° C., it was found that the solvent of the polypropylene carbonate-containing solution disappeared and that the weight decreased remarkably due to the decomposition or disappearance of part of the polypropylene carbonate itself. .. It is considered that polypropylene carbonate is changed into carbon dioxide and water by this decomposition. From the results shown in FIG. 1, it was confirmed that the polypropylene carbonate was decomposed by 90 wt% or more at around 190 ° C. and removed. More specifically, it can be seen that the polypropylene carbonate is decomposed by 95 wt% or more at around 250 ° C. and almost all (99 wt% or more) is decomposed at around 260 ° C. Therefore, the layer of the polypropylene carbonate-containing solution is heated by adopting the polypropylene carbonate-containing solution which is substantially or almost completely eliminated or removed by performing the heat treatment at 250 ° C. or higher (more preferably 260 ° C. or higher). The polypropylene carbonate-containing layer thus formed can be decomposed or removed.

  Therefore, for example, it can serve as a sacrificial layer for forming a metal layer formed by using the pattern of the polypropylene carbonate-containing layer formed from the polypropylene carbonate-containing layer having irregularities. In other words, the pattern of the polypropylene carbonate-containing layer can be decomposed or removed substantially without leaving its own residue. The polypropylene carbonate-containing layer has a high oxygen content and is a very suitable material as a so-called sacrifice layer from the viewpoint of decomposing into a low-molecular compound at a relatively low temperature.

  Note that the above results are the results of decomposition of the polypropylene carbonate by heat treatment for a relatively short time, but when heat treatment is performed for a longer time, a lower temperature (eg, 180 ° C.) is sufficient. It has been confirmed that the polypropylene carbonate decomposes. In other words, it can be said that the lower limit of the temperature at which the polypropylene carbonate is decomposed or removed by heating is typically 180 ° C. However, this lower limit temperature does not mean a temperature at which only one or several bonds in the polypropylene carbonate are broken, but the decomposition of the polypropylene carbonate causes the polypropylene carbonate to substantially or almost decompose so that the mass of This is the temperature at which the decrease is confirmed.

  Therefore, by adopting a polypropylene carbonate-containing layer that is substantially or almost decomposed or removed when heated at 180 ° C. or higher, for example, using the pattern of the polypropylene carbonate-containing layer, as in the above, Can serve as a sacrificial layer for the formation of the deposited metal layer. In other words, the pattern of the polypropylene carbonate-containing layer can be decomposed or removed substantially without leaving its own residue.

  Incidentally, a typical example of the pattern of the polypropylene carbonate-containing layer is a pattern represented by lines and spaces or dots which can be adopted in the field of nanoimprint, semiconductor, or electronic device. The shape of the pattern of the embodiment is not limited to them. The polypropylene carbonate-containing layer having various known pattern shapes may also be included in the “pattern of the polypropylene carbonate-containing layer” of the present embodiment.

(About polypropylene carbonate)
In the present embodiment, polypropylene carbonate obtained by polymerizing an epoxide and carbon dioxide is adopted as a suitable aspect.

  Further, the above-mentioned epoxide is not particularly limited as long as it is an epoxide which becomes a polypropylene carbonate having a structure containing an aliphatic group in its main chain by polymerizing with carbon dioxide. For example, propylene oxide is an example that can be adopted in this embodiment. Propylene oxide is preferably used from the viewpoint of having high polymerization reactivity with carbon dioxide.

(About the manufacturing method of polypropylene carbonate)
As an example of the method for producing the polypropylene carbonate of the present embodiment, a method of polymerizing an epoxide and carbon dioxide in the presence of a metal catalyst can be adopted.

Here, a production example of polypropylene carbonate is as follows.
The inside of an autoclave with a volume of 1 L (liter) equipped with a stirrer, a gas introduction tube, and a thermometer was previously replaced with a nitrogen atmosphere, and then a reaction solution containing an organozinc catalyst, hexane, and propylene oxide were charged. Next, the reaction system was replaced with a carbon dioxide atmosphere by adding carbon dioxide with stirring, and carbon dioxide was charged until the reaction system became about 1.5 MPa. Then, the autoclave was heated to 60 ° C., and a polymerization reaction was carried out for several hours while supplementing carbon dioxide consumed by the reaction. After completion of the reaction, the autoclave was cooled, depressurized and filtered. Then, it was dried under reduced pressure to obtain polypropylene carbonate.

  As the above-mentioned metal catalyst, the catalyst disclosed in International Publication No. WO2016 / 098423, particularly an organozinc catalyst, is preferably used.

  Further, as the above-mentioned organozinc catalyst, the catalyst disclosed in International Publication No. WO2016 / 098423 is preferably used.

Here, a production example of the organic zinc catalyst is as follows.
First, zinc oxide, glutaric acid, acetic acid, and toluene were charged into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, and a reflux condenser. Next, after replacing the inside of the reaction system with a nitrogen atmosphere, the flask was heated to 55 ° C. and stirred at the same temperature for 4 hours to carry out the reaction treatment of each of the above-mentioned materials. Then, the temperature was raised to 110 ° C., and the mixture was stirred at the same temperature for 4 hours for azeotropic dehydration to remove only water. Then, the flask was cooled to room temperature to obtain a reaction solution containing an organozinc catalyst. An IR was measured (trade name: AVATAR360 manufactured by Thermo Nicolet Japan Co., Ltd.) with respect to the organozinc catalyst obtained by collecting and filtering a part of this reaction solution. As a result, no peak based on the carboxylic acid group was observed.

  The amount of the above-mentioned metal catalyst used in the polymerization reaction is preferably the amount disclosed in International Publication No. WO2016 / 098423.

Note that the present inventors have adopted a cobalt complex disclosed in, for example, International Publication No. WO2012 / 114939, instead of the above catalyst, so that the main chain is represented by the following general formula (I). It was confirmed that it is possible to produce a polypropylene carbonate containing a polypropylene carbonate containing a repeating unit having the following structural units and having a structure regularity of 99% or more. The state in which the structural regularity is impaired means that, for example, a state in which CO ₂ is deficient in the polymer chain is formed.

  Further, the reaction solvent used as necessary in the above-mentioned polymerization reaction is not particularly limited. Specifically, the example disclosed in International Publication No. WO2016 / 098423 can be adopted.

  The amount of the above-mentioned reaction solvent used is preferably the amount disclosed in International Publication No. WO2016 / 098423.

  Moreover, in the above-mentioned polymerization reaction, the method of reacting the epoxide and carbon dioxide in the presence of a metal catalyst is not particularly limited. For example, the method disclosed in International Publication No. WO2016 / 098423 can be adopted.

  In addition, the working pressure of carbon dioxide used in the above-mentioned polymerization reaction is not particularly limited. Typically, the pressure disclosed in International Publication No. WO2016 / 098423 can be adopted.

  Furthermore, the polymerization reaction temperature in the above-mentioned polymerization reaction is not particularly limited. Typically, it is preferably 30 ° C or higher and 100 ° C or lower, and more preferably 40 ° C or higher and 80 ° C or lower. When the polymerization reaction temperature is lower than 30 ° C, the polymerization reaction may take a long time. Further, when the polymerization reaction temperature exceeds 100 ° C., a side reaction may occur and the yield may be reduced. The polymerization reaction time cannot be generally stated because it depends on the polymerization reaction temperature, but it is typically preferably 2 hours to 40 hours.

  After the completion of the polymerization reaction, the above-mentioned polypropylene carbonate is dissolved in the already-described organic solvent capable of dissolving polypropylene carbonate (for example, diethylene glycol monoethyl ether acetate), and then the above-mentioned catalyst is removed by filtration. As a result, the polypropylene carbonate-containing solution of this embodiment is manufactured.

<Second Embodiment>
Next, the present inventors manufactured the composite member 100 provided with the base material 10 and the polypropylene carbonate-containing layer using the polypropylene carbonate-containing solution of the first embodiment.

(Method of manufacturing composite member)
A method of manufacturing the composite member 100 according to this embodiment will be described with reference to FIGS. 2 to 4.

[Process for producing polypropylene carbonate-containing layer]
In the present embodiment, as shown in FIG. 2, the polypropylene carbonate-containing layer 22 is formed on glass or polyimide, which is an example of the base material 10, by a known spin coating method or a bar coating method. This step is an example of the polypropylene carbonate-containing layer forming step. The thickness of the polypropylene carbonate-containing layer 22 of the present embodiment is not particularly limited, but its typical thickness is 300 nm or more and 4000 nm or less.

In addition, the base material 10 of the present embodiment is not particularly limited. For example, the base material 10 is a silicon (Si) substrate, high heat resistant glass, SiO ₂ / Si substrate (that is, a substrate in which a silicon oxide layer is formed on a silicon substrate), an alumina (Al ₂ O ₃ ) substrate, STO (SrTiO ₃ ). ) Substrates, insulating substrates in which STO (SrTiO) layers are formed by interposing SiO ₂ layers and Ti layers on the surface of silicon substrates, semiconductor substrates (for example, Si substrates, SiC substrates, Ge substrates, etc.) A substrate can be applied. In addition, the insulating base material includes, for example, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins, cellulose triacetate, polycarbonate, polyamide, polyimide, polyamide imide, polysulfone, aramid, aromatic polyamide and the like. It includes a film or sheet. The thickness of the base material 10 is not particularly limited, but is, for example, 3 μm or more and 300 μm or less. Further, the base material 10 may be rigid or flexible. The base material 10 may include the base material 10 on which an insulating layer, a semiconductor layer, or a conductive material layer or a pattern thereof is formed in advance.

  Next, the step of removing the solvent component contained in the polypropylene carbonate-containing layer 22 by preliminary heating of the polypropylene carbonate-containing layer 22 (pre-baking step or drying step, hereinafter collectively referred to as "pre-baking step") That is done). In the present embodiment, heat treatment at 100 ° C. to 150 ° C. was performed as the preliminary firing process.

(Exposure process by oxygen plasma)
Then, a step of exposing the entire surface of the polypropylene carbonate-containing layer 22 to plasma (hereinafter, also referred to as “oxygen plasma”) generated by exciting a gas containing oxygen in an atmospheric pressure atmosphere is performed. The specific gases introduced into the processing chamber to form the plasma of the present embodiment are oxygen, argon, and helium. Further, the applied high frequency power (that is, the applied power) is about 500W. In this embodiment, an atmospheric pressure plasma device manufactured by Yamato Scientific Co., Ltd. (model, YAP510S) was used. The applied power is not limited to 500W. The applied power can be appropriately changed within a range in which the plasma can be formed.

  By the way, in addition to the above-mentioned plasma generated in an atmospheric pressure atmosphere, an etching treatment using oxygen plasma under reduced pressure may be additionally used, which is the same as the technical idea disclosed in WO2017 / 047227. is there.

  In the present embodiment, the present inventor changes the liquid repellency of the surface of the polypropylene carbonate-containing layer 22 by performing the step of exposing at least the surface of the polypropylene carbonate-containing layer 22 to the plasma described above. I tried.

  Specifically, the contact angle of the surface before and after the exposure to the oxygen plasma was measured when the exposure time when exposing at least the surface of the polypropylene carbonate-containing layer 22 to the oxygen plasma was changed.

  Table 1 shows the relationship between the exposure time to oxygen plasma and the contact angle for three types of samples (Sample 1a, Sample 2a, Sample 3a).

  Sample 1a is a polypropylene carbonate having a mass average molecular weight of about 360,000 and a polypropylene carbonate having a structural regularity of about 94% in the main chain structure represented by the following general formula (I). It is a carbonate-containing layer. Sample 2a is a polypropylene carbonate having a mass average molecular weight of about 113,000 and a main chain structure represented by the following general formula (I) having a structure regularity of 99% or more. The polypropylene carbonate-containing layer. Further, the sample 3a is polypropylene carbonate having a mass average molecular weight of about 3540,000, and the main chain structure represented by the following general formula (I) is polypropylene carbonate having a structural regularity of 99% or more. The polypropylene carbonate-containing layer.

  In addition, “5 times” in Table 1 means that the polypropylene carbonate-containing layer at a certain position is defined as an exposure condition of oxygen plasma (circular region having a diameter of 200 mm) that moves at a sweeping speed of 100 mm / min as an oxygen plasma exposure condition. This means that it was swept five times. Thus, for that particular location of exposure, "five times" means a total of 600 seconds of exposure by the oxygen plasma. In addition, "15 times" in Table 1 means that the number of sweeps is 15 times. According to the above conditions, the exposure condition of oxygen plasma means that the exposure was performed by oxygen plasma for a total of 1800 seconds. Therefore, in the example of Table 1, an example of the contact angle when the exposure time to oxygen plasma changes substantially in the range of 0 seconds to 1800 seconds is shown.

  In addition, as shown in Table 1, the contact angle (deg.) Is displayed in the upper part of each column, and the contact angle of the surface of the polypropylene carbonate-containing layer 22 before exposure to oxygen plasma is 100 (in the lower part). %), The ratio (%) of the contact angle of the surface after being exposed to the oxygen plasma is displayed. For example, the calculation formula of the retention rate of “5 times” in the sample 1a is (69.5 ÷ 74.3) × 100, and the second decimal place is rounded off.

  As a result, interesting results were obtained in the relationship between the contact angle of the surface of the polypropylene carbonate-containing layer 22 before being exposed to oxygen plasma and the contact angle of the surface after being exposed to oxygen plasma. As shown in the retention rate in Table 1, by exposing at least the surface of the polypropylene carbonate-containing layer 22 to oxygen plasma, the oxygen plasma when the contact angle of the surface before being exposed to oxygen plasma is 1. It has been revealed that the contact angle of the surface after being exposed to is changeable in the range of 0.70 or more and 0.95 or less. Further, the inventors of the present invention conducted a study including lower molecular weight polypropylene carbonate or higher molecular weight polypropylene carbonate, and as a result, the contact angle of the surface of the polypropylene carbonate-containing layer 22 before being exposed to oxygen plasma was set to 1. It was revealed that the contact angle of the surface after being exposed to the oxygen plasma can be changed within the range of 0.70 or more and 0.99 or less.

  From a different point of view, the treatment described above changes the contact angle of the surface of the polypropylene carbonate-containing layer 22 before exposure to the oxygen plasma by varying the exposure time when exposing at least the surface to the oxygen plasma. In other words, the contact angle changing step of differentiating the contact angle of the surface after being exposed to the oxygen plasma in the range of 0.70 or more and 0.99 or less.

  Further, in all of the three types of samples shown in Table 1, at least the contact angle of 50 ° (50 deg.) Or more was achieved, so that even when exposed to oxygen plasma, the polypropylene carbonate-containing layer It was confirmed that the surface of No. 22 maintained a certain level of high liquid repellency. As a comparative example, as a result of exposing a layer made of a known acrylic resin (more specifically, polymethylmethacrylate resin (PMMA)) having a mass average molecular weight of about 350,000 to oxygen plasma, The contact angle was 65.6 °, but the contact angle decreased to 48.1 ° under the above 15 conditions.

  As described above, the present inventor changed the contact time (that is, liquid repellency) on the surface of the polypropylene carbonate-containing layer 22 by changing the exposure time to oxygen plasma while maintaining the liquid repellency to some extent. I learned that it is possible to change with. As a result, the present inventor has found that by utilizing this characteristic, the polypropylene carbonate-containing layer 22 having a surface that realizes different contact angles in a plurality of partitioned areas can be manufactured.

  In addition, based on the above-mentioned findings, the present inventors form the polypropylene carbonate-containing layer 22 even if the exposure time to the oxygen plasma when the surface is exposed to the oxygen plasma is the same. It has been found that when the applied power is changed, the contact angle of the surface before and after exposure to the oxygen plasma can change. Specifically, the higher the applied power for generating the plasma, the greater the degree of decrease in the contact angle as compared with that before the exposure to the plasma. Further, the present inventors also exposed to at least the surface of the polypropylene carbonate-containing layer 22 by changing both the exposure time to the oxygen plasma and the applied power when the oxygen plasma is exposed. We have found that the contact angle of the front and back surfaces can change. Specifically, the longer the exposure time to the plasma, or the higher the applied power for generating the plasma, the greater the degree of decrease in the contact angle as compared with that before the exposure to the plasma. Will be done.

  FIG. 3 is a schematic cross-sectional view showing one step (oxygen plasma exposure step) of the method for manufacturing the composite member 100 of this embodiment. As shown in FIG. 3, a known resist layer 50 having a plurality of thicknesses is formed by a screen printing method on a part of the surface of the polypropylene carbonate-containing layer 22 arranged on the base material 10. Further, FIG. 3 shows a state in which the polypropylene carbonate-containing layer 22 and the resist layer 50 are exposed to the oxygen plasma 70.

As a result, the polypropylene carbonate-containing layer 22 in the area indicated by A ₁ in FIG. 3 is exposed to the oxygen plasma 70 for the longest time because the resist layer 50 is not provided. Further, the polypropylene carbonate-containing layer 22 in the region indicated by B ₁ in FIG. 3 is exposed to the oxygen plasma 70 after the relatively thin resist layer 50 is removed by the oxygen plasma 70. Therefore, the exposure time to oxygen plasma becomes shorter than that of the polypropylene carbonate-containing layer 22 in the region indicated by A ₁ . Further, the polypropylene carbonate-containing layer 22 in the region indicated by C ₁ in FIG. 3 is exposed to the oxygen plasma 70 after the relatively thick resist layer 50 is removed by the oxygen plasma 70. Therefore, the exposure time to oxygen plasma becomes shorter than that of the polypropylene carbonate-containing layer 22 in the region shown by B ₁ .

As a result of performing the above-described oxygen plasma exposure step, as shown in FIG. 4, polypropylene carbonate having at least a surface having different exposure times to oxygen plasma in each region (A ₁ , B ₁ , C ₁ ). The containing layer 22 can be formed.

  In addition, when the time of exposure to oxygen plasma is at least 10 minutes or less, the exposure to oxygen plasma when the contact angle of the surface of the polypropylene carbonate-containing layer 22 before exposure to oxygen plasma is 1 It is possible to provide the polypropylene carbonate-containing layer 22 in which the contact angle of the surface after being adjusted is adjusted in the range of at least 0.70 and not more than 0.99. If the exposure time to oxygen plasma is at least 10 minutes or less, the polypropylene carbonate-containing layer 22 that is exposed to oxygen plasma for a long time tends to have a lower contact angle than the polypropylene carbonate-containing layer 22 that is exposed for a short time. Therefore, it can be rephrased as follows in this example.

When the region B ₁ of the polypropylene carbonate-containing layer 22 shown in FIG. 4 is regarded as, for example, the first polypropylene carbonate-containing layer, and the region A ₁ of the polypropylene carbonate-containing layer 22 is regarded as, for example, the second polypropylene carbonate-containing layer. The base material 10 of the present embodiment includes the first polypropylene carbonate-containing layer 22 in the region B ₁ having a surface with a high contact angle and the second polypropylene carbonate-containing layer in the region A _{1 having} a surface with a low contact angle. 22 and.

In the above example, the region B ₁ is regarded as the first polypropylene carbonate-containing layer 22 and the region A ₁ is regarded as the second polypropylene carbonate-containing layer 22, but each region and the first or second The correspondence with the polypropylene carbonate-containing layer is not limited to the above example. For example, the region C ₁ can be regarded as the first polypropylene carbonate-containing layer 22 and the region B ₁ can be regarded as the second polypropylene carbonate-containing layer 22. Further, the region C ₁ can be regarded as the first polypropylene carbonate-containing layer 22 and the region A ₁ can be regarded as the second polypropylene carbonate-containing layer 22.

  In addition, for example, when the liquid metal ink is arranged on the above-mentioned polypropylene carbonate-containing layer 22, it can be said from the viewpoint of realizing the voluntary arrangement of the metal ink with high accuracy by forming a so-called “wettability” gradient. For example, the contact angle of the surface of the first polypropylene carbonate-containing layer 22 is higher than the contact angle of the surface of the second polypropylene carbonate-containing layer 10 ° or more (more preferably 15 ° or more, or more than 15 °). Is a preferred embodiment. Even when maintaining such a high wettability gradient, the contact angle of the surface of the second polypropylene carbonate-containing layer 22 is preferably 50 ° or more.

<Third Embodiment>
Next, the polypropylene carbonate-containing layer 222 formed on the substrate 10 by the same manufacturing method as the polypropylene carbonate-containing layer 22 of the first embodiment using the polypropylene carbonate-containing solution of the first embodiment, and the polypropylene thereof. The composite member 200a including the carbonate-containing layer 222 will be described. Note that the description overlapping with the first or second embodiment may be omitted.

(Method of manufacturing composite member)
A method of manufacturing the composite member 200a of the present embodiment will be described with reference to FIGS.

(UV irradiation process)
In the present embodiment, a known ultraviolet irradiation source (ultraviolet irradiation device) 80 (manufactured by Multiply Co., model, MHU-110WB) is used to cover the entire surface of the polypropylene carbonate-containing layer 222 that has undergone the preliminary firing step. An ultraviolet irradiation step of irradiating an ultraviolet ray having a wavelength of 180 nm or more and 370 nm or less is performed. In the present embodiment, another example of the ultraviolet ray irradiation source for irradiating the ultraviolet ray having a wavelength of 180 nm or more and 370 nm or less is a commercially available ultraviolet ray lamp having a main wavelength of 365 nm (manufactured by AS ONE Corporation, model, SLW-8). is there.

In addition, in this embodiment, the distance between the ultraviolet irradiation source 80 and the surface of the polypropylene carbonate-containing layer 222 is 10 mm. Further, in the present application, when measuring the distance between the ultraviolet irradiation source 80 and the surface of the polypropylene carbonate-containing layer, the location of the light source in the ultraviolet irradiation source 80 is used as the measurement reference. The ultraviolet intensity (or ultraviolet illuminance) in this embodiment is 0.275 mW / cm ² .

  In the present embodiment, the present inventor tried to change the liquid repellency of the surface of the polypropylene carbonate-containing layer 222 by performing the above-mentioned ultraviolet irradiation step on at least the surface of the polypropylene carbonate-containing layer 222. ..

  Specifically, the contact angle of the surface before and after the irradiation of the ultraviolet rays was measured when the irradiation time of irradiating the surface of the polypropylene carbonate-containing layer 222 with the ultraviolet rays was changed.

  Table 2 shows the relationship between the irradiation time of ultraviolet rays and the contact angle for two types of samples (Sample 1b and Sample 2b).

  Sample 1b is a polypropylene carbonate having a mass average molecular weight of about 360,000 and a polypropylene carbonate having a structural regularity of about 94% in the main chain structure represented by the following general formula (I). It is a carbonate-containing layer. Sample 2b is a polypropylene carbonate having a mass average molecular weight of about 360,000 and a polypropylene carbonate having a structural regularity of about 94% in the main chain structure represented by the following general formula (I). It is a carbonate-containing layer.

  As a result, interesting results were obtained in the relationship between the contact angle of the surface of the polypropylene carbonate-containing layer 222 before irradiation with ultraviolet light and the contact angle of the surface after irradiation with ultraviolet light. As shown in the retention rate in Table 2, by irradiating at least the surface of the polypropylene carbonate-containing layer 222 with ultraviolet rays, after irradiating the ultraviolet rays, when the contact angle of the surface before irradiating the ultraviolet rays is 1 It has been revealed that the contact angle of the surface can be changed within the range of 0.85 or more and 0.95 or less. Furthermore, as a result of further studies by the present inventors including a lower molecular weight polypropylene carbonate or a higher molecular weight polypropylene carbonate, by irradiating at least the surface of the polypropylene carbonate-containing layer 222 with ultraviolet light, It was clarified that the contact angle of the surface after irradiation of the ultraviolet rays, where the contact angle of the surface of 1 was 1, can be changed within the range of 0.70 or more and 0.99 or less.

  From a different point of view, the above-described treatment is performed when the contact angle of the surface before irradiation with the ultraviolet rays is set to 1 by changing the irradiation time when the ultraviolet rays are applied to at least the surface of the polypropylene carbonate-containing layer 222. In other words, it can be rephrased as a contact angle changing step in which the contact angle of the surface after being irradiated with the ultraviolet rays is made different in the range of 0.70 or more and 0.99 or less.

  Further, based on the sample 1b shown in Table 2 and other research results, since the contact angle of at least 50 ° (50 deg.) Or more is realized, the polypropylene carbonate-containing layer is exposed even when ultraviolet rays are irradiated. It was confirmed that the surface of 222 maintains a certain degree of high liquid repellency. As a comparative example, as a result of irradiating a layer made of a known acrylic resin (more specifically, polymethylmethacrylate resin (PMMA)) having a mass average molecular weight of about 350,000 with ultraviolet rays, contact before exposure was performed. The angle was 63.0 °, but the contact angle decreased to 27.7 ° (holding rate: about 44%) under the above-mentioned condition of 20 minutes.

  As described above, the present inventor changed the contact angle (that is, liquid repellency) on the surface of the polypropylene carbonate-containing layer 222 by changing the time of irradiating the ultraviolet light while maintaining the liquid repellency to some extent. I knew that it was possible to change. As a result, the present inventor has found that by utilizing this characteristic, it is possible to manufacture the polypropylene carbonate-containing layer 222 having a surface that realizes different contact angles in a plurality of partitioned areas.

  5 and 6 are schematic cross-sectional views showing one step (ultraviolet irradiation step) of the method for manufacturing the composite member 200a of the present embodiment. As shown in FIGS. 5 and 6, ultraviolet rays are not substantially transmitted above the surface of a part of the polypropylene carbonate-containing layer 222 disposed on the base material 10 (in other words, the ultraviolet rays are substantially blocked). ) A mask 82 provided with a known material is movably arranged.

5 and 6 show a state in which the polypropylene carbonate-containing layer 222 is exposed to ultraviolet rays. In addition, the state shown in FIG. 6 shows a state formed after a certain time has passed in the state shown in FIG. Therefore, when the area indicated by B ₂ in FIG. 6 starts to be irradiated with the ultraviolet rays, the area indicated by A ₂ has already been irradiated with the ultraviolet rays for a certain period of time.

As a result, the polypropylene carbonate-containing layer 222 in the area indicated by A ₂ in FIGS. 5 and 6 is irradiated with ultraviolet rays for the longest time because the ultraviolet rays are not blocked by the mask 82 for the longest time. Further, in the polypropylene carbonate-containing layer 222 in the area B ₂ in FIGS. 5 and 6, the time during which the ultraviolet light is not blocked by the mask 82 (in other words, the time when the ultraviolet light is irradiated) is more than that in the area A _2. It gets shorter. In addition, the polypropylene carbonate-containing layer 222 in the region C ₂ in FIGS. 5 and 6 is not substantially irradiated with ultraviolet light, or is irradiated with ultraviolet light for a shorter time than the polypropylene carbonate-containing layer 222 in the region B ₂ is illustrated. become.

By performing the above-mentioned ultraviolet ray irradiation step, as shown in FIG. 7, a polypropylene carbonate-containing layer 222 having at least a surface where the time of ultraviolet ray irradiation differs for each region (A ₂ , B ₂ , C ₂ ) is formed. Can be formed.

  The contact angle of the surface after being irradiated with the ultraviolet ray is at least 0, where the contact angle of the surface before being irradiated with the ultraviolet ray is 1 according to the change of the irradiation time of irradiating the ultraviolet ray. The polypropylene carbonate-containing layer 222 adjusted in the range of 70 or more and 0.99 or less can be provided. Further, when the irradiation time of irradiating ultraviolet rays is at least 10 minutes or less, the polypropylene carbonate-containing layer 222 having a longer irradiation time of ultraviolet rays tends to have a lower contact angle than the polypropylene carbonate-containing layer 222 having a shorter irradiation time. Therefore, it can be rephrased as follows in this example.

When the B ₂ region of the polypropylene carbonate-containing layer 222 shown in FIG. 7 is regarded as, for example, the first polypropylene carbonate-containing layer, and the A ₂ region of the polypropylene carbonate-containing layer 222 is regarded as, for example, the second polypropylene carbonate-containing layer. The substrate 10 of the present embodiment has a first polypropylene carbonate-containing layer 22 in a region B ₂ having a surface having a high contact angle and a _second polypropylene carbonate-containing layer 22 in a region A _{2 having} a surface having a low contact angle. 22 and.

In the above example, the B ₂ region is regarded as the first polypropylene carbonate-containing layer 22 and the A ₂ region is regarded as the second polypropylene carbonate-containing layer 22, but each region and the first or second The correspondence relationship with the polypropylene carbonate-containing layer is not limited to the above-mentioned example, as in the contents described in the second embodiment.

  In addition, for example, when the liquid metal ink is arranged on the above-mentioned polypropylene carbonate-containing layer 222, it can be said from the viewpoint of realizing the voluntary arrangement of the metal ink with high accuracy by forming a so-called “wettability” gradient. For example, the contact angle on the surface of the first polypropylene carbonate-containing layer 222 is higher than the contact angle on the surface of the second polypropylene carbonate-containing layer 10 ° or more (more preferably 15 ° or more or more than 15 °). Is a preferred embodiment. Even when the height of the wettability gradient is maintained, the contact angle of the surface of the second polypropylene carbonate-containing layer 222 is preferably 50 ° or more.

<Modification of Third Embodiment>
By the way, in the contact angle changing step of changing the contact angle of the surface of the polypropylene carbonate-containing layer, instead of changing the irradiation time of the ultraviolet rays in the third embodiment, at least the surface of the layer is irradiated with the ultraviolet rays. An example in which a change in the distance between the surface and the ultraviolet irradiation source 80 is adopted will be described below. Note that the description overlapping with the first, second, or third embodiment may be omitted.

  In this modification, the polypropylene carbonate-containing layer 322 is formed on the substrate 10 by the same manufacturing method as the polypropylene carbonate-containing layer 22 of the first embodiment using the polypropylene carbonate-containing solution of the first embodiment, And the composite member 200b including the polypropylene carbonate-containing layer 322 is manufactured.

(Method of manufacturing composite member)
A method for manufacturing the composite member 200b of the present embodiment will be described with reference to FIGS.

(UV irradiation process)
In the present embodiment, the ultraviolet irradiation step of irradiating the entire surface of the polypropylene carbonate-containing layer 322 that has undergone the pre-baking step with the ultraviolet irradiation source (ultraviolet irradiation apparatus) 80 of the third embodiment is performed. Be seen.

  Specifically, when at least the surface of the polypropylene carbonate-containing layer 322 containing a low to high molecular weight polypropylene carbonate is irradiated with ultraviolet rays, the distance between the surface and the ultraviolet ray irradiation source 80 is between 1 mm and 150 mm. The contact angle of the surface was measured before and after the irradiation with the ultraviolet rays when changed. As a result, it was confirmed that the shorter the distance between the surface of the polypropylene carbonate-containing layer 322 and the ultraviolet irradiation source 80, the lower the contact angle. Furthermore, as a result of the inventors further carrying out research including a lower molecular weight polypropylene carbonate or a higher molecular weight polypropylene carbonate, by irradiating at least the surface of the polypropylene carbonate-containing layer 322 with ultraviolet light, It was clarified that the contact angle of the surface after irradiation of the ultraviolet rays, where the contact angle of the surface of 1 was 1, can be changed within the range of 0.70 or more and 0.99 or less.

  From a different point of view, the above-mentioned treatment is performed by irradiating at least the surface of the polypropylene carbonate-containing layer 322 with ultraviolet rays by changing the distance between the surface and the ultraviolet ray irradiation source, so that the surface before being irradiated with the ultraviolet rays is changed. In other words, the contact angle changing step of changing the contact angle of the surface after irradiation of the ultraviolet rays in the range of 0.70 or more and 0.99 or less when the contact angle of 1 is set to 1.

  As described above, the present inventor changed the contact angle (that is, liquid repellency) on the surface of the polypropylene carbonate-containing layer 322 by changing the time for irradiating the ultraviolet light while maintaining the liquid repellency to some extent. I knew that it was possible to change. As a result, the present inventor has found that by utilizing this characteristic, the polypropylene carbonate-containing layer 322 having a surface that realizes different contact angles can be manufactured in a plurality of partitioned areas.

  8 and 9 are schematic cross-sectional views showing one step (ultraviolet ray irradiation step) of the method for manufacturing the composite member 200b of this embodiment. As shown in FIGS. 8 and 9, ultraviolet rays are not substantially transmitted above a part of the surface of the polypropylene carbonate-containing layer 322 arranged on the base material 10 (in other words, the ultraviolet rays are substantially blocked). ) A mask 82 provided with a known material is movably or repositionably arranged.

8 and 9 show a state in which the polypropylene carbonate-containing layer 322 is exposed to ultraviolet rays emitted from different distances. Specifically, the distance (h ₂ ) between the layer 322 and the light source of the ultraviolet light with which the polypropylene carbonate-containing layer 322 in the region A ₃ is irradiated is irradiated to the polypropylene carbonate-containing layer 322 in the region B _3. Is shorter than the distance (h ₁ ) between the ultraviolet light source and the layer 322. In addition, the state shown in FIG. 9 shows a state formed after a certain time has passed in the state shown in FIG.

As a result, the polypropylene carbonate-containing layer 322 in the area A ₃ in FIGS. 8 and 9 is irradiated with ultraviolet light from a light source closer to the light source irradiated on the polypropylene carbonate-containing layer 322 in the area B ₃ . In addition, the polypropylene carbonate-containing layer 322 in the region indicated by C ₃ in FIGS. 8 and 9 is in a state in which almost no ultraviolet rays are irradiated.

By performing the above-described ultraviolet irradiation step, as shown in FIG. 10, a surface where the distance between the surface of the polypropylene carbonate-containing layer 322 and the ultraviolet irradiation source 80 is different for each region (A ₃ , B ₃ , C ₃ ). It is possible to form the polypropylene carbonate-containing layer 322 including at least.

  By the way, "UV irradiation time" adopted in the third embodiment described above and "UV irradiation surface and polypropylene carbonate-containing layer surface adopted in the modification of the third embodiment" Changing both "the distance from the irradiation source" is another preferable mode from the viewpoint of contributing to the realization of finer adjustment of the contact angle.

<Other embodiment (1)>
According to the analysis of the present inventor, in each of the above-described embodiments and modified examples, the number average molecular weight of 3 × 10 ³ or more and 5 × 10 ⁵ or less is a viewpoint that the contact angle can be adjusted more accurately. Therefore, it is a preferable embodiment.

<Other embodiment (2)>
Further, when the present inventor uses the polypropylene carbonate-containing layer of the above-described first embodiment to form an uneven shape by a known embossing method disclosed by the applicant of the present invention, the dimensional accuracy of the unevenness is formed. As a result of further research and analysis to further improve the above, it was found that a polypropylene carbonate-containing layer satisfying the following conditions can greatly contribute to the improvement of dimensional accuracy.

Specifically, in the polypropylene carbonate-containing solution according to the present embodiment, the polypropylene carbonate having a molecular weight of 1 × 10 ⁴ or more is 99.0 mass% or more and the number average molecular weight is 1 × 10 ⁴ among all polypropylene carbonates. It is a solution in which polypropylene carbonate of ⁴ or more is dissolved in a certain solvent (typically, an organic solvent). Adopting another way, has a molecular weight distribution curve having a molecular weight is 1 × 10 ⁴ or more portions accounts for more than 99.0% of the total area, the polypropylene carbonate is and the number average molecular weight of 1 × 10 ⁴ or more The polypropylene carbonate-containing solution that is contained is the “polypropylene carbonate-containing solution” of the present embodiment.

(About manufacturing method of polypropylene carbonate-containing solution)
In the present embodiment, similarly to the first embodiment, after dissolving polypropylene carbonate in an organic solvent capable of dissolving polypropylene carbonate, a catalyst-free polypropylene carbonate-containing solution is obtained.

  Then, the polypropylene carbonate-containing solution of the present embodiment is manufactured by adopting the following separation step of separating polypropylene carbonate having a molecular weight within a specific numerical range as much as possible.

[Separation process]
Specifically, in the step of separating the embodiment, the filtered filtrate described above, molecular weight cut off with 1 × 10 ⁴ of ultrafiltration membrane (UF membrane), a molecular weight of less than 1 × 10 ⁴ The polypropylene carbonate is separated by discharging it to the permeate filtrate side. Then, the filtrate that did not permeate is concentrated and dried. As a result, in this embodiment, this separation step results in a polypropylene carbonate-containing solution that does not substantially contain polypropylene carbonate having a molecular weight of less than 1 × 10 ⁴ , or a polypropylene carbonate-containing solution that contains less than 1.0% by mass. Can be manufactured.

Polypropylene carbonate having a molecular weight within a specific numerical range, which is obtained by performing the above-mentioned separation step, is dissolved in an organic solvent capable of dissolving polypropylene carbonate (for example, diethylene glycol monoethyl ether acetate). As a result, the polypropylene carbonate-containing solution of the present embodiment satisfying the following (X) or (Y) can be produced as a result of the analysis described below.
(X) Of all polypropylene carbonates, the polypropylene carbonate having a molecular weight of 1 × 10 ⁴ or more is 99.0 mass% or more, and the polypropylene carbonate containing the polypropylene carbonate having a number average molecular weight of 1 × 10 ⁴ or more. containing solution (Y) molecular weight of 1 × 10 ⁴ or more portions has a molecular weight distribution curve, which accounts for more than 99.0% of the total area, and polypropylene having a number average molecular weight containing polypropylene carbonate is 1 × 10 ⁴ or more Carbonate-containing solution

  The polypropylene carbonate-containing solution of the present embodiment is used to form the polypropylene carbonate-containing layer 22 of the present embodiment in the same manner as in the first embodiment, thereby forming irregularities using, for example, the nano imprint method. At this time, a polypropylene carbonate-containing layer having irregularities with high dimensional accuracy can be realized with high accuracy.

  A specific example will be described below. FIG. 11 is a schematic cross-sectional view showing a step in the method of manufacturing the composite member 300 according to this embodiment. FIG. 12 is a side view showing the overall structure of the composite member 300 in this embodiment. As shown in FIG. 12, the composite member 300 includes a polypropylene carbonate-containing layer 22 having irregularities on the base material 10.

  In the present embodiment, the pre-baking step is performed on the polypropylene carbonate-containing layer 22 as in the first embodiment. Thereafter, as shown in FIG. 11, a mold for forming the embossed structure of the polypropylene carbonate-containing layer 22 by pressing the mold M1 against the polypropylene carbonate-containing layer 22 by applying a pressure of 0.1 MPa or more and 20 MPa or less. The pushing process is performed. By performing the embossing process, as shown in FIG. 12, the thickness of the region 22a pressed by the convex portion of the mold M1 becomes thinner than the other regions, so that the concave portion is formed. Therefore, in the present embodiment, the step in which the above-described embossing process is performed is the recess forming step / embossing step. It should be noted that the formation of the concave portion can be said to be a step of forming the convex portion from a different viewpoint.

  The present inventors have also studied and analyzed the embossed structure of the polypropylene carbonate-containing layer 22 and found that the number average molecular weight, not the mass average molecular weight, predominantly affects the dimensional accuracy of the uneven shape. .. Therefore, by forming the polypropylene carbonate-containing layer using the polypropylene carbonate-containing solution of the first embodiment as the starting material, which satisfies the above conditions (X) and / or (Y), the occurrence of problems described below can be suppressed with high accuracy. I was able to do it. As a result, the present inventors have found that a polypropylene carbonate-containing layer having irregularities with high dimensional accuracy can be realized with high accuracy as shown in FIG.

  FIG. 13 is an example of a graph showing a step measurement result showing one process of the method for manufacturing the composite member in the present embodiment. Like the portion indicated by “S” in FIG. 13, the shape of the edge of the recessed portion of the polypropylene carbonate-containing layer of the present embodiment is substantially vertical, and no defect such as the protrusion 23a in FIG. 14 is found. In addition, as shown in FIG. 13, the defect that the bottom portion 23b of the concave portion of the polypropylene carbonate-containing layer of the present embodiment rises is not found as shown in FIG. As a result, it is possible to manufacture the polypropylene carbonate-containing layer 22 having unevenness with excellent dimensional accuracy.

  In the present embodiment, the height of the edge of the recess with respect to the plane of the projection is 0 or more and 0.5 or less (more preferably 0 or more and 0.15 or less) when the thickness of the plane is 1. Then, the composite member 300 with high accuracy can be finally obtained. Incidentally, the above-mentioned “plane” means that when the layered polypropylene carbonate-containing layer having a uniform thickness is formed and then the above-mentioned embossing is performed, as in the region shown by F in FIG. It means a place that is sufficiently distant from the protrusion 23a and slightly beyond the end of the skirt of the protrusion 23a (typically, a place 1 μm away from the apex of the protrusion 23a).

  In the present embodiment, thereafter, an etching treatment is performed in which the entire surface of the polypropylene carbonate-containing layer 22 having the embossed structure formed by the nano imprint method is exposed by exposing it to plasma generated in an atmospheric pressure atmosphere. May be done.

  As described above, the disclosure of each of the above-described embodiments is provided for the purpose of describing the embodiments and is not intended to limit the present invention. In addition, the modification which exists in the scope of the present invention including other combinations of each embodiment is also included in a claim.

  The present invention relates to an electronic device field including a mobile terminal including various semiconductor elements, information home appliances, sensors, other known electric appliances, MEMS (Micro Electro Mechanical Systems) or NEMS (Nano Electro Mechanical Systems), medical equipment, and the like. And so on.

10 Base Material 22, 222, 322 Polypropylene Carbonate-Containing Layer 22a Region Pressed by Convex Part of Type M1 23a Protrusion 23b Bottom 70 Oxygen Plasma 80 Ultraviolet Irradiation Source 82 Mask 100, 200a, 200b Composite Member

Claims (10)

A layer containing polypropylene carbonate,
The oxygen plasma when the contact angle of the surface before being exposed to the oxygen plasma is 1 according to a change in exposure time and / or applied power when at least the surface of the layer is exposed to the oxygen plasma. The contact angle of the surface after being exposed to is changeable in the range of 0.70 or more and 0.99 or less,
A layer containing polypropylene carbonate. A layer containing polypropylene carbonate,
Before irradiating the ultraviolet rays, depending on the irradiation time for irradiating at least the surface of the layer with ultraviolet rays and / or the change in the distance between the surface and the ultraviolet irradiation source when irradiating at least the surface of the layer with ultraviolet rays. The contact angle of the surface after the irradiation of the ultraviolet rays, where the contact angle of the surface is 1, can be changed within a range of 0.70 or more and 0.99 or less,
A layer containing polypropylene carbonate. The contact angle of the surface after being exposed to the oxygen plasma is 50 ° or greater,
The polypropylene carbonate-containing layer according to claim 1. The contact angle of the surface after irradiation with the ultraviolet rays is 50 ° or more,
The polypropylene carbonate-containing layer according to claim 2. A number average molecular weight of 3 × 10 ³ or more and 5 × 10 ⁵ or less,
The polypropylene carbonate-containing layer according to any one of claims 1 to 4. Of all the polypropylene carbonates, the polypropylene carbonate having a molecular weight of 1 × 10 ⁴ or more is 99.0 mass% or more, and the number average molecular weight is 1 × 10 ⁴ or more,
The polypropylene carbonate-containing layer according to any one of claims 1 to 4. By changing the exposure time and / or the applied power when at least the surface of the layer containing polypropylene carbonate is exposed to oxygen plasma, the contact angle of the surface before exposure to oxygen plasma is set to 1. A contact angle changing step of varying the contact angle of the surface after being exposed to the oxygen plasma in a range of 0.70 or more and 0.99 or less,
Method for producing polypropylene carbonate-containing layer. By changing the irradiation time of irradiating at least the surface of the layer containing polypropylene carbonate with ultraviolet rays, and / or the distance between the surface and the ultraviolet irradiation source when irradiating the ultraviolet rays of at least the surface of the layer, Changing the contact angle of the surface after irradiating the ultraviolet rays, where the contact angle of the surface before irradiating the ultraviolet rays is 1, within the range of 0.70 or more and 0.99 or less Including the process
Method for producing polypropylene carbonate-containing layer. A first polypropylene carbonate-containing layer and a second polypropylene carbonate-containing layer,
The first polypropylene carbonate-containing layer having a surface having a high contact angle, and the second polypropylene carbonate-containing layer having a surface having a low contact angle,
Base material. The contact angle of the surface of the first polypropylene carbonate-containing layer is 10 ° or more higher than the contact angle of the surface of the second polypropylene carbonate-containing layer,
The base material according to claim 9.