阅读说明：本技术 树脂制光学部件及其制造方法 (Resin optical component and method for manufacturing same ) 是由 中尾茂树 近藤宏司 宫野博宇 都外川真志 于 2018-06-15 设计创作，主要内容包括：本发明涉及具有树脂制的基材(2)、形成于其表面的含有金属氧化物的被膜(3)和将基材(2)与被膜(3)之间连结的连结分子链(4)的树脂制光学部件(1)及其制造方法。连结分子链(4)具有式1所示的特定结构。在制造树脂制光学部件(1)时，使含有连结分子的表面处理剂附着于树脂制的基材(2)，照射紫外线，所述连结分子具有键合有烷氧基甲硅烷基或硅烷醇基和叠氮基的三嗪环。接着，在附着面上形成含有金属氧化物的被膜(3)。在上述式1中，A表示任意的2价的连结基团或表示直接键合，R<Sup>1</Sup>表示氢或碳原子数1～6的烷基。<Image he="208" wi="700" file="DDA0002321667250000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to a resin optical component (1) having a resin base material (2), a coating (3) containing a metal oxide formed on the surface thereof, and a connecting molecular chain (4) connecting the base material (2) and the coating (3), and a method for producing the same. The linking molecular chain (4) has a specific structure represented by formula 1. In the production of a resin optical member (1), a surface treatment agent containing a linking molecule having a triazine ring to which an alkoxysilyl group or silanol group and an azide group are bonded is attached to a resin base material (2), and ultraviolet light is irradiated. Then, a coating film (3) containing a metal oxide is formed on the adhesion surface. In the formula 1, A represents an arbitrary 2-valent linking group or represents a direct bond, and R 1 Represents hydrogen or an alkyl group having 1 to 6 carbon atoms.)

1. A resin optical component (1) is provided with:

a resin base material (2),

a coating film (3) containing a metal oxide formed on the surface of the substrate,

a connecting molecular chain (4) connecting the substrate and the coating film;

the connecting molecular chain has a structure represented by the following formula 1, wherein the N-terminal of the following formula 1 forms a covalent bond with a carbon atom of the hydrocarbon skeleton in the base material, the O-terminal of the following formula 1 forms a covalent bond with a metal atom in the coating film,

in the formula 1, A represents an arbitrary 2-valent linking group or represents a direct bond, and R¹Represents hydrogen or an alkyl group having 1 to 6 carbon atoms.

2. The resin optical member according to claim 1, wherein A in the formula 1 is the following formula 2,

-NHR²- … (formula 2)

R in the formula 2²Is an alkylene group having 1 to 6 carbon atoms.

3. The resin optical member according to claim 2, wherein the alkylene group in the formula 2 is a propylene group.

4. The resin optical member according to any one of claims 1 to 3, wherein the metal oxide in the coating film contains at least one of Si and Ti, and the O-terminal of the connecting molecular chain forms a covalent bond with an Si atom or a Ti atom of the metal oxide.

5. The resin optical member according to any one of claims 1 to 4, wherein the coating film contains at least one of an antireflection film and a reflection-enhancing film.

6. The resin optical member according to any one of claims 1 to 5, wherein the coating film has a multilayer structure.

7. The resin optical member according to claim 6, wherein the coating film has at least a first layer (31) containing silicon oxide or titanium oxide and facing the base material, and a second layer (32) containing tantalum oxide.

8. The resin optical component according to any one of claims 1 to 7, wherein the resin optical component is a lens or a mirror for vehicle mounting.

9. A method for manufacturing a resin optical component (1),

attaching a surface treatment agent (40) containing a linking molecule (401) to a resin base material (2), wherein the linking molecule (401) has a triazine ring to which an alkoxysilyl group or silanol group having 1 to 6 carbon atoms and an azide group are bonded,

irradiating the surface (21) of the surface treatment agent with ultraviolet rays,

a coating film (3) containing a metal oxide is formed on the adhesion surface.

10. The method for manufacturing a resin optical component according to claim 9, wherein the linking molecule is represented by the following formula 3,

in the formula 3, A represents an arbitrary 2-valent linking group or represents a direct bond, and R¹Represents hydrogen or an alkyl group having 1 to 6 carbon atoms.

11. The method for producing a resin optical member according to claim 10, wherein A in the formula 3 is the following formula 2,

-NHR²- … (formula 2)

R in the formula 2²Is an alkylene group having 1 to 6 carbon atoms.

12. The method for producing a resin optical member according to claim 11, wherein the alkylene group in the formula 2 is a propylene group.

13. The method for producing a resin optical member according to any one of claims 9 to 12, wherein the surface treatment agent contains the linking molecule and an alcohol dissolving the linking molecule.

14. The method of manufacturing a resin optical member according to any one of claims 9 to 13, wherein the adhesion of the surface treatment agent to the base material is performed by dipping or spraying.

15. The method for producing a resin optical member according to any one of claims 9 to 14, wherein at least one of an antireflection film and a reflection increasing film is formed as the coating film.

16. The method of manufacturing a resin optical member according to any one of claims 9 to 15, wherein a coating film having a multilayer structure is formed as the coating film.

17. The method of manufacturing a resin optical member according to any one of claims 9 to 16, wherein at least a first layer (31) containing silicon oxide or titanium oxide and facing the base material and a second layer (32) containing tantalum oxide are formed as the coating film.

18. The method for manufacturing a resin optical member according to any one of claims 9 to 17, wherein the coating film is formed by vapor deposition of the metal oxide.

Technical Field

The present invention relates to a resin optical component having a resin base material and a coating film formed thereon, and a method for manufacturing the same.

Background

Optical members such as lenses and mirrors are composed of, for example, a glass substrate and a functional film formed on the substrate. In recent years, replacement of a glass substrate with a resin substrate has been studied for the purpose of improving the degree of freedom of shape, reducing the weight, reducing the cost of raw materials, and the like.

As an optical member having a resin substrate and a coating film formed thereon, for example, patent document 1 discloses an antireflection film in which a plurality of layers such as a layer containing silica-based fine particles are formed on the surface of a substrate film.

Disclosure of Invention

However, in the conventional optical member having a resin substrate and a coating film formed on the surface thereof, the adhesiveness between the substrate and the coating film is not sufficient. In other words, since the resin has a higher linear expansion coefficient than glass, the resin substrate is easily deformed in a high-temperature region. Therefore, if a film is formed on a resin base material, a large thermal stress is applied to the film in a high-temperature environment, and cracks may occur.

In addition, under a high-humidity environment, the resin base material may absorb water to swell. Therefore, the film is locally subjected to tensile stress due to swelling of the resin base material, and the film may peel off as the resin base material shrinks.

The present disclosure has been made in view of the above problems, and provides a resin optical component having high adhesion between a resin substrate and a coating film and capable of preventing peeling of the coating film and generation of cracks, and a method for manufacturing the same.

One embodiment of the present disclosure relates to a resin optical component including:

a base material made of a resin, wherein,

a coating film containing a metal oxide formed on the surface of the substrate,

a connecting molecular chain connecting the substrate and the coating film;

the connecting molecular chain has a structure represented by formula 1, wherein the N-terminal in formula 1 forms a covalent bond with a carbon atom of the hydrocarbon skeleton in the base material, and the O-terminal in formula 1 forms a covalent bond with a metal atom in the coating film.

In the formula 1, A represents an arbitrary 2-valent linking group or represents a direct bond, and R¹Represents hydrogen or an alkyl group having 1 to 6 carbon atoms.

Another aspect of the present disclosure relates to a method for manufacturing a resin optical component, including the steps of: adhering a surface treatment agent containing a linking molecule to a resin base material, the linking molecule having a triazine ring to which an alkoxysilyl group having 1 to 6 carbon atoms or a silanol group and an azide group are bonded,

irradiating the surface of the surface treatment agent with ultraviolet rays,

a coating film containing a metal oxide is formed on the adhesion surface.

The resin optical member has a connecting molecular chain for connecting the substrate and the coating film, and the connecting molecular chain forms a covalent bond with each of the substrate and the coating film. In other words, the molecular chain base material and the coating film are bonded to each other through a strong chemical bond such as a covalent bond. Therefore, the adhesion between the substrate and the coating film of the resin optical member is high. Therefore, even when exposed to a high-temperature environment or a high-humidity environment, for example, peeling of the coating film and generation of cracks can be prevented.

In the above production method, a surface treatment agent containing a linker molecule having the specific structure is attached to a resin base material. In this case, the connecting molecules are likely to be sufficiently close to the hydrocarbon skeleton of the substrate, and can be adsorbed on the surface of the substrate. The triazine ring of the linker molecule contains an electron-withdrawing nitrogen atom and has an asymmetric structure with the central vertical line of the ring plane as the axis, and therefore, it is considered that the linker molecule has a non-uniform distribution state of the combined electrons around the molecule.

Subsequently, the surface of the surface treatment agent is irradiated with ultraviolet light. Thereby, the nitrogen molecule is detached from the azide group bonded to the triazine ring to generate a nitrene. When the nitrene is generated, since the linker molecule is adsorbed on the surface of the substrate as described above, a covalent bond is formed between the nitrene derived from the azide group of the linker molecule and the hydrocarbon skeleton of the substrate.

Next, a coating film containing a metal oxide is formed on the adhesion surface. Thus, a covalent bond called Si-O-M is formed between silicon in the silanol group or alkoxysilyl group of the linker molecule and the metal atom M in the metal oxide.

In this way, in the above-described production method, the substrate and the coating film can be bonded by covalent bonds via the connecting molecular chains. Therefore, it is possible to manufacture a resin optical component which has excellent adhesion between the substrate and the coating film and can prevent peeling of the coating film and occurrence of cracks.

As described above, according to the above aspect, it is possible to provide a resin optical member and a method for manufacturing the same, in which adhesion between a resin base material and a film is high, and peeling of the film and generation of cracks can be prevented.

Drawings

Fig. 1 is a sectional view of a resin optical component according to embodiment 1.

Fig. 2 is an enlarged cross-sectional view of a main portion of the resin optical component according to embodiment 1.

Fig. 3 is an explanatory view showing a linking molecular chain linking a base material and a film in the resin optical component of embodiment 1.

Fig. 4 is an enlarged cross-sectional view of a main portion of a substrate having a surface treatment agent adhered thereto in embodiment 1 (a), and (b) is an explanatory view showing a case where ultraviolet rays are irradiated to an adhering surface of the substrate.

Fig. 5 is an explanatory view (a) of embodiment 1 showing a substrate to which a binding molecule is adsorbed, and (b) showing a substrate to which a binding molecule is covalently bonded.

Fig. 6 is a diagram of (a) one mode of showing the state of non-uniform distribution of electrons in the azide group in the linker molecule, (b) another mode of showing the state of non-uniform distribution of electrons in the azide group in the linker molecule, and (c) a diagram showing the nitrene produced from the azide group in the linker molecule in embodiment 1.

Fig. 7 is a sectional view of a resin optical component in embodiment 2.

Detailed Description

(embodiment mode 1)

Embodiments of a resin optical component and a method for manufacturing the same will be described with reference to fig. 1 to 6. As illustrated in fig. 1 and 2, the resin optical member 1 includes a base 2 and a film 3.

The base material 2 is made of resin and has a hydrocarbon skeleton. The substrate 2 contains, for example, cyclic olefin resin, acrylic resin, polycarbonate resin, polyethylene resin, polypropylene resin, acrylonitrile butadiene styrene, and the like. The base material 2 may contain 1 kind of resin, or may contain 2 or more kinds of resins. The shape of the substrate 2 is not particularly limited, and may have a shape suitable for various optical member applications.

The coating film 3 is formed on the surface of the substrate 2. The coating film 3 may cover the entire surface of the substrate 2, or may partially cover the surface of the substrate 2. The coating film 3 is, for example, a functional film or the like capable of imparting a specific function or improving a function to the substrate 2.

The coating 3 contains a metal oxide. The coating film 3 may have 1 layer, or may have a multilayer structure of 2 or more layers as exemplified in embodiment 2 described later. In the case of 2 or more layers, for example, layers having different materials may be formed, or layers having the same material may be included.

As illustrated in fig. 3, the resin optical member 1 includes a connecting molecular chain 4 connecting the substrate 2 and the film 3. In other words, the connecting molecular chains 4 crosslink the substrate 2 and the coating film 3. The linking molecular chain 4 may have a structure illustrated in fig. 3, or may have a structure represented by the following formula 1.

In the formula 1, R¹Represents hydrogen or an alkyl group having 1 to 6 carbon atoms. R¹When the number of carbon atoms of (2) exceeds 6, the production becomes difficult. In this case, it may be difficult to dissolve the linker molecule described later in a solvent such as alcohol during production. R¹Depending on the solvent in which the linker molecule is dissolved at the time of manufacture. For example, R in the case of using ethanol as solvent¹Being ethyl, e.g. R in the case of using propanol as solvent¹Is propyl.

In formula 1, A represents an arbitrary 2-valent linking group or a direct bond. When a is a direct bond, formula 1 is represented by formula 1a below.

The linking group is, for example, an alkylene group. The alkylene group may be linear or branched. The alkylene group may contain an ether, an amine, a carboxyl group, a thioether group, a ketone, or the like.

A in the formula (1) is preferably the following formula 2. In this case, the synthesis of the linker molecule becomes easy.

-NHR²-. DEG (formula 2)

In the formula 2, R²Is an alkylene group having 1 to 6 carbon atoms. The alkylene group may be linear or branched. Alkylene is preferablyIs a propylene group having 3 carbon atoms. In this case, the synthesis of the linker molecule becomes easier.

Fig. 3 shows an example of the linked molecular chain represented by formula 1. As illustrated in fig. 3, in the resin optical member 1, the N-terminal of the connecting molecular chain 4 represented by formula 1 forms a covalent bond with a carbon atom of the hydrocarbon skeleton in the base material 2. The N-terminus is a nitrogen atom attached to the amino group of the triazine ring. The amino group is derived, for example, from an azide group.

In the resin optical component 1, the O-terminal of the connecting molecular chain 4 represented by formula 1 is covalently bonded to a metal atom such as Si in the film 3. The O-terminus is an oxygen atom directly or indirectly bonded to a silanol group or alkoxysilyl group of the triazine ring.

The metal oxide of the coating film 3 may contain at least 1 selected from Si, Ti, Ta, Nb, Zr, Al, Mg, and the like. The metal oxide may be an oxide containing 1 metal atom, or may be a composite oxide containing 2 or more metals.

Preferably, the metal oxide of the coating 3 may contain at least one of Si and Ti. When the metal oxide contains Si, the coating film 3 and the connecting molecular chain 4 are connected by a siloxane bond (i.e., -Si-O-Si-). When the metal oxide contains Ti, the coating 3 and the connecting molecular chain 4 are connected by a — Ti — O — Si bond. In either case, the bonding between the substrate 2 and the film 3 via the connecting molecular chains 4 becomes stronger, and the peeling of the film 3 and the generation of cracks can be further prevented. Fig. 3 illustrates a case where the coating film 3 and the connecting molecular chain 4 are connected by a siloxane bond.

The resin optical member 1 may have, for example, at least one of an antireflection film and a reflection increasing film as the coating film 3. When the coating film 3 made of an antireflection film is provided, the resin optical component 1 is suitable for use in, for example, a camera lens, a display, and the like of various sensors and the like. When the coating film 3 made of a reflection increasing film is provided, the resin optical member 1 is suitable for a mirror, for example.

The antireflection film may contain, for example, a metal oxide having a high refractive index of 2.0 or more. Examples of such a metal oxide includeOut of Ta₂O₅、ZrO₂、TiO₂、Nb₂O₅And the like.

The reflection increasing film may contain, for example, a metal oxide having a low refractive index of less than 2.0. Examples of such a metal oxide include SiO₂、Al₂O₃、MgO、Y₂O₃And the like.

Next, a method for manufacturing the resin optical component 1 will be described. First, as illustrated in fig. 4(a), a surface treatment agent 40 is attached to the surface of a resin base material 2. The surface treatment agent 40 can be attached by immersing the base material 2 in the surface treatment agent 40 (i.e., immersion method), spraying, and the like.

The surface treatment agent 40 contains a linking molecule and a solvent for dissolving the linking molecule. The linking molecule has a triazine ring to which an alkoxysilyl group or silanol group having 1 to 6 carbon atoms and an azide group are bonded. As the linker molecule, for example, a substance represented by the following formula 3 can be used. In formula 3, A and R¹The same as in the above formula 1.

As the solvent, alcohols such as methanol, ethanol, propanol, and butanol can be used. In addition, water, acetone, benzene, toluene, xylene, and the like can be used. As the solvent, lower alcohols are preferably used.

For example, for the use of ethanol as the solvent, the use of formula 3 wherein A is-NHCH₂CH₂CH₂-、R¹Is ethyl (i.e. -CH)₂CH₃) The substance (2) is explained as an example of a linker molecule. In other words, an example in which a substance represented by the following formula 3a is used as a linker molecule will be described.

When the surface treatment agent 40 is attached to the substrate 2, as illustrated in fig. 5(a), the connecting molecules 401 contained in the surface treatment agent 40 are close to the hydrocarbon skeleton of the substrate 2 and can be adsorbed on the surface of the substrate 2. This is because the triazine ring of the linker molecule 401 contains an electron-withdrawing nitrogen atom, and has an asymmetric structure with the central vertical line of the ring plane as the axis, and therefore, the electrons are unevenly distributed around the molecule. Then, as illustrated in fig. 6(a) and 6(b), the azide group bonded to the triazine ring has polarity. Therefore, for example, even when the substrate 2 contains a resin having a small polarity such as a polyethylene resin or a polypropylene resin, the connecting molecules 401 can be adsorbed to the small polar portions between the carbon atoms and the hydrogen atoms in the hydrocarbon skeleton. In other words, the connecting molecules 401 can be adsorbed to the substrate 2 having a hydrocarbon skeleton.

Next, as illustrated in fig. 4(b), the surface 21 of the surface treatment agent 40 is irradiated with ultraviolet rays Hv. Thereby, as illustrated in fig. 6(c), the nitrogen molecule is detached from the azide group bonded to the triazine ring, and a nitrene is produced. At this time, as illustrated in fig. 5(a) and 5(b), since the connecting molecule 401 is adsorbed on the surface of the substrate 2, a covalent bond is formed between the nitrene derived from the azide group of the connecting molecule 401 and the hydrocarbon skeleton of the substrate 2.

Fig. 5(a) and (b) show an example in which a covalent bond is formed between 1 azide group of the linker molecule 401 and a carbon atom of the hydrocarbon skeleton in the substrate 2. It is also possible that both the 2 azido groups of the linker molecule 401 form covalent bonds with carbon atoms in the substrate 2.

Next, a coating film 3 containing a metal oxide is formed on the adhesion surface 21. The method for forming the coating 3 is not particularly limited, and the coating can be formed by a dipping method, spray coating, vacuum deposition, sputtering, plasma CVD method, ALD (i.e., atomic layer deposition) method, or the like. Preferably, vacuum evaporation is used.

An example in which the coating film 3 containing silicon oxide is formed on the adhesion surface 21 will be described below. As illustrated in fig. 5(b), since the connecting molecules 401 are bonded to the attachment surfaces 21, the coating film 3 is formed on the attachment surfaces 21 to which the connecting molecules 401 are bonded. At this time, as illustrated in fig. 3, a covalent bond such as a siloxane bond is formed between the Si atom in the silicon oxide in the coating film 3 and the alkoxysilyl group of the linker molecule 401.

Although not shown, when titanium oxide is used in place of silicon oxide, a Ti-O-Si bond is formed between the Ti atom of titanium oxide in the coating film and the alkoxysilyl group of the linker molecule. Even when the coating contains an oxide of another metal atom M instead of silicon oxide or titanium oxide, an M-O-Si bond can be formed.

As illustrated in fig. 3, the substrate 2 and the film 3 are connected to each other through the connecting molecular chains 4, whereby the resin optical component 1 can be obtained. Fig. 3 shows an example in which Si atoms in the connecting molecular chain 4 form covalent bonds with Si atoms in the coating film 3 via one oxygen atom. The Si atom of the connecting molecular chain 4 may form a covalent bond with 2 or more Si atoms in the coating film 3 via other 2 or more oxygen atoms bonded to the Si atom.

In the resin optical member 1, as illustrated in fig. 1 to 3, the substrate 2 and the film 3 are bonded by covalent bonds via the connecting molecular chains 4. Therefore, the adhesion between the substrate 2 and the film 3 is excellent. Therefore, for example, even when exposed to a high-temperature environment or a high-humidity environment, peeling of the coating film 3 and generation of cracks can be prevented.

Such a resin optical component 1 is suitable for, for example, vehicle-mounted applications in which it is easily exposed to a high-temperature environment or a high-humidity environment. When the resin optical component 1 has, for example, an antireflection film as the coating film 3, the resin optical component 1 is suitable for a lens of a sensor camera for vehicle mounting. In addition, when the resin optical component 1 has a reflection increasing film as the coating film 3, for example, the resin optical component 1 is suitable for a mirror for vehicle mounting.

(Experimental example)

This example is an example of evaluating the adhesive strength of a resin optical member. First, the resin optical member of the example was produced in the same manner as in embodiment 1. The resin optical member of the example has the same configuration as that of embodiment 1. In the production of the resin optical member of the example, the molecules represented by formula 3a were used as the connecting molecules, and a coating film was formed by vacuum deposition of silicon oxide.

In addition, as a comparative example of the examples, a resin optical member was prepared in which a coating film containing silicon oxide was formed on a base material without using a surface treatment agent. The resin optical member of this comparative example was obtained in the same manner as in example except that no surface treatment agent was used.

The resin optical members of examples and comparative examples were left to stand in a high-temperature and high-humidity environment having a relative humidity of 85% for 1000 hours, and then each resin optical member was subjected to a tape peeling test. Specifically, first, 3 tapes each having different adhesive strength were attached to the film of the resin optical component. The adhesive surface between the tape and the film was a 5mm square area. Further, a push-pull pressure gauge "SV 3" manufactured by Toyota was attached to the end of the tape. Then, the adhesion strength (unit: N/5mm) when the tape was peeled from the resin optical member was measured by a push-pull pressure gauge.

In comparative example 3, the adhesive tape was peeled off from the coating film. Of these, the adhesive strength in the peel test using the adhesive tape having the weakest adhesive strength was 0.1N/5 mm.

In contrast, in the examples, the film was not peeled off even when any of the 3 kinds of tapes was used. Of these, the adhesive strength in the peel test using the adhesive tape having the strongest adhesive strength was 1.2N/5 mm.

In other words, the adhesion force of the example having the linked molecular chains between the substrate and the film was improved by at least 12 times as compared with the comparative example having no linked molecular chains. Further, the resin optical member of the example was visually observed under a high-temperature and high-humidity environment, and as a result, cracking and peeling were not generated.

As described above, according to this example, as in embodiment 1, the adhesion is improved by bringing the base material into close contact with the film via the connecting molecular chains. The resin optical member having such a connection structure can exhibit excellent adhesion even under a high-temperature and high-humidity environment.

(embodiment mode 2)

In this embodiment, a resin optical component having a coating film with a multilayer structure will be described. As illustrated in fig. 7, the resin optical member 1 may have a coating film 3 having a multilayer structure. The same elements as those used in the above embodiment among the symbols used in embodiment 2 and thereafter are not particularly limited as long as they represent the same constituent elements as those in the above embodiment.

In the case of the coating 3 having a multilayer structure, the coating 3 preferably has a first layer 31 containing silicon oxide or titanium oxide and facing the substrate 2. In other words, the first layer in contact with the substrate 2 preferably has silicon oxide or titanium oxide. At this time, the connecting molecular chains 4 and the first layer 31 are bonded by Si — O — Si bonds or Si — O — Ti bonds, and thus the adhesion is further improved.

In addition, it is preferable to have the second layer 32 containing tantalum oxide. In this case, a chemically stable and amorphous film is easily formed, and an effect of preventing molecules such as water from penetrating through gaps of the film can be obtained. The second layer 32 can be formed on the first layer 31. As illustrated in fig. 7, the second layer 32 faces the first layer 31, and the first layer 31 and the second layer 32 can be in direct contact with each other. Further, another layer, not shown, may be provided between the first layer 31 and the second layer 32.

In the example of fig. 7, the coating 3 having a 2-layer structure is shown, but the coating 3 may have 3 or more layers. When the coating 3 having a multilayer structure is formed, the coating 3 may include, for example, an ultraviolet (i.e., UV) cut filter, an infrared (i.e., IR) cut filter, a hydrophilic hydrophobic film, a hard coat film, and the like, in addition to the above-described antireflection film and reflection increasing film.

As described above, the embodiments of the present disclosure have been described, but the present disclosure is not limited to the above embodiments, and can be applied to various embodiments within a range not departing from the gist thereof. The present disclosure also includes various modifications and modifications within an equivalent range. Also, various combinations and modes and other combinations and modes in which only 1 element, more or less elements are included are also included in the scope and concept of the present disclosure.