KR20190094100A - Polypropylene carbonate containing solution and polypropylene carbonate containing layer - Google Patents

Abstract

Provided is a polypropylene carbonate-containing layer capable of maintaining high liquid repellency even when irradiated with ultraviolet rays. One polypropylene carbonate-containing layer of the present invention is a copolymer of carbon dioxide and epoxide, a main chain has a repeating unit represented by general formula (I), and a structure of the main chain is a layer containing polypropylene carbonate having a structural regularity of 99% or more. A contact angle of the surface after irradiating ultraviolet rays continuously to at least the surface of the layer for 10 minutes is 0.88 or more when the surface contact angle before irradiating the ultraviolet rays is 1.

Description

Polypropylene carbonate containing solution and polypropylene carbonate containing layer {POLYPROPYLENE CARBONATE CONTAINING SOLUTION AND POLYPROPYLENE CARBONATE CONTAINING LAYER}

The present invention relates to a polypropylene carbonate containing solution and a polypropylene carbonate containing layer.

As various types of information terminals and information appliances are demanded by the industry and consumers, methods of forming wirings and the like for various devices in various fields represented by miniaturized electronic devices continue to evolve.

As a method of forming wirings 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.

Until now, the applicant of the present application has used an oxide semiconductor precursor in which a compound of a metal, which is an oxide semiconductor, when oxidized is dispersed in a solution containing a binder made of an aliphatic polycarbonate, so that crack formation is reduced, and the oxide is excellent in electrical properties and stability. The technique which provides a semiconductor layer and the semiconductor element provided with the oxide semiconductor layer, and an electronic device is disclosed (patent document 1).

In addition, the applicant of the present application, when at least the surface of the plurality of island-like aliphatic polycarbonate-containing layer disposed on the substrate is exposed (exposed or exposed) to ultraviolet light containing a wavelength of 180 nm or more and 370 nm or less for 15 minutes The composite member which has the metal ink on the base material mentioned above in at least one part of the area | region sandwiched between each pure water precursor layer whose pure water and its surface contact angle is 50 degrees or more is disclosed (patent document 2).

International Publication WO2015 / 019771 International Publication WO2017 / 047227

As mentioned above, the manufacturing method represented by the process using a vacuum process or the photolithography method requires many processes and a long time in order to manufacture various devices, and leads to the fall or deterioration of the use efficiency of a raw material or manufacturing energy. Therefore, employing such a manufacturing method is not only preferable from the viewpoint of industrial or mass productivity, but also makes relatively large area difficult.

On the other hand, the low energy manufacturing process represented by the printing method is drawing attention especially in the industry from the viewpoint of the flexibility of an electronic device, and the industrial or mass productivity mentioned above. By using the printing method or the application method, the advantage is obtained that the vacuum process for patterning can be omitted since the desired layer can be patterned directly on the substrate. Therefore, it is disclosed in Patent Document 1 to realize fine patterning using a layer containing an aliphatic polycarbonate (particularly, a layer containing a polypropylene carbonate (hereinafter referred to as a "polypropylene carbonate containing layer")). By using the rare features of this layer, it is possible to lead to the provision of a very attractive technique in various devices.

Thus, in the case of forming a metal wiring pattern formed using, for example, a metal ink as a starting material using the pattern of the polypropylene carbonate-containing layer, in order to realize the selective arrangement of the metal ink, the polypropylene carbonate-containing layer Surface High liquid repellency is required for the metal ink. Therefore, exhibiting a very high liquid repellency of the liquid material can greatly contribute to improving the material properties of the liquid material arrangement.

On the other hand, as disclosed in Patent Literature 2, it is confirmed that the liquid repellency (the contact angle of pure water as a representative index) decreases to some extent by irradiating the surface of the polypropylene carbonate-containing layer with ultraviolet rays for 5 minutes. It is becoming.

As described above, in the case of forming a metal wiring pattern formed on the substrate by using the pattern of the polypropylene carbonate-containing layer on the substrate, in the case of using ultraviolet rays to facilitate the selective arrangement of the metal ink. There is. This is because the liquid repellency for the metal ink on each surface of the substrate is significantly different between the location where the polypropylene carbonate-containing layer is disposed on the substrate and the location where the layer does not exist, and thus the layer is present. It is because it is preferable to make the said surface lyophilic by removing the organic substance etc. which are not on the surface of the said base material which are not used using an ultraviolet-ray. However, since the above-mentioned treatment also causes ultraviolet rays to be irradiated to the surface of the polypropylene carbonate-containing layer at the same time, a dilemma arises that the surface liquid repellency of the layer cannot be sacrificed to some extent.

Therefore, it is very useful that the polypropylene carbonate-containing layer, which is likely to be used in various devices represented by micronized electronic devices, can maintain high liquid repellency even after irradiation with ultraviolet rays, for example. And development is still in progress.

The present invention can greatly contribute to the realization of a polypropylene carbonate-containing layer capable of maintaining high liquid repellency even when irradiated with ultraviolet rays and a polypropylene carbonate-containing solution which is a raw material thereof.

The present inventors made extensive studies and analyzes in order not to reduce the surface liquid repellency of the polypropylene carbonate containing layer or to suppress the fall, even when exposed to ultraviolet rays. As a result, by studying the polymer chain of polypropylene carbonate itself, it was found that the polypropylene carbonate-containing layer having a very high resistance to ultraviolet rays can be realized. The present invention has been created by the above research.

One polypropylene carbonate-containing solution of the present invention is a copolymer of carbon dioxide and epoxide, has a repeating unit whose main chain structure is represented by the following general formula (I), and whose main chain structure has a structural regularity of 99% or more. When the layer containing propylene carbonate is contained by heating and the layer containing the polypropylene carbonate is formed, the contact angle of the surface after irradiating ultraviolet light continuously to at least the surface of the layer for 10 minutes is the surface contact angle before irradiating the ultraviolet light. When it is set to 1, it is 0.88 or more.

[Tue 1]

By forming a polypropylene carbonate containing layer using this polypropylene carbonate containing solution, even if it is irradiated with ultraviolet-ray continuously, when compared with before the said ultraviolet-ray was irradiated, the surface of the said polypropylene carbonate containing layer The fall of the contact angle at can be suppressed with high accuracy. Therefore, the polypropylene carbonate containing layer formed using this polypropylene carbonate containing solution becomes high with respect to the ultraviolet-ray regarding the liquid repellency of the surface.

In addition, one polypropylene carbonate-containing layer of the present invention is a copolymer of carbon dioxide and epoxide, has a repeating unit whose main chain structure is represented by the following general formula (I), and whose main chain structure has a structural regularity of 99% or more. As a layer containing polypropylene carbonate, the contact angle of the said surface after irradiating an ultraviolet-ray continuously for at least the surface of the said layer for 10 minutes is 0.88 or more when the said surface contact angle before irradiating the said ultraviolet-ray is 1.

[Tue 2]

By employing this polypropylene carbonate-containing layer, even if the ultraviolet rays are continuously irradiated, for example, compared with before the ultraviolet rays are irradiated, a decrease in the contact angle at the surface of the polypropylene carbonate-containing layer is highly accurate. Can be suppressed. Therefore, this polypropylene carbonate containing layer becomes high with respect to the ultraviolet-ray regarding the liquid repellency of the surface.

In the present application, the "gel state" is a representative example, in which the solvent is removed from the liquid state to some extent (typically 80% or more in the mass ratio to the entire solvent, but not limited to this value). Polypropylene carbonate refers to a situation where it is not substantially decomposed or removed.

In addition, the "layer" in this application is the concept containing not only a layer but a film | membrane. In contrast, the term "membrane" herein is intended to include not only membranes but also layers. In addition, the "contact angle" in this application means the contact angle of pure water in the surface of a polypropylene carbonate containing layer. In addition, the state in which structural regularity is impaired means that the state, such as a CO ₂ deficiency, is formed in a polymer chain, for example.

In addition, the "substrate" in this application is not limited to the base of a plate-shaped object, The base of a different form (for example, curved surface) is included. In addition, in each embodiment mentioned later in this application, "application" means a layer on a base material by a low energy manufacturing process, typically, a printing method, a spin coating method, a bar coating method, a slit coating method, or a nanoimprint method. I say that.

According to one polypropylene carbonate-containing solution of the present invention, by forming the polypropylene carbonate-containing layer by using the solution, even if the ultraviolet rays are continuously irradiated, for example, compared with before the ultraviolet rays are irradiated. At the time, the fall of the contact angle in the surface of the said polypropylene carbonate containing layer can be suppressed with high accuracy.

Moreover, according to one polypropylene carbonate containing layer of this invention, even if it is irradiated with ultraviolet-ray continuously, when compared with before the said ultraviolet-ray is irradiated, the fall of the contact angle in the surface of the said polypropylene carbonate containing layer Can be suppressed with high accuracy.

1 is a graph showing an example of TG-DTA properties of a general polypropylene carbonate-containing solution.
2 is a schematic cross-sectional view showing one process of the method for manufacturing a composite member in the first embodiment.
3 is a schematic cross-sectional view showing one process of the method for manufacturing a composite member in the first embodiment.
4 is a cross-sectional schematic diagram showing one process of the method for manufacturing a composite member in the first embodiment.
5 is a schematic sectional view showing one step of the method for manufacturing a composite member in a modification of the second embodiment.
6 is a schematic sectional view showing one step of the method for manufacturing a composite member in a modification of the second embodiment.
7 is a schematic sectional view showing one step of the method for manufacturing a composite member in a modification of the second embodiment.
8 is a schematic sectional view showing one step of the method for manufacturing a composite member in a modification of the second embodiment.
9 is a schematic sectional view showing one step of the method for manufacturing a composite member in a modification of the second embodiment.
FIG. 10 is a schematic sectional view showing one step of the method for manufacturing a composite member in a modification of the second embodiment. FIG.
It is a cross-sectional schematic diagram which shows one process of the composite member manufacturing method in the modification of 2nd Embodiment.

EMBODIMENT OF THE INVENTION The composite member which is embodiment of this invention, a polypropylene carbonate containing layer, and the manufacturing method of the said composite member are described in detail based on attached drawing. In addition, in this description, unless otherwise indicated throughout the drawings, common reference numerals are assigned to common parts. In addition, in the figure, the elements of each embodiment are not necessarily described while keeping the mutual scale. In addition, some symbols may be omitted in order to make the angular plane easier to see.

First Embodiment

[Polypropylene carbonate containing solution and polypropylene carbonate containing layer, and their manufacturing method]

The polypropylene carbonate-containing solution of the present embodiment (which may include unavoidable impurities. Hereinafter, the same) is a raw material for producing the polypropylene carbonate-containing layer of the present embodiment (which may contain unavoidable impurities. Hereinafter, the same). .

In the present embodiment, by employing the polypropylene carbonate-containing layer formed of the polypropylene carbonate-containing solution of the present embodiment, even when ultraviolet rays are irradiated, the polypropylene carbonate-containing layer of the polypropylene carbonate-containing layer The fall of the contact angle at the surface can be suppressed with high accuracy. Below, the polypropylene carbonate containing solution of this embodiment and the polypropylene carbonate containing layer of this embodiment are demonstrated.

(About polypropylene carbonate containing solution and polypropylene carbonate containing layer)

In this embodiment, the state which melt | dissolved the polypropylene carbonate of 1 * 10 <^3> or more and 2 * 10 <^6> or less in some solvent (typically organic solvent) is the "polypropylene carbonate containing solution" of this embodiment. Configure

The solvent is removed to the extent that the polypropylene carbonate-containing solution can be used for the nanoimprint method or various printing methods (for example, the screen printing method) (typically, "gel state"). The layer of is a "polypropylene carbonate containing layer" of the present embodiment.

The polypropylene carbonate-containing solution of the present embodiment mainly contains polypropylene carbonate, but may include a compound, composition, or material other than polypropylene carbonate. Moreover, although the lower limit of the polypropylene carbonate content in the said polypropylene carbonate containing solution is not specifically limited, Typically, the mass ratio with respect to the total amount of the solute of the said polypropylene carbonate is 80% or more. Moreover, although the upper limit of the polypropylene carbonate content in the said polypropylene carbonate containing solution is not specifically limited, Typically, the mass ratio with respect to the total amount of the solute of the said polypropylene carbonate is 100% or less.

In addition, the said polypropylene carbonate containing layer becomes the said polypropylene carbonate containing layer in which the unevenness | corrugation was formed, for example by the embossing process mentioned later.

(Example of polypropylene carbonate containing solution and polypropylene carbonate containing layer)

In this embodiment, polypropylene carbonate having good thermal decomposition is used. Such polypropylene carbonate has a high oxygen content and can be decomposed into a low molecular weight compound at a relatively low temperature.

In addition, the organic solvent which can be employ | adopted for the "polypropylene carbonate containing solution" which is a solution containing polypropylene carbonate in this embodiment is not specifically limited if it is an organic solvent which can melt | dissolve polypropylene carbonate. Specific examples of the organic solvent are preferably organic solvents disclosed in International Publication WO2016 / 098423.

Further, to the polypropylene carbonate-containing solution which is a solution containing polypropylene carbonate, a dispersant and / or plasticizer disclosed in International Publication WO2016 / 098423 can be further added as desired.

Moreover, the method of forming the polypropylene carbonate containing layer of this embodiment is not specifically limited. Formation of the layer by a low energy manufacturing process is one suitable form. When forming the polypropylene carbonate containing layer in which the unevenness | corrugation was formed on the base material, the nanoimprint method etc. which are a simple method can be employ | adopted, for example.

<TG-DTA (thermogravimetric and differential thermal) characteristics>

Here, with respect to the polypropylene carbonate which can be decomposed into a low molecular weight compound at a relatively low temperature, the present inventors more specifically investigated the processes of decomposition and disappearance.

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which shows an example of TG-DTA characteristic of the solution which makes a general polypropylene carbonate the solute. In addition, although FIG. 1 is not TG-DTA characteristic of the polypropylene carbonate which has high structure regularity, this embodiment is shown conveniently in order to demonstrate the characteristic of the polypropylene carbonate containing layer which can be decomposed | disassembled or removed by heating. This graph also shows the results under normal pressure of a DEGMEA solution containing 6.25% by mass of polypropylene carbonate. 1, the solid line in a figure is a thermogravimetric (TG) measurement result, and the dotted line in a figure is a differential parallax (DTA) measurement result.

According to the thermogravimetry shown in FIG. 1, the weight loss due to partial decomposition or disappearance of the polypropylene carbonate itself is recognized along with the solvent loss of the polypropylene carbonate-containing solution from around 140 ° C to around 190 ° C. Moreover, it is thought that polypropylene carbonate is changing into carbon dioxide and water by this decomposition. Moreover, the result shown in FIG. 1 confirms that the said polypropylene carbonate decompose | disassembles and removes 90 wt% or more in the vicinity of 190 degreeC. In detail, the polypropylene carbonate decomposes at least 95 wt% at around 250 ° C., and almost all of the polypropylene carbonate decomposes at about 260 ° C. (at least 99 wt%). Therefore, in this general example, a polypropylene carbonate-containing solution is employed by subjecting the polypropylene carbonate-containing solution to be substantially or substantially lost or removed by performing a heat treatment at 250 ° C or higher (more preferably 260 ° C or higher). The polypropylene carbonate containing layer formed by heating the layer of can be decomposed or removed.

As a whole tendency, the polypropylene carbonate containing layer formed from the polypropylene carbonate containing layer of this embodiment by which unevenness | corrugation was formed by employ | adopting the polypropylene carbonate of this embodiment which has the characteristics similar to the characteristic of the general example mentioned above, for example It can serve as a sacrificial layer for forming a metal layer formed using the pattern of. In other words, the pattern of the polypropylene carbonate-containing layer can be decomposed or removed without substantially leaving its own residue. The polypropylene carbonate-containing layer has a high oxygen content and is a very suitable material as a sacrificial layer from the viewpoint of decomposing into a low molecular compound at a relatively low temperature.

In addition, although the result of the above-mentioned general example is a result regarding the decomposition | disassembly of the said polypropylene carbonate by heat processing in a comparatively short time, when heat-processing for a long time, even if it is low temperature (for example, 180 degreeC), the polypropylene of general example is sufficient. It is confirmed that carbonate decomposes. In other words, it can be said that the lower limit of the temperature which the decomposition | disassembly or removal of the polypropylene carbonate of the general example by heating is typically 180 degreeC. However, the lower limit temperature does not mean a temperature at which only one or several bonds in the polypropylene carbonate of the general example are broken, but the polypropylene carbonate is substantially or almost decomposed by the decomposition of the polypropylene carbonate of the general example. The temperature at which a decrease in mass is observed. In addition, the description regarding the above-described general example is also suitable for the polypropylene carbonate-containing layer of the present embodiment.

Therefore, by employing a polypropylene carbonate-containing layer that is substantially or substantially decomposed or removed when heated to 180 ° C. or higher, for example, formation of a metal layer formed by using the pattern of the polypropylene carbonate-containing layer as described above. It can serve as a sacrificial layer for people. In other words, the pattern of the polypropylene carbonate-containing layer can be decomposed or removed without substantially leaving its own residue.

Moreover, although the pattern typical example of the said polypropylene carbonate containing layer is a pattern represented by the line and space or the dot which can be employ | adopted in the field of nanoimprint, a semiconductor, or an electronic device, the pattern shape of this embodiment is those It is not limited to. The polypropylene carbonate containing layer which has various well-known pattern shapes can also be contained in the "pattern of a polypropylene carbonate containing layer" of this embodiment.

(About polypropylene carbonate)

In this embodiment, the polypropylene carbonate which superposed | polymerized the epoxide and carbon dioxide is employ | adopted as one suitable form.

Moreover, the epoxide mentioned above will not be specifically limited if it is an epoxide which superposes | polymerizes with carbon dioxide and becomes polypropylene carbonate which has a structure containing an aliphatic in a principal chain. For example, propylene oxide is an example that can be employed in the present embodiment. Moreover, propylene oxide can be used suitably from the viewpoint of having high polymerization reactivity with carbon dioxide.

(About the manufacturing method of polypropylene carbonate)

As an example of the manufacturing method of the polypropylene carbonate of this embodiment, the method of superposing | polymerizing-reacting epoxide and carbon dioxide in presence of a metal catalyst, etc. can be employ | adopted.

Here, the manufacture example of polypropylene carbonate is as follows.

A cobalt complex as a catalyst was added to a 1 L (liter) autoclave equipped with a stirrer, a gas introduction tube, and a thermometer, and after replacing the system with a nitrogen atmosphere in advance, propylene oxide was added. Next, by adding carbon dioxide while stirring, the inside of the reaction system was replaced with a carbon dioxide atmosphere, and carbon dioxide was charged until the reaction system became about 1.5 MPa. Thereafter, the autoclave was heated to 40 ° C, and polymerization was carried out for several hours while supplying carbon dioxide consumed by the reaction. After the reaction was completed, the autoclave was cooled and depressurized, and the reaction product was washed with methanol. Then, the polypropylene carbonate was obtained by drying under reduced pressure.

One specific example of the metal catalyst described above is the cobalt complex disclosed in WO2012 / 114939. By employing as the catalyst, a polypropylene carbonate which is a copolymer of carbon dioxide and epoxide, the main chain has a repeating unit represented by the following general formula (I), and the main chain structure has a structural regularity of 99% or more. It was confirmed that it is possible to generate.

[Tue 3]

In addition, the reaction solvent used as needed in the above-mentioned polymerization reaction is not specifically limited. Specifically, examples disclosed in International Publication WO2016 / 098423 can be adopted.

The amount of the reaction solvent described above is preferably an amount disclosed in WO2016 / 098423.

In addition, the method of reacting epoxide and carbon dioxide in presence of a metal catalyst in the above-mentioned polymerization reaction is not specifically limited. For example, the method disclosed in International Publication WO2016 / 098423 can be adopted.

In addition, the working pressure of carbon dioxide used in the above-described polymerization reaction is not particularly limited. Typically, the pressure disclosed in WO2016 / 098423 may be employed.

In addition, the polymerization temperature in the polymerization reaction mentioned above is not specifically limited. Representatively, it is preferable that they are 30 degreeC or more and 100 degrees C or less, and it is more preferable that they are 40 degreeC or more and 80 degrees C or less. When the polymerization reaction temperature is less than 30 ° C., there is a fear that a long time is required for the polymerization reaction. Moreover, when a polymerization reaction temperature exceeds 100 degreeC, a side reaction may arise and a yield may fall. Although the polymerization reaction time varies depending on the polymerization reaction temperature, it cannot be said uniformly, but it is preferable that they are typically 2 hours-40 hours.

The polypropylene carbonate containing solution of this embodiment is manufactured by performing the following process about the obtained polypropylene carbonate after completion | finish of a polymerization reaction.

(About the manufacturing method of the solution containing a polypropylene carbonate)

In this embodiment, the above-mentioned polypropylene carbonate is dissolved in the organic solvent (for example, diethylene glycol monoethyl ether acetate) which can melt | dissolve the above-mentioned polypropylene carbonate. As a result, the polypropylene carbonate containing solution of this embodiment which manufactures the above-mentioned main chain structure of general formula (I) containing the polypropylene carbonate which has 99% or more of structural regularity 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 1st Embodiment.

(Method of manufacturing composite member)

The manufacturing method of the composite member 100 of this embodiment is demonstrated, showing FIG.

[Manufacturing process of polypropylene carbonate containing layer]

In this embodiment, as shown in FIG. 2, the polypropylene carbonate containing layer 22 is formed on the glass or polyimide which is the base material 10 using a well-known spin coating method or the bar coating method. This step is an example of the polypropylene carbonate-containing layer forming step. Moreover, although the thickness of the polypropylene carbonate containing layer 22 of this embodiment is not specifically limited, The typical thickness is 300 nm or more and 4000 nm or less.

Next, the polypropylene carbonate-containing layer 22 is preliminarily heated to remove the solvent component contained in the polypropylene carbonate-containing layer 22 (preliminary firing step or drying step, hereafter collectively referred to as "preliminary firing"). Step "). In this embodiment, 100 degreeC-150 degreeC heat processing was performed as a preliminary baking process.

UV irradiation process

In this embodiment, as shown in FIG. 2, the polypropylene carbonate containing layer which went through the preliminary baking process using the well-known ultraviolet irradiation source (ultraviolet irradiation apparatus) 80 (Multiply Co., Ltd., model: MHU-110WB). About the whole surface of (22), the ultraviolet irradiation process which irradiates continuously the ultraviolet-ray containing wavelength 180nm or more and 370nm or less is implemented. Moreover, the other example of the ultraviolet irradiation source which irradiates the ultraviolet-ray which irradiates the ultraviolet-ray containing wavelength 180nm or more and 370nm or less in this embodiment is an ultraviolet lamp (AS ONE Corporation., Model: SLW-8) which makes a commercial wavelength 365 nm.

Moreover, in this embodiment, the distance between the ultraviolet irradiation source 80 and the surface of the polypropylene carbonate containing layer 22 is 10 mm. Moreover, the ultraviolet intensity (or ultraviolet illuminance) in this embodiment is 0.275 mW / cm <2>.

In this embodiment, by performing the above-mentioned ultraviolet irradiation process on at least the surface of the polypropylene carbonate containing layer 22, as shown in FIG. 3, the ultraviolet-ray-irradiated (in other words, exposed to the ultraviolet-ray) polypropylene carbonate containing layer The composite member 100 of the present embodiment including the 24 can be manufactured.

The present inventors investigated the presence or absence of the surface liquid repellency of the polypropylene carbonate-containing layer 24 in the composite member 100 of the present embodiment.

Table 1 has shown the relationship between the ultraviolet irradiation time and the contact angle (contact angle with pure water) at the time of performing the ultraviolet irradiation process with respect to two types of samples (sample 1 and sample 2).

In addition, the sample (1) is a polypropylene carbonate having a mass average molecular weight of about 350,000, which is one of the present embodiments in which the main chain structure of the general formula (I) employs a polypropylene carbonate having a structural regularity of about 99%. It is a polypropylene carbonate containing layer. In addition, the sample (2) is a polypropylene carbonate having a mass average molecular weight of about 11.3 million, the main chain having a repeating unit represented by the following general formula (I), and the structure of the main chain having a structural regularity of 99% or more It is the polypropylene carbonate containing layer which is one of this embodiment which employ | adopted carbonate.

[Tue 4]

The comparative example is a polypropylene carbonate-containing layer having a mass average molecular weight of about 300,000 irradiated under the same conditions as the above-described ultraviolet irradiation step, wherein the main chain structure of the formula (I) has a structure regularity of about 94% Polypropylene carbonate containing layer which employ | adopted. The polypropylene carbonate of the comparative example is different from the catalyst used in the production of the polypropylene carbonate of the present embodiment, and an organic zinc catalyst disclosed in International Publication No. WO2016 / 098423 is used.

Moreover, as shown in Table 1, the contact angle (deg.) Is displayed in the upper end in each column, and the ultraviolet-ray when the surface contact angle of the polypropylene carbonate containing layer 22 before ultraviolet irradiation is made into 100 (%) at the lower end. The contact angle ratio (%) of the surface after the irradiation step is indicated. For example, the calculation formula of the retention rate after "10 minutes" in the sample 1 is (63.6 / 71.3) x 100, and rounds off the second decimal place. Moreover, in the example of Table 1, the example of the contact angle when the irradiation time of an ultraviolet-ray changed in the range of 0 second-600 second is shown.

As a result, as shown in Table 1, the contact angle of the comparative example was about the retention rate (%) of the contact angle in the surface of two types of polypropylene carbonate containing layers in this embodiment 10 minutes after ultraviolet irradiation was 88% or more. The percent retention was a smaller value of 86.4%. Therefore, the present inventors found that a significant difference exists between the retention rates of the samples (1) and (2) and the retention rates of the comparative examples.

As described above, by adopting the polypropylene carbonate-containing layer 24 of the present embodiment, the surface contact angle of the polypropylene carbonate-containing layer 24 after continuously irradiating ultraviolet light for 10 minutes is the surface contact angle before irradiating the ultraviolet light. It is worth mentioning that when it is set to 1, the high liquid repellency of 0.88 or more can be realized. In other words, the polypropylene carbonate-containing layer of the comparative example employing a polypropylene carbonate having a structural regularity of less than 99% (specifically, about 94%) of the main chain of the formula (I) is about 3 minutes of ultraviolet irradiation. Although high liquid repellency was exhibited, it became clear that the resistance to liquid repellency maintenance was reduced with respect to 10 minutes of ultraviolet irradiation.

<Of 2nd embodiment Variant >

In the present embodiment, the composite member 200 including the polypropylene carbonate-containing layer 24 and the metal ink 72 in which the pattern is formed utilizing the characteristics of the polypropylene carbonate-containing layer 24 having the high liquid repellency according to the second embodiment. And the composite member 300 provided with the metal layer 74 was manufactured.

Below, the manufacturing method of the composite member 200 and the composite member 300 is shown and demonstrated to FIG. 5 thru | or FIG.

[Polypropylene carbonate containing layer forming process]

In this embodiment, as shown in FIG. 2 of 2nd Embodiment, the polypropylene carbonate containing layer which is an example of the polypropylene carbonate containing layer 22 is formed on the base material 10 using a well-known spin coating method or the bar coating method. do. This step is an example of the polypropylene carbonate-containing layer forming step.

[Concave part formation process / embossing process]

Next, the process of removing the solvent component contained in the polypropylene carbonate containing layer 22 by heating the polypropylene carbonate containing layer 22 to the extent that the embossed structure by a subsequent nanoimprint method can be formed ( A preliminary baking process or a drying process, hereafter collectively called a "preliminary baking process", is performed. In this embodiment, 100 degreeC-150 degreeC heat processing was performed as a preliminary baking process.

Subsequently, as shown in FIG. 5, the embossing structure of the polypropylene carbonate containing layer 22 is pressurized by applying the pressure of 0.1 Mpa or more and 20 MPa or less to the polypropylene carbonate containing layer 22. The embossing process to form is performed. By performing embossing, as shown in FIG. 6, the recessed part is formed by thinning the thickness of the area | region 22a pressed by the convex part of the mold M1 compared with another area | region. Therefore, in this embodiment, the process of embossing mentioned above is a recess formation process / embossing process. In addition, formation of the said recessed part can also be said to be a process of forming a convex part, from a viewpoint.

By the way, in the nanoimprinting method of this embodiment, embossing is performed in the state in which the polypropylene carbonate containing layer 22 of several island shape was heated to 40 degreeC or more and 150 degrees C or less. In addition, during embossing, in other words, under pressure, the polypropylene carbonate-containing layer 22 may remain without being completely decomposed. In addition, while performing the embossing process, the base material 10 is heated with a known heater in the same manner as in the technical concept disclosed in, for example, International Publication No. WO2013 / 069686, and the mold M1 itself is also heated. It is heated by a well-known heater. While each temperature of the base material 10 and the mold M1 during embossing is adjusted suitably, the heating temperature of the typical base material 10 is 40 degreeC or more and 150 degrees C or less, and the typical mold in the meantime. The heating temperature of (M1) is 40 degreeC or more and 150 degrees C or less.

In addition, the technical idea of the numerical range of the above-mentioned pressure is the same as the technical idea disclosed by Unexamined-Japanese-Patent No. 2017/047227.

Moreover, since the technical field to which the polypropylene carbonate containing layer and the polypropylene carbonate containing solution of this 1st and 2nd embodiment of this invention can be applied is extensive, it is added that those uses are not restrict | limited. For example, one advantage of employing a polypropylene carbonate-containing layer having irregularities of high dimensional accuracy is obtained by decomposing or removing the polypropylene carbonate in the recess using a known ashing device, as described later. That is, the pattern of the polypropylene carbonate-containing layer can be realized. When the pattern of the polypropylene carbonate-containing layer is employed, the polypropylene carbonate-containing layer is very simple and high accuracy only by relatively low-temperature heat treatment without using plasma or stripping liquid as in the case of a known resist. Can be decomposed or removed. Therefore, by forming a pattern of the polypropylene carbonate-containing layer, even if a material having low resistance is used as a substrate in an environment of high heat (for example, 300 ° C. or more), the versatility does not deteriorate the substrate phase. It is worth mentioning that this very high technology will be provided.

Thereafter, in the present embodiment, etching is performed by exposing the entire surface of the polypropylene carbonate-containing layer 22 having the embossed structure formed by the nanoimprint method to the plasma generated in the atmospheric pressure atmosphere. In addition, specific gases introduced into the processing chamber to form the plasma of the present embodiment are oxygen, argon, and helium. The applied high frequency power is about 500W. In this embodiment, the atmospheric plasma apparatus of YAMATO SCIENTIFIC CO., LTD. (Model: YAP510S) was used. As a result, as shown in FIG. 7, the plurality of island-like polypropylene carbonate containing layers 22, 22, 22 are formed.

In addition to the plasma generated in the atmospheric pressure atmosphere, the etching treatment by oxygen plasma under reduced pressure can be used in combination with the technical idea disclosed in International Publication No. 2017/047227.

Here, the shortest distance between each of the polypropylene carbonate-containing layers 22, 22, and 22 in the plurality of island-like polypropylene carbonate-containing layers 22, 22, 22 (in other words, each of the polypropylene carbonate-containing layers 22, 22, 22) can realize 500 nm or more and 20 micrometers or less when using at least the pattern formation method represented by the imprint method.

Moreover, in this embodiment, the process which etches the whole surface of the polypropylene carbonate containing layer 22 which has an embossed structure using the plasma under atmospheric pressure is performed, and the several island shape polypropylene carbonate containing layer 22 is performed. , 22, 22) are formed. However, the formation method of the some island-like polypropylene carbonate containing layers 22, 22, 22 is not limited to the above-mentioned method. For example, using the screen printing method, when the polypropylene carbonate-containing layer 22 is applied on the substrate 10, a plurality of island-like polypropylene carbonate-containing layers 22, 22, 22 can already be formed. have.

Next, in this embodiment, as shown in FIG. 8, it uses the well-known ultraviolet irradiation source (ultraviolet irradiation apparatus) 80 (Multiply Co., Ltd., model: MHU-110WB), and is a plurality of island-like polypropylene carbonate. The wavelength of 180 nm or more and 370 nm or less is contained also in any of the surface 10a of the base material 10 in which the containing layers 22, 22, 22, 24, 24 and 24 and the polypropylene carbonate containing layers 22 and 24 are not arrange | positioned. An ultraviolet irradiation step of irradiating ultraviolet rays is performed. Moreover, another example of the ultraviolet irradiation device which irradiates the ultraviolet-ray which irradiates the ultraviolet-ray containing wavelength 180 nm or more and 370 nm or less in this embodiment is an ultraviolet lamp (AS ONE Corporation., Model: SLW-8) which makes a commercial wavelength 365 nm into the market. .

As a result, contaminants such as organic substances on the surface 10a by exposure to ultraviolet rays, and the like, organic substances adhered by exposure to external air over time, etc. Can be decomposed and / or removed. In addition, since the surface 10a of the substrate 10 can be obtained with high accuracy, high affinity between the metal ink and the substrate 10 when the subsequent metal ink arrangement is performed, in other words, High wettability (hereinafter, collectively referred to as "high wettability") can be realized.

In addition, the base material 10 of this embodiment can contain the thing in which the pattern of a conductor layer, a semiconductor layer, or an insulator layer was previously formed on the base material 10. Here, for example, when the base material is a silicon substrate and another layer (for example, a silicon oxide layer) is interposed between the surface of the base material and the polypropylene carbonate-containing layer 22, the metal ink and the "other" It is necessary to realize a high wettability with the surface of the layer ”. In the ultraviolet irradiation process in that case, the ultraviolet-ray mentioned above is irradiated directly to the surface of the "other layer". Therefore, the base material 10 in that case recognizes the silicon substrate which is a base material, and the "other layer" formed on the surface of the said silicon substrate as an integrated body.

On the other hand, since the polypropylene carbonate-containing layer 24 irradiated with ultraviolet rays by the ultraviolet irradiation step contains a polypropylene carbonate having a structure regularity of 99% or more as described above, When the metal ink arrangement is carried out, high liquid repellency to the metal ink can be maintained.

In this embodiment, after forming the polypropylene carbonate containing layer 24, 24, 24 irradiated with the ultraviolet-ray of several island shape (typically the pattern was formed), as shown in FIG. 9, a well-known metal ink application apparatus A placement step of arranging the metal ink 72 on the base material 10 using (for example, a coating device by an inkjet method) 90 is performed. In addition, the metal ink 72 of this embodiment can employ | adopt well-known metal catalyst nanoparticle. Moreover, in this embodiment, the metal ink 72 is arrange | positioned only in one part among the area | region sandwiched between each said polypropylene carbonate containing layer 24, 24, 24, but the metal ink 72 is arrange | positioned in all said area | regions. It is another one form which can be employ | adopted.

The composite member 200 shown in FIG. 10 is manufactured by going through the arrangement process of the metal ink 72 described above. This metal ink 72 can play a role as an intermediate material for metal wiring, as will be described later.

In the present embodiment, the polypropylene carbonate-containing layers 24, 24 and 24 and the metal ink 72 are more than the temperature at which the polypropylene carbonate-containing layers 24, 24 and 24 are decomposed or removed after the above-described arrangement process. In addition, a heating step of heating above the temperature at which the metal layer 74 is formed in the metal ink 72 is performed.

As a result, as shown in FIG. 11, the composite member 300 in which the metal layer 74 is arrange | positioned on the base material 10 can be manufactured. Here, by this heating step, the polypropylene carbonate-containing layers 24, 24, and 24 as the sacrificial layer are substantially decomposed or removed with high accuracy. As a result, the composite member 300 becomes a composite member having high reliability and stability because it includes the metal layer 74 disposed on the substrate 10 in which substantially no residue remains.

In addition, when the metal ink 72 plays a role as an intermediate material for metal wiring, the metal layer 74 formed by heat treatment of the metal ink 72 becomes metal wiring. However, the metal layer 74 formed using the metal ink 72 as a starting material may also play a role (for example, an electrode) other than the role as the wiring.

The heating process of this embodiment is demonstrated further more concretely. In this embodiment, the polypropylene carbonate-containing layers 24, 24, 24 and the metal ink 72 disposed on the substrate 10 are, for example, about 150 ° C or 180 ° C using a known heater. The heat treatment which heats from about ten minutes to about 30 minutes above was performed (preferably 250 degreeC or more, More preferably, 260 degreeC or more). As a result, the composite member 200 having the metal layer 74 having a fine width can be manufactured. In addition, although the well-known heater of this embodiment is a hot plate (model: TH-900) of AS ONE Corporation., A heating means is not limited to such a heater. For example, another well-known heater, such as a hotplate, is another form which can be employ | adopted.

As described above, the disclosure of each of the above-described embodiments has been described for the purpose of describing those embodiments, and is not described to limit the present invention. In addition, modifications that fall within the scope of the invention, including other combinations of the embodiments, are also included in the claims.

The present invention relates to a mobile terminal including various semiconductor devices, information appliances, sensors, other well-known electronic products, electronic devices including MEMS (Micro Electro Mechanical Systems) or NEMS (Nano Electro Mechanical Systems), and medical devices. It can be widely applied to the field of devices.

10: description
10a: surface of substrate
22: polypropylene carbonate containing layer
22a: area pressed by the convex portion of type M1
24: polypropylene carbonate containing layer irradiated with ultraviolet rays
72: metal ink
74: metal layer
80: ultraviolet radiation source
90: applicator
100, 200, 300: composite member

Claims (4)

A copolymer of carbon dioxide and epoxide, the main chain having a repeating unit represented by the following general formula (I), the main chain contains polypropylene carbonate having a structural regularity of 99% or more,
When forming the layer containing the said polypropylene carbonate by heating, when the contact angle of the said surface after irradiating an ultraviolet-ray continuously to at least the surface of the said layer for 10 minutes made the said surface contact angle before irradiating the said ultraviolet-ray to 1, A solution containing polypropylene carbonate that is at least 0.88.
[Tue 1]

The polypropylene carbonate-containing solution according to claim 1, wherein the polypropylene carbonate has a number average molecular weight of 1 × 10 ³ or more and 2 × 10 ⁶ or less. A copolymer of carbon dioxide and epoxide, the main chain having a repeating unit represented by the following general formula (I), wherein the structure of the main chain contains polypropylene carbonate having a structural regularity of 99% or more,
The polypropylene carbonate containing layer which is 0.88 or more, when the contact angle of the said surface after irradiating an ultraviolet-ray continuously to at least the surface of the said layer for 10 minutes makes said surface contact angle before irradiating the said ultraviolet-ray 1.
[Tue 2]

The polypropylene carbonate-containing layer according to claim 3, wherein the polypropylene carbonate has a number average molecular weight of 1 × 10 ³ or more and 2 × 10 ⁶ or less.

Images