JP2007269038A - Polylactic acid-based multilayered sheet for thermo-forming, and its formed body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polylactic acid-based multilayered sheet for thermo-forming which shows excellent forming workability and gives a formed body having a thermal resistance and a shock resistance. <P>SOLUTION: The polylactic acid-based multilayered sheet for thermo-forming has one layer composed of a polylactic acid-based polymer as a major component, stretched and thermo-fixed and the other layer composed of a polylactic acid-based polymer having a melting point by 2°C or more lower than that of the polylactic acid-based polymer of the one layer. The tensile strength of the polylactic acid-based multilayered sheet is 2 to 30 kg/cm<SP>2</SP>at 135°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polylactic acid-based multilayer sheet for thermoforming and a molded body using the sheet.

Blister processed products and box-shaped processed products widely used for display and packaging of various products are made by molding resin sheets with desired characteristics by thermoforming methods such as vacuum forming, pressure forming, bending forming, etc. It is common. For blister and box-shaped applications, transparent ones are preferred so that the product inside can be seen through the molded body. From such points, sheets of polyvinyl chloride, polyethylene terephthalate, polystyrene and the like have been used so far for resin sheets for blister applications.
In addition, PTP (press-through pack) packaging containers used for packaging pharmaceutical tablets and capsules are also molded by thermoforming, and the resin sheet is polyvinyl chloride with transparency, moldability and water vapor barrier properties. Sheets such as polyethylene terephthalate and polypropylene are used.

  However, since the resin sheet is chemically and biologically stable, it remains and accumulates with almost no decomposition even when left in a natural environment. These not only scatter and pollute the living environment of animals and plants, but even if landed as garbage, there is a problem of shortening the life of the landfill without being decomposed.

  Therefore, from the viewpoint of environmental protection, research and development of biodegradable materials have been actively conducted in recent years. One of the biodegradable materials that has been attracting attention is polylactic acid. Since the polylactic acid-based resin is biodegradable, it naturally hydrolyzes in soil or water and becomes a harmless decomposition product by microorganisms. Moreover, since the amount of combustion heat is small, even if incineration is performed, the furnace is not damaged. Furthermore, since the starting material is derived from a plant, it has features such as being able to escape from exhausted petroleum resources.

  However, since the polylactic acid-based resin has low heat resistance, problems such as deformation and fusion may occur when the sheet and the molded body thereof are stored and transported. In particular, in the summer, etc., the storage warehouse and the inside of the transportation means (for example, trucks and ships) become hot, and deformation and fusion are likely to occur. Furthermore, polylactic acid-based resins are brittle, and ordinary sheet-like materials are difficult to use.

  On the other hand, JP-A-8-73628 discloses a blister sheet and a molded article excellent in transparency and impact resistance obtained by stretching a polylactic acid-based sheet biaxially and applying a predetermined orientation. However, if sufficient impact strength is to be obtained, the required sheet thickness increases, the pressure during molding becomes excessive, and the desired shape is difficult to obtain, which is not practical.

JP-A-8-73628

  An object of the present invention is a polylactic acid-based multilayer sheet for thermoforming, which is excellent in molding processability and capable of obtaining a molded body having heat resistance and impact resistance.

The gist of the present invention is that one layer mainly composed of a polylactic acid polymer is stretched and heat-set, and a polylactic acid polymer having a melting point of 2 ° C. lower than that of the polylactic acid polymer constituting the one layer. A polylactic acid-based multilayer sheet having the other layer mainly composed of coalescence, wherein the polylactic acid-based multilayer sheet has a tensile strength at 135 ° C. of ² to 30 kg / cm ^2. It is a sheet.
Here, the other layer may contain a biodegradable aliphatic polyester other than polylactic acid.
Further, the one layer may be both outer layers, and the other layer may be at least one layer sandwiched between both outer layers.
The molded article of the present invention is characterized by being molded by thermoforming the polylactic acid-based multilayer sheet.

  A molded product obtained by thermoforming from the polylactic acid-based multilayer sheet for thermoforming of the present invention is excellent in moldability, heat resistance and impact resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

  The multi-layer polylactic acid sheet of the present invention comprises a polylactic acid-based polymer having a lower melting point than that of one layer mainly composed of a polylactic acid-based polymer and stretched and heat-set, and the polylactic acid-based polymer constituting the one layer. It is composed of the other layer whose main component is coalescence.

One layer, which is mainly composed of a polylactic acid polymer and is stretched and heat-set, will be described. The stretching is not particularly limited, but it is preferable to obtain a sheet oriented by biaxial stretching (hereinafter referred to as “biaxially oriented sheet”). The orientation index at this time is preferably 3.0 × 10 ⁻³ or more in terms of the plane orientation ΔP. In order to achieve this, it is preferable to stretch at least 1.5 times in a uniaxial direction. The stretch-oriented layer enhances impact resistance against dropping of a molded product and impact when applied to other articles.

  Following this biaxial stretching, heat treatment is performed while fixing. Thereby, the biaxially oriented sheet heat-fixed is obtained. Heat-fixing improves heat resistance. The heat setting is at a temperature of 110 to less than the melting point, and the processing time is usually in the range of 1 to 120 seconds. If it is this range, the shrinkage | contraction rate in 90 degreeC 30 minutes of the vertical direction and a horizontal direction of a biaxially oriented sheet can be 10% or less, More preferably, it can be 5% or less. If the shrinkage rate exceeds 10%, heat shrinkage tends to occur when the sheet is formed. The polylactic acid polymer used for this layer is preferably polylactic acid in which the mass ratio of either D-lactic acid or L-lactic acid is 3% or less. Excellent resistance to impact and heat at 3% or less.

  The other layer will be described. The polylactic acid polymer used has a lower melting point than the polymer used in one layer. The melting point was measured by the method shown in the examples. Each melting point difference is not particularly limited, but 2 ° C. or higher is preferable. If there is a difference in this range, it is easy to impart formability to the sheet. Specifically, a mixture of polylactic acid having a mass ratio of D-lactic acid and L-lactic acid of 3:97 to 97: 3 and an aliphatic polyester other than polylactic acid is preferable. Within this range, formability is easily imparted.

  The method for obtaining the difference in melting point between the polylactic acid polymers used in the other layer and the one layer is not particularly limited. For example, the polylactic acid polymer is obtained by the mixing ratio of D-lactic acid and L-lactic acid. Can do. It can also be obtained by including a plasticizer.

  Furthermore, it is preferable that aliphatic polyester other than the polylactic acid mentioned later is 0.1-20 mass parts with respect to 100 mass parts of polylactic acid-type resin. An impact resistance improving effect can be expected at 0.1 parts by mass or more, and transparency is excellent at 20 parts by mass or less. More preferably, it is 1-12 mass parts.

Further, the polylactic acid-based multilayer sheet of the present invention has a tensile strength of ² to 30 kg / cm ² or less. Tensile strength is defined as follows.
Curvature radius RMD (cm) of the molded product in one sheet direction (longitudinal direction), curvature radius RTD (cm) in the direction perpendicular to the sheet (lateral direction), tensile strength σMD (kg / cm ² ) of the longitudinal sheet, lateral direction When the sheet tensile strength σTD (kg / cm ² ) and the sheet thickness is t (cm), the pressure P (kg / cm ² ) required for forming is P = σMD × t / RMD + σTD × t / RTD・ ・ ・ ・ ・ Formula (1)
(See FIG. 1).

In order to obtain a uniform shape, the sheet for thermoforming is prepared in such a range that the directionality of the sheet is ignored. Therefore, Equation (1) is
P = 2σ × t / R (2)
It can be expressed as
Then, from the equation (2), the tensile strength σ
σ = P × R / 2t Equation (3)
It is.

  That is, the tensile strength σ can be obtained from the value obtained by measuring the sheet thickness t, the pressure P required for molding, and the curvature radius R of the corner of the obtained molded product with an R gauge.

  FIG. 1 will be described. The sheet 1 having a sheet thickness t fed into the mold 2 is heated by the hot platen 3. As will be described later, when the tensile strength is measured, the temperature of the sheet 1 is set to 135 ° C. When the compressed air 4 with the pressure P is injected, the sheet 1 is shaped according to the shape of the mold 2 to obtain a molded body 5. Let R be the radius of curvature of the corner of the molded body 5. From the sheet thickness t, the pressure P, and the radius of curvature R, the tensile strength σ can be obtained by Expression (3).

When the value of the tensile strength σ exceeds 30 kg / cm ² , the shape of the mold cannot be accurately shaped. If it is less than 2 kg / cm ² , sufficient heat resistance cannot be imparted. Preferably, it is 4-25 kg / cm < ² >.

  The tensile strength can be adjusted to a desired range depending on the material of the other layer having a low melting point and the layer thickness of the stretched and heat-set one layer. In addition, the range in which the directionality of the sheet described above is ignored is a range in which the ratio of the longitudinal and lateral stretch ratios is 2.5 times. That is, a sheet having a longitudinal / lateral stretching ratio ratio exceeding 2.5 is not suitable as a thermoforming sheet.

  In the present invention, one of the stretched and heat-set layers ensures the hardness of the sheet, the other layer having a low melting point ensures the softness, and the moldability is obtained with a desired range of tensile strength. In this way, a thermoforming sheet made of a biodegradable plastic, which can easily obtain a desired shape and has an appropriate strength, is provided.

  In addition, the sheet | seat temperature at the time of shaping | molding at the time of measuring a tensile strength shall be 135 degreeC. This temperature is approximately between the melting point (Tm) of polylactic acid and the melting point (Tm) of biodegradable aliphatic polyesters other than polylactic acid. That is, polylactic acid is Tg or more, and the biodegradable aliphatic polyester is in a molten state. The characteristic of the molded object which can obtain the tensile strength (sigma) of the sheet | seat in the state is pointed out.

  The tensile strength σ indicates the formability of the sheet in two dimensions (sheet plane). Viscoelasticity is a value indicating the one-dimensional forming of the sheet, but the tensile strength is excellent in showing the formability of the actual sheet.

Below, the structure of the multilayer sheet | seat of this invention is demonstrated.
The thickness of the polylactic acid-based multilayer sheet is not particularly limited as long as it is a thickness that can be used for a normal thermoforming technique, but the total thickness is usually in the range of 0.07 to 2.0 mm. In the relationship between one layer thickness and the total layer thickness of the present invention, the one layer thickness ratio is 0.07 to 0.65 with respect to the total layer thickness. Specifically, the thickness of one layer is preferably 0.005 mm or more, and more preferably 0.01 mm or more. The thickness of the other layer is a thickness obtained by subtracting the thickness of one layer from the thickness of all layers.

The polylactic acid-based multilayer sheet of the present invention may be two or more layers. However, in the case of three or more layers, the above one layer is both outer layers, and the other layer is at least one layer sandwiched between both outer layers.
Moreover, the end material generated in the manufacturing process may be regenerated and mixed in the other layer within a range not impairing the object of the present invention.
The haze of the polylactic acid-based multilayer sheet can be determined by measuring based on JIS K 7105. The haze indicates the transparency of the sheet, and when the value exceeds 20%, it is difficult to see through the article to be incorporated when the sheet is formed into a blister or the like. In particular, if a transparent molded body is desired, the haze of the polylactic acid-based multilayer sheet is preferably 20% or less.

  The manufacturing method of the polylactic acid-type multilayer sheet of this invention is demonstrated concretely. For example, (i) one layer and the other layer are coextruded and then stretched, and (ii) each layer is extruded and bonded. In any case, one layer is stretched and further heat treated under tension.

  The method (i) described above will be described. First, aliphatic polyester, inorganic particles, and the like including polylactic acid polymer and aliphatic polyester forming each layer are supplied to an extrusion apparatus for coextrusion lamination. Pellets may be produced in advance by extrusion into a strand shape with another extruder. In any case, a decrease in molecular weight due to decomposition must be taken into consideration, but the latter is preferred for uniform mixing.

  The aliphatic polyester is sufficiently dried to remove moisture, and then melted with an extruder. In consideration of changes in melting point due to composition ratio of L-lactic acid and D-lactic acid in polylactic acid polymer, melting point of aliphatic polyester, mixing ratio of polylactic acid polymer and aliphatic polyester, etc. select. In practice, a temperature range of 100 to 250 ° C. is usually selected.

  Laminate using 2 or 3 or more multi-manifolds or feed blocks, and extrude as a molten sheet of 3 or more layers from a slit die. At that time, the thickness of each layer can be set by adjusting the flow rate of the polymer with a quantitative feeder such as a gear pump installed in the melt line.

Next, the molten sheet extruded from the die is rapidly cooled and solidified on the rotating cooling drum below the glass transition temperature to obtain a substantially amorphous unoriented sheet. At this time, it is preferable to improve the adhesion between the sheet and the rotary cooling drum for the purpose of improving the smoothness and thickness unevenness of the sheet. In the present invention, the electrostatic application adhesion method and / or the liquid application adhesion method are used. Preferably it is used.
In order to adjust various physical properties, a heat stabilizer, a light stabilizer, a light absorber, a plasticizer, an inorganic filler, a colorant, a pigment, and the like can be added to these mixtures.

  Further, the above-described method (ii), a method of extruding each layer and then bonding, so-called extrusion lamination will be described. Specifically, a biaxially stretched and oriented sheet (one layer) and a molten sheet (the other layer) extruded from a die are bonded together with a rotating cooling drum and a silicon lining roll, and glass transition Rapidly solidifies below the temperature. Thus, one layer is crystallized and the other layer is a low crystalline sheet.

  The method of thermoforming the sheet obtained in the above (i) and (ii) is a vacuum forming method, a plug assist forming method, a pressure forming method, a male / female forming method, and a deformed sheet along the forming male die. Later, there is a method of expanding the molded male mold. In addition, the shape, size, etc. of the molded product shall be appropriately selected according to the application. The sheet heating method includes an infrared heater, a hot plate heater, and hot air. The sheet is preheated up to the molding temperature and thermoformed to form a blister molded product, a container-shaped molded product, and the like.

  In addition, since the outer layer is covered with a polylactic acid polymer excellent in food hygiene, the manufactured container-like molded product is directly applied to food. It can also be used as a touching container.

Hereinafter, polylactic acid and biodegradable aliphatic polyesters other than polylactic acid will be described in detail.
The polylactic acid referred to in the present invention is a homopolymer whose structural unit is L-lactic acid or D-lactic acid, that is, poly (L-lactic acid) or poly (D-lactic acid), and the structural units are L-lactic acid and D-lactic acid. The copolymer which is both, ie, poly (DL-lactic acid), and these mixtures are mentioned.

  As a polymerization method of the polylactic acid resin, any known method such as a condensation polymerization method or a ring-opening polymerization method can be employed. For example, in the polycondensation method, L-lactic acid or D-lactic acid, or a mixture thereof can be directly dehydrated and polycondensed to obtain a polylactic acid resin having an arbitrary composition.

  In the ring-opening polymerization method, a polylactic acid-based resin can be obtained using lactide, which is a cyclic dimer of lactic acid, using a catalyst appropriately selected while using a polymerization regulator or the like as necessary. Lactide includes L-lactide, which is a dimer of L-lactic acid, D-lactide, which is a dimer of D-lactic acid, and DL-lactide composed of L-lactic acid and D-lactic acid. By mixing and polymerizing, a polylactic acid resin having an arbitrary composition and crystallinity can be obtained.

Furthermore, a small amount of copolymerization component can be added as required for improving heat resistance, etc., and non-aliphatic diols such as non-aliphatic dicarboxylic acids such as terephthalic acid and ethylene oxide adducts of bisphenol A are used. You can also.
Furthermore, for the purpose of increasing the molecular weight, a small amount of a chain extender such as a diisocyanate compound, an epoxy compound, or an acid anhydride can be used.

  The polylactic acid-based resin may be a copolymer with another hydroxycarboxylic acid unit such as an α-hydroxycarboxylic acid or a copolymer with an aliphatic diol / aliphatic dicarboxylic acid.

  As other hydroxy-carboxylic acid units, optical isomers of lactic acid (D-lactic acid for L-lactic acid, L-lactic acid for D-lactic acid), glycolic acid, 3-hydroxybutyric acid, 4-hydroxy Bifunctional aliphatic hydroxy-carboxylic acids such as butyric acid, 2-hydroxy-n-butyric acid, 2-hydroxy3,3-dimethylbutyric acid, 2-hydroxy3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid and caprolactone Lactones such as butyrolactone and valerolactone.

  Examples of the aliphatic diol copolymerized with the polylactic acid resin include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid.

  The preferred range of the weight average molecular weight of the polylactic acid polymer used in the present invention is 60,000 to 700,000, more preferably 60,000 to 400,000, particularly preferably 60,000 to 300,000. When the molecular weight is less than 60,000, practical properties such as mechanical properties and heat resistance are hardly exhibited, and when it is more than 700,000, the melt viscosity is too high and the molding processability may be inferior.

  The aliphatic polyester other than polylactic acid used in the present invention will be described. The aliphatic polyester is preferably an aliphatic polyester other than polylactic acid having a glass transition temperature (Tg) of 0 ° C. or lower and a melting point (Tm) of 60 ° C. or higher. When Tg is 0 ° C. or lower, the impact resistance of the sheet is improved, and transparency is not deteriorated by preventing spherulite crystallization of the aliphatic polyester. When Tm is 60 ° C. or higher, the heat resistance is improved.

  Examples of biodegradable aliphatic polyesters other than polylactic acid include aliphatic polyesters obtained by condensing aliphatic diols and aliphatic dicarboxylic acids, aliphatic polyesters obtained by ring-opening polymerization of cyclic lactones, and synthetic aliphatics. Examples include polyesters and aliphatic polyesters biosynthesized in bacterial cells.

  An aliphatic polyester obtained by condensing an aliphatic diol and an aliphatic dicarboxylic acid is an aliphatic polyester such as ethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. It can be obtained by condensation polymerization by selecting at least one of acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid and the like. Furthermore, a desired polymer can be obtained by jumping up with an isocyanate compound or the like as necessary.

  Representative examples of the aliphatic polyester obtained by ring-opening polymerization of ring-opening lactones include ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone and the like, which are cyclic monomers, and one or more of these are selected. And polymerized.

  Examples of synthetic aliphatic polyesters include cyclic acid anhydrides and oxiranes, such as copolymers of succinic anhydride with ethylene oxide, propylene oxide, and the like.

  As the aliphatic polyester biosynthesized in the fungus body, an aliphatic polyester biosynthesized by acetylcoenteam A (acetyl CoA) in the fungus body, such as Alkaline geneus eutrophus, is known. This aliphatic polyester is mainly poly-β-hydroxybutyric acid (poly-3HB), but in order to improve practicality as a plastic, valeric acid unit (HV) is copolymerized to produce poly (3HB-co-3HV). It is industrially advantageous to use a copolymer of The HV copolymerization ratio is generally 0 to 40%. Further, a long-chain hydroxyalkanoate may be copolymerized.

  Examples of aliphatic polyesters that can be used in the present invention include polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, polycaprolactone, polyglycolic acid, polyester carbonate, polyhydroxybutyrate and polyhydroxyvalylate And at least one selected from the group consisting of copolymers and copolymers of polyhydroxybutyrate and polyhydroxyhexanoate, aliphatic or cycloaliphatic diols, aliphatic dicarboxylic acids and aliphatic oxycarboxylic acids. Can be.

The copolymer of the aliphatic or alicyclic diol, the aliphatic dicarboxylic acid and the aliphatic oxycarboxylic acid will be further described. Specific examples of the aliphatic or alicyclic diol include ethylene glycol, trimethylene glycol, 1, 3 -Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexadiol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol are preferred. In view of the physical properties of the resulting copolymer, 1,4-butanediol is preferred. Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, and lower alcohol esters thereof, succinic anhydride, adipic anhydride and the like. Succinic acid, succinic anhydride, or a mixture thereof is preferred from the viewpoint of the physical properties of the resulting copolymer. Specific examples of the aliphatic oxycarboxylic acid include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 2-hydroxy3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2 -Hydroxyisocaproic acid or a mixture thereof. Of these, lactic acid or glycolic acid is preferred for the purpose of the present invention.

  The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

The measurement method and evaluation method used in the present invention will be described.
(1) Weight average molecular weight: Using a Tosoh HLC-8120GPC gel permeation chromatograph apparatus, a calibration curve was prepared with standard polystyrene under the following measurement conditions to determine the weight average molecular weight.
Column used: Shimadzu Shim-Pack series
GPC-801C
GPC-804C
GPC-806C
GPC-8025C
GPC-800CP
Solvent: Chloroform
Sample solution concentration: O.D. 2wt / vol%
Sample solution injection volume: 200 μl
Solvent flow rate: 1.0 ml / min
Pump, column, detector temperature: 40 ° C

(2) Sheet thickness: Ten points were measured with a dial gauge SM-1201 manufactured by Teclock Co., Ltd., and the average value was used as the thickness. The unit is μm.

(3) Measurement of glass transition temperature and melting point of sheet Based on JIS-K-7121, the glass transition temperature (Tg) and melting point of polyester at a heating rate of 10 ° C./min by differential scanning calorimetry (DSC) ( Tm) was measured.

(4) Tensile Strength of Sheet After preheating the obtained sheet to 135 ° C., a mold having a diameter of 100 mm, a depth of 30 mm, a drawing ratio of 0.3, and a bottom corner R of 0.01 (cm) shown in FIG. Was molded under the conditions of a mold temperature of 50 ° C. and pressure forming (air pressure: 4 kg / cm ² ). The corner R of the obtained molded product was measured with an R gauge, and the tensile strength at the time of molding was determined from the above-described formula σ = P × R / 2t.

(5) Shape of molded body The mold forming state of the molded body obtained in the above (4) was observed and evaluated in three stages. The evaluation criteria are indicated by “◯” when a molded body having a good shape is formed, “Δ” when it is at a practical level, and “X” when the molded body has a defective shape.

(6) Impact resistance of molded body: Drop test Filled molded body obtained in (4) above is filled with water, the opening is sealed, dropped onto concrete from a height of 1 m, and the molded body is damaged. The presence or absence was examined.

(7) Heat resistance of molded body After the molded body obtained in the above (4) was allowed to stand at 60 ° C for 30 minutes in a thermostatic bath, the volume reduction rate (%) of the molded body was calculated by the following formula.
Volume reduction rate =
{1- (Molded body volume after heat treatment / Molded body volume before heat treatment)} × 100
When the volume change rate is less than 3%, it is excellent, and when it is 6% or less, it is in the practical range, and when it exceeds 6%, it cannot be used.

(8) Comprehensive evaluation Comprehensive evaluation of the molded object obtained by said (4) is shown. The evaluation criteria are “◯” that can be used satisfactorily in practical use, “Δ” that is practically usable, and “X” that is not suitable for practical use.

(Production example of polylactic acid resin)
Production Example 1
What added 15 ppm of tin octylates to 100 kg of L-lactide (trade name: PURASORB L) manufactured by Pulac Japan Co., Ltd. was put in a 500 L batch polymerization tank equipped with a stirrer and a heating device. Nitrogen substitution was performed, and polymerization was performed at 185 ° C. and a stirring speed of 100 rpm for 60 minutes. The obtained melt was supplied to a 40 mmφ co-directional twin-screw extruder manufactured by Mitsubishi Heavy Industries, which was equipped with three stages of vacuum vents, and extruded into a strand at 200 ° C. while being devolatilized at a vent pressure of 4 torr. .
The obtained polylactic acid-based resin had a weight average molecular weight of 200,000 and an L-form content of 99.5%. Moreover, the glass transition temperature by DSC was 58 degreeC, and melting | fusing point was 171 degreeC.

Production Example 2
A polylactic acid resin having a weight average molecular weight of 200,000 and an L-form content of 94.8% was obtained in the same manner as in Experimental Example 1 except that 90 kg of L-lactide and 10 kg of DL-lactide were used. The glass transition temperature by DSC was 56 ° C., and the melting point was 165 ° C.

Production Example 3
A polylactic acid resin having a weight average molecular weight of 200,000 and an L-form content of 89.7% was obtained in the same manner as in Experimental Example 1 except that 80 kg of L-lactide and 20 kg of DL-lactide were used. There was no melting point by DSC and it was confirmed to be amorphous.

(Examples 1-8 , Comparative Examples 1 and 2)
Polylactic acid-based resin obtained in Production Example 2 (L-lactic acid: D-lactic acid = 94.8: 5.2, glass transition temperature 56 ° C., melting point 165 ° C.) has a glass transition point of −45 ° C. at 100 parts by mass. Polybutylene succinate / adipate (trade name: Bionore # 3003, manufactured by Showa Polymer Co., Ltd.), which is a biodegradable aliphatic polyester having a melting point of 94 ° C., is dried, mixed and melt extruded. The pellet obtained in the above was extruded from a multi-manifold die as an intermediate layer (for the other layer) at 210 ° C. with a 40 mmφ single-screw extruder.

  Moreover, the average particle diameter 1 dried to 100 weight part of polylactic acid-type resin (L-lactic acid: D-lactic acid = 99.5: 0.5, glass transition temperature 58 degreeC, melting | fusing point 171 degreeC) obtained by manufacture example 1 .4 μm granular silica (trade name: Cicilia 100, manufactured by Fuji Silysia Chemical Co., Ltd.) 0.1 parts by weight are mixed and front and back layers (for one layer) from the above die by a 25 mmφ same-direction biaxial extruder. Extruded at 210 ° C.

  The extrusion amount was adjusted so that the thickness ratio of the surface layer, the intermediate layer, and the back layer was about 1: 5: 1. This coextruded sheet was quenched with a casting roll at about 43 ° C. to obtain an unstretched sheet. Subsequently, the obtained sheet was heated to 75 ° C. using an infrared heater in contact with a hot water circulation roll using a film tenter manufactured by Mitsubishi Heavy Industries, Ltd. Then, this longitudinally stretched sheet is guided to a tenter while being gripped with a clip, stretched 2.8 times at 75 ° C. in the vertical direction of the sheet flow, and then heat treated at 135 ° C. for about 30 seconds to create a 300 μm thick sheet did. This sheet was used as the sheet of Example 1.

  Note that the front and back layers are one layer indicated in the present application, and the intermediate layer is the other layer indicated in the present application. Further, as described above, the melting point of the polylactic acid polymer portion of the front and back layers is 171 ° C., and the melting point of the polylactic acid polymer portion of the intermediate layer is 165 ° C.

Hereinafter, the amount of polybutylene succinate / adipate, which is a biodegradable aliphatic polyester, was changed as shown in Table 1, and Examples 2 to 5 were changed, and the configurations of the front and back layers were changed to Examples 6 to 8 and Comparative Examples. 1 and 2 were created.
The tensile strength of the obtained sheet is shown in Table 1. Examples are within the scope of the present invention and comparative examples are out of scope. Further, Table 1 shows the formability, heat resistance, impact resistance, and comprehensive evaluation showing the shape of the molded body obtained from the sheet.

Examples 1 to 8 show results above the practical range for each of the above evaluation measurements, and the overall evaluation is Δ or more. In particular, in Examples 2 to 6 in which the tensile strength is in the range of 4 to 25 kg / cm ² , the overall evaluation is “good”. On the other hand, Comparative Example 1 in which the tensile strength is outside the scope of the present invention has a poor shape of the obtained molded product, and Comparative Example 2 has insufficient heat resistance.

(Examples 9-11, Comparative Examples 3-5)
As shown in Table 2, Examples 9 to 11 and Comparative Examples 3 and 4 were obtained in the same manner as Example 4 except as described below.
In Examples 9 to 11, the following compounds were used as the biodegradable aliphatic polyester used for the intermediate layer. Example 9 uses polycaprolactone (trade name Cell Green P-H7, manufactured by Daicel Chemical Industries, glass transition temperature −60 ° C., melting point 60 ° C.), and Example 10 uses polybutylene succinate (trade name Bionore). # 1001, Showa Polymer Co., Ltd., glass transition temperature −40 ° C., melting point 111 ° C., and Example 11 was polybutylene adipate terephthalate (trade name Ecoflex, manufactured by BASF, glass transition temperature −30 ° C., Melting point 109 ° C.) was used.
In Comparative Example 3, polyhydroxybutyrate (trade name Biogreen, manufactured by Mitsubishi Gas Chemical Co., Ltd., glass transition temperature 4 ° C., melting point 180 ° C.) was used for the intermediate layer. In Comparative Example 4, no heat treatment was performed after stretching. In Comparative Example 5, stretching and heat treatment were not performed.
The tensile strength of the obtained sheet is shown in Table 2. Examples 9-11 and Comparative Example 4 are within the scope of the present invention, and Comparative Examples 3 and 5 are out of range. Further, Table 2 shows the moldability, heat resistance, impact resistance, and comprehensive evaluation showing the shape of the molded body obtained from the sheet.
The melting point of the polylactic acid polymer portion of the front and back layers (one layer) is 171 ° C., and the melting point of the polylactic acid polymer portion of the intermediate layer (the other layer) is 165 ° C.
Examples 9 to 11 show results above the practical range for each of the above evaluation measurements, and the overall evaluation is Δ or more. In particular, in Examples 10 and 11, the overall evaluation is particularly good. On the other hand, in Comparative Example 3 where the tensile strength is larger than the invention range, the shape of the molded body is poor. Further, Comparative Example 4 without heat treatment has insufficient heat resistance even if the tensile strength is within the range of the invention. Further, Comparative Example 5 which is not stretched and heat-fixed and the front and back layers are not stretched is inferior in heat resistance and impact resistance even if the tensile strength is within the range of the invention.

(Examples 12 and 13)
Extruded sheets were obtained in the same manner as in Example 1 using the polylactic acid resin (L-lactic acid: D-lactic acid = 99.5: 0.5) obtained in Production Example 1. Subsequently, the obtained sheet was heated to 75 ° C. using an infrared heater in contact with a hot water circulating roll using a film tenter manufactured by Mitsubishi Heavy Industries, Ltd., and 3.0 in the longitudinal direction between the peripheral speed difference rolls. Then, this longitudinally stretched sheet is guided to a tenter while being gripped with a clip, stretched 3.0 times at 75 ° C. in the vertical direction of the sheet flow, and then subjected to heat treatment for about 15 seconds at 135 ° C. for 15 μm and 25 μm thickness. A stretched sheet was prepared.

  Next, the polylactic acid resin obtained in Production Example 2 (L-lactic acid: D-lactic acid = 94.8: 5.2) was sufficiently dried by mixing 7 parts by weight of Bionore 3003 as a biodegradable polyester. Thereafter, the molten sheet extruded from the die as an intermediate layer was supplied to a single-screw extruder, and the above-mentioned 15 μm-thick stretched and oriented biaxial sheet was used as the front and back layers, and the front and back sheets were lined up at 40 ° C. A sheet of Example 12 having a thickness of 300 μm and having a low crystallinity in the surface layer and a substantially crystalline intermediate layer was obtained by sandwiching between a rotary cooling drum and a silicon lining roll, each of which was temperature-controlled.

Furthermore, the raw material of the polylactic acid resin obtained in Production Example 3 (L-lactic acid: D-lactic acid = 89.7: 10.3, non-melting point amorphous) was used for the intermediate layer, and the surface layer was 25 μm as described above. Example 13 sheet of 300 μm was obtained in the same manner as Example 12 except that the biaxially stretched sheet was used.
The tensile strength of the obtained sheet is shown in Table 2. Further, Table 2 shows the moldability, heat resistance, impact resistance, and comprehensive evaluation showing the shape of the molded body obtained from the sheet.
Examples 12 and 13 show results beyond the practical range in each of the above evaluation measurements, and the overall evaluation is Δ.

  A molded product obtained by thermoforming from the polylactic acid-based multilayer sheet for thermoforming of the present invention is excellent in moldability, heat resistance and impact resistance.

It is sectional drawing which shows the structure of the apparatus for forming the molding of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sheet 2 Mold 3 Hot platen 4 Pressure air 5 Molded object

Claims (3)

One layer mainly composed of a polylactic acid polymer and stretched and heat-set, and a polylactic acid polymer whose melting point is 2 ° C. lower than the polylactic acid polymer constituting the one layer as a main component A polylactic acid-based multilayer sheet having the other layer, wherein the polylactic acid-based multilayer sheet has a tensile strength at 135 ° C. of 2-30 kg / cm ² .   The polylactic acid-based multilayer sheet for thermoforming according to claim 1, wherein the other layer contains a biodegradable aliphatic polyester other than polylactic acid.   3. A molded article obtained by thermoforming the polylactic acid-based multilayer sheet according to claim 1 or 2.

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