JPH08295838A - Coating agent and thermoplastic resin molding with coating film of resin - Google Patents

Abstract

PURPOSE: To obtain a coating agent capable of forming a coating film of a resin showing sufficiently high oxygen gas barrier properties, sufficiently maintaining the high oxygen gas barrier properties even at a high humidity, not evolving a harmful component in incineration, excellent in environmental compatibility, etc., having gas oxygen barrier properties on the surface of a thermoplastic molding such as a film, sheet, container, etc., composed of a thermoplastic resin. CONSTITUTION: This coating agent is a liquid or slurried coating agent useful for forming a coating film of a resin composition on the surface of a base by evaporating a solvent applied to the base, is obtained by blending an ethylene-vinyl alcohol copolymer resin with at least a solvent to dissolve the copolymer resin and a silica particle in the blending ratio of 0.01-100 pts.wt. of the silica particle to 100 pts.wt. of the ethylene-vinyl alcohol copolymer resin. A thermoplastic resin molding with a coating film of a resin is obtained by forming the coating film of the coating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating agent effective for forming a resin film having a good oxygen gas barrier property and a thermoplastic resin molded article having a resin film having an oxygen gas barrier property using the coating agent.

[0002]

2. Description of the Related Art For the packaging of foods, beverages, pharmaceuticals, etc., various thermoplastic resin films and sheets or their processed products (tubes, pipes, bags, capsules, bottles, trays, cups, caps). , Containers or container members such as lids, etc.) are used in various forms. The packaging of such foods and pharmaceuticals often requires reliable packaging and storage so that the contents are not damaged by oxygen as much as possible. However,
Films and sheets, conventional thermoplastic resin-based packaging materials used in the form of molded products thereof have excellent basic physical properties such as strength, but generally have the drawback of insufficient oxygen gas barrier properties. There is. Since this problem is caused by the fact that the thermoplastic resin is generally inferior in oxygen gas barrier property, it is likely to occur not only in the packaging material but also in general thermoplastic resin molded articles such as films and sheets having a limited thickness.

Therefore, a film or sheet made of such a thermoplastic resin, or a molded product thereof such as a container is used as a base material, and a polyvinyl alcohol solution or an ethylene-vinyl alcohol copolymer resin solution is placed on the surface of the base material. Is proposed, and a technique of improving the oxygen gas barrier property by the cured film is proposed.
The method of forming a cured resin film with such a liquid or slurry coating agent to improve the oxygen gas barrier property by this method is simple in process, various coating methods can be applied, and various forms can be applied. It has various advantages such that it can be applied to any of the substrates described above, and that a transparent film that is generally homogeneous and has good adhesion can be easily formed on a desired surface.

However, in the above conventional method, when the obtained coated resin film or sheet is used under low humidity, the oxygen gas barrier property is sufficiently improved and the high oxygen gas barrier property is maintained, but the humidity is high. When the value becomes high, the oxygen gas barrier property is remarkably lowered, the improvement effect is hardly seen, and eventually, in a general environment where the humidity becomes high, the desired high oxygen gas barrier property cannot be effectively maintained, which is a serious problem. Turned out to be. That is, this means that a cured resin film obtained by coating a solution of a conventional polyvinyl alcohol or ethylene-vinyl alcohol copolymer resin shows a sufficiently high oxygen gas barrier property under low humidity, but when the humidity becomes high, This means that the oxygen gas barrier property is rapidly impaired, and sufficient oxygen gas barrier property is not exhibited.

Similarly, as a method of improving the oxygen gas barrier property by a resin film, a method of coating an emulsion of a polyvinylidene chloride copolymer has been proposed. However, in this case, even if the oxygen gas barrier property is improved, since a chlorine-based resin film is formed, after use, harmful components such as chlorinated aromatic compounds are generated during incineration. There is a problem that it is not preferable in terms of sex.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances.

The first object of the present invention is to easily form a transparent cured resin film on a desired surface of a base material by various coating methods directly or through an intermediate layer such as an adhesive layer as appropriate and with good adhesion. A coating agent made of a liquid or slurry resin composition that can be formed into a variety of materials, including a wide variety of thermoplastic resin molded products such as films, sheets and containers made of a thermoplastic resin. It shows a sufficiently high oxygen gas barrier property on the specified surface of the base material of the material and form, and yet retains the high oxygen gas barrier property even under high humidity, and does not generate harmful components even when incinerated. A high-performance oxygen gas barrier resin film with excellent environmental compatibility can be easily formed.
For example, improvement of oxygen gas barrier properties of various conventional thermoplastic resin products such as packaging materials for foods and pharmaceuticals, production of various resin molded products including sufficient oxygen gas barrier properties, or Another object of the present invention is to provide a practically extremely useful coating agent that can be advantageously used in various applications such as protection by a film or coating of a metal that is easily damaged by oxygen or a printed wiring board.

The present invention is also a resin film-coated thermoplastic resin molded article having a cured resin film formed by using the coating agent of the present invention, wherein the cured resin film sufficiently improves the oxygen gas barrier property. Has been done, and
It can sufficiently maintain its high oxygen gas barrier property even under high humidity, and it is possible to satisfy the environmental compatibility by selecting the material of the base material without generating harmful components from the cured resin film even when incinerated, For example, it can be advantageously used in various applications requiring high oxygen gas barrier properties such as packaging materials for foods, pharmaceuticals, etc., and it is remarkably useful for practical purposes in various forms of resin film-coated thermoplastic resin molded products (films and Sheet,
Or tubes, pipes, bags, capsules, bottles,
Containers and container members such as trays, cups, caps, lid materials,
And so on).

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have found that a solution of the ethylene-vinyl alcohol copolymer resin as the conventional coating agent is obtained. It was found that the problem of deterioration of the oxygen gas barrier property under high humidity can be easily solved by an extremely simple means of adding an appropriate amount of finely divided silica (gel, sol, etc.), and based on this finding, the present invention Came to complete.

That is, the present invention is a liquid or slurry coating agent used for forming a film of a resin composition on the surface of a substrate by coating the substrate and evaporating the solvent, An ethylene-vinyl alcohol copolymer resin, a solvent that dissolves the copolymer resin, and silica particles are blended, and the blending ratio of the silica particles is 100 parts by weight of the ethylene-vinyl alcohol copolymer resin. The coating agent is provided in the range of 0.01 to 100 parts by weight.

The present invention is also a preferred application of the coating agent of the present invention, wherein the surface of a base material made of a thermoplastic resin is coated with the coating agent of the present invention directly or through an intermediate layer. The present invention provides a thermoplastic resin molded article with a resin film, characterized in that a cured film of a resin composition comprising ethylene-vinyl alcohol copolymer resin and silica particles is formed by evaporating the solvent. .

The coating agent of the present invention comprises at least
It comprises an ethylene-vinyl alcohol copolymer resin, a solvent that dissolves the copolymer resin, and silica particles.

In preparing this coating agent, the order of addition and mixing of various components is not particularly limited, but usually, a solution of ethylene-vinyl alcohol copolymer and a uniform dispersion of silica particles are separately prepared. A method of preparing or preparing, mixing these liquids at an appropriate time prior to coating, and further adding a solvent, if necessary, is preferably adopted, but the method is not necessarily limited to this. .

Since ethylene-vinyl alcohol copolymer resins, including commercially available products, are usually obtained in the form of a solution for the purpose of preventing gelation, the solutions of the commercially available products are directly used as raw materials for preparation. It may be used, or a solution whose concentration and composition have been adjusted by appropriately diluting it with a solvent, evaporating a part of the solvent, or replacing it may be used as a raw material for preparation. Further, as for the already dispersed water or aqueous solution such as siligasol, it may be used as it is or after being sufficiently dispersed by adding an appropriate solvent before use.

In any case, at least during coating, the ethylene-vinyl alcohol copolymer resin is sufficiently dissolved, and the silica particles are prepared so as to be uniformly dispersed in the solution. It is preferable.

Examples of the ethylene-vinyl alcohol copolymer resin include acetoxy in an ethylene-vinyl acetate copolymer having various molecular weights or molecular weight distributions obtained by copolymerizing ethylene and vinyl acetate at various ratios. It is possible to use those having various compositions, molecular weights, molecular weight distributions and saponification degrees obtained by various known production methods, including those in which some or all of the groups are converted into hydroxyl groups by hydrolysis or saponification. That is, here referred ethylene - the vinyl alcohol copolymer resin, an ethylene unit [-CH ₂ CH _2] and hydroxyethylene unit _{[-CH 2 CH (OH) -} ] is not limited to those consisting only of, For example, ethylene unit, hydroxyethylene unit, acetoxyethylene unit [—CH ₂ CH
(OCOCH ₃ )-], and those having at least ethylene units and hydroxyethylene units, such as those having monomer units such as vinyl compounds and olefins, and other vinyl compounds, and various compositions of various compositions. Things are applicable.

The ratio of ethylene units to hydroxyethylene units is not particularly limited, but the ratio of the hydroxyethylene units to the total of ethylene units and hydroxyethylene units is usually 50 to 8 in terms of molar ratio.
Those in the range of 0% are preferably used. Further, in the case of a copolymer resin composed of an ethylene unit, a hydroxyethylene unit and another monomer unit such as a copolymer resin composed of an ethylene unit, a hydroxyethylene unit and an acetoxyethylene unit, the content ratio of the total of the ethylene unit and the hydroxyethylene unit is contained. Is preferably 70 mol% or more,
Particularly, 80% or more is preferable. That is, any of those containing acetoxyethylene units and other monomer units in an arbitrary ratio or those not containing them is preferably used as long as the above conditions are satisfied.

As mentioned above, since many of these ethylene-vinyl alcohol copolymer resins are generally marketed in the form of a solution, such a solution form may be used as it is or by adding a solvent appropriately. It is convenient to use it as a raw material for the preparation of the coating agent of the present invention after adjusting the concentration and composition thereof. As an example of such a solution-like commercial product, a soarnol solution [trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like can be mentioned.

The above-mentioned solvent may basically be one that dissolves the ethylene-vinyl alcohol copolymer resin used, and various single solvents or mixed solvents of various compositions can be applied, but usually, It is preferable to select a material having a relatively low boiling point that easily evaporates during or after coating.

Specific examples of preferred solvents or solvent components include, for example, n-butanol, isopropanol,
Examples thereof include n-propanol, formic acid, ethylene chlorohydrin, dimethylsulfoxide, methanol, ethanol and water. Of these, isopropanol, methanol, ethanol and water are particularly preferable.

These may be used alone or as a mixed solvent of two or more kinds. Usually, from the viewpoint of the stability of the coating agent (liquid) and the homogeneity of the cured resin film to be formed, it is preferable to appropriately mix two or several kinds at a suitable ratio and use as a mixed solvent.

Particularly preferred mixed solvent systems include, for example:
Examples of the solvent include water-isopropanol-based mixed solvent, water-methanol-based mixed solvent, water-ethanol-based mixed solvent, but are not limited thereto.

Various solvents such as these mixed solvents may be used, for example, when preparing the coating agent of the present invention.
It can be preferably used also for diluting a solution of a commercially available ethylene-vinyl alcohol copolymer resin, and prior to mixing with the copolymer resin solution, when a dispersion of silica particles is prepared in advance. It can also be suitably used as a solvent or a solvent for dilution.

As the silica particles, for example, colloidal silica such as Aerosil, silica sol, silica gel in the form of fine particles and the like can be dispersed in the coating agent (liquid) and the obtained cured resin film with sufficient uniformity. Fine particles are preferable. The average primary particle size is usually preferably 1 μm or less, and 100 nm
The following are more preferable, and those of 10 nm or less are more preferable.

The silica particles are not necessarily limited to pure silica, and as long as they do not impair the object of the present invention, those containing various other components are also applicable. Commercial products obtained by various production methods such as containing alkali metal ions such as Na and other oxide components such as alumina components as impurities and the like are also applicable.

The coating agent of the present invention comprises at least
It is composed of the ethylene-vinyl alcohol copolymer resin, the solvent, and the silica particles, and the mixing ratio of the silica particles is 0.01 to 100 relative to 100 parts by weight of the ethylene-vinyl alcohol copolymer resin. It is important to be in the range of parts by weight. Also here, if the compounding ratio of the silica particles is less than 0.01 part by weight based on the above criteria,
The effect of adding silica particles is not sufficiently obtained, and with such a coating agent, even if it is possible to form a cured resin film exhibiting a sufficiently high oxygen gas barrier property under low humidity, even under high humidity. It is difficult to form a desired cured resin film that maintains a sufficiently high oxygen gas barrier property, and therefore, the object of the present invention cannot be achieved sufficiently. On the other hand, if the compounding ratio of the silica particles exceeds 100 parts by weight based on the above criteria, the resulting cured resin film may have poor denseness or adhesion to a substrate, or may have whiteness resulting in reduced transparency, Surface roughness occurs, and further,
Problems such as failure to exhibit sufficient oxygen gas barrier properties are likely to occur, and the object of the present invention cannot be achieved sufficiently.

The preferable range of the silica particles is 0.01 to 100 parts by weight with respect to 100 parts by weight of the ethylene-vinyl alcohol copolymer resin.

The coating agent of the present invention comprises at least:
At the time of coating on the substrate, it is preferable that the ethylene-vinyl alcohol copolymer resin is dissolved in a solvent to form a solution, and the silica particles are uniformly dispersed in the solution. When storing for a long time,
Similarly, it is preferable that the above state is maintained.

The suitable blending ratio of the ethylene-vinyl alcohol copolymer resin to the solvent in the coating agent of the present invention varies depending on the characteristics of the copolymer resin to be used, the type and composition of the solvent, the coating method, etc., and therefore should be specified uniformly. However, for 100 parts by weight of solvent, usually,
It is preferable to select in the range of 5 to 100 parts by weight, and it is particularly preferable to select in the range of 10 to 50 parts by weight.
Here, when the ratio of the ethylene-vinyl alcohol copolymer resin to 100 parts by weight of the solvent is larger than 100 parts by weight, even if the resin is sufficiently dissolved, the resin concentration is high, so that gelation or aggregation is likely to occur in some cases. However, depending on the coating method, problems such as the inability to obtain a uniform coating film may occur. On the other hand, when the ratio is less than 5 parts by weight, the resin concentration is low and the amount of the solvent is excessive, so that the solvent is wasted and it takes a lot of time to form a cured resin film having a sufficient film thickness. However, there is a problem in that it may take a lot of time and labor, and in some cases, the denseness and homogeneity of the film may not be sufficiently ensured.

The suitable blending ratio of silica particles to the solution (solution comprising ethylene-vinyl alcohol copolymer resin and solvent) in the coating agent of the present invention is the concentration of the copolymer resin in the solution, the physical properties of the solution, and necessary Depending on the type and concentration of the additive to be added, the particle size of the silica particles used, the type and composition of the solvent, the coating method, etc., it cannot be uniformly specified, but 100 parts by weight of the solution On the other hand, usually 0.01 to 1
It is preferable to select in the range of 0 parts by weight, particularly 0.1
It is preferable to select in the range of 5 parts by weight. Here, if the ratio of silica particles to 100 parts by weight of the solution is more than 10 parts by weight, the dispersibility of the silica particles becomes insufficient, and gelation or aggregation of the resin easily occurs during storage, and However, a uniform coating film may not be obtained, and properties such as homogeneity of the cured resin film may be deteriorated, and a desired oxygen gas barrier property may not be sufficiently ensured. On the other hand, when the ratio is less than 0.01 part by weight, ethylene-
Since the concentration of vinyl alcohol copolymer resin will also be low, the amount of solvent will be excessive, the solvent will be wasted,
It takes a lot of time to form a cured resin film of sufficient thickness, extra work is required, and in some cases, the denseness and homogeneity of the film cannot be ensured. It will be easier.

In the coating agent of the present invention, if necessary, the above-mentioned ethylene-vinyl alcohol copolymer resin,
Other components and additives than the solvent and silica particles may be added and blended.

Examples of such additives include antifoaming agents, antigelling agents, stabilizers, viscosity modifiers, nucleating agents, antilocking agents, pigments, lubricants, coupling agents, adhesion improvers and adhesives. , Anchoring agents, etc., but not limited to these. Various kinds of known additives can be applied to these various kinds of additives, and one kind or two or more kinds may be added in an appropriate amount, if necessary.

In the coating agent of the present invention, various resins other than the ethylene-vinyl alcohol copolymer resin (for example, polyvinyl alcohol, etc.) may be added to the coating agent, if necessary, within a range not impairing the object of the present invention. Then, you may add and mix.

According to the coating agent of the present invention, by coating it on the surface of various base materials, it has excellent oxygen gas barrier properties, environmental compatibility, etc., and in particular, it exhibits sufficiently high oxygen gas barrier properties even under high humidity. A high-performance cured resin film that holds can be easily formed, which allows
It is possible to easily realize a resin film, a sheet, a container, or the like having a high oxygen gas barrier property to a substrate and having a sufficiently high oxygen gas barrier property even when used in a high humidity atmosphere. In addition, the coating agent of the present invention can be generally applied to base materials of various materials and forms, and above all, it can be suitably applied to base materials made of thermoplastic resin.

The resin film-coated thermoplastic resin molded product of the present invention, which is a preferred application example of the coating agent of the present invention, will be described in detail below.

The thermoplastic resin molded article with a resin film of the present invention is coated with the coating agent of the present invention on the surface of a substrate made of a thermoplastic resin directly or through an intermediate layer to evaporate the solvent, It can be produced by forming a cured film of a resin composition comprising at least an ethylene-vinyl alcohol copolymer resin and silica particles.

Here, the thermoplastic resin is not particularly limited, and examples thereof include polyethylene, polypropylene,
Polybutene, ethylene-propylene copolymer, polymethylpentene, ethylene-vinyl acetate copolymer, polyolefin acid graft copolymer, ionomer, ethylene-acrylic acid ester copolymer, and mixtures of these polyolefins, cellulose, polyamide, A wide variety of materials such as polyester, polystyrene, ABS resin, methacrylic resin, polyvinyl chloride, and polycarbonate can be applied. Note that these thermoplastic resins may be appropriately used as a composition, if necessary.

That is, the base material made of the thermoplastic resin may be made of only the thermoplastic resin, or may be made of a composition of the thermoplastic resin and other components.

The form of the base material made of the thermoplastic resin is not particularly limited, and the coating agent of the present invention includes, for example, films, sheets, tubes, pipes, bags, capsules, containers (bottles, trays, cups, etc.). No. 1) or a container member (such as a cap member).

The coating may be performed on both sides of the substrate, only on one side, or on desired partial surfaces.

For the purpose of improving the adhesiveness of the coating film, an adhesive layer (eg, maleic anhydride graft modified product, ethylene-vinyl acetate copolymer, or , An adhesive resin such as a blend thereof, or the like) may be provided, or the substrate may be appropriately pretreated by, for example, corona discharge treatment, anchor coat treatment, or the like, and then coated on the surface thereof. .

The coating can be carried out by various methods such as a known method such as a roll method, a dipping method, a dipping method, a spray method, a brush method (brush coating method) and a roller method. Any 1 depending on the form etc.
It can be made by applying one kind or two or more kinds of methods.

As described above, the coating agent of the present invention is coated, heat treatment is appropriately performed, and the solvent is evaporated to form a cured resin film on a predetermined surface of the base material. After forming the film, if necessary,
Further, a post-treatment such as heating may be performed.

Further, after forming the resin film in this way, for the purpose of protecting the coated surface and the like, further, for example, silica or acrylic resin is formed on a predetermined surface (or the entire surface) of the substrate containing the cured resin film. May be provided, or laminated with a film made of a thermoplastic resin or the like, or a sandwich type multilayer film or sheet having a configuration in which a cured resin film is sandwiched may be used.

As described above, the thermoplastic resin molded article with the resin film of the present invention in various forms, which is a preferable application example of the coating agent of the present invention, can be easily produced.

The thermoplastic resin molded article with a resin film of the present invention thus obtained has an oxygen gas barrier property remarkably higher than that when the cured resin film is not provided due to the excellent oxygen gas barrier property of the cured resin film. Has significantly improved,
Moreover, since it retains a sufficiently high oxygen gas barrier property even when used in a high humidity atmosphere, for example, films, sheets, tubes, pipes, bags, capsules, containers (bottles,
Oxygen gas barrier property is required for various forms such as trays, cups, etc.) or container members (caps, etc.), including packaging materials with oxygen gas barrier properties, their members, or intermediate materials. It can be advantageously used for various purposes.

[0047]

EXAMPLES Examples of the present invention and comparative examples will be shown below.
The present invention will be described in more detail with reference to these, but the present invention is not limited to the following examples.

Example 1 An EVOH solution (Soarnol solution 16D: manufactured by Nippon Synthetic Chemical Industry Co., Ltd., EVOH concentration 16% by weight) was added to 100 parts by weight of a solvent (water: isopropanol = 1: 1) of silica (AEROSIL380: Japan). Aerosil Co., Ltd., 1 part by weight of average primary particle size (7 nm) was added, and the mixture was stirred and dispersed to be diluted twice and mixed with stirring. Further, the mixture was stirred at 50 ° C. without heating. This mixed solution was coated on a corona-treated stretched nylon (ONY) film (15 μm). The coating was performed with a coating bar (RDS24) using a film applicator. This one
It was dried at 20 ° C. for 4 minutes to obtain a coating film having a thickness of 3 μm. 0% RH and 100% RH of this film
The oxygen permeability was measured in accordance with JIS K 1126.
Method B). The results are shown in Table 1.

Example 2 The coating solution used in Example 1 was coated on a polypropylene (PP) sheet in the same manner. PP
The sheet used was corona-treated and then anchor-coated. (Anchor coating agent: AP-335A /
cat-10 manufactured by Toyo Morton Co., Ltd., film thickness 1 μm. ) This was dried at 100 ° C. for 4 minutes to obtain a coating sheet having a film thickness of 3 μm. The transmittance is measured in the same manner as in Example 1,
The results are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that silica was not added to the coating solution.

Comparative Example 2 The procedure of Example 2 was repeated except that silica was not added to the coating solution.

[0052]

[Table 1] Compared with the comparative example, in the example, high humidity (100% RH)
It can be seen that there is little increase in oxygen permeability at.

[0053]

EFFECT OF THE INVENTION The coating agent of the present invention has a wide variety of materials and forms, such as thermoplastic resin molded products of various forms such as films, sheets and containers made of thermoplastic resin, on a predetermined surface of a base material. In addition, it shows a sufficiently high oxygen gas barrier property, and yet retains its high oxygen gas barrier property even under high humidity, and it does not generate harmful components even when incinerated, and it has excellent environmental compatibility. The oxygen gas barrier cured resin film can be easily formed.

Therefore, the coating agent of the present invention is
For example, improvement of oxygen gas barrier properties of various conventional thermoplastic resin products such as packaging materials for foods and pharmaceuticals, production of various resin molded products including sufficient oxygen gas barrier properties, or It can be advantageously used for various applications such as protection by a film or coating of a metal or a printed wiring board which is easily damaged by oxygen.

Further, the resin film-coated thermoplastic resin molded product of the present invention has the advantage that it retains a sufficiently high oxygen gas barrier property even when used in a high humidity atmosphere.

Claims (4)

[Claims] 1. A liquid or slurry coating agent used for forming a film of a resin composition on the surface of a substrate by applying the solvent to a substrate and evaporating the solvent, wherein the coating agent is at least ethylene-vinyl. An alcohol copolymer resin, a solvent that dissolves the copolymer resin, and silica particles are blended, and the blending ratio of the silica particles is 0.1 to 100 parts by weight of the ethylene-vinyl alcohol copolymer resin.
The coating agent is in the range of 01 to 100 parts by weight. 2. The blending ratio of the ethylene-vinyl alcohol copolymer resin is 5 with respect to 100 parts by weight of the solvent.
To 100 parts by weight, and the mixing ratio of the silica particles to 100 parts by weight of the solution comprising the copolymer resin and the solvent is in the range of 0.01 to 10 parts by weight. Coating agent. 3. An ethylene-vinyl compound by coating the surface of a base material made of a thermoplastic resin with the coating agent according to claim 1 directly or through an intermediate layer and evaporating the solvent. A thermoplastic resin molded article with a resin film, comprising a cured film of a resin composition comprising an alcohol copolymer resin and silica particles. 4. The resin-coated thermoplastic resin according to claim 3, wherein the form of the molded article after the formation of the cured film is in the form of a film, sheet, tube, pipe, bag, capsule, container or container member. Molded body.