JP6191360B2 - Polylactic acid resin sheet and molded product - Google Patents

Description

  The present invention relates to a polylactic acid resin sheet which is excellent in moldability and rigid property and is particularly suitable for use as a deep-drawn molded product.

  In recent years, with the growing awareness of the environment, the disposal of plastic products has been attracting attention. For shape retainers, food trays and beverage cups used for display and packaging of various products, etc. A variety of biodegradable plastic sheets have been developed. Among them, polylactic acid is particularly attracting attention as a promising material because it has a high glass transition point of about 60 ° C. and is transparent as a biodegradable plastic.

  However, impact resistance is low when compared with conventional petroleum-derived raw materials such as polyethylene terephthalate, and it is necessary to improve impact resistance when the current uses are replaced with polylactic acid. As an improvement method, it is known that an improvement effect can be obtained by adding rubber particles to polylactic acid (see Patent Documents 1 to 3). However, the impact resistance is not sufficient when used in applications requiring higher impact resistance such as exemplified by deep-drawn molded article applications, and further improvement in impact resistance is required.

  By the way, as an application of a deep-drawn molded article of a plastic sheet, a food container application can be cited as a representative example, and a chilled cup beverage container, a jelly cup, a miso container, and the like can be exemplified. In many cases, it is a food containing a lot of moisture, a food with an odor, and the like, and a deep-drawn molded product often requires a gas barrier property. As a method for improving the gas barrier property of a molded product having a normal drawing ratio, it is known to obtain a molded product by molding a sheet laminated with a resin having a high gas barrier property (see Patent Documents 3 to 5). With these techniques, it is difficult to obtain sufficient moldability, and it has not been possible to apply to deep-drawn molded products.

WO11 / 092989 pamphlet JP 2009-169577 A JP 2010-1111094 A JP 2009-028988 JP 2008-273147 A

  Accordingly, an object of the present invention is to provide a polylactic acid-based resin sheet that is excellent in moldability and rigid property and is particularly suitable for use in deep-drawn molded products in view of the background of the above-described prior art.

The present invention for achieving the above object is as follows.
1) A sheet containing a polylactic acid resin and rubber particles,
Charpy impact strength is 0.20 MJ / m ² or more,
Young's modulus of Ri der more 3.0GPa,
The sheet has a laminated structure having a layer A containing a polylactic acid-based resin and rubber particles and a layer B containing a polylactic acid-based resin and rubber particles,
Satisfy the following conditions (1), and the layer B, the layer A, and the layer B, polylactic acid-based resin sheet, wherein Rukoto to Yusuke in this order.
Condition (1): Ma> Mb
However,
Ma: Content (% by mass) of rubber particles in layer A when the total component constituting layer A is 100% by mass
Mb: content (% by mass) of rubber particles in the layer B when all components constituting the layer B are 100% by mass
2) The polylactic acid resin sheet according to 1) , wherein the haze is 25% or less.
3) Thickness is 0.75 mm or more and 1.50 mm or less, The polylactic acid-type resin sheet as described in 1) or 2) characterized by the above-mentioned.
4) The polylactic acid resin sheet according to any one of 1) to 3), wherein the rubber particles are a multilayer structure polymer .

5 ) The polylactic acid resin sheet according to any one of 1) to 4), wherein the following condition (2) is satisfied.

Condition (2): 0 <Ma−Mb ≦ 5
6 ) The polylactic acid resin sheet according to any one of 1) to 5 ), which is an unstretched sheet.
7 ) The polylactic acid resin sheet according to any one of 1) to 6 ), wherein the oxygen permeability is 3.0 cc / m ² / day or less.
Characterized in that 8) water vapor transmission rate is less than ^{12.0g / m 2 / day, 1} ) polylactic acid-based resin sheet according to any one of 1 to 7).
9 ) The polylactic acid resin sheet according to any one of 1) to 8 ), wherein the polylactic acid resin sheet has a layer containing an ethylene-vinyl acetate copolymer saponified resin.
1 0 ) A molded article comprising the polylactic acid resin sheet according to any one of 1) to 9 ).
1 1 ) The molded article according to 1 0 ), wherein the drawing ratio is 0.5 or more.

  According to the present invention, it is possible to obtain a polylactic acid-based resin sheet that is excellent in moldability and rigid property and that is particularly suitable for deep-drawn molded product applications. The polylactic acid-based resin sheet of the present invention can be preferably used for molded products such as chilled cup beverage containers, jelly cups, and miso containers that require deep drawability.

The present invention is a sheet containing a polylactic acid-based resin and rubber particles, and has a Charpy impact strength of 0.20 MJ / m ² or more and a Young's modulus of 3.0 GPa or more. Each requirement of the present invention will be described below.

  In the present invention, the “sheet” means a two-dimensional structure, and includes, for example, a film and a plate. The “molded product” means a three-dimensional structure, and includes a three-dimensional structure obtained by processing the sheet, such as a container or a printed material.

  It is important that the polylactic acid resin sheet of the present invention contains a polylactic acid resin and rubber particles. When a polylactic acid-based resin is not contained, a conventional petroleum-derived raw material such as a polyethylene terephthalate resin is used, resulting in a sheet having a large environmental load. Moreover, when it does not contain a rubber particle, impact resistance becomes low and it becomes difficult to use it as a deep drawing molded product use.

  The content of the polylactic acid resin in the sheet is preferably 70% by mass or more and 95% by mass or less, and 75% by mass or more and 94% by mass or less when all the components constituting the sheet are 100% by mass. More preferably, it is 80 mass% or more and 92 mass% or less. The content of the rubber particles in the sheet when the total component constituting the sheet is 100% by mass is preferably 5% by mass or more and 30% by mass or less, and 6% by mass or more and 25% by mass or less. Is more preferable, and it is particularly preferably 8% by mass or more and 20% by mass or less.

It is important that the polylactic acid resin sheet of the present invention has a Charpy impact strength of 0.20 MJ / m ² or more. When the Charpy impact strength is less than 0.20 MJ / m ² , the moldability is often insufficient, and even when deep drawing is difficult or a molded product is obtained, the impact resistance of the molded product is low. , It may not be practical for use as a container. The polylactic acid resin sheet of the present invention preferably has a Charpy impact strength of 0.23 MJ / m ² or more, particularly preferably 0.25 MJ / m ² or more. On the other hand, the upper limit value of the Charpy impact strength is not particularly limited, but 0.40 MJ / m ² is considered to be a substantial upper limit in consideration of the Young's modulus described later.

In order to set the Charpy impact strength to 0.20 MJ / m ² or more, a method of forming a sheet that satisfies the condition (1) described later, a method of setting the thickness in the range of 0.75 mm to 1.50 mm, and the like are given. be able to.

  It is important that the polylactic acid-based resin sheet of the present invention has a Young's modulus of 3.0 GPa or more. If the Young's modulus is less than 3.0 GPa, uneven drawing may occur during molding, such as deep drawing is difficult, or even when the molded product is obtained, the molded product has low rigid properties, so it can be used for containers. May not be able to withstand practical use. The polylactic acid-based resin sheet of the present invention preferably has a Young's modulus of 3.1 GPa or more, particularly preferably 3.2 GPa or more. On the other hand, the upper limit value of Young's modulus is not particularly limited, but 4.0 GPa is considered to be a substantial upper limit in view of the aforementioned Charpy impact strength.

  In order to set the Young's modulus to 3.0 GPa or more, a method of forming a sheet that satisfies the condition (1) described later, a method of setting the thickness in a range of 0.75 mm to 1.50 mm, and the like can be given.

  The polylactic acid resin sheet of the present invention preferably has a haze of 25% or less. If the haze is 25% or less, a molded product using such a polylactic acid-based resin sheet is excellent in visibility of contents and good in appearance as a product. It can be preferably used as a sheet. On the other hand, when the haze is larger than 25%, the transparency is insufficient, which may not be preferable for practical use. The haze of the polylactic acid resin sheet of the present invention is particularly preferably 20% or less. On the other hand, the lower limit of haze is not particularly limited, but 1% is considered to be a substantial lower limit from the technical idea of the polylactic acid resin sheet of the present invention, and the lower limit is 10%. If there is, it is sufficient for practical use.

  In order to adjust the haze to 25% or less, the rubber particle content in the entire sheet is set to 5% by mass or more and 30% by mass, or the thickness is set in the range of 0.75 mm or more and 1.50 mm or less. be able to.

The polylactic acid resin sheet of the present invention preferably has a thickness of 0.75 mm or more and 1.50 mm or less. If the thickness is in the range of 0.75 mm or more and 1.50 mm or less, it is often easy to make Charpy impact strength 0.20 MJ / m ² or more and Young's modulus 3.0 GPa or more. As a result, deep drawing can be easily performed, and the molded product can be preferably used as a sheet for molding a molded product. When the thickness of the polylactic acid-based resin sheet of the present invention is less than 0.75 mm, the rigid property of the molded product may be inferior. Moreover, when the thickness of the polylactic acid-type resin sheet of this invention exceeds 1.50 mm, deep drawing shaping | molding may be difficult, for example, uneven thickness will arise at the time of shaping | molding. As for the polylactic acid-type resin sheet of this invention, it is especially preferable that thickness is 0.80 mm or more and 1.20 mm or less.

  The rubber particles in the present invention are composed of a polymer component having rubber elasticity, that is, a composition containing a rubber component, and have a particulate shape. Examples of the rubber component include components composed of polymerized acrylic components, silicone components, styrene components, nitrile components, conjugated diene components, urethane components, ethylene propylene components, and the like. , Acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, acrylonitrile units and methacrylonitrile units. Examples thereof include a component composed of a nitrile component and a polymerized conjugated diene component such as a butadiene unit or an isoprene unit. Moreover, the component comprised from what copolymerized these components in combination of 2 or more types can also be used preferably.

  Although the rubber particle used for the polylactic acid-type resin sheet of this invention is not specifically limited, It is preferable that it is a multilayer structure polymer. In the case of rubber particles consisting of a single-layer structure consisting only of the rubber component, the impact resistance is excellent, but the compatibility between the rubber particles and the polylactic acid resin is poor, and it is relatively easy to obtain the Charpy impact strength required for the present invention. It may be necessary to add a large amount of rubber particles. On the other hand, by using the rubber particles of the multilayer structure polymer, particularly the rubber particles of the multilayer structure polymer having a shell layer covering the rubber component layer as the core layer, the compatibility between the rubber particles and the polylactic acid resin is improved. The Charpy impact strength required for the present invention can be easily obtained by incorporating a relatively small amount of rubber particles in the sheet.

  The multilayer polymer is a so-called core shell composed of an innermost layer (core layer) and one or more layers (shell layer) covering the innermost layer (core layer), and adjacent layers are composed of different polymers. It is a polymer having a structure called a mold. The number of layers constituting the multilayer structure polymer may be two or more (one core layer and one or more shell layers), and three or more layers (one core layer and two or more layers). Shell layer) or four or more layers (one core layer and three or more shell layers). A particularly preferred multilayer structure polymer rubber particle is composed of one core layer and one shell layer. The multilayer structure polymer is preferably a multilayer structure polymer having at least a rubber layer in a layer other than the outermost layer.

  In the case where the rubber particles used in the polylactic acid-based resin sheet of the present invention is a multilayer structure polymer, the rubber layer may be a polymer component having rubber elasticity, that is, a composition containing a rubber component. Good. Examples of the rubber component include rubber composed of polymerized acrylic component, silicone component, styrene component, nitrile component, conjugated diene component, urethane component or ethylene propylene component. Examples of the polymer component preferably used as the rubber component include acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene units and α-methylstyrene units. Styrene components, nitrile components such as acrylonitrile units and methacrylonitrile units, and components constituted by polymerizing conjugated diene components such as butadiene units and isoprene units. Moreover, the component comprised from what copolymerized these components in combination of 2 or more types can also be used preferably.

  In the case where the rubber particles used in the polylactic acid resin sheet of the present invention is a multi-layer polymer, the layers other than the rubber layer do not have rubber elasticity and are composed of a polymer component having thermoplasticity. The glass transition temperature is preferably composed of a polymer component higher than that of the composition constituting the rubber layer. Examples of the thermoplastic polymer include unsaturated carboxylic acid alkyl ester units, glycidyl group-containing vinyl units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, aromatic vinyl units, cyanide. Examples thereof include polymers containing at least one unit selected from a vinyl fluoride unit, a maleimide unit, an unsaturated dicarboxylic acid unit, or other vinyl units, among which an unsaturated carboxylic acid alkyl ester unit In addition, a polymer containing at least one unit selected from unsaturated glycidyl group-containing units and unsaturated dicarboxylic anhydride-based units is preferred, and further from unsaturated glycidyl group-containing units or unsaturated dicarboxylic anhydride-based units. A polymer containing at least one selected unit is more preferably used.

  In the case where the rubber particles used in the polylactic acid resin sheet of the present invention is a multilayer polymer, the outermost layer is an unsaturated carboxylic acid alkyl ester unit, a glycidyl group-containing vinyl unit, an aliphatic vinyl unit, an aromatic It is preferably composed of a polymer containing vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units and / or other vinyl units. Among them, it is more preferable to be composed of a polymer containing an unsaturated carboxylic acid alkyl ester-based unit, an unsaturated glycidyl group-containing unit and / or an unsaturated dicarboxylic acid anhydride-based unit, and further an unsaturated carboxylic acid alkyl ester-based unit. More preferably, it is composed of a polymer containing units. Although it does not specifically limit as an unsaturated carboxylic-acid alkylester type | system | group unit, (meth) acrylic-acid alkylester is preferable and also (meth) acrylic-acid methyl is used preferably.

  In the case where the rubber particles used in the polylactic acid-based resin sheet of the present invention is a multilayer structure polymer, a preferable example of the multilayer structure polymer is a multilayer structure polymer composed of a core layer and one shell layer. The core layer is dimethylsiloxane / butyl acrylate polymer, the outermost layer is methyl methacrylate polymer, the core layer is butadiene / styrene polymer, the outermost layer is methyl methacrylate polymer, and the core layer is butyl acrylate polymer. For example, the outer layer is a methyl methacrylate polymer. Furthermore, it is a more preferable embodiment that any one of the core layer and the outermost layer, or both layers are polymers containing glycidyl methacrylate units.

  In the case where the rubber particles used in the polylactic acid-based resin sheet of the present invention is a multilayer structure polymer, the mass ratio of the core layer to the shell layer is such that the core layer is 50 mass% or more and 90 mass% with respect to the entire multilayer structure polymer. The core layer is more preferably 60% by mass or more and 80% by mass or less.

The polylactic acid-based resin sheet of the present invention has a layered structure including a layer A containing a polylactic acid-based resin and rubber particles, and a layer B containing a polylactic acid-based resin and rubber particles. The rubber in the layer B when the content (% by mass) of the rubber particles in the layer A is 100% by mass and the total component constituting the layer B is 100% by mass. When the particle content (% by mass) is Mb, it is important to satisfy the following condition (1).

Condition (1): Ma> Mb
By setting it as the laminated structure which satisfy | fills condition (1), it becomes possible to make Charpy impact strength 0.20 MJ / m < ² > or more and Young's modulus to 3.0 GPa or more. Furthermore, by setting it as the laminated structure which satisfy | fills conditions (1), compared with the case where it is not set as a laminated structure, it becomes possible to reduce content of the rubber particle in the whole sheet | seat, As a result, the polylactic acid-type resin in the whole sheet | seat Therefore, it is possible to obtain a polylactic acid resin sheet that is excellent in terms of environmental performance and cost.

  In the case where the polylactic acid-based resin sheet of the present invention has the layer A and the layer B described above and further satisfies the condition (1), other layers not corresponding to the layer A and the layer B may be disposed. Well, if this other layer is assumed to be layer C, layer 5 / layer C such as layer B / layer C / layer A / layer C / layer B, layer B / layer A / layer C / layer A / layer B, etc. A configuration or a three-layer / three-layer configuration of layer B / layer A / layer C may be employed.

From the viewpoint of curling suppression of the sheet, it is important that the polylactic acid-based resin sheet of the present invention has the layer B, the layer A, and the layer B in this order. In addition, in the polylactic acid resin sheet of the present invention having the layer B, the layer A, and the layer B in this order, it is possible to have another layer between the layer B and the layer A, but it is particularly preferable. It is preferable that no other layer be interposed between the layer B and the layer A. That is, the polylactic acid-based resin sheet of the present invention that is particularly preferable has the layer B, the layer A, and the layer B in this order, and the layer B and the layer A are directly laminated (layer B / layer A / layer B). is there. Moreover, in the laminated structure which has the layer B, the layer A, and the layer B in this order, it is especially preferable that the thickness of the two layers B is the same thickness. By laminating the layer B having a relatively small rubber particle content on both surfaces of the layer A having a relatively large rubber particle content, for example, the polylactic acid resin sheet of the present invention by T-die casting method. In the case of manufacturing, it is easy to improve the productivity, for example, it is difficult for the molten sheet to adhere to the cast drum. Similarly, when molding is performed using a polylactic acid-based resin sheet, the mold releasability after molding is easily improved.

  When the polylactic acid-based resin sheet of the present invention has a laminated structure having the layer A and the layer B, the content of the rubber particles in the layer A (when the total component constituting the layer A is 100% by mass ( (Mass%) (Ma) is 5 mass% or more and 25 mass% or less, and preferably satisfies the condition (1). When Ma is less than 5% by mass, deep drawing may be difficult due to uneven thickness at the time of molding. Moreover, when Ma exceeds 25 mass%, the rigid property of a molded product may be inferior. Ma is particularly preferably 7% by mass or more and 20% by mass or less.

  When the polylactic acid-based resin sheet of the present invention has a laminated structure having the layer A and the layer B, the content of the rubber particles in the layer B when the total components constituting the layer B are 100% by mass ( (Mass%) (Mb) is 8 mass% or more and 30 mass% or less, and it is preferable to satisfy the condition (1). If Mb is less than 8% by mass, deep drawing may be difficult, for example, uneven thickness may occur during molding. Moreover, when Mb exceeds 30 mass%, the rigid property of a molded product may be inferior or productivity may deteriorate. Mb is particularly preferably 9% by mass or more and 25% by mass or less.

  When the polylactic acid-based resin sheet of the present invention has a layer A and a layer B and has a laminated structure that satisfies the condition (1), it is preferable that the following condition (2) is further satisfied.

Condition (2): 0 <Ma−Mb ≦ 5
When Ma-Mb exceeds 5 mass%, peeling may occur between layer A and layer B when deep drawing is performed. Ma-Mb is particularly preferably greater than 0 and 4 or less.

When the polylactic acid-based resin sheet of the present invention has a laminated structure having the layer A and the layer B, the thickness of the layer A with respect to the total thickness of the sheet is preferably 50% or more and 95% or less, particularly preferably. 75% or more and 90% or less. When the thickness of the layer A is less than 50% with respect to the total thickness of the sheet, the environmental and cost aspects may not be excellent, and when the thickness of the layer A with respect to the total thickness of the sheet exceeds 95%, a laminated sheet In some cases, appearance defects may occur due to laminated spots. When there are a plurality of layers A, the total thickness of each layer A is considered. That is, the total thickness of the layer A with respect to the thickness of the entire sheet is preferably 50% or more and 95% or less, and particularly preferably 75% or more and 90% or less.

The polylactic acid based resin sheet of the present invention may be any of an unstretched sheet, a uniaxially stretched sheet, a biaxially stretched sheet, or a restretched sheet obtained by restretching a biaxially stretched sheet. In the case of stretching, from the viewpoint of moldability, the surface magnification indicated by the product of the stretching ratios of the respective stretching axes is preferably 3 or less, and particularly preferably an unstretched sheet. The polylactic acid based resin sheet of the present invention is either a uniaxially stretched sheet, a biaxially stretched sheet, or a restretched sheet obtained by restretching a biaxially stretched sheet, and the product of the stretch ratios of the respective stretch axes. When the surface magnification shown is greater than 3, there may be a problem such that molding defects are likely to occur when deep drawing with a drawing ratio of 0.6 or more is performed.

The polylactic acid-based resin sheet of the present invention preferably has an oxygen permeability of 3.0 cc / m ² / day or less. When the oxygen permeability exceeds 3.0 cc / m ² / day, when the polylactic acid resin sheet of the present invention is molded and used as a food container, problems such as easy deterioration of contents occur. There is a case. The oxygen permeability of the polylactic acid resin sheet of the present invention is preferably 2.0 cc / m ² / day or less, particularly preferably 1.5 cc / m ² / day or less. On the other hand, the lower limit value of the oxygen permeability is not particularly limited, but 0.01 cc / m ² / day is considered to be a substantial lower limit from the technical idea of the polylactic acid resin sheet of the present invention. It is done.

The polylactic acid based resin sheet of the present invention preferably has a water vapor transmission rate of 12.0 g / m ² / day or less. When the water vapor transmission rate exceeds 12.0 g / m ² / day, when the polylactic acid resin sheet of the present invention is molded and used as a food container, problems such as easy deterioration of contents occur. There is a case. The water vapor transmission rate of the polylactic acid-based resin sheet of the present invention is preferably 9.0 g / m ² / day or less, particularly preferably 6.0 g / m ² / day or less. On the other hand, the lower limit value of the water vapor transmission rate is not particularly limited, but 0.05 g / m ² / day is considered to be a substantial lower limit from the technical idea of the polylactic acid resin sheet of the present invention. It is done.

As a method for reducing the oxygen transmission rate to 3.0 cc / m ² / day or lowering the water vapor transmission rate to 12.0 g / m ² / day or lower, a method of depositing a metal, an inorganic oxide or the like on the sheet surface Well-known methods such as a method of laminating a layer containing a gas barrier resin, a method of coating a layer containing a gas barrier resin, or a method combining these methods can be used. From this point of view, it is preferable to employ a method of laminating a layer containing a gas barrier resin. As a method for laminating a layer containing a gas barrier resin, a known laminating method such as a dry laminating method, an extrusion laminating method, a coextrusion laminating method, a coextrusion coating method, a coextrusion method or the like can be employed.

  When a dry laminating method or an extrusion laminating method is adopted as a method for laminating a layer containing a gas barrier resin, a polyhydric alcohol having a main chain of polyester, polyether, polyurethane, etc. is used as a main agent, and isocyanate is a curing agent. A two-component curable adhesive or an anchor coating agent is used as an adhesive layer, and the adhesive layer is provided on the surface of a gas barrier film made of a composition containing a gas barrier resin, and a polylactic acid resin sheet is formed on the surface. Dry laminating or extrusion laminating is preferable so as to come into contact. When a coextrusion laminating method or a coextrusion coating method is adopted as a method for laminating a layer containing a gas barrier resin, an adhesive resin such as an acid-modified olefin is provided on at least one surface of the polylactic acid resin sheet. It is preferable that the gas barrier film made of the composition containing the gas barrier resin is extrusion laminated or extrusion coated on the surface on which the adhesive resin is arranged. When a coextrusion method is employed as a method of laminating a layer containing a gas barrier resin, adhesion of, for example, an acid-modified olefin between the layer A and / or layer B and the layer containing the gas barrier resin It is preferable to perform co-extrusion so as to dispose an adhesive layer composed of a conductive resin.

  When the polylactic acid-based resin sheet of the present invention has a layer containing a gas barrier resin, the gas barrier resin is not particularly limited, but a polyethylene resin, a polypropylene resin, a polyamide resin, a polyvinyl alcohol resin, ethylene-acetic acid Examples thereof include vinyl saponified saponified resins and polyvinylidene chloride-based resins, and the like depending on a gas barrier function required for a molded product obtained by molding a polylactic acid-based resin sheet or a polylactic acid-based resin sheet. Can be selected. For example, an ethylene-vinyl acetate copolymer saponified resin is preferably selected when oxygen barrier properties are required, and a polypropylene resin is preferably selected when water vapor barrier properties are required. Furthermore, when both oxygen barrier properties and water vapor barrier properties are required, it is preferable to select a polyvinylidene chloride resin.

  From the viewpoint of gas barrier properties, the content of the gas barrier resin in 100% by mass of all components of the layer containing the gas barrier resin is preferably 60% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass. It is particularly preferred that

  When the polylactic acid-based resin sheet of the present invention has a layer containing a gas barrier resin, the gas barrier resin is an ethylene-vinyl acetate copolymer saponified resin (hereinafter referred to as EVOH) from the viewpoint of moldability and productivity. Is particularly preferred. That is, the polylactic acid-based resin sheet of the present invention particularly preferably has a layer containing EVOH.

  When the polylactic acid resin sheet of the present invention has a layer containing EVOH, the EVOH preferably has an ethylene content of 29 mol% or more and 47 mol% or less, and 32 mol% or more and 44 mol% or less. Is particularly preferred. When EVOH is used as the gas barrier resin, the EVOH saponification rate is preferably 90 mol% or more and 100 mol% or less, and particularly preferably 95 mol% or more and 100 mol% or less. When the EVOH has an ethylene content of 29 mol% or more and 47 mol% or less, or the saponification rate is out of the range of 90 mol% or more and 100 mol% or less, particularly when EVOH is melt-extruded by a method such as a coextrusion method, Productivity may deteriorate.

  When the polylactic acid resin sheet of the present invention has a layer containing EVOH, the thickness of the layer containing EVOH is preferably 3 μm or more and 100 μm or less, and more preferably 5 μm or more and 80 μm or less. The particularly preferred thickness of the EVOH-containing layer is 5 μm or more and 30 μm or less when the EVOH-containing layer is laminated by the laminating method, and 15 μm or more and 80 μm or less when the EVOH layer-containing layer is laminated by the coextrusion method. It is. If the thickness of the EVOH-containing layer is less than 3 μm, sufficient gas barrier properties may not be obtained, and if the thickness of the EVOH-containing layer exceeds 100 μm, the moldability may deteriorate. .

  The polylactic acid-based resin used in the polylactic acid-based resin sheet of the present invention is composed of L-lactic acid and / or D-lactic acid as a main component, and the components derived from lactic acid are all monomer components constituting the polylactic acid-based resin. 100 mol% means 70 mol% or more and 100 mol% or less, and homopolylactic acid consisting essentially of L-lactic acid and / or D-lactic acid is preferably used.

  The polylactic acid resin used in the present invention preferably has crystallinity. The polylactic acid resin has crystallinity when the polylactic acid resin is sufficiently crystallized under heating and then subjected to differential scanning calorimetry (DSC) measurement in an appropriate temperature range. This means that the heat of crystal melting derived from is observed. In general, homopolylactic acid has higher melting point and crystallinity as the optical purity is higher. The melting point and crystallinity of the polylactic acid resin are affected by the molecular weight and the catalyst used at the time of polymerization. Usually, homopolylactic acid having an optical purity of 98% or more has a melting point of about 170 ° C. and a relatively high crystallinity. Further, as the optical purity is lowered, the melting point and crystallinity are lowered. For example, the homopolylactic acid having an optical purity of 88% has a melting point of about 145 ° C., and the homopolylactic acid having an optical purity of 75% has a melting point of about 120 ° C. . Homopolylactic acid with an optical purity lower than 70% does not show a clear melting point and is amorphous.

  The polylactic acid resin used in the present invention can be mixed with crystalline homopolylactic acid and amorphous homopolylactic acid. In this case, the ratio of the amorphous homopolylactic acid may be determined within a range that does not impair the effects of the present invention. In particular, when relatively high heat resistance is desired, at least one polylactic acid resin to be used is used. It is preferable to contain a polylactic acid resin having an optical purity of 95% or more.

  The mass average molecular weight of the polylactic acid resin used in the present invention is usually at least 50,000, preferably 80,000 to 400,000, and more preferably 100,000 to 300,000. In addition, the mass average molecular weight as used in the field of this invention is a gel permeation chromatography (GPC), measured using a column with Shodex GPCHFIP-806M and Shodex GPC HFIP-LG connected in series with a chloroform solvent. The molecular weight calculated by the polymethylmethacrylate (PMMA) conversion method.

  By setting the mass average molecular weight of the polylactic acid-based resin to 50,000 or more, the polylactic acid-based resin sheet of the present invention can be excellent in mechanical properties, and further obtained from the polylactic acid-based resin sheet of the present invention. The molded article can also have excellent mechanical properties.

  The polylactic acid resin used in the present invention may be a copolymerized polylactic acid obtained by copolymerizing other monomer components having ester forming ability in addition to L-lactic acid and D-lactic acid. Examples of copolymerizable monomer components include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid and other hydroxycarboxylic acids, ethylene glycol, propylene glycol, butane Compounds containing a plurality of hydroxyl groups in the molecule such as diol, neopentyl glycol, polyethylene glycol, glycerin and pentaerythritol or derivatives thereof, succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2 , 6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid and the like, or compounds containing a plurality of carboxylic acid groups in the molecule. These copolymer components are preferably contained in an amount of 0 mol% to 30 mol% in 100 mol% of all monomer components constituting the polylactic acid resin.

  Examples of the method for producing the polylactic acid resin used in the present invention include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide. For example, in the case of producing by direct dehydration condensation, lactic acid or lactic acid and hydroxycarboxylic acid are preferably subjected to azeotropic dehydration condensation in the presence of an organic solvent, particularly a phenyl ether solvent, and particularly preferably distilled by azeotropic distillation. Polymerization is performed by a method in which water is removed from the solvent thus obtained and the solvent which has been made substantially anhydrous is returned to the reaction system, whereby a high molecular weight polymer is obtained. In addition, as a ring-opening polymerization method, a high molecular weight can also be obtained by subjecting a cyclic ester intermediate of hydroxycarboxylic acid, for example, a cyclic ester intermediate such as lactide or glycolide, to a ring-opening polymerization under reduced pressure using a catalyst such as tin octylate. It is also known that polymers can be obtained. At this time, a method for adjusting the conditions for removing moisture and low molecular weight compounds during heating and refluxing in an organic solvent, a method for suppressing the depolymerization reaction by deactivating the catalyst after completion of the polymerization reaction, and a method for heat-treating the produced polymer Can be used to obtain a polymer with a small amount of lactide.

  The polylactic acid-based resin sheet of the present invention is a known antioxidant, UV stabilizer, anti-coloring agent, matting agent, deodorant, flame retardant, weathering agent, anti-resistance, and the like within a range that does not impair the effects of the present invention. As necessary, inorganic particles, organic particles, and organic lubricants may be added as oxidizing agents, ion exchange agents, crystal nucleating agents, coloring pigments, and the like, or as lubricants. In addition, these additives may be added to all layers or may be added to any one layer or a plurality of layers when the polylactic acid resin sheet of the present invention has a laminated structure. . The organic particles mentioned here are organic particles different from the rubber particles.

  In obtaining the polylactic acid resin sheet of the present invention, it is possible to produce a composition by uniformly mixing a solution in which each component is dissolved in a solvent, and then removing the solvent. It is preferable to employ a melt-kneading method for producing a composition by melt-kneading each component, which is a more practical production method that does not require a step such as solvent removal.

  As for the melt-kneading method, commonly used mixers such as a kneader, a roll mill, a Banbury mixer, and a single-screw or twin-screw extruder can be used. Among these, from the viewpoint of productivity, it is preferable to use a single screw or twin screw extruder.

  Regarding the order of mixing, for example, a method of subjecting a polylactic acid resin and rubber particles to a dry kneading machine after dry blending, or after preparing a master batch in which rubber particles such as polylactic acid and a multilayer structure polymer are previously melt-kneaded, Examples thereof include a method of melt-kneading the master batch and polylactic acid. In addition, if necessary, a method of simultaneously melting and kneading other components, or after preparing a master batch in which a polylactic acid-based resin and other additives are melt-kneaded in advance, the master batch and a master batch including the rubber particles described above You may use the method of melt-kneading a polylactic acid-type resin.

  The polylactic acid-based resin sheet of the present invention can be obtained by, for example, an existing film production method such as a T-die casting method, an inflation method, or a calendar method, but is preferably produced by the T-die casting method. For example, as a manufacturing example by the T die casting method, pellets are dried at a temperature of 60 to 110 ° C. for 3 hours or more, and pellets having a moisture content of 400 ppm or less on a mass basis are used. After performing melt-kneading using a twin screw extruder in the following range and extruding from a T die in a die temperature range of 150 ° C. to 240 ° C., it is cooled using a cooling roll at a temperature of 30 to 40 ° C. Obtaining a sheet of about 0.75 mm to 1.50 mm can be mentioned. In this case, the temperature range of the cylinder temperature and the die is preferably set to a temperature range of 200 ° C. or higher and 220 ° C. or lower from the viewpoint of suppressing thermal deterioration of the raw material.

  The polylactic acid resin sheet of the present invention may be subjected to various surface treatments for the purpose of improving coating suitability. Examples of the surface treatment method include corona discharge treatment, plasma treatment, flame treatment, and acid treatment.

  The molded product of the present invention is a molded product obtained by using the above-described polylactic acid resin sheet of the present invention. In order to obtain the molded product of the present invention using the polylactic acid-based resin sheet of the present invention, the polylactic acid-based resin sheet of the present invention is formed by vacuum molding, vacuum / pressure forming, plug assist molding, straight molding, free drawing molding, This is possible by applying to various molding methods such as plug-and-ring molding and skeleton molding. As a sheet preheating method in various molding methods, it can be preferably used for either an indirect heating method or a hot plate direct heating method. For example, when performing deep drawing forming described later, preheating by an indirect heating method is performed. It is particularly preferred.

  Molded articles obtained using the polylactic acid resin sheet of the present invention are used in various applications such as various shape retainers such as blister packs, containers such as food trays and beverage cups, and display bottles for beverage vending machines. Although the molded product of the present invention can be used, it can be preferably used for the application of deep drawing with a drawing ratio of 0.5 or more, more preferably 0.6 or more, and further, a chilled cup beverage container and a jelly cup. , And deep drawing as exemplified in miso containers and the like, and can be particularly preferably used for applications requiring gas barrier properties.

  The molded product obtained using the polylactic acid-based resin sheet of the present invention is not particularly limited in its drawing ratio, but when the drawing ratio exceeds 2.5, molding defects such as uneven thickness are likely to occur. In practice, the aperture ratio of 2.5 is considered to be the upper limit.

  The polylactic acid based resin sheet and / or molded product of the present invention may be subjected to printing or the like. For example, the polylactic acid-based resin sheet of the present invention that has undergone printing processing can be preferably used for various containers, blister packs, cards, clear files, clear cases, and the like. When the polylactic acid resin sheet is transparent, an existing printing machine can be used, and it can be particularly preferably used for a clear case, a desktop calendar case, and a clear file.

  On the other hand, when the polylactic acid-based resin sheet and / or molded product of the present invention is colored white or the like by a known method, it can be preferably used for card applications. As the order of the printing process, when a polylactic acid resin sheet is molded, the printing process may be performed before the molding process or after the molding process.

Next, although the polylactic acid-type resin sheet of this invention is demonstrated in detail according to an Example, this invention is not limited by these Examples. Examples 1 to 5, 8, and 10 are referred to as Reference Examples 1 to 7 in order.

[Measurement and evaluation methods]
Measurements and evaluations shown in the examples were performed under the following conditions.

(1) Thickness ratio of each layer A cross section of a polylactic acid resin sheet is photographed with a transmitted light using a metal microscope Leica DMLM manufactured by Leica Microsystems Co., Ltd., and the thickness of each layer is measured. The thickness ratio was determined.

(2) Film thickness and sheet thickness (mm)
Using a micro gauge, the thickness of 10 points was measured with respect to the entire width of the film or sheet, and the average value of the 10 points of thickness was defined as the film thickness or the sheet thickness.

(3) Charpy impact strength (MJ / m ² )
Create a strip-shaped sample piece with a width of 1 mm and a length of 60 mm so that the flow direction of the polylactic acid resin sheet is the longitudinal direction, and use a double-sided tape to prepare a sample stand for a Charpy impact tester (manufactured by Toyo Seiki Seisakusho) The sample piece was fixed so that the sheet surface was in contact with the hammer, and the measurement was performed. Each measurement was performed 10 times, and the average value was defined as Charpy impact strength (MJ / m ² ). The Charpy impact strength was measured according to JIS-K-7111-1 (2012).

(4) Young's modulus (GPa)
A strip-shaped sample piece having a width of 10 mm and a length of 150 mm is prepared so that the flow direction of the polylactic acid-based resin sheet is the longitudinal direction, and a test length of 50 mm and tensile using Tensilon UCT-100 (manufactured by Orientec). A tensile test was performed under measurement conditions at a speed of 300 mm / min. The measurement was performed 5 times each, and the average value was defined as Young's modulus (GPa). Young's modulus was measured according to JIS-K-7127 (1999).

(5) Haze (%)
According to JIS-K-7105 (1981), the haze meter HGM-2DP type (manufactured by Suga Test Instruments Co., Ltd.) was used, and the average value of the three measurements was taken as haze (%).

(6) Oxygen permeability (cc / m ² / day)
In accordance with JIS-K-7126 (2000) B method (isobaric method), using an oxygen permeability measuring device OXTRAN 2 / 21MH type (manufactured by MOCON) under the conditions of a temperature of 23 ° C. and a humidity of 90% RH. went. The measurement was performed twice, and the average value was defined as oxygen transmission rate (cc / m ² / day).

(7) Water vapor transmission rate (g / m ² / day)
According to JIS-K-7129 (2000) B method (infrared sensor method), using a water vapor transmission rate measuring device PERMATRAN W3 / 33MG type (manufactured by MOCON) under conditions of a temperature of 23 ° C. and a humidity of 90% RH. Measurements were made. The measurement was performed twice, and the average value was defined as the water vapor transmission rate (g / m ² / day).

(8) Using a formable ceramic heater heating type vacuum forming machine, the heater set temperature is set to 300 to 400 ° C, and preheating is performed under preheating conditions such that the sheet temperature during forming is in the range of 90 ° C to 120 ° C. Molding was performed using a cylindrical female die having a diameter of 70 mm set at a temperature of 40 ° C. Molding was performed at drawing ratios of 0.5, 0.7, and 1.0 by arbitrarily changing the depth of the mold, and evaluation was performed according to the following criteria.
A: Molding with a drawing ratio of 0.5, 0.7, 1.0 was possible.
Δ: Molding with a drawing ratio of 0.5 and 0.7 was possible, but molding with a drawing ratio of 1.0 had molding defects.
X: When neither of ○ and △ is applicable.

(9) Among molded products prepared for the evaluation of rigid formability, a molded product with a drawing ratio of 0.7 is cut out at the opening, and the body of the molded product cut out (a portion 3 cm from the bottom) Pick up with a thumb and forefinger (both fingers are evaluated in the dry state), lift the molded product, and slowly irrigate 150cc or 100cc water from the opening of the molded product. Observed and evaluated according to the following criteria.

  ○: 150 cc of water could be poured without sliding the molded product from the finger, and the difference between the major axis and the minor axis was 1 cm or less with respect to the shape of the opening at this time.

  Δ: 150 cc of water could be poured without the molded product slipping from the finger, but it was necessary to put force on the finger so that it did not slide. The difference between the major axis and minor axis of the opening was 1 cm. Exceeded. Or, when trying to pour 150 cc of water, the molded product slipped, but the molded product could be poured without slid from the finger, and about the shape of the opening at this time, The difference between the major axis and the minor axis was 1 cm or less.

  X: When neither of ○ and △ is applicable.

(10) Gas barrier properties From the evaluation results of (6) oxygen permeability and (7) water vapor permeability, the following criteria were used.
A: The value of oxygen permeability was 2.0 cc / m ² / day or less, and the value of water vapor permeability was 9.0 g / m ² / day or less.
○: The value of oxygen permeability was 3.0 cc / m ² / day or less, the value of water vapor permeability was 12.0 g / m ² / day or less, and deviated from the standard of ◎.
Δ: Not applicable to either ◎ or ○.

[Raw materials]
[Polylactic acid resin used]
(PLA-1):
A polylactic acid resin having a D-form content ratio of 5 mol%, an L-form content ratio of 95 mol%, and a weight average molecular weight of 190,000 in terms of PMMA.

(PLA-2):
A polylactic acid resin having a D-form content ratio of 1 mol%, an L-form content ratio of 99 mol%, and a weight average molecular weight of 190,000 in terms of PMMA.

[Rubber particles used]
(SP-1): Core-shell type rubber particles ("Parroid" (registered trademark) BPM500 manufactured by Rohm and Haas Japan Co., Ltd. (core layer: butyl acrylate polymer, shell layer: methyl methacrylate polymer))
(SP-2): Core-shell type rubber particles (“Metblene” (registered trademark) S2001 manufactured by Mitsubishi Rayon Co., Ltd. (core layer: silicone / acrylic polymer, shell layer: methyl methacrylate polymer))
[EVOH used]
(EVOH-1): EVOH ("EVAL" (registered trademark) resin E104B manufactured by Kuraray Co., Ltd.)
(EVOH-2): EVOH ("EVAL" (registered trademark) resin E105B manufactured by Kuraray Co., Ltd.)
[Other raw materials used]
(TO-MB):
A titanium oxide master batch containing 25% by mass of titanium oxide (anatase type titanium oxide, average particle size: 0.2 μm) and 75% by mass of PLA-1 as a polylactic acid resin.

(S-MB):
A silica particle masterbatch containing 10% by mass of silica particles (average particle size: 3.2 μm) and 90% by mass of PLA-1 as a polylactic acid resin.

(PBSA): Polybutylene succinate adipate (“Bionore” (registered trademark) # 3001 manufactured by Showa Denko KK)
(PBS): Polybutylene succinate (manufactured by Mitsubishi Chemical Corporation, “GS-Pla” (registered trademark) AZ91TN ”)
(PBAT): Polybutylene terephthalate adipate ("ECOFLEX" (registered trademark) FBX7011 manufactured by BASF Japan Ltd.)
(D-PMMA): Block copolymer of methyl methacrylate and butyl acrylate ("Kurarit" (registered trademark) LA2250, manufactured by Kuraray Co., Ltd.)
[Used gas barrier resin film]
(LF-1): EVOH film (“EVAL” (registered trademark) film EF-E, thickness: 20 μm, manufactured by Kuraray Co., Ltd.)
(LF-2): EVOH film (“EVAL” (registered trademark) film EF-E, thickness: 15 μm, manufactured by Kuraray Co., Ltd.)
[Preparation of polylactic acid resin sheet]
(Examples 1-3)
From the T-die die, the raw materials listed in Table 1 are supplied to the vent type twin screw extruder at the ratio of each mass% shown in Table 1, and melt kneaded while degassing the vacuum vent part, and the die temperature is set to 210 ° C. The molten sheet is cooled and solidified using a casting drum (set temperature: 40 ° C.) and a polishing roll (set temperature: 40 ° C.) which are arranged so as to rotate in a direction in contact with the extruded molten sheet. Obtained.

After applying 3 g / m ² of A-385 / A-50 manufactured by Takeda Pharmaceutical Co., Ltd. as a solid content as an adhesive for dry lamination to the obtained sheet and evaporating the solvent at 80 ° C., Table 1 The gas barrier resin film described above was bonded and aged at 40 ° C. for 3 days to obtain a polylactic acid resin sheet of the present invention.

  The evaluation results of the obtained polylactic acid resin sheet are shown in Table 1.

  The polylactic acid-based resin sheets of Examples 1 to 3 can be suitably used as deep-drawn molded product applications that require gas barrier properties.

Example 4
The raw materials listed in Table 1 are supplied to each independent vent type twin-screw extruder in the proportion of each mass% listed in Table 1, and further, Mitsui Chemicals serves as an adhesive layer disposed between the gas barrier layer and layer A. "Admer" (registered trademark) VF-600 manufactured by Co., Ltd. is used, and this is supplied to another vent type twin screw extruder to supply each resin composition of layer A, adhesive layer and gas barrier layer 3 The extruder was melted and kneaded while degassing the vacuum vent part by a single extruder, co-extruded from a T-die die having a die temperature set at 210 ° C., and arranged so as to rotate in a direction in contact with the co-extruded molten sheet. The molten sheet was cooled and solidified using a casting drum (set temperature: 40 ° C.) and a polishing roll (set temperature: 40 ° C.) to obtain the polylactic acid resin sheet of the present invention having the thickness shown in Table 1.

  The polylactic acid-based resin sheet of Example 4 can be suitably used as a deep-drawn molded product application that requires gas barrier properties.

(Example 5)
The raw materials listed in Table 1 are supplied to each independent vent type twin screw extruder in the proportion of each mass% described in Table 1, and are further arranged between the gas barrier layer and layer A and between the gas barrier layer and layer B. "Admer" (registered trademark) VF-600 manufactured by Mitsui Chemicals, Inc. is used as an adhesive layer to be used, and this is supplied to another vent type twin-screw extruder, and layer A, layer B, adhesive layer, gas barrier layer Were melted and kneaded while degassing the vacuum vent part, and co-extruded from a T-die die set at a die temperature of 210 ° C., and the co-extruded molten sheet was obtained. The molten sheet is cooled and solidified using a casting drum (set temperature: 40 ° C.) and a polishing roll (set temperature: 40 ° C.) arranged so as to rotate in a direction in contact with each other. Polylactic acid resin It was obtained over door.

  The polylactic acid-based resin sheet of Example 5 can be suitably used as a deep-drawn molded product application that requires gas barrier properties.

(Examples 6 to 9)
The raw materials listed in Table 2 are supplied to each independent vent type twin screw extruder in the proportion of each mass% listed in Table 1, and melt-kneaded while degassing the vacuum vent, and the die temperature is set to 210 ° C. A melt sheet using a casting drum (set temperature: 40 ° C.) and a polishing drum (set temperature: 40 ° C.) that are co-extruded from the set T die die and arranged to rotate in a direction in contact with the co-extruded molten sheet. Was cooled and solidified to obtain a sheet.

  The obtained sheet was dry laminated and aged in the same manner as in Example 1 to obtain the polylactic acid resin sheet of the present invention.

  The evaluation results of the obtained polylactic acid resin sheet are shown in Table 2.

  The polylactic acid-based resin sheets of Examples 6 to 9 can be suitably used as deep-drawn molded product applications that require gas barrier properties.

(Example 10)
The polylactic acid resin sheet of the present invention was obtained by the same method as the method for obtaining the sheet described in Example 2.

  The evaluation results of the obtained polylactic acid resin sheet are shown in Table 2.

  The polylactic acid-based resin sheet of Example 10 can be suitably used as a deep-drawn molded product application.

(Examples 11 and 12)
The polylactic acid resin sheet of the present invention was obtained by the same method as the method for obtaining the sheet described in Example 6.

  The evaluation results of the obtained polylactic acid resin sheet are shown in Table 2.

  The polylactic acid-based resin sheets of Examples 11 and 12 can be suitably used for deep-drawn molded product applications.

In the layer structure in the table, the layer A is A, the layer B is B, the gas barrier layer is gb, and the adhesive layer is ad. The same applies below.

(Comparative Examples 1-3)
A polylactic acid resin sheet was obtained by the same method as the method for obtaining the sheet described in Example 1, except that the raw materials described in Table 3 were supplied to the extruder at the ratio of each mass% described in Table 3.

  The evaluation results of the obtained polylactic acid resin sheet are shown in Table 3.

  The polylactic acid-based resin sheets of Comparative Examples 1 to 3 could not be used for deep-drawn molded product applications.

(Comparative Examples 4-6)
A polylactic acid-based resin sheet was obtained by the same method as the method for obtaining the polylactic acid-based resin sheet described in Example 1, except that the raw materials listed in Table 3 were supplied to the extruder at a ratio of each mass% described in Table 3. Obtained.

  The evaluation results of the obtained polylactic acid resin sheet are shown in Table 3.

  The polylactic acid-based resin sheets of Comparative Examples 4 to 6 could not be used as deep-drawn molded product applications.

(Comparative Examples 7 to 10)
A polylactic acid resin sheet was obtained by the same method as the method for obtaining the polylactic acid resin sheet described in Example 6 except that the raw materials listed in Table 4 were supplied to the extruder at the ratio of each mass% described in Table 4. Obtained.

  The evaluation results of the obtained polylactic acid resin sheet are shown in Table 4.

  The polylactic acid-based resin sheets of Comparative Examples 7 to 10 were not usable for deep-drawn molded product applications.

Claims (11)

A sheet containing a polylactic acid resin and rubber particles,
Charpy impact strength is 0.20 MJ / m ² or more,
Young's modulus of Ri der more 3.0GPa,
The sheet has a laminated structure having a layer A containing a polylactic acid-based resin and rubber particles and a layer B containing a polylactic acid-based resin and rubber particles,
Satisfy the following conditions (1), and the layer B, the layer A, and the layer B, polylactic acid-based resin sheet, wherein Rukoto to Yusuke in this order.
Condition (1): Ma> Mb
However,
Ma: Content (% by mass) of rubber particles in layer A when the total component constituting layer A is 100% by mass
Mb: content (% by mass) of rubber particles in the layer B when all components constituting the layer B are 100% by mass   The polylactic acid resin sheet according to claim 1, wherein the haze is 25% or less.   The polylactic acid resin sheet according to claim 1 or 2, wherein the thickness is 0.75 mm or more and 1.50 mm or less. The polylactic acid resin sheet according to any one of claims 1 to 3, wherein the rubber particles are a multilayer structure polymer . And it satisfies the following condition (2), polylactic acid-based resin sheet according to claim 1.
Condition (2): 0 <Ma−Mb ≦ 5 Characterized in that it is a non-stretched sheet, polylactic acid-based resin sheet according to any one of claims 1-5. Wherein the oxygen transmission rate is less 3.0cc ^/ m 2 ^/ day, the polylactic acid resin sheet according to any one of claims 1-6. Wherein the water vapor transmission rate is less than 12.0g ^/ m 2 ^/ day, the polylactic acid resin sheet according to any one of claims 1-7. Ethylene - characterized by having a layer containing a vinyl acetate copolymer saponified resins, polylactic acid-based resin sheet according to any one of claims 1-8. A molded article comprising the polylactic acid-based resin sheet according to any one of claims 1 to 9 . Wherein the drawing ratio is 0.5 or more, the molded article according to claim 1 0.