WO2020262619A1

WO2020262619A1 - Molded body and use thereof

Info

Publication number: WO2020262619A1
Application number: PCT/JP2020/025255
Authority: WO
Inventors: 智亮齋藤; 中村　信雄
Original assignee: 株式会社カネカ
Priority date: 2019-06-28
Filing date: 2020-06-26
Publication date: 2020-12-30
Also published as: JP7467454B2; JPWO2020262619A1

Abstract

The purpose of the present invention is to provide a molded body and a technique for using the molded body, wherein the molded body improves adhesion between a biodegradable resin layer using a poly(3-hydroxybutyrate) resin and a vapor-deposited layer, has excellent gas barrier properties, and has a resin layer with high transparency. The purpose is achieved by providing a molded body including a laminate in which a vapor-deposited layer containing an inorganic material is provided on at least one surface of a resin layer containing a poly(3-hydroxyalkanoate), wherein the vapor-deposited layer is formed on a surface of the resin layer having a surface tension of at least 36 mN/m.

Description

Mold and its use

The present invention relates to a molded product containing poly (3-hydroxyalkanoate) and its use.

Most of the plastic containers will eventually become solid waste. While efforts for recycling are increasing, repeated processing will result in deterioration of mechanical properties. Therefore, a plastic container that decomposes in the soil environment is desired. As an example of such a plastic product, a product using a biodegradable resin such as polylactic acid as a main component is known.

On the other hand, the environmental problems caused by waste plastics have been highlighted, and it has become clear that a large amount of plastics that have flowed into the sea via ocean dumping or rivers are drifting in the ocean on a global scale. Since such plastics maintain their shape for a long period of time, they have an impact on the ecosystem, such as so-called ghost fishing, which restrains and captures marine organisms, and when ingested by marine organisms, they remain in the digestive tract and cause eating disorders. Has been pointed out.

Furthermore, it has been pointed out that microplastics, which are disintegrated and atomized by ultraviolet rays, adsorb harmful compounds in seawater, and when marine organisms ingest them, harmful substances are taken into the food chain. There is. Among the plastic waste drifting in the ocean, films such as labels and food packaging and bottle containers such as PET bottles are very common and are regarded as a problem.

Biodegradable plastics are expected to be used for marine pollution caused by such plastics, but in the report (Non-Patent Document 1) compiled by the United Nations Environmental Plan in 2015, biodegradable with compost such as polylactic acid is possible. It has been pointed out that such plastics cannot be used as a countermeasure against marine pollution because they cannot be expected to decompose in a short period of time in the real ocean where the temperature is low. However, on the other hand, the bottle container itself is particularly useful for carrying beverages and foods, and continuous use is desired.

Under these circumstances, poly (3-hydroxybutyrate) -based resin is attracting attention as a material that solves the problem of marine pollution because it is a material that can undergo biodegradation even in seawater.

By the way, since food packaging films and bottle containers are used for storing beverages and foods, gas barrier properties and transparency are required. In order to improve the gas barrier property of such a biodegradable resin, it is widely known to produce a gas barrier film by depositing a metal or the like on the biodegradable resin. However, in general, the adhesion between the biodegradable resin and the vapor-deposited layer of metal or the like is not good. In order to solve such a problem, for example, in Patent Document 1, an anchor coat layer made of a specific polyurethane resin composition is formed on a biodegradable resin film to improve adhesion to a vapor-deposited layer such as a metal. The technology to make it is reported. Further, Patent Document 2 discloses a thermoplastic biodegradable polymer mixture containing starch as an essential component as a biodegradable substance.

International Publication No. 2012/0392959 US2014 / 0087106

However, in the technique of Patent Document 1, since it is necessary to form an anchor coat layer made of a non-biodegradable polyurethane resin composition, there is room for improvement from the viewpoint of biodegradability. Further, the technique of Patent Document 2 has a problem that the transparency of the film is low and it is difficult to visually recognize the print layer and the contents.

Therefore, one aspect of the present invention is to improve the adhesion between the biodegradable resin layer using a poly (3-hydroxybutyrate) resin and the vapor-deposited layer, to have excellent gas barrier properties and to have high transparency of the resin layer. It is an object of the present invention to provide a molded product and a technique for utilizing the molded product.

As a result of diligent studies to solve the above problems, the present inventors have (1) a biodegradable resin layer and a vapor deposition layer using a poly (3-hydroxybutyrate) resin which is a material that biodegrades in seawater. To complete the present invention by finding new findings regarding the possibility of enhancing the adhesion with the resin, (2) excellent gas barrier property of the obtained laminate, and (3) obtaining a highly transparent resin layer. I arrived.

Therefore, one aspect of the present invention is a molded product including a laminated body in which a vapor-deposited layer containing an inorganic material is provided on at least one surface of a resin layer containing poly (3-hydroxyalkanoate), and the resin layer. It is a molded product in which a vapor-deposited layer is formed on a surface having a surface tension of 36 mN / m or more.

According to one aspect of the present invention, it is possible to provide a molded product having excellent adhesion to the vapor-deposited layer, good gas barrier property, and high transparency of the resin layer.

An embodiment of the present invention will be described in detail below. Unless otherwise specified in the present specification, "A to B" representing a numerical range means "A or more and B or less". In addition, all the documents described in the present specification are incorporated as references in the present specification.

[1. Overview〕
A molded product according to an embodiment of the present invention (hereinafter, referred to as "the present molded product") is provided with a vapor-deposited layer containing an inorganic material on at least one surface of a resin layer containing poly (3-hydroxyalkanoate). It is a molded product containing the laminated body, characterized in that a vapor-deposited layer is formed on the surface of the resin layer having a surface tension of 36 mN / m or more. In other words, it is a molded product containing a laminated body in which a layer containing an inorganic material is vapor-deposited on at least one surface of a resin layer containing poly (3-hydroxyalkanoate), and the surface tension of the resin layer is 36 mN / m. It can be said that it is a molded product in which an inorganic material is vapor-deposited on the above surface.

The present inventors have succeeded in obtaining the following findings as a result of diligent studies on a molded product containing a poly (3-hydroxybutyrate) resin.

In forming a molded product in which a metal or the like is vapor-deposited on a resin layer containing a poly (3-hydroxybutyrate) resin, the surface tension of the resin layer containing the poly (3-hydroxybutyrate) resin is 36 mN. By depositing an inorganic material on the surface at / m or more, the adhesion between the resin layer containing the poly (3-hydroxybutyrate) resin and the vapor deposition layer (hereinafter, also referred to as "deposited adhesion"). Yes), and found that the gas barrier property of the molded product is enhanced. It was also found that the obtained resin layer is highly transparent. Details of the means for setting the surface tension of the resin layer to 36 mN / m or more will be described later, but examples thereof include a method in which the resin layer does not substantially contain an outer lubricant.

In the research and development so far, the molded product containing a poly (3-hydroxybutyrate) resin has a significantly narrower processable temperature range when inflating a film than a general-purpose resin, and has formability and productivity. Had the problem of worsening. In order to solve such a problem, when molding a poly (3-hydroxybutyrate) resin, it is usually necessary to add an outer lubricant to ensure moldability and productivity (for example, internationally). Publication No. 2018/181500).

Under such common general knowledge, when handling a resin containing a poly (3-hydroxybutyrate) resin, a person skilled in the art naturally imposes an outer lubricant in the mixture in the molding process. , It does not come to the idea that the outer lubricant is removed from the molding mixture containing the poly (3-hydroxybutyrate) resin. Therefore, it can be said that the above findings obtained by the present inventors are surprising.

Since the molded product has a structure in which a vapor-deposited layer containing an inorganic material is provided on at least one side of the resin layer containing poly (3-hydroxyalkanoate), the vapor-deposited layer is hard to peel off, has excellent gas barrier properties, and is a resin layer. It has the effect of being highly transparent. In the present specification, the gas barrier property means, for example, water vapor permeability and / or oxygen permeability. Hereinafter, the configuration of the molded product will be described in detail.

[2. Resin layer]
The resin layer in this molded product contains poly (3-hydroxy alkanoate). In the following, poly (3-hydroxy alkanoate) may be abbreviated as P3HA.

(Poly (3-hydroxy alkanoate) (P3HA))
As used herein, the term "P3HA" means a biodegradable aliphatic polyester (preferably a polyester containing no aromatic ring). P3HA is a 3-hydroxyalkanoic acid repeating unit represented by the general formula: [-CHR-CH _2- CO-O-] (in the formula, R is an alkyl group represented by C _n H _{2n + 1} and n is an alkyl group. It is a polyhydroxyalkanoate containing 1 or more and 15 or less as an essential repeating unit. Among them, the repeating unit is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, based on the total monomer repeating unit (100 mol%).

More specifically, as P3HA, for example, poly (3-hydroxybutyrate) (P3HB), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HB3HV), poly (3-hydroxybutyrate- Co-3-hydroxyhexanoate) (P3HB3HH), poly (3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (P3HB3HV3HH), poly (3-hydroxybutyrate- Co-4-hydroxybutyrate) (P3HB4HB), poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), poly (3-hydroxybutyrate-co-3-hydroxydecanoate), etc. Be done.

Note that P3HA produced by microorganisms (microorganism-produced P3HA) is usually P3HA composed only of D-form (R-form) polyhydroxyalkanoic acid monomer units. Among the microbially produced P3HA, P3HB, P3HB3HH, P3HB3HV, P3HB3HV3HH, and P3HB4HB are preferable, and P3HB, P3HB3HH, P3HB3HV, and P3HB4HB are more preferable, because industrial production is easy.

In one embodiment of the invention, P3HA is poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate). Hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3) -Hydroxyoctanoate) and poly (3-hydroxybutyrate-co-3-hydroxydecanoate) are at least one selected from the group.

When P3HA (particularly, microbially produced P3HA) contains a 3-hydroxybutanoic acid (3HB) repeating unit as an essential monomer unit, the monomer composition ratio is set to the total repeating unit (100) from the viewpoint of the balance between flexibility and strength. In mol%), the 3-hydroxybutanoic acid (3HB) repeating unit is preferably 80 mol% to 99 mol%, more preferably 85 mol% to 97 mol%. When the composition ratio of the 3HB repeating unit is 80 mol% or more, the rigidity of P3HA is further improved, and the crystallinity does not become too low, which tends to facilitate purification. On the other hand, when the composition ratio of the 3HB repeating unit is 99 mol% or less, the flexibility tends to be further improved. The monomer composition ratio of P3HA can be measured by gas chromatography or the like (see, for example, International Publication No. 2014/02038).

The microorganism that produces microorganism-produced P3HA is not particularly limited as long as it is a microorganism capable of producing P3HAs. For example, as a P3HB-producing bacterium, Bacillus megaterium discovered in 1925 is the first, and in addition, Cupriavidus necator (former classification: Alcaligenes eutrophos, Ralstonia eutropha) (Ralstonia eutropha) Natural microorganisms such as Alcaligenes ratus can be mentioned. It is known that P3HB is accumulated in the cells of these microorganisms.

Examples of the bacterium producing a copolymer of hydroxybutyrate and other hydroxyalkanoates include Aeromonas caviae, which is a P3HB3HV and P3HB3HH-producing bacterium, and Alcaligenes, which is a P3HB4HB-producing bacterium. It has been known. In particular, regarding P3HB3HH, in order to increase the productivity of P3HB3HH, Alcaligenes utrophas AC32 strain (Alcaligenes europhos AC32, FERM BP-6038) (T. Fukui, Y. Doi, J. Baeri) into which the gene of the P3HA synthase group was introduced. , 179, p4821-4830 (1997)) and the like are more preferable, and microbial cells in which P3HB3HH is accumulated in the cells by culturing these microorganisms under appropriate conditions are used. In addition to the above, a recombinant microorganism into which various P3HA synthesis-related genes have been introduced may be used according to the P3HA to be produced, or the culture conditions including the type of substrate may be optimized.

The molecular weight of P3HA is not particularly limited as long as it exhibits substantially sufficient physical properties for the intended use. The weight average molecular weight range of P3HA is preferably 50,000 to 3,000,000, more preferably 100,000 to 1,000,000, and even more preferably 300,000 to 700,000. By setting the weight average molecular weight to 50,000 or more, the strength of the film tends to be further improved. On the other hand, when the weight average molecular weight is 3,000,000 or less, the processability tends to be further improved and the molding tends to be easier. As will be described later, the P3HA is preferably a uniformly and appropriately crosslinked P3HA, but the value of the weight average molecular weight is a value measured before the P3HA is crosslinked.

As the method for measuring the weight average molecular weight, gel permeation chromatography (GPC) (“Shodex GPC-101” manufactured by Showa Denko Co., Ltd.) was used, and polystyrene gel (“Shodex K-804” manufactured by Showa Denko Co., Ltd.) was used for the column. It can be determined as the molecular weight when chloroform is used as the mobile phase and converted to polystyrene. At this time, the calibration curve is prepared using polystyrene having a weight average molecular weight of 31,400, 197,000, 668,000, and 1,920,000. As the column in the GPC, a column suitable for measuring the molecular weight may be used.

In one embodiment of the present invention, one type of P3HA may be used alone, or two or more types may be used in combination.

In one embodiment of the present invention, the content of P3HA in the resin layer is not particularly limited, but is preferably 20% by weight or more, more preferably 30% by weight or more, still more preferably 40% by weight or more, still more preferably 60% by weight. % Or more, more preferably 70% by weight or more. When the content of P3HA is 20% by weight or more, the biodegradability of the resin layer tends to be further improved. The upper limit of the content of P3HA is not particularly limited, but is preferably 95% by weight or less, more preferably 92% by weight or less, and further preferably 90% by weight or less.

The surface tension of at least one side of the molded product before vapor deposition in the present molded product is preferably 36 mN / m or more, more preferably 37 mN / m or more, and particularly preferably 38 mN / m or more. By providing the vapor-deposited layer on the surface having a surface tension of 36 mN / m or more, the gas barrier property and the adhesion between the vapor-deposited layer and the resin layer tend to be excellent. The method for setting the surface tension to 36 mN / m or more is not particularly limited as long as the surface tension can be set to 36 mN / m or more, but a method that substantially does not use an outer lubricant, a discharge treatment such as corona treatment or plasma treatment, A method of cleaning the surface with liquids or the like, a method of roughening the surface, or the like can be preferably used.

Further, in the molded product before vapor deposition in the present molded product, the surface friction coefficient of at least one side is preferably 0.17 or more, more preferably 0.18 or more, and particularly preferably 0.19 or more. By providing the vapor-deposited layer on the surface having a surface friction coefficient of 0.17 or more, the gas barrier property and the adhesion between the vapor-deposited layer and the resin layer tend to be excellent. The method of setting the surface friction coefficient to 0.17 or more is not particularly limited as long as the surface friction coefficient can be set to 0.17 or more, but a method that does not substantially use an outer lubricant, a discharge such as corona treatment or plasma treatment, etc. Treatment, a method of cleaning the surface with liquids or the like, a method of smoothing the surface, or the like can be preferably used.

(Outer lubricant)
It is preferable that the resin layer in the present molded product is substantially free of the outer lubricant. Since the resin layer does not substantially contain the outer lubricant, there is an advantage that the adhesion between the resin layer and the vapor-deposited layer is increased when the vapor-deposited layer containing the inorganic material is vapor-deposited on the resin layer. It also has a high gas barrier property.

In the present specification, the "outer lubricant" bleeds on the surface of a molded product to promote peeling from a roll or mold of a molding machine and opening of a double-layered film such as an inflation film. Means a substance. The outer lubricant is not particularly limited as long as it satisfies the above definition, and examples thereof include a fatty acid monoamide and a fatty acid bisamide. Examples of the fatty acid constituting the fatty acid amide include fatty acids having 12 to 30 carbon atoms and fatty acids having 18 to 22 carbon atoms, and examples thereof include higher fatty acids such as erucic acid, palmitic acid, and oleic acid. Specific examples of the fatty acid amide include erucic acid amide, palmitate amide, oleic acid amide, stearic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide, ethylene bisoleic acid amide, and ethylene biseramic acid amide. Can be mentioned.

In the present specification, "substantially free of external lubricant" means that the resin layer does not contain external lubricant to the extent that it affects the effects of the present invention. In other words, "substantially free of external lubricant" means that the resin layer may contain less than enough external lubricant to affect the effectiveness of the present invention.

In one embodiment of the present invention, the content of the outer lubricant in the resin layer is preferably 0.5% by weight or less, more preferably 0.3% by weight or less, still more preferably 0.1% by weight. It is as follows. Most preferably, the resin layer does not contain any external lubricant. When the content of the outer lubricant in the resin layer is 0.5% by weight or less, high adhesion to the vapor-deposited layer is ensured and high gas barrier property is exhibited.

(Crystal nucleating agent)
The resin layer in the present molded product may contain a crystal nucleating agent. When the resin layer in the molded product contains a crystal nucleating agent, the crystallization rate of P3HA can be improved and the molding processability can be improved. As the crystal nucleating agent, for example, a polyhydric alcohol or the like is preferably used. Examples of polyhydric alcohols include pentaerythritol, galactitol, mannitol and the like. As the crystal nucleating agent, one type may be used alone, or two or more types may be used in combination. The content of the crystal nucleating agent can be appropriately set and is not particularly limited.

(Other resins)
The resin layer in the present molded product may contain a resin other than P3HA (hereinafter, may be referred to as "another resin"). The other resin is not particularly limited as long as the compatibility, molding processability, and mechanical properties are not significantly reduced when molding the molded product according to the embodiment of the present invention, but the present molded product is a feature of P3HA. When used in applications requiring degradability, it is preferably a biodegradable resin. Examples of other resins include aliphatic polyesters having a structure in which an aliphatic diol and an aliphatic dicarboxylic acid are polycondensed, and an aliphatic aromatic polyester using both an aliphatic compound and an aromatic compound as monomers. Be done. Examples of the former are polyethylene succinate, polybutylene succinate (PBS), polyhexamethylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene succinate adipate (PBSA), polyethylene sevacate, poly. Butylene succinate and the like can be mentioned. Examples of the latter include poly (butylene adipate-co-butylene terephthalate) (PBAT), poly (butylene sebacate-co-butylene terephthalate), poly (butylene azelate-co-butylene terephthalate), poly (butylene succinate-). Co-butylene terephthalate) (PBST) and the like. As for other resins, one type may be used alone, or two or more types may be used in combination.

In one embodiment of the present invention, the content of the other resin in the resin layer is not particularly limited, but is preferably 250 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 100 parts by weight or less, based on 100 parts by weight of P3HA. Is 50 parts by weight or less, particularly preferably 20 parts by weight or less. The lower limit of the content of the other resin is not particularly limited and may be 0 parts by weight.

(Other ingredients)
The resin layer in the present molded product may contain other components other than the above. For example, an organic or inorganic filler may be contained as long as the effect of the present invention is not impaired. Among them, from the viewpoint of biodegradability and carbon neutrality of the obtained film, for example, wood-based materials such as wood chips, wood flour, and ogas, rice husks, rice flour, starch, cornstarch, rice straw, straw, natural rubber and the like are natural. Derived material is preferred. The content of the organic or inorganic filler can be appropriately set and is not particularly limited. As the organic or inorganic filler, one type may be used alone, or two or more types may be used in combination. In addition to the above-mentioned organic or inorganic filler, the effects of the present invention may be exhibited. Pigments used as ordinary additives, colorants such as dyes, odor absorbers such as activated charcoal and zeolite, fragrances such as vanillin and dextrin, antioxidants, antioxidants, weather resistance improvers, as long as they do not inhibit It may contain one or more of UV absorbers, water repellents, antibacterial agents, sliding improvers and other secondary additives. The content of the additive can also be set as appropriate.

[3. Thin film deposition layer]
The vapor-deposited layer in the present molded body may be one containing an inorganic material, but may be composed of only an inorganic material.

The inorganic material in one embodiment of the present invention can be exemplified by a metal or an inorganic oxide, and is not particularly limited. Preferred examples may be, for example, aluminum, aluminum oxide, silicon oxide (eg, silicon monoxide, silicon dioxide, silicon nitride, etc.), cerium oxide, calcium oxide, diamond-like carbon film, or a mixture thereof. .. In one embodiment of the present invention, the inorganic material is preferably aluminum or silicon dioxide from the viewpoint of vapor deposition adhesion.

The thickness of the thin-film vapor deposition layer is not particularly limited, but is preferably 5 nm to 100 nm, more preferably 5 nm to 60 nm, from the viewpoint of productivity, handleability, appearance, and the like. When the thickness of the thin-film deposition layer is 5 nm or more, the vapor-film deposition layer is less likely to be chipped (peeling of the vapor-deposited layer from the resin layer), and the gas barrier property is good. Further, when the thickness of the layer is less than 100 nm, the cost at the time of vapor deposition is low, the coloring of the vapor deposition layer is not conspicuous, and the appearance is good.

[4. Specific configuration of molded product and its manufacturing method]
(Composition of molded product)
In the present molded product, the thin-film deposition layer may be vapor-deposited on only one side of the resin layer, or may be vapor-deposited on both sides. From the viewpoint of ensuring the biodegradability of P3HA, the vapor deposition layer is preferably vapor-deposited on only one side of the resin layer. Further, it is preferable that the vapor-deposited layer is directly vapor-deposited on the resin layer without interposing another layer.

In one embodiment of the present invention, the vapor-deposited layer in the molded product may be further laminated with a resin layer or the like. For example, when heat-sealing is performed as a molded product, a resin layer may be further laminated on the vapor-deposited layer.

The molded product is not particularly limited as long as it has a structure in which a vapor-deposited layer containing an inorganic material is vapor-deposited on at least one surface of a resin layer containing poly (3-hydroxyalkanoate), and is not particularly limited. Examples include sheets, tubes, plates, rods, containers (eg, bottle containers), bags, parts and the like. The molded product is preferably a film or a bottle container from the viewpoint of measures against marine pollution.

In one embodiment of the present invention, the haze value of the resin layer in the molded product is, for example, 40% or less, preferably 35% or less, more preferably 30% or less, still more preferably 25% or less. It is particularly preferably 20% or less, and further preferably 10% or less. When the haze value of the resin layer is 40% or less, there is an advantage that the transparency of the resin layer is good and the visibility of the contents is excellent when used as a packaging material. The lower limit of the haze value of the resin layer is preferably as low as possible from the viewpoint of transparency, and is not particularly limited, but is, for example, 1% or more. The haze value in the present specification is a value measured by the method described in JIS K7136-1: 1999 and K7316: 2000 on a sheet (film) having a thickness of 30 μm.

A film (resin layer) having a haze value of 40% or less raises the resin temperature in the extruder to the extent that the resin extruded from the extruder outlet does not cause surface roughness when forming the resin layer, or has a high haze value. It can be obtained by not blending a certain amount of resin (for example, a resin having a thickness of 30 μm and a haze value of 40% or more) or by not blending a constant amount of a filler that increases the haze value.

The water vapor permeability of the molded product is, for example, less than 1.00 g / m ² / 24h, preferably less than 0.95 g / m ² / 24h, and more preferably less than 0.90 g / m ² / 24h. Yes, more preferably less than 0.85 g / m ² / 24h. When the water vapor permeability is within the above range, a good water vapor gas barrier property can be obtained. Further, the lower the water vapor permeability, the better, and the lower limit thereof is not particularly limited, but it is presumed that about 0.01 g / m ² / 24h is a feasible lower limit. The water vapor permeability depends on the average surface roughness of the layer on which the vapor deposition layer is formed, the fn of the film, the type of inorganic material of the vapor deposition layer, the thickness of the vapor deposition layer, the amount of defects (pinholes, scratches, etc.) in the vapor deposition layer. Can be controlled. The water vapor permeability is measured and evaluated by the method described in Examples.

The oxygen permeability of the molded product is, for example, 3.00 g / m ² / 24h / atm or less, preferably 2.85 g / m ² / 24h / atm or less, and more preferably 2.80 g / m. It is m ² / 24h / atm or less, more preferably 2.75 g / m ² / 24h / atm or less. When the oxygen permeability is within the above range, good oxygen gas barrier property can be obtained. The oxygen permeability may lower the, its lower limit is not particularly ^limited, about 0.01g / m 2 / 24h / atm are presumed feasible lower limit. Oxygen permeability depends on the average surface roughness of the layer on which the vapor deposition layer is formed, the fn of the film, the type of inorganic material of the vapor deposition layer, the thickness of the vapor deposition layer, the amount of defects (pinholes, scratches, etc.) in the vapor deposition layer, etc. Can be controlled. The oxygen permeability is measured and evaluated by the method described in Examples.

The vapor deposition adhesion of this molded product is measured and evaluated by the method described in Examples.

Further, in one embodiment of the present invention, in order to improve the physical properties of the molded body, the molded body (for example, fiber, thread, rope, woven fabric, knitted fabric, non-woven fabric) composed of a material different from the present molded body , Paper, film, sheet, tube, board, rod, container, bag, part, foam, etc.). These materials are also preferably biodegradable.

In one embodiment of the present invention, the vapor-deposited film can be used in various packaging materials as a packaging material. The package is not particularly limited, and examples thereof include a side-seal package, a three-way seal package, a pillow package, and a standing pouch.

(Example of manufacturing method)
When the molded product is a thin-film film or a thin-film bottle container, they are manufactured by, for example, the methods described below.

<Film manufacturing method>
In one embodiment of the invention, the film can be produced by a molding method consisting of extrusion film molding. For example, a process in which a poly (3-hydroxybutyrate) resin is melted in an extruder and then extruded into a film shape from a T-die connected to the extruder outlet, and the molten resin is applied to a roll to cool and solidify. It can be manufactured by the process of taking it as a film. Specific conditions for extrusion film molding can be appropriately set by those skilled in the art according to a conventional method.

<Manufacturing method of bottle container>
In one embodiment of the invention, the bottle container can be manufactured by a molding method consisting of extrusion blow molding. For example, a process in which a poly (3-hydroxybutyrate) resin is melted in an extruder and then extruded into a tube shape from an annular die connected to the extruder outlet. It can be manufactured by a step of sandwiching from a surface and by blowing air into the tube whose one end is closed to form a bottle shape according to a mold and at the same time cooling and solidifying. Specific conditions for extrusion blow molding can be appropriately set by those skilled in the art according to a conventional method. The bottle container can also be manufactured by a molding method consisting of injection blow molding.

<Vacuum vapor deposition>
In one embodiment of the present invention, the thin-film deposition film and the vapor-deposited bottle container are manufactured by depositing the thin-film deposition layer on the film and the bottle container obtained above. The vapor deposition method is not particularly limited, and a vacuum vapor deposition method, a sputtering method, a chemical vapor deposition method, an ion plating method and the like are used.

In order to improve the gas barrier property of the molded product, it is preferable to corona-treat or plasma-treat the surface of the molded product before vapor deposition. The processing strength at the time of performing the corona treatment is preferably 5 to 80 W · min / m ² , and more preferably 10 to 60 W · min / m ² . Further, it is preferable to provide the cored metal vapor deposition layer under plasma discharge before providing the vapor deposition layer from the viewpoint of improving the adhesion of the vapor deposition layer and, by extension, improving the gas barrier property. In this case, the plasma discharge is preferably carried out in an oxygen and / or nitrogen gas atmosphere, and copper is preferably used as the nucleating metal.

To vaporize aluminum oxide by the reactive vapor deposition method, aluminum metal or alumina is evaporated by resistance heating boat method, high frequency induction heating of crucible, electron beam heating method, etc., and aluminum oxide is deposited on the film in an oxidizing atmosphere. The method of depositing is preferably used. Oxygen is used as the reactive gas for forming the oxidizing atmosphere, but a gas containing mainly oxygen and water vapor or a rare gas may also be used. Further, a method of adding ozone or promoting a reaction such as ion assist may be used in combination. In order to form the silicon oxide vapor deposition layer by the reactive vapor deposition method, a method of evaporating Si metal, SiO or SiO ₂ by an electron beam heating method and depositing silicon oxide on the film in an oxidizing atmosphere is adopted. As a method for forming an oxidizing atmosphere, the same method as described above is used.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

That is, one embodiment of the present invention is as follows.
<1> A molded product containing a laminated body in which a vapor-deposited layer containing an inorganic material is provided on at least one surface of a resin layer containing poly (3-hydroxyalkanoate), and the surface tension of the resin layer is 36 mN / m. A molded product having a vapor-deposited layer formed on the above surface.
<2> The molded product according to <1>, wherein the resin layer substantially does not contain an outer lubricant.
<3> The molded product according to <1> or <2>, wherein the haze value of the resin layer is 40% or less.
<4> The inorganic material is at least one selected from the group consisting of aluminum, aluminum oxide, silicon oxide, cerium oxide, calcium oxide, diamond-like carbon film, and a mixture thereof, <1> to <. The molded body according to any one of 3>.
<5> The molded product according to any one of <1> to <4>, wherein the water vapor permeability is less than 1.00 g / m ² / 24h.
<6> The poly (3-hydroxyalkanoate) is poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly. (3-Hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate- Any one of <1> to <5>, which is at least one selected from the group consisting of co-3-hydroxyoctanoate) and poly (3-hydroxybutyrate-co-3-hydroxydecanoate). The molded body described in.
<7> The molded product according to any one of <1> to <6>, which is a thin-film film or a thin-film bottle container.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

〔material〕
The following materials were used in the examples and comparative examples.

(P3HA)
A-1: The 3-hydroxyhexanoate (3HH) composition obtained according to the method described in International Publication No. 2013/147139, 11.2 mol%, weight average in terms of standard polystyrene measured by GPC. Poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) having a molecular weight of 580,000 (P3HB3HH)
A-2: P3HB3HH having a 3HH composition of 5.4 mol% and a standard polystyrene-equivalent weight average molecular weight of 620,000 obtained according to the method described in WO 2008/010296.
A-3: Ecomann EM5400F [Poly (3-hydroxybutyrate-4-hydroxybutyrate) (P3HB4HB)]
PBAT / Start: A mixture obtained according to the method described in US2014 / 0087106, having a PBAT (poly (butylene adipate-co-butylene terephthalate)) composition of 75% by weight and a potato-derived natural starch composition of 25% by weight. ..

(Outer lubricant)
B-1: Erucic acid amide (manufactured by Nippon Fine Chemical Co., Ltd.)
(Crystal nucleating agent)
C-1: Pentaerythritol (manufactured by Nippon Synthetic Chemistry Co., Ltd.)
(Inorganic material)
D-1: Aluminum (manufactured by High Purity Chemical Laboratory)
D-2: Silicon dioxide (manufactured by Optoscience)
[Measurement and evaluation method]
Evaluation in Examples and Comparative Examples was carried out by the following method.

(Water vapor permeability)
The water vapor permeability was measured using PERMATRAN-W3 / 33MG + manufactured by MOCON. The temperature of the permeation cell was 38 ° C., the relative humidity was 90%, the test gas nitrogen, the permeation area was 50 cm ² , and the number of tests was one.

(Oxygen permeability)
Oxygen permeability was measured using OX-TRAN ML2 / 21 manufactured by MOCON. The test was carried out under temperature conditions of 23 ° C., humidity of 50% RH, test gas oxygen of 100%, permeation area of 5 cm ² , and one test sheet.

(Evaporation adhesion)
A cellophane tape was attached to the surface of the laminate (deposited film) and peeled off instantly. If the vapor-deposited film did not peel off, it was evaluated as ◯, and if it peeled off, it was evaluated as ×. In addition, this measurement was performed three times, and if it peeled off even once, it was marked as x.

(surface tension)
Using a cotton swab, quickly spread the surface tension test mixture manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. to an area of 6 cm ² or more, and keep the state when it was applied for 2 seconds or more. It was evaluated as x. Starting with the test mixture of 50 mN / m, the surface tension of the test mixture marked with ◯ was set as a numerical value.

(Haze value)
The haze value of a film (resin layer) having a thickness of 30 μm was measured by the method described in JIS K7136-1: 1999 and K7316: 2000 using a haze meter HZ-V3 manufactured by Suga Test Instruments.

[Example 1]
P3HA (A-1), an outer lubricant (B-1) and a crystal nucleating agent (C-1) were dry-blended at the blending ratios shown in Table 1. The obtained mixture is put into a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM26ss) in the same direction, melt-kneaded at a set temperature of 120 to 160 ° C. and a screw rotation speed of 100 rpm, and pellets are cut by strand cutting. Obtained.

Using the obtained pellets, a film (sheet) is manufactured by T-die molding under the initial conditions of an extruder set temperature of 130 to 160 ° C, an adapter and die set temperature (resin temperature) of 160 ° C, and a take-up speed of 1 m / min. Carried out. The conditions for extrusion were a screw rotation speed of 30 rpm and a die gap of 250 um, and after extrusion, a roll adjusted to a temperature of 60 ° C. was applied to the sheet and taken up at 1 m / min to produce a film (resin layer). Then, the haze value of the obtained film was measured. The results are shown in Table 1.

Further, the above film was vacuum-deposited using an inorganic material (D-1) to obtain a laminate. Then, the water vapor permeability, oxygen permeability and vapor deposition adhesion of the laminate were measured and evaluated by the above method. The results are shown in Table 1.

[Example 2]
A film and a laminate were produced in the same manner as in Example 1 except that the types of the inorganic materials were changed as shown in Table 1. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 3]
A film and a laminate were produced in the same manner as in Example 1 except that the crystal nucleating agent was removed. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 4]
A film and a laminate were produced in the same manner as in Example 1 except that the type of the inorganic material was changed as shown in Table 1 except for the crystal nucleating agent. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 5]
A film and a laminate were produced in the same manner as in Example 1 except that the type of P3HA was changed as shown in Table 1. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 6]
A film and a laminate were produced in the same manner as in Example 1 except that the type of P3HA and the type of the inorganic material were changed as shown in Table 1. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 7]
A film and a laminate were produced in the same manner as in Example 1 except that the type of P3HA was changed as shown in Table 1 except for the crystal nucleating agent. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 8]
A film and a laminate were produced in the same manner as in Example 1 except that the type of P3HA and the type of the inorganic material were changed as shown in Table 1 except for the crystal nucleating agent. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 9]
A film and a laminate were produced in the same manner as in Example 1 except that the type of P3HA was changed as shown in Table 1. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 10]
A film and a laminate were produced in the same manner as in Example 1 except that the type of P3HA and the type of the inorganic material were changed as shown in Table 1. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 11]
A film and a laminate were produced in the same manner as in Example 1 except that the type of P3HA was changed as shown in Table 1 except for the crystal nucleating agent. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 12]
A film and a laminate were produced in the same manner as in Example 1 except that the type of P3HA and the type of the inorganic material were changed as shown in Table 1 except for the crystal nucleating agent. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
A film was produced in the same manner as in Example 1 except that vacuum deposition was not performed except for the crystal nucleating agent. In addition, the haze value, water vapor permeability and oxygen permeability of the obtained film were measured by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 2]
A film was produced in the same manner as in Example 1 except that the type of P3HA was changed as shown in Table 2 except for the crystal nucleating agent and vacuum deposition was not performed. In addition, the haze value, water vapor permeability and oxygen permeability of the obtained film were measured by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 3]
A film was produced in the same manner as in Example 1 except that the type of P3HA was changed as shown in Table 2 except for the crystal nucleating agent and vacuum deposition was not performed. In addition, the haze value, water vapor permeability and oxygen permeability of the obtained film were measured by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 4]
A film and a laminate were produced in the same manner as in Example 1 except that an outer lubricant was added. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 5]
A film and a laminate were produced in the same manner as in Example 1 except that an outer lubricant was added, a crystal nucleating agent was removed, and the types of inorganic materials were changed as shown in Table 2. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 6]
A film and a laminate were produced in the same manner as in Example 1 except that an outer lubricant was added and the type of P3HA was changed as shown in Table 2. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 7]
A film and a laminate were produced in the same manner as in Example 1 except that an outer lubricant was added, a crystal nucleating agent was removed, and the types of P3HA and the types of inorganic materials were changed as shown in Table 2. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 8]
A film and a laminate were produced in the same manner as in Example 1 except that an outer lubricant was added and the type of P3HA was changed as shown in Table 2. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 9]
A film and a laminate were produced in the same manner as in Example 1 except that an outer lubricant was added, a crystal nucleating agent was removed, and the types of P3HA and the types of inorganic materials were changed as shown in Table 2. Further, the haze value of the obtained film and the water vapor permeability, oxygen permeability and vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 10]
A film and a laminate were produced in the same manner as in Example 1 except that P3HA was changed to PBAT / Starch except for the crystal nucleating agent. Further, the haze value of the obtained film and the vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 2.

[Comparative Example 11]
A film and a laminate were produced in the same manner as in Example 1 except that the crystal nucleating agent was removed, P3HA was changed to PBAT / Starch, and the type of the inorganic material was changed as shown in Table 2. Further, the haze value of the obtained film and the vapor deposition adhesion of the obtained laminate were measured and evaluated by the same method as in Example 1. The results are shown in Table 2.

〔result〕
From Tables 1 and 2, in the examples, the water vapor permeability and the oxygen permeability of the laminated body were lower than those in the comparative example. Moreover, in all the examples, the vapor deposition adhesion and the haze value of the resin layer were good results.

From the above, it was found that the molded product (laminated product) of the present invention is a molded product in which the vapor-deposited layer is hard to peel off, the gas barrier property is excellent, and the resin layer is highly transparent.

This molded product can be suitably used in agriculture, fisheries, forestry, horticulture, medicine, sanitary goods, clothing, non-clothing, packaging, automobiles, building materials, and other fields.

Claims

A molded product containing a laminate in which a vapor-deposited layer containing an inorganic material is provided on at least one surface of a resin layer containing poly (3-hydroxyalkanoate), and the surface tension of the resin layer is 36 mN / m or more. A molded body in which a thin-film deposition layer is formed.
The molded product according to claim 1, wherein the resin layer does not substantially contain an outer lubricant.
The molded product according to claim 1 or 2, wherein the haze value of the resin layer is 40% or less.
Any of claims 1 to 3, wherein the inorganic material is at least one selected from the group consisting of aluminum, aluminum oxide, silicon oxide, cerium oxide, calcium oxide, diamond-like carbon film, and a mixture thereof. The molded body according to item 1.
The molded product according to any one of claims 1 to 4, wherein the water vapor permeability is less than 1.00 g / m 2 / 24h.
The poly (3-hydroxyalkanoate) is poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (3-hydroxyvalerate). Hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3) The item according to any one of claims 1 to 5, which is at least one selected from the group consisting of -hydroxyoctanoate) and poly (3-hydroxybutyrate-co-3-hydroxydecanoate). Molded body.
The molded product according to any one of claims 1 to 6, which is a thin-film film or a thin-film bottle container.