Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/306—Resistant to heat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles

Definitions

• the present invention relates to a polylactic acid resin sheet which is excellent in environmental properties, heat resistance, transparency, moldability and productivity, and is particularly suitable for use in molded products.
• the glass transition point is about 20 ° C. lower than that of conventional petroleum-derived raw materials such as polyethylene terephthalate, and there is a problem that heat resistance is insufficient when each of the current uses is replaced with polylactic acid.
• mixing two or more kinds of polymers is widely known as a polymer blend or a polymer alloy, and is widely used as a method for improving the defects of individual polymers.
• a polymer blend or a polymer alloy is widely used as a method for improving the defects of individual polymers.
• many of them are separated into individual phases, and one phase generally has a non-uniform coarse dispersion structure of several ⁇ m or more.
• the polymer alloy is opaque, has low mechanical strength, and tends to cause a ballast effect upon discharge during melt kneading and often has poor productivity.
• two or more polymers may be uniformly mixed, but this combination of polymers is generally called a compatible polymer or miscible polymer and exhibits excellent properties. Is expected, but examples are limited.
• Non-Patent Documents 1 and 2 As a method of mixing a resin having compatibility with polylactic acid, for example, by mixing polymethyl methacrylate having a glass transition point of about 100 ° C. with polylactic acid, the glass transition point of the resin composition is improved.
• a mixture of an ⁇ -hydroxycarboxylic acid polymer containing polylactic acid and a poly (meth) acrylate resin produces a resin having excellent hydrolyzability (see Patent Document 1), and an acrylic compound is blended with polylactic acid.
• Patent Document 2 it is known that a resin composition excellent in weather resistance and molding processability can be obtained (see Patent Document 2), but none of them disclose heat resistance and high-temperature rigidity.
• Patent Documents 5 to 9 As methods for improving heat resistance by mixing polylactic acid and poly (meth) acrylate resin, methods exemplified in Patent Documents 5 to 9 are known. In the method of improving the heat resistance of the polylactic acid resin composition by mixing lactic acid resin and polymethylmethacrylate, the heat resistance obtained is limited, and high heat resistance cannot be obtained. Patent Documents 6 to 9 propose a technique for achieving both environmental properties and heat resistance by laminating a plurality of layers having different poly (meth) acrylate resin contents. Attempting to make both heat resistance compatible at a higher level leads to deterioration in productivity, so the range in which both environmental properties and heat resistance can be achieved has been limited.
• the object of the present invention is excellent in environmental properties, heat resistance, transparency, moldability and productivity, and in particular, can achieve both environmental properties and heat resistance at a high level, and can be used for molded products.
• An object is to provide a suitable polylactic acid resin sheet.
• the polylactic acid-type resin sheet of this invention is a polylactic acid-type resin sheet characterized by including the polylactic acid-type resin and satisfy
• ⁇ Condition 1 Polylactic acid resin content ⁇ heat-resistant temperature ⁇ heat-resistant temperature ⁇ 320,000 (However, the polylactic acid resin content is the content (% by mass) of the polylactic acid resin in the polylactic acid resin sheet when all the components constituting the sheet are 100% by mass, and the heat resistant temperature is The highest temperature (° C.) among the temperatures where the heat sag value was less than 30 mm.)
• the polylactic acid resin sheet of the present invention the polylactic acid resin sheet further contains a poly (meth) acrylate resin.
• the polylactic acid-based resin sheet has a laminated structure including a layer A containing a polylactic acid-based resin and a layer B containing a polylactic acid-based resin. It is a sheet, and the layer B is at least one outermost layer of the sheet and satisfies the following condition 2.
• Za is the content (% by mass) of the poly (meth) acrylate resin in the layer A when all the components constituting the layer A are 100% by mass
• Zb is all the components constituting the layer B
• the polylactic acid resin constituting the polylactic acid resin sheet satisfies the following condition 3.
• Condition 3 Ma1> Mb1 (However, Ma1 is the weight average molecular weight of the polylactic acid resin in layer A, and Mb1 is the weight average molecular weight of the polylactic acid resin in layer B.)
• the polylactic acid resin constituting the polylactic acid resin sheet satisfies the following conditions 4 and 5.
• ⁇ Condition 4 160,000 ⁇ Ma2 ⁇ 240,000
• ⁇ Condition 5 80,000 ⁇ Mb2 ⁇ 120,000 (where Ma2 is the weight average molecular weight of the polylactic acid resin that is the raw material of layer A, and Mb2 is the raw material of layer B) This is the weight average molecular weight of the polylactic acid resin.
• the polylactic acid resin sheet is an unstretched sheet.
• the haze of the polylactic acid resin sheet is 0% or more and 5% or less.
• the polylactic acid resin sheet of the present invention has a crystallinity of 10% or less.
• a molded product made of the polylactic acid resin sheet can be obtained.
• a polylactic acid-based resin sheet excellent in environmental properties, heat resistance, transparency, moldability, and productivity can achieve both environmental properties and heat resistance at a high level and is suitable for use in molded products. It is done.
• the polylactic acid-based resin sheet of the present invention is used for molded products such as various shape holders such as blister packs that require heat resistance, containers such as food trays and beverage cups, and display bottles for beverage vending machines. It can be preferably used.
• the “sheet” is used to mean a two-dimensional structure such as a film and a plate
• the “molded product” is a three-dimensional structure such as a container or a printed material. , Used to mean that the sheet is processed.
• the polylactic acid resin sheet of the present invention contains a polylactic acid resin and satisfies the following condition 1.
• ⁇ Condition 1 Polylactic acid resin content ⁇ heat-resistant temperature ⁇ heat-resistant temperature ⁇ 320,000
• the polylactic acid resin content is the content (% by mass) of the polylactic acid resin in the polylactic acid resin sheet when all the components constituting the sheet are 100% by mass
• the heat resistant temperature is The highest temperature (° C.) among the temperatures where the heat sag value was less than 30 mm.
• the heat resistant temperature defined in the present invention is 50 ° C., 55 ° C., 60 ° C., 65 ° C., 70 ° C., 75 ° C., 80 ° C., 85 ° C., 90 ° C., 95 ° C. using a gear oven.
• the heat sag value was measured when heat treatment was performed for 1 hour under the respective temperature conditions of 100 ° C., and the highest temperature (° C.) among the temperatures at which
• the above condition 1 may be displayed as a heat resistance parameter.
• the heat resistance parameter is 320,000 or more.
• the heat resistance parameter can be obtained from the formula of polylactic acid resin content ⁇ heat resistant temperature ⁇ heat resistant temperature, and is an index of the balance between environmental properties and heat resistance.
• a sheet composed of 100% by mass of polylactic acid has a heat resistance temperature of 55 ° C., so the heat resistance parameter is 302500 (see Comparative Example 1).
• a method for imparting heat resistance to the polylactic acid-based resin sheet a method for improving the heat resistance of the polylactic acid resin composition by mixing polylactic acid resin and polymethyl methacrylate, as exemplified in Patent Document 5.
• the polylactic acid-based resin sheet of the present invention can achieve both environmental properties and heat resistance at a high level by a method described later, but employs a heat resistance parameter as an indicator of the balance between environmental properties and heat resistance.
• a heat resistance parameter as an indicator of the balance between environmental properties and heat resistance.
• the heat resistance parameter is less than 320,000, it is impossible to achieve both environmental properties and heat resistance, and heat resistance is inferior to environmental properties, or environmental properties are inferior to heat resistance.
• the polylactic acid resin sheet of the present invention preferably has a heat resistance parameter of 340000 or more, particularly preferably 400000 or more.
• the upper limit value of the heat resistance parameter is not particularly limited, but from the technical idea of the polylactic acid resin sheet of the present invention, the heat resistance temperature is 85 ° C. when the plant degree is 95% by mass. Is considered a substantial upper limit and 650250 is considered a substantial upper limit.
• the polylactic acid resin content of the polylactic acid resin sheet of the present invention is preferably in the range of 50% by mass to 98% by mass, and particularly preferably 75% by mass to 95% by mass.
• the polylactic acid resin content is less than 50% by mass, it may be difficult to obtain high environmental properties.
• the polylactic acid resin content exceeds 98% by mass, high heat resistance is obtained. Can be difficult.
• the heat-resistant temperature of the polylactic acid resin sheet of the present invention satisfies the above condition 1, but is substantially in the range of 60 ° C. or higher and 90 ° C. or lower.
• the heat-resistant temperature is less than 60 ° C., it can be used for molded products such as various shape-holding tools such as blister packs, containers such as food trays and beverage cups, and display bottles for beverage vending machines. If it is difficult or the heat-resistant temperature exceeds 90 ° C., it may be difficult to achieve both environmental friendliness.
• the heat resistance parameter it is important to set the heat resistance parameter to 320,000 or more.
• a method for controlling the heat resistance parameter it is preferable to control the sheet configuration of the polylactic acid resin sheet. .
• a method for controlling the heat resistance parameter will be described in detail below.
• the polylactic acid resin sheet of the present invention further contains a poly (meth) acrylate resin.
• a poly (meth) acrylate resin By including a poly (meth) acrylate resin, it becomes easy to satisfy the above condition 1, and it becomes easy to achieve both environmental properties and heat resistance.
• the poly (meth) acrylate resin that can be contained in the polylactic acid-based resin sheet of the present invention is a resin having at least one monomer selected from acrylate and methacrylate as a structural unit, or two or more single monomers You may use resin obtained by copolymerizing a body.
• the acrylate and methacrylate constituting the poly (meth) acrylate include acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, cyanoethyl acrylate and cyanobutyl acrylate, methyl methacrylate, ethyl methacrylate and cyclohexyl.
• methacrylates such as methacrylate and 2-hydroxyethyl methacrylate are exemplified
• polymethyl methacrylate is preferably used in order to impart higher heat resistance.
• polymethylmethacrylate is used as the poly (meth) acrylate resin
• JIS-K-7210 (1999) from the viewpoint of compatibility with the polylactic acid resin and from the viewpoint of adjusting the viscosity of each layer during lamination film formation.
• the fluidity of polymethyl methacrylate measured at a temperature of 230 ° C. and a load of 3.80 kg is preferably 1 to 22 g / 10 min, more preferably 1.5 to 15 g / 10 min. Those having a molecular weight of ⁇ 10 g / 10 min are particularly preferably used.
• the weight average molecular weight of the poly (meth) acrylate resin that can be contained in the polylactic acid resin sheet of the present invention is preferably 20,000 to 500,000, more preferably 100,000 to 200,000. If the weight average molecular weight is less than 20,000, the impact resistance of the sheet may deteriorate, and if the weight average molecular weight exceeds 500,000, appearance defects due to lamination spots will occur during the production of the laminated sheet. Or fluidity during molding may be reduced.
• a weight average molecular weight here means the molecular weight which measured with the chloroform solvent by the gel permeation chromatography, and was calculated by the polymethylmethacrylate conversion method.
• the polylactic acid-based resin sheet of the present invention has a laminated structure including a layer A containing a polylactic acid-based resin and a layer B containing a polylactic acid-based resin, and the layer B is disposed on at least one outermost layer of the sheet.
• the content (% by mass) of the poly (meth) acrylate resin in the layer B ie, Zb) when the total component constituting the layer B is 100% by mass is preferable. It is a particularly preferable embodiment that the content is larger than the content (% by mass) (that is, Za) of the poly (meth) acrylate-based resin in the layer A when the total component constituting the layer A is 100% by mass.
• the content (% by mass) (that is, Za) of the poly (meth) acrylate resin in the layer A when all the components constituting the layer A are 100% by mass is 0% by mass or more and 5% by mass or less. It is preferable. When Za exceeds 5 mass%, it may be difficult to obtain high environmental properties. Za is more preferably 0% by mass or more and 2% by mass or less, and particularly preferably 0% by mass.
• content (mass%) (namely, Zb) of the poly (meth) acrylate-type resin in the layer B when all the components which comprise the layer B are 100 mass% is 50 mass% or more and 98 mass% or less. It is preferable that When Zb is less than 50% by mass, it may be difficult to obtain heat resistance. On the other hand, when Zb exceeds 98% by mass, an appearance defect caused by lamination spots may occur during the production of a laminated sheet. It may cause a decrease in fluidity and it may be difficult to obtain high environmental properties.
• Za is more preferably 60% by mass or more and 95% by mass or less, and particularly preferably 70% by mass or more and 90% by mass or less.
• the layer structure may be a two-layer two-layer structure of layer B / layer A, but it is a two-layer three-layer structure of layer B / layer A / layer B from the viewpoint of suppressing curling of the sheet. Further, it is a particularly preferable aspect that the two layers B positioned on both outermost layers have the same laminated thickness. In addition, a layer not corresponding to the layer A and the layer B may be arranged.
• this layer is a layer C
• the layer B / layer C / layer A / layer C / layer B, layer B / layer A / layer A three-kind five-layer laminated structure such as C / layer A / layer B or a three-kind three-layer laminated structure of layer B / layer A / layer C may be employed.
• the lamination ratio of the layer A with respect to the entire sheet is preferably 50% or more and 95% or less, and particularly preferably 75% or more and 90% or less.
• the lamination ratio of the layer A with respect to the whole sheet is less than 50%, it may be difficult to obtain high environmental properties, and when the lamination ratio of the layer A with respect to the whole sheet exceeds 95%, the lamination sheet In some cases, appearance defects may occur due to laminated spots.
• the cross section of the sheet was photographed with 100 times magnification, transmitted light using a metal microscope Leica DMLM manufactured by Leica Microsystems Co., Ltd., and the thickness of each layer was measured. The stacking ratio can be calculated.
• the weight average molecular weight (Ma1) of the polylactic acid resin in layer A is greater than the weight average molecular weight (Mb1) of the polylactic acid resin in layer B. Is preferably large.
• the polylactic acid resin contained in layers A and B has the same weight average molecular weight (Ma1 and Mb1), or the polylactic acid resin in layer A has the same weight average molecular weight (Ma1).
• the weight average molecular weights (Ma1 and Mb1) of the polylactic acid resins contained in the layers A and B are preferably Ma1> Mb1, but Ma1> Mb1 + 20,000. It is more preferable that Ma1> Mb1 + 40,000 is a particularly preferable aspect.
• a weight average molecular weight here means the molecular weight which measured with the chloroform solvent by the gel permeation chromatography, and was calculated by the polymethylmethacrylate conversion method.
• the sample is a laminated sheet, it is possible to confirm by performing measurement after obtaining a sample piece composed of only the target layer by polishing and removing the non-target layer while observing under a microscope. It is.
• the temperature condition of the extruder for supplying the resin composition of the layer B is set as follows. Setting higher than the temperature condition of the extruder supplying the resin composition of layer A, adding a known end-capping agent to suppress a decrease in molecular weight in the extrusion step of the polylactic acid resin in layer A, Alternatively, for example, polylactic acid resins having different weight average molecular weights can be selected as the polylactic acid resin used as the raw material for the layer A and the layer B.
• the temperature condition of the extruder for supplying the resin composition of the layer B is defined as layer
• the temperature condition of the extruder for supplying the resin composition of the layer B is supplied to the resin composition of the layer A. It is preferable to set higher in the temperature range of 20 ° C. or more and 40 ° C. or less than the temperature condition of the extruder.
• the added end-capping agent may be a compound that can block the carboxyl terminal group or hydroxyl group of the polylactic acid resin, and can be preferably used.
• the agent include carbodiimide compounds, epoxy compounds, and oxazoline compounds, and it is particularly preferable to use carbodiimide compounds.
• the polylactic acid resin used as the raw material of the layer A and the layer B is different.
• a polylactic acid resin having a weight average molecular weight it is preferable to use a polylactic acid resin material having a weight average molecular weight difference of 20,000 to 200,000, and a weight average molecular weight difference of 40,000 to 160,000 is preferred. It is more preferable to use a certain polylactic acid resin raw material.
• the difference in weight average molecular weight of the polylactic acid resin used as the raw material for layer A and layer B exceeds 200,000, or the difference in weight average molecular weight of the polylactic acid resin used as the raw material for layer A and layer B is less than 20,000. In some cases, appearance defects may occur due to stacking spots.
• the weight average molecular weight (ie, Ma2) of the polylactic acid resin used as the raw material of the layer A is 160,000 to 240,000
• the weight average molecular weight of the polylactic acid resin used as the raw material of the layer B (ie, , Mb2) is 80,000 to 120,000.
• the weight average molecular weight is a molecular weight calculated by a polymethyl methacrylate conversion method after measurement with a chloroform solvent by gel permeation chromatography.
• the weight average molecular weight of the polylactic acid resin in the layer A larger than the weight average molecular weight of the polylactic acid resin in the layer B
• a method that can be adopted by the polylactic acid resin sheet of the present invention is used.
• the most preferable method is to select polylactic acid resins having different weight average molecular weights as the polylactic acid resins used as the raw materials of the layer A and the layer B. is there.
• the polylactic acid based resin sheet of the present invention may be any sheet of an unstretched sheet, a uniaxially stretched sheet, a biaxially stretched sheet, or a restretched sheet obtained by restretching a biaxially stretched sheet.
• the surface magnification indicated by the product of the draw ratios of the respective draw axes is 3 or less, and in particular, various shape retainers such as blister packs, containers such as food trays and beverage cups, and beverage automatics
• an unstretched sheet is particularly preferable because it is easy to perform deep drawing with a drawing ratio of 0.3 or more.
• 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.
• the surface magnification shown is greater than 3, there may be a problem such that a molding defect is likely to occur when deep drawing with a drawing ratio of 0.5 or more is performed.
• the polylactic acid resin sheet of the present invention preferably has a haze of 0% or more and 5% or less. If the haze is in the range of 0% or more and 5% or less, a molded product using such a polylactic acid resin sheet has high designability such as excellent visibility of the contents and good appearance as a product. It can be preferably used as a packaging container or a packaging sheet. On the other hand, when the haze is larger than 5%, 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 0.5% or more and 3% or less.
• the polylactic acid resin sheet of the present invention preferably has a crystallinity of 10% or less, and particularly preferably a crystallinity of 5% or less.
• the degree of crystallinity exceeds 10%, the transparency and moldability may be deteriorated. In particular, there is a problem such that molding defects are likely to occur when performing deep drawing with a drawing ratio of 0.5 or more.
• the lower limit value of the degree of crystallinity is not particularly limited, but when the crystallization heat generation amount and the crystal melting endotherm amount are substantially equal, that is, 0% is the lower limit.
• the degree of crystallinity is a difference between about 5 mg of a polylactic acid resin sheet piece as a sample, held at ⁇ 50 ° C. for 5 minutes in a nitrogen atmosphere, and at a temperature increase rate of 10 ° C./min up to a temperature of 220 ° C.
• Scanning calorimeter (DSC) measurement was performed, and from the observed thermograph, the crystallization exotherm caused by crystallization during temperature rise derived from polylactic acid resin: ⁇ Hc (J / g) and the crystal melting endotherm : ⁇ Hm (J / g) is read and calculated according to the following equation.
• the polylactic acid resin sheet of the present invention may contain an impact resistance improver.
• the polylactic acid-based resin sheet of the present invention has a single-layer structure composed of a resin composition in which the content (mass%) of the poly (meth) acrylate resin exceeds 40 mass%, or poly (meth) acrylate
• the content (mass%) of the poly (meth) acrylate resin is a single-layer structure composed of a resin composition exceeding 40 mass%, or the content (mass%) of the poly (meth) acrylate resin is 40 mass %
• various shape retainers such as blister packs, food trays and beverage cups
• there may be problems such as cracking of the molded products.
• the content of the impact resistance improver is 15 with respect to the total mass of the polylactic acid-based resin sheet from the viewpoint of transparency and environmental properties.
• the content is preferably less than mass%, more preferably 10 mass% or less.
• the polylactic acid resin sheet of the present invention has a laminated structure, it may be added to all layers, or may be added to any one layer or a plurality of layers. It is preferable to add only to the layer which consists of a resin composition in which content (mass%) of poly (meth) acrylate resin exceeds 40 mass%.
• the addition amount is from an environmental viewpoint. It is preferable to set it as 10 to 30 mass% with respect to content (mass%) of the poly (meth) acrylate type resin of a layer.
• Examples of impact modifiers that can be used in the polylactic acid resin sheet of the present invention include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, and ethylene-butene-1 copolymer.
• Copolymers various acrylic rubbers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-glycidyl (meth) acrylate copolymers, ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-acrylic acid) Ethyl copolymer, ethylene-butyl acrylate copolymer), acid-modified ethylene-propylene copolymer, diene rubber (eg, polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (eg, styrene) -Butadiene random copolymerization Styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene
• the rubber particles are preferably a multilayer structure polymer.
• the impact resistance is excellent, but the adhesiveness and compatibility with polylactic acid may be inferior.
• the rubber particles of the multilayer structure polymer having a shell layer covering the rubber component layer can improve the adhesion and compatibility between the rubber particles and polylactic acid.
• a polymer is preferred.
• 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).
• 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.
• the type of the rubber layer may be any one that is composed of a polymer component having rubber elasticity.
• a rubber composed of a polymer obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, or the like can be given.
• Examples of the polymer component preferably used as the rubber layer include acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene units and ⁇ -methylstyrene units.
• the rubber is constituted by polymerizing a styrene component, a nitrile component such as an acrylonitrile unit or a methacrylonitrile unit, and a conjugated diene component such as a butadiene unit or an isoprene unit.
• a rubber composed of a combination of two or more of these components and copolymerized can also be preferably used.
• the types of layers other than the rubber layer are composed of a polymer component having thermoplasticity that does not have rubber elasticity.
• a polymer component having a glass transition point higher than that of rubber is preferable.
• 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.
• 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.
• the outermost layer types are unsaturated carboxylic acid alkyl ester units, glycidyl group-containing vinyl units, aliphatic vinyls
• examples include polymers containing system units, aromatic vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units and / or other vinyl units.
• polymers containing unsaturated carboxylic acid alkyl ester units preferred are polymers containing unsaturated carboxylic acid alkyl ester units, unsaturated glycidyl group-containing units and / or unsaturated dicarboxylic anhydride units, and polymers containing unsaturated carboxylic acid alkyl ester units. Coalescence is more preferably used. Although it does not specifically limit as an unsaturated carboxylic-acid alkylester type
• the rubber particles that can be used in the polylactic acid resin sheet of the present invention are a multilayer structure polymer
• a preferable example of the multilayer structure polymer is a multilayer structure weight composed of a core layer and one shell layer.
• the core layer is a dimethylsiloxane / butyl acrylate polymer
• the outermost layer is a methyl methacrylate polymer
• the core layer is a butadiene / styrene polymer
• the outermost layer is a methyl methacrylate polymer
• the core layer is a butyl acrylate polymer.
• the outermost layer is a methyl methacrylate polymer.
• either one or both of the rubber layer and the outermost layer is a polymer containing glycidyl methacrylate units.
• the mass ratio of the core layer to the shell layer is 50% by mass of the core layer with respect to the entire multilayer structure polymer.
• the content is preferably 90% by mass or less and more preferably 60% by mass or more and 80% by mass or less of the core layer.
• the polylactic acid resin used in the polylactic acid resin sheet of the present invention is mainly composed of L-lactic acid and / or D-lactic acid, and the components derived from lactic acid are 100 mol of all monomer components constituting polylactic acid.
• the homopolylactic acid consisting essentially of L-lactic acid and / or D-lactic acid is preferably used.
• the polylactic acid resin used in the polylactic acid resin sheet of the present invention preferably has crystallinity.
• the polylactic acid-based resin has crystallinity when the polylactic acid-based resin is sufficiently crystallized under heating and then subjected to differential scanning calorimetry (DSC) measurement in an appropriate temperature range. It means that the heat of crystal melting derived from the resin component is observed.
• DSC differential scanning calorimetry
• 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.
• homopolylactic acid having an optical purity of 98% or more has a melting point of about 170 ° C. and a relatively high crystallinity.
• the homopolylactic acid having an optical purity of 88% has a melting point of about 145 ° C.
• 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 polylactic acid resin sheet of the present invention can be a mixture of crystalline homopolylactic acid and amorphous homopolylactic acid.
• the ratio of the amorphous homopolylactic acid may be determined within a range that does not impair the effects of the present invention.
• 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 polylactic acid resin used in the polylactic acid resin sheet of the present invention may be a polylactic acid resin that forms a stereocomplex crystal.
• Stereocomplex crystals include, for example, Macromolecules, vol. 20, 904 (1987), a crystal in which a poly-L-lactic acid unit and a poly-D-lactic acid unit are paired.
• Poly-L-lactic acid has a left-handed helical structure
• the optical isomer poly-D-lactic acid has a right-handed helical structure.
• stereocomplex crystal A crystal structure closer to and stronger than the crystal structure formed when poly-L-lactic acid or poly-D-lactic acid is used alone is called a stereocomplex crystal.
• the polylactic acid resin forming the stereocomplex crystal has a higher melting point due to the formation of the stereocomplex crystal, whereas the melting point of ordinary poly-L-lactic acid or poly-D-lactic acid is 165 to 180 ° C.
• the melting point of the polylactic acid resin forming the stereocomplex crystal may be 190 ° C. to 250 ° C.
• the use of a polylactic acid resin capable of forming a stereocomplex crystal in the present invention means that the polylactic acid resin sheet of the present invention has a polylactic acid resin in which a stereocomplex crystal is formed. Since it can be a lactic acid resin sheet, it is suitably used for applications requiring high heat resistance, such as for microwave ovens.
• a method for producing a polylactic acid-based resin for forming a stereocomplex crystal that can be used in the present invention, it can be produced by a known method, for example, a poly-polymer as exemplified in JP-A-2006-036808.
• the polylactic acid resin used in the polylactic acid resin sheet of the present invention is a copolymerized polylactic acid obtained by copolymerizing other monomer components having ester forming ability in addition to L-lactic acid and D-lactic acid. There may be.
• copolymerizable monomer components include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid and 6-hydroxycaproic acid, as well as ethylenecarboxylic acid, propylene glycol, butane.
• Examples of the method for producing a polylactic acid-based resin include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.
• 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.
• 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.
• 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.
• 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.
• 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.
• a solution in which each component is dissolved in a solvent is uniformly mixed, and then the solvent is removed to produce a composition.
• a melt-kneading method for producing a composition by melt-kneading each component which is a more practical production method that does not require steps such as dissolution of the raw material in the solvent or solvent removal. Is preferred.
• 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.
• a method of subjecting a polylactic acid resin and rubber particles to a dry kneading machine after dry blending, or a master batch in which rubber particles such as a polylactic acid resin and a multilayer structure polymer are melt-kneaded in advance are prepared. Later, the method of melt-kneading the masterbatch and polylactic acid-type resin etc. are mentioned.
• a method for simultaneously melting and kneading other components, or a master batch including a master batch in which a polylactic acid resin and other additives are melt-kneaded in advance, and the master batch including the rubber particles described above A method of melt-kneading the lactic acid resin and polylactic acid resin may be used.
• 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 a T-die casting method.
• pellets are dried at a temperature of 60 to 110 ° C. for 3 hours or more to use a pellet having a moisture content of 400 ppm or less, and a cylinder temperature of 150 ° C. to 240 ° C.
• melt kneading is performed using a twin screw extruder, extruded from a T die at a die temperature of 150 ° C. or higher and 240 ° C.
• 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 temperature range of the cylinder temperature and the base is the melting temperature of the stereocomplex crystal.
• the melting temperature of the stereocomplex crystal is preferably set to a temperature range of less than 20 ° C.
• heat treatment can be performed in the production process of the polylactic acid resin sheet of the present invention.
• An oven heat treatment step may be provided.
• the polylactic acid resin sheet of the present invention may be subjected to various surface treatments for the purpose of improving coating suitability.
• the surface treatment method include corona discharge treatment, plasma treatment, flame treatment, and acid treatment.
• the thickness of the polylactic acid resin sheet of the present invention is usually about 0.1 mm to 1.0 mm.
• the polylactic acid-based resin sheet of the present invention is usually preferably about 0.15 mm to 0.7 mm thick.
• the polylactic acid resin sheet is preferably about 0.1 mm to 0.4 mm in thickness.
• the molded product of the present invention is a molded product obtained using the above-described polylactic acid resin sheet of the present invention.
• the polylactic acid-based sheet of the present invention can be obtained by vacuum forming, vacuum / pressure forming, plug assist forming, straight forming, It is possible to apply various molding methods such as a drawing molding method, a plug-and-ring molding method, and a skeleton molding method.
• the sheet preheating method in various molding methods includes the indirect heating method and the hot plate direct heating method.
• the indirect heating method is a method in which the sheet is preheated by a heating device installed at a position away from the sheet, and the hot plate is directly heated.
• the method is a method in which the sheet is preheated by contacting the sheet and the hot plate, but the polylactic acid resin sheet of the present invention is a hot plate direct heating method vacuum forming method and a hot plate direct heating method vacuum pressure forming method. Is preferably used.
• Molded products obtained by using the polylactic acid resin sheet of the present invention are used for various shape holders such as blister packs that require heat resistance, containers such as food trays and beverage cups, and displays for beverage vending machines. It can use preferably for various uses, such as a bottle.
• the polylactic acid resin sheet and / or molded product of the present invention may be subjected to printing or the like.
• 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.
• the polylactic acid-based resin sheet is transparent, it can be particularly preferably used for clear cases, desktop calendar cases, clear file applications, etc. by using an existing printing processing machine.
• 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.
• 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.
• 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.
• a strip-shaped sample piece having a width of 10 mm and a length of 80 mm is prepared so that the sheet flow direction at the time of sheet production of the polylactic acid-based resin sheet is the longitudinal direction, and using a double-sided tape, a metal rectangular parallelepiped base, The length of the projecting portion of the sample piece was 60 mm (that is, the portion to be bonded to the pedestal of the sample piece was 20 mm), and the sample piece was fixed so that the non-contact surface of the cooling roll faced the pedestal surface.
• the pedestal to which the sample piece is fixed is left in a gear oven set to an arbitrary temperature for 1 hour, and the center point of the overhanging portion of the sample piece (that is, the position on the pedestal side 30 mm from the tip of the overhanging portion of the sample).
• the amount of sag (mm, the distance in the vertical direction from the position fixed to the pedestal) was measured and used as the heat sag value.
• the heat sag value was measured at each temperature condition of 50 ° C, 55 ° C, 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 95 ° C, and 100 ° C, and the heat sag value was 30 mm. Among the temperature conditions that were less than, the highest temperature was defined as the heat resistant temperature (° C.) of the sample.
• the method for obtaining the heat sag value was evaluated according to JIS-K-7195 (1993) unless otherwise specified.
• Heat resistance parameter It calculated with the following formula
• Heat resistance parameter polylactic acid resin content (% by mass) ⁇ heat resistant temperature (° C.) ⁇ heat resistant temperature (° C.).
• Za and Zb Content of poly (meth) acrylate resin in layer A and layer B (% by mass) The content (% by mass) of the poly (meth) acrylate resin in the entire resin composition constituting the layer A or the layer B was calculated from the blending amount supplied to each extruder during production.
• Ma1 and Mb1 Weight average molecular weight of polylactic acid-based resin in layers A and B Measured by using Waters 2690 manufactured by Japan Waters Co., Ltd., using PMMA as a standard, column temperature of 40 ° C., and chloroform solvent. .
• the sample was a laminated sheet, the non-target layer was removed by polishing while observing under a microscope, and measurement was performed after obtaining a sample piece composed of only the target layer.
• Ma2 and Mb2 Weight average molecular weight of polylactic acid-based resin that is a raw material of layer A and layer B Using Waters 2690 manufactured by Japan Waters Co., Ltd., using PMMA as a standard, column temperature of 40 ° C., and chloroform solvent It was measured.
• Crystallinity (%) About 5 mg of a polylactic acid resin sheet piece is weighed, held in a nitrogen atmosphere at a temperature of ⁇ 50 ° C. for 5 minutes, and then at a heating rate of 10 ° C./min up to a temperature of 240 ° C. A differential scanning calorimeter (DSC ) Measurements were made, and from the observed thermograph, the crystallization exotherm caused by crystallization during temperature rise derived from the polylactic acid resin: ⁇ Hc (J / g) and the crystal melting endotherm: ⁇ Hm (J / g) ) And calculated according to the following formula.
• Crystallinity (%) ⁇ ( ⁇ Hm ⁇ Hc) /93.6 ⁇ ⁇ 100 (11)
• AA The heat resistance parameter was 400,000 or more.
• 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 0.3, 0.5, and 0.7 by arbitrarily changing the depth of the mold, and evaluation was performed according to the following criteria.
• A Molding with a drawing ratio of 0.3, 0.5, 0.7 was possible.
• B Molding with a drawing ratio of 0.3, 0.5 was possible, but molding with a drawing ratio of 0.7 had molding defects.
• C When neither A nor B is applicable.
• Polylactic acid resin used (PLA-1): 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.
• PMMA-2 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.
• PMMA-3 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 130,000 in terms of PMMA.
• PMMA-4 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 100,000 in terms of PMMA.
• PHA-5 After adding 50 g of L-lactide (made by Musashino Chemical Laboratory Co., Ltd.) to the flask and uniformly dissolving it at a temperature of 120 ° C. under a nitrogen atmosphere, the temperature is adjusted to 150 ° C., and 0.05 g of tin octylate is added. Polymerization was carried out for minutes to obtain poly-L-lactic acid. On the other hand, poly-D-lactic acid was obtained by the same production method as poly-L-lactic acid except that D-lactide (manufactured by Musashino Chemical Laboratory Co., Ltd.) was used.
• poly-L-lactic acid and poly-D-lactic acid 50 parts by mass of each of poly-L-lactic acid and poly-D-lactic acid and 0.1 parts by mass of tin octylate were vented.
• Poly-L-lactic acid and poly-D-lactic acid polylactic acid by feeding to a twin screw extruder with melt, kneading at 220 ° C. under reduced pressure (residence time 2 minutes), and pelletizing with a strand cutter Mixture pellets were obtained.
• the obtained polylactic acid mixture pellets were put into a vacuum dryer and reacted at a temperature of 13.3 Pa at a temperature of 140 ° C. for 20 hours and further at a temperature of 180 ° C. for 30 hours to obtain PLA-5.
• PLA-5 forms a stereocomplex crystal by heat treatment.
• the weight average molecular weight in terms of PMMA is 190,000.
• PM-1 Polymethylmethacrylate (“Delpet” (registered trademark) 80NH manufactured by Asahi Kasei Chemicals Corporation, MFR: 5.5 g / 10 min (230 ° C., 3.8 kg load)
• PM-2) Polymethyl methacrylate (“SUMIPEX” (registered trademark) LG21, manufactured by Sumitomo Chemical Co., Ltd., MFR: 21 g / 10 min (230 ° C., 3.8 kg load))
• SP-1 Core-shell type rubber particles (“METABRENE” (registered trademark) S2001 manufactured by Mitsubishi Rayon Co., Ltd.
• S-MB A silica particle masterbatch containing 10% by mass of silica particles (average particle size: 3.2 ⁇ m) and 90% by mass of PLA-1 as a polylactic acid resin.
• TO-MB A titanium oxide masterbatch containing 25% by mass of titanium oxide (anatase type titanium oxide, average particle size: 0.2 ⁇ m) and 75% by mass of PLA-1 as a polylactic acid resin.
• TU-MB A talc particle masterbatch containing 20% by mass of talc particles (average particle size: 2.75 ⁇ m) and 80% by mass of PLA-1 as a polylactic acid resin.
• each vent type twin-screw extruder is basically 210 ° C., but when an appearance defect (flow mark) or the like due to laminated spots of the polylactic acid resin sheet occurs, 200 ° C. to 240 ° C. It can be changed as appropriate within the temperature range of ° C.
• the polylactic acid-based resin sheets of Examples 1 and 3 are both environmentally and heat resistant at a fairly high level, and further excellent in moldability, productivity and transparency, and suitable for use as a molded product. It was usable.
• the set temperature of the extruder that supplies the resin composition of the layer B is changed to a temperature of 225 ° C. in order to eliminate the appearance defect (flow mark) caused by the laminated spots of the sheets.
• the environmental properties and the heat resistance were compatible at a considerably high level, and further, the moldability and transparency were excellent, and it could be suitably used as a molded product application.
• the polylactic acid resin sheet of Example 4 is compatible with environmental and heat resistance at a high level, and further has excellent moldability, productivity, and transparency, and can be suitably used as a molded product. Met.
• the polylactic acid-based resin sheets of Examples 5, 7 and 8 have both environmental properties and heat resistance, and are excellent in moldability, productivity and transparency, and can be suitably used as molded product applications. It was a thing.
• the set temperature of the extruder that supplies the resin composition of the layer A is changed to a temperature of 240 ° C. in order to eliminate the appearance defect (flow mark) caused by the laminated spots of the sheets.
• it was necessary to have both environmental and heat resistance at a high level it was also excellent in moldability, productivity, and transparency, and can be suitably used as a molded product. there were.
• the preset temperature of the extruder for supplying the resin composition of the layer B was changed to a temperature of 240 ° C. in order to eliminate the appearance defect (flow mark) caused by the laminated spots of the sheets.
• the appearance defect flow mark
• both environmental properties and heat resistance were compatible, and the moldability and transparency were also excellent, and it could be suitably used as a molded product application.
• the polylactic acid-based resin sheet of Example 10 is manufactured as a white sheet and thus has low transparency, but is compatible with environmental and heat resistance at a high level, and also has excellent moldability and productivity. In addition, it can be suitably used as a molded product for which design properties such as printing are required.
• Example 11 Except that the raw materials listed in Table 1 were used in the proportions of each mass% listed in Table 1 to produce a two-layer two-layer structure consisting of layer A and layer B, and that layer A was in contact with the casting drum.
• a polylactic acid resin sheet of the present invention was obtained in the same manner as in Example 1. The evaluation results of the obtained polylactic acid resin sheet are shown in Table 2.
• the polylactic acid-based resin sheet of Example 11 is compatible with environmental and heat resistance at a high level, and has excellent transparency, moldability and productivity, and can be suitably used as a molded product. Met.
• Example 12 The polylactic acid resin sheet of the present invention was prepared in the same manner as in Example 1 except that the raw materials shown in Table 3 were used in the proportions of each mass% shown in Table 3 to form a single-layer structure consisting of only layer A. Got. The evaluation results of the obtained polylactic acid resin sheet are shown in Table 4.
• the polylactic acid resin sheet of Example 12 is compatible with environmental and heat resistance at a high level, and also has excellent transparency, moldability and productivity, and can be suitably used as a molded product application. Met.
• Example 13 A non-stretched sheet having a thickness of 1.00 mm was obtained by the same method as in Example 1 except that a single-layer structure consisting of only layer A was used.
• the unstretched sheet was 3.3 times in width in the flow direction.
• the polylactic acid resin sheet of the present invention was obtained by stretching 3 times in the direction and subjecting it to a heat setting treatment at a temperature of 100 ° C. for 20 seconds.
• the raw materials and evaluation results of the obtained polylactic acid resin sheet are shown in Tables 3 and 4.
• the polylactic acid-based resin sheet of Example 13 is slightly inferior in transparency and moldability, it is compatible with environmental and heat resistance at a high level, has excellent productivity, and is suitably used as a molded product. It was possible.
• Example 14 A non-stretched sheet having a thickness of 0.30 mm was obtained in the same manner as in Example 1 except that only a single layer A was formed, and the unstretched sheet was heat-treated at a temperature of 160 ° C. for 20 seconds. To obtain a polylactic acid resin sheet of the present invention. The raw materials and evaluation results of the obtained polylactic acid resin sheet are shown in Tables 3 and 4. Although the polylactic acid-based resin sheet of Example 14 is slightly inferior in transparency and moldability, it is compatible with environmental and heat resistance at a considerably high level, is excellent in productivity, and is suitable for use as a molded product. It was usable.
• Example 15 A sheet having a thickness of 0.30 mm was obtained by the same method as in Example 1 except that only a single layer A was used, and the unstretched sheet was subjected to heat treatment at a temperature of 100 ° C. for 20 seconds.
• the polylactic acid-type resin sheet of this invention was obtained.
• the raw materials and evaluation results of the obtained polylactic acid resin sheet are shown in Tables 3 and 4.
• the polylactic acid-based resin sheet of Example 15 is slightly inferior in transparency and moldability, but is compatible with environmental and heat resistance at a considerably high level, is excellent in productivity, and is suitable for use as a molded product. It was usable.
• Example 1 A polylactic acid resin sheet was obtained in the same manner as in Example 1 except that a single layer structure consisting only of the layer A was used.
• the raw materials and evaluation results of the obtained polylactic acid resin sheet are shown in Tables 5 and 6.
• the polylactic acid-based resin sheets of Comparative Examples 1, 2, 3 and 4 have a low polylactic acid-based resin content compared to the heat-resistant function, and cannot be said to have both environmental properties and heat resistance. there were.
• Example 5 In the same manner as in Example 1, a polylactic acid resin sheet was obtained. The raw materials and evaluation results of the obtained polylactic acid resin sheet are shown in Tables 5 and 6.
• the polylactic acid resin sheets of Comparative Examples 5, 6, 7, 8, 9, 10 and 11 are similar to the polylactic acid resin sheets of Comparative Examples 1 to 4 in comparison with the heat resistant function. The content was small and it could not be said that both environmental properties and heat resistance were compatible.

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• 2014
  • 2014-07-11 WO PCT/JP2014/068561 patent/WO2015012125A1/ja active Application Filing
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